JP2008019237A - Method for producing bis(3-hydroxy-4-aminophenyl) compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a bis(3-hydroxy-4-aminophenyl) compound and to provide related compounds such as its intermediate. <P>SOLUTION: The method for producing the bis(3-hydroxy-4-aminophenyl) compound represented by general formula (3) comprises reacting a (3-halogeno-4-acylaminophenyl) compound with a base to provide a compound represented by general formula (2) and hydrolyzing the compound represented by general formula (2). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel method for producing a bis (3-hydroxy-4-aminophenyl) compound useful as a raw material for polymers or functional materials, and related compounds such as intermediates thereof.

  Bis (3-hydroxy-4-aminophenyl) compounds are useful as raw materials for polyimide resins and polybenzoxazole resins.

For example, 2,2-bis (3-hydroxy-4-aminophenyl) propane is known to be useful as an additive for a polyimide silicon resin used as an electrode composition or the like (see Patent Documents 1 and 2). ). Further, for example, 2,2-bis (3-hydroxy-4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane is known to be useful as a raw material for plastic optical waveguide materials. (See Patent Document 3).

  However, the above 2,2-bis (3-hydroxy-4-aminophenyl) propane and 2,2-bis (3-hydroxy-4-aminophenyl) -1,1,1,3,3,3-hexa Although a so-called CAS registration number is given to fluoropropane, there is no document disclosing information on its production method and physical properties.

JP 2005-113059 A JP 2002-289196 A JP 2004-3000255 A

  There has been a demand for the development of a production method suitable for industrial production of a bis (3-hydroxy-4-aminophenyl) compound useful as a raw material for polymers or functional materials.

  In view of the situation as described above, the present inventors have conducted extensive research on a method for producing a bis (3-hydroxy-4-aminophenyl) compound, and as a result, bis (4-aminophenyl) that can be produced by a known method. Bis (3-halogeno) obtained by N-acylation of a compound followed by halogenation or by N-acylation of a bis (3-halogeno-4-aminophenyl) compound that can be produced by a known method The bis (benzoxazol-6-yl) compound can be easily synthesized by reacting the base with the base, preferably in the presence of a copper catalyst, and then the bis (benzoxazole- 6-yl) By hydrolyzing the compound, the desired bis (3-hydroxy-4-aminophenyl) compound can be easily obtained in good yield. It found that obtained, and have completed the present invention based on this finding.

  The method of the present invention provides a method for easily producing a bis (3-hydroxy-4-aminophenyl) compound. That is, according to the present invention, bis (4-aminophenyl) compound that can be produced by a known method is N-acylated and then halogenated, or bis (3-halogeno-4-amino that can be produced by a known method. Phenyl) compound is N-acylated to obtain a bis (3-halogeno-4-acylaminophenyl) compound, etc., and is hydrolyzed to be useful as a raw material for polymers or functional materials. The desired bis (3-hydroxy-4-aminophenyl) compound can be produced in a high yield with a simple operation. Moreover, the method of manufacturing efficiently the bis (3-hydroxy-4-aminophenyl) compound which has not been reported by the literature conventionally is provided. In addition, according to the present invention, an aniline compound that is inexpensive and easily available is used as a starting material, a bis (3-halogeno-4-acylaminophenyl) derivative is synthesized, and then this is led to a bisbenzoxazole derivative, which is then hydrolyzed. Get the object. The method of the present invention is an industrially excellent method that can produce the desired bisaminophenols with high selectivity and efficiency by a simple operation without using a special reaction apparatus.

  Hereinafter, the present invention will be described in detail.

  The present invention solves the above-mentioned problems by providing the inventions described in the following items [1] to [99].

[1] General formula (1)

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent,
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or a substituted group. An aryl group which may have a group,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )

(3-halogeno-4-acylaminophenyl) represented by general formula (2)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A represent the same meaning as described above.)

And then hydrolyzing the bis (benzoxazol-6-yl) compound represented by the general formula (3)

(Wherein R ₁ , R ₂ , R ₃ and A represent the same meaning as described above.)

The manufacturing method of the bis (3-hydroxy-4-aminophenyl) compound represented by these.

[2] The bis (1) described in [1], wherein the reaction between the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) and a base is performed in the presence of a copper compound. 3-hydroxy-4-aminophenyl) compound production method.

[3] A reaction between a bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) and a base is converted to 8-hydroxyquinoline copper (II) (hereinafter referred to as “this”). In the presence of “Oxin Copper”.) The process for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1].

[4] Bis (3-hydroxy-4-amino) according to [1], wherein the bis (benzoxazol-6-yl) compound represented by the general formula (2) is hydrolyzed under acidic conditions. (Phenyl) Compound Production Method.

[5] The reaction between the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) and a base is carried out in the presence of a copper compound, and the bis ( The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1], wherein hydrolysis of the benzoxazol-6-yl) compound is performed under acidic conditions.

[6] The reaction of the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) with a base is carried out in the presence of 8-hydroxyquinoline copper (II), and the general formula (2) The process for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1], wherein the hydrolysis of the bis (benzoxazol-6-yl) compound represented by formula (1) is carried out under acidic conditions.

[7] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1. The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a -C8 alkyl group or a C1-C8 substituted alkyl group substituted with one or more halogen atoms.

[8] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or a phenyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1. The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a -C8 alkyl group.

[9] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl. A method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a group.

[10] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are 1 The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a C1-C8 substituted alkyl group substituted with the above halogen atom.

[11] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ , R ₆ are tri The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a fluoromethyl group.

[12] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. Or a method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a C1-C8 substituted alkyl group substituted with a group or one or more halogen atoms.

[13] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. A method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a group.

[14] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl groups. And [1] to [6]. A method for producing a bis (3-hydroxy-4-aminophenyl) compound.

[15] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are one or more halogen atoms The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a C1-C8 substituted alkyl group substituted with an atom.

[16] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are trifluoromethyl groups. The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6].

[17] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl groups or 1 The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a C1-C8 substituted alkyl group substituted with the above halogen atom.

[18] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl groups. And [1] to [6]. A method for producing a bis (3-hydroxy-4-aminophenyl) compound.

[19] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl groups. ] The manufacturing method of the bis (3-hydroxy-4-aminophenyl) compound as described in [6].

[20] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are substituted with one or more halogen atoms. The method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [1] to [6], which is a C1-C8 substituted alkyl group.

[21] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are trifluoromethyl groups. [1] A method for producing a bis (3-hydroxy-4-aminophenyl) compound according to [6].

[22] The bis of any one of [1] to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, and A is —O—. A method for producing a (3-hydroxy-4-aminophenyl) compound.

[23] R ₁ , R ₂ , R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is —O—. (Hydroxy-4-aminophenyl) compound production method.

[24] Bis (3-hydroxy-4) according to [1] to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is —O—. -Aminophenyl) Compound production method.

[25] The description of [1] to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, and A is —SO ₂ —. A method for producing a bis (3-hydroxy-4-aminophenyl) compound.

[26] The bis (3) according to [1] to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is —SO ₂ —. -Hydroxy-4-aminophenyl) compound production method.

[27] Bis (3-hydroxy-) according to [1] to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group and A is —SO ₂ —. 4-aminophenyl) compound production method.

[28] The bis (1) to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, and A is a single bond. 3-hydroxy-4-aminophenyl) compound production method.

[39] The bis (3-hydroxy group according to [1] to [6], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is a single bond. -4-aminophenyl) compound production method.

[30] _{R 1,} R 2, _{R 3} are all hydrogen atoms, _{R 4} is a methyl group, A is a single bond, [1] to [6], wherein the (3-hydroxy-4-amino (Phenyl) Compound Production Method.

[31] General formula (1)

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent,
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or a substituted group. An aryl group which may have a group,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )

A base is reacted with a bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (2)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A represent the same meaning as described above.)

The manufacturing method of the bis (benzoxazol-6-yl) compound represented by these.

[32] The bis (31) according to [31], wherein the reaction between the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) and the base is carried out in the presence of a copper compound. Benzoxazol-6-yl) compound production method.

[33] The reaction of the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) with a base is performed in the presence of 8-hydroxyquinoline copper (II). 31] The manufacturing method of the bis (benzoxazol-6-yl) compound of description.

[34] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1. The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a -C8 alkyl group or a C1-C8 substituted alkyl group substituted with one or more halogen atoms.

[35] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or a phenyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1. The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a -C8 alkyl group.

[36] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl. A method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a group.

[37] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are 1 The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a C1-C8 substituted alkyl group substituted with the above halogen atom.

[38] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are tri The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a fluoromethyl group.

[39] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. Or a method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a C1-C8 substituted alkyl group substituted with one or more halogen atoms.

[40] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. A method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a group.

[41] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl groups. [31] to [33], a method for producing a bis (benzoxazol-6-yl) compound.

[42] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are one or more halogen atoms The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a C1-C8 substituted alkyl group substituted with an atom.

[43] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are trifluoromethyl groups. The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33].

[44] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, R ₅ and R ₆ are C1-C8 alkyl groups or 1 The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a C1-C8 substituted alkyl group substituted with the above halogen atom.

[45] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl groups. [31] to [33], a method for producing a bis (benzoxazol-6-yl) compound.

[46] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl groups. ] Thru | or the manufacturing method of the bis (benzoxazol-6-yl) compound of [33] description.

[47] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are substituted with one or more halogen atoms The method for producing a bis (benzoxazol-6-yl) compound according to [31] to [33], which is a C1-C8 substituted alkyl group.

[48] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are trifluoromethyl groups. [31] The method for producing a bis (benzoxazol-6-yl) compound according to [33].

[49] The bis according to [31] to [33], wherein R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, and A is —O—. A method for producing a (benzoxazol-6-yl) compound.

[50] _{R 1,} R 2, _{R 3} are all hydrogen atoms, _{R 4} is a C1-C8 alkyl group, A is -O-, and claims 12 to according bis (benzoxazol-6 I) Compound production method.

[51] Bis (benzoxazole-6- 6) according to [31] to [33], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is —O—. I) Compound production method.

[52] is _{R 1,} R 2, _{R 3} are all hydrogen atoms, _{R 4} is a C1-C8 alkyl group or an aryl group, A is -SO ₂ - is, [31] to [33] described A method for producing a bis (benzoxazol-6-yl) compound.

[53] The bis (benzoate) according to [31] to [33], wherein R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is —SO ₂ —. Method for producing oxazol-6-yl) compound.

[54] Bis (benzoxazole-6) according to [31] to [33], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is —SO ₂ —. -Yl) A method for producing a compound.

[55] The bis (31) to [33], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, and A is a single bond. Benzoxazol-6-yl) compound production method.

[56] Bis (benzoxazole-) according to [31] to [33], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is a single bond. 6-yl) A method for producing a compound.

[57] Bis (benzoxazol-6-yl) according to [31] to [33], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is a single bond. ) Method for producing compound.

[58] General formula (2)

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent,
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or a substituted group. An aryl group which may have a group,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )

The bis (benzoxazol-6-yl) compound represented by these.

[59] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1. The bis (benzoxazol-6-yl) compound according to [58], which is a -C8 alkyl group or a C1-C8 substituted alkyl group substituted with one or more halogen atoms.

[60] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or a phenyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1. The bis (benzoxazol-6-yl) compound according to [58], which is a -C8 alkyl group.

[61] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl. The bis (benzoxazol-6-yl) compound according to [58], which is a group.

[62] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are 1 The bis (benzoxazol-6-yl) compound according to [58], which is a C1-C8 substituted alkyl group substituted with the above halogen atom.

[63] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are tri The bis (benzoxazol-6-yl) compound according to [58], which is a fluoromethyl group.

[64] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. The bis (benzoxazol-6-yl) compound according to [58], which is a C1-C8 substituted alkyl group substituted with a group or one or more halogen atoms.

[65] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. The bis (benzoxazol-6-yl) compound according to [58], which is a group.

[66] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl groups. [58] The bis (benzoxazol-6-yl) compound according to [58].

[67] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are one or more halogen atoms The bis (benzoxazol-6-yl) compound according to [58], which is a C1-C8 substituted alkyl group substituted with an atom.

[68] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are trifluoromethyl groups. The bis (benzoxazol-6-yl) compound according to [58].

[69] R ₁ , R ₂ , R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, R ₅ , R ₆ are C1-C8 alkyl groups or 1 The bis (benzoxazol-6-yl) compound according to [58], which is a C1-C8 substituted alkyl group substituted with the above halogen atom.

[70] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl groups. [58] The bis (benzoxazol-6-yl) compound according to [58].

[71] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are methyl groups. ] The bis (benzoxazol-6-yl) compound of description.

[72] R ₁ , R ₂ , and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are substituted with one or more halogen atoms The bis (benzoxazol-6-yl) compound according to [58], which is a C1-C8 substituted alkyl group.

[73] R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are trifluoromethyl groups. [58] The bis (benzoxazol-6-yl) compound according to [58].

[74] The bis (benzoxazole-) according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, and A is —O—. 6-yl) compounds.

[75] Bis (benzoxazol-6-yl) according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is —O—. )Compound.
[76] The bis (benzoxazol-6-yl) compound according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is —O—.

[77] The bis (benzoxazole) according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, and A is —SO ₂ —. -6-yl) compound.

[78] The bis (benzoxazole-6- 6) according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is —SO ₂ —. Yl) compounds.

[79] The bis (benzoxazol-6-yl) compound according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is —SO ₂ —. .

[80] Bis (benzoxazole-6) according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or an aryl group, and A is a single bond. -Yl) compounds.

[81] Bis (benzoxazol-6-yl) according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group, and A is a single bond. Compound.

[82] The bis (benzoxazol-6-yl) compound according to [58], wherein R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a methyl group, and A is a single bond.

[83] General formula (4)

(R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or An aryl group which may have a substituent,
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )

A bis (3-halogeno-4-acylaminophenyl) methane compound represented by the formula:

[84] The description of [83], wherein R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are a C1-C8 alkyl group or a C1-C8 alkyl group substituted with one or more halogen atoms. Of the bis (3-halogeno-4-acylaminophenyl) methane compound.

[85] The bis (3-halogeno-4-acylaminophenyl) methane compound according to [83], wherein R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are C1-C8 alkyl groups. .

[86] The bis (3-halogeno-4-acylaminophenyl) methane compound according to [83], wherein R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are methyl groups.

[87] The bis (3-halogenocene according to [83], wherein R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are C1-C8 alkyl groups substituted with one or more halogen atoms. -4-acylaminophenyl) methane compound.

[88] The bis (3-halogeno-4-acylaminophenyl) methane compound according to [83], wherein R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are a trifluoromethyl group.

[89] X is bromine, R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are C1-C8 alkyl groups or a C1-C8 alkyl group substituted with one or more halogen atoms. A bis (3-halogeno-4-acylaminophenyl) methane compound according to [83].

[90] Bis (3-halogeno-4-yl according to [83], wherein X is bromine, R ₄ is a C1-C8 alkyl group or aryl group, and R ₅ and R ₆ are C1-C8 alkyl groups. Acylaminophenyl) methane compound.

[91] Bis (3-halogeno-4-acylaminophenyl) according to [83], wherein X is bromine, R ₄ is a C1-C8 alkyl group or aryl group, and R ₅ and R ₆ are methyl groups. ) Methane compounds.

[92] The description of [83], wherein X is bromine, R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are C1-C8 alkyl groups substituted with one or more halogen atoms. Of the bis (3-halogeno-4-acylaminophenyl) methane compound.

[93] Bis (3-halogeno-4-acyl) according to [83], wherein X is bromine, R ₄ is a C1-C8 alkyl group or aryl group, and R ₅ and R ₆ are trifluoromethyl groups. Aminophenyl) methane compounds.

[94] The bis (3-halogeno-4-acylaminophenyl) methane compound according to [83], wherein X is chlorine and R ₄ is a phenyl group.

[95] General formula (5)

(Wherein R ₇ and R ₈ may be the same or different and each independently represents a C1 to C8 alkyl group or a C1 to C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Good. )

A bis (3-hydroxy-4-aminophenyl) compound represented by the formula:

[96] The bis (3-hydroxy-4-aminophenyl) compound according to [95], wherein R ₇ and R ₈ are C1-C8 alkyl groups.

[97] The bis (3-halogeno-4-acylaminophenyl) methane compound according to [95], wherein R ₇ and R ₈ are methyl groups.

[98] The bis (3-hydroxy-4-aminophenyl) compound according to [95], wherein R ₇ and R ₈ are C1-C8 alkyl groups substituted with one or more halogen atoms.

[99] The bis (3-halogeno-4-acylaminophenyl) methane compound according to [95], wherein R ₇ and R ₈ are trifluoromethyl groups.

  Hereinafter, the present invention will be described in detail.

  First, terms used in this specification will be described.

“Halogen atom” means, for example, fluorine, chlorine, bromine or iodine.
“C1-C8 alkyl group” means, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group. , N-heptyl group, and n-octyl group, including 1 to 8 carbon atoms (hereinafter, when the carbon number is, for example, 1 to 8 carbon atoms, this is expressed as “C1-C8”. ) Linear or branched alkyl group.

  The “C3-C8 cycloalkyl group” means a C3-C8 cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like.

  “C1-C8 alkyl group substituted with one or more halogen atoms” means, for example, a fluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group Or a group substituted with one or more halogen atoms (C1-C8 alkyl having the above meaning).

  “C1-C8 alkoxy group” means, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n- It means a (C1-C8 alkyl having the above-mentioned meaning) -O- group in which the alkyl moiety includes the hexyloxy group, n-heptyloxy group, n-octyloxy group, and the like.

  “Mono or di (C1-C8 alkyl) amino group” means, for example, methylamino group, dimethylamino group, propylamino group, di (isopropyl) amino group, N, N-methylpropylamino group, butylamino group, A mono- or di (C1-C8 alkyl having the above-mentioned meaning) amino group having an above-mentioned meaning, including an octylamino group and the like.

  Examples of the “aryl group optionally having a substituent” include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, 4-methoxyphenyl group, 3-methoxy-4-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 3-aminophenyl group, 4-aminophenyl group, 3-amino-4-hydroxyphenyl group, 3-methylaminophenyl group, 4-methylaminophenyl group, 3- Including dimethylaminophenyl group, 4-dimethylaminophenyl group, 1-naphthyl group, 2-naphthyl group, etc. 1-C6 alkyl group, C1-C6 alkoxy group, halogen atom, nitro group, hydroxyl group, amino group, mono (C1-C6 alkyl) amino group, di (C1-C6 alkyl) amino group and the like may be substituted. Mean a mono- or fused-ring C6-C14 aryl group.

  Production method of bis (3-hydroxy-4-aminophenyl) compound represented by general formula (3) from bis (3-halogeno-4-acylaminophenyl) compound represented by general formula (1) ( This corresponds to the present invention [1] to [30].

  The methods [1] to [30] of the present invention comprise reacting a bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) with a base, preferably in the presence of a copper catalyst. A bis (benzoxazol-6-yl) compound represented by the formula (2) is obtained (corresponding to the present invention [31] to [57]) and is further hydrolyzed. It is a manufacturing method of the bis (3-hydroxy-4-aminophenyl) compound represented by Formula (3).

  First, a base is reacted with the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1), preferably in the presence of a copper catalyst, and the corresponding bis (benzoxazol-6-yl). The step of obtaining compounds (corresponding to the present invention [31] to [57]) will be described.

  First, the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) used as a raw material for the inventive methods [1] to [30] will be described.

R ₁ , R ₂ and R ₃ in the general formula (1) may be the same or different and are each independently a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group 1 A C1-C8 alkyl group substituted with the above halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent; Show
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, or an aryl group which may have a substituent,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine.

For substituents R _{1 to} R ₆ , if possible, these substituents are further
For example, linear or branched C1-C6 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group; for example, a cyclic C1-C8 alkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; a hydroxy group; for example, a straight chain such as a methoxy group, an ethoxy group, an n-propoxy group, Chain or branched C1-C6 alkoxy group; for example, linear or branched C1-C6 haloalkyl group such as fluoromethyl group, difluoromethyl group, trifluoromethyl group; nitro group; amino group; for example, methylamino group, ethylamino A linear or branched C1-C6 alkylamino group, such as a group or a dimethylamino group;
It may be substituted with a substituent such as an aryl group such as a phenyl group or a naphthyl group; an aryloxy group such as a phenoxy group or a naphthyloxy group;

Specific examples of the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) that can be used in this reaction include, for example,
2,2-bis (3-chloro-4-formylaminophenyl) propane, 2,2-bis (4-acetylamino-3-chlorophenyl) propane, 2,2-bis (3-chlorophenyl-4-propionylamino) Propane, 2,2-bis (3-chlorophenyl-4-iso-propionylamino) propane, 2,2-bis (4-butyrylamino-3-chlorophenyl) propane, 2,2-bis (4-sec-butyrylamino-3) -Chlorophenyl) propane, 2,2-bis (4-tert-butyrylamino-3-chlorophenyl) propane, 2,2-bis (4-pentanoylamino-3-chlorophenyl) propane, 2,2-bis (3-chlorophenyl) -4-hexanoylamino) propane, 2,2-bis (3-chlorophenyl-4-octanoyl) Amino) propane, 2,2-bis (4-benzoylamino-3-chlorophenyl) propane, 2,2-bis (3-chloro-4- (2′-methyl) benzoylaminophenyl) propane, 2,2-bis (3-chloro-4- (3'-methyl) benzoylaminophenyl) propane, 2,2-bis (3-chloro-4- (4'-methyl) benzoylaminophenyl) propane, 2,2-bis (3 -Chloro-4- (2'-methoxy) benzoylaminophenyl) propane, 2,2-bis (3-chloro-4- (3'-methoxy) benzoylaminophenyl) propane, 2,2-bis (3-chloro -4- (4'-methoxy) benzoylaminophenyl) propane, 2,2-bis (3-chloro-4- (2'-chloro) benzoylamino-phenyl) propane, 2,2-bi (3-chloro-4- (3′-chloro) benzoylamino-phenyl) propane, 2,2-bis (3-chloro-4- (4′-chloro) benzoylaminophenyl) propane, 2,2-bis (3-chloro-4- (2 ′, 4′dichloro-) benzoylaminophenyl) propane, 2,2-bis (3-chloro-4- (3′-nitro) benzoylaminophenyl) propane, 2,2- Bis (3-chloro-4- (4′-nitro) benzoylaminophenyl) propane, 2,2-bis (4-acetylamino-3-chloro-5-methylphenyl) propane, 2,2-bis (4- tert-butyrylamino-3-chloro-5-methylphenyl) propane, 2,2-bis (4-benzoylamino-3-chloro-5-methylphenyl) propane, 2,2-bis (4-acetyl) Amino-3-chloro-6-methylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-chloro-6-methylphenyl) propane, 2,2-bis (4-benzoylamino-3-chloro) -6-methylphenyl) propane, 2,2-bis (4-acetylamino-3-chloro-2-methylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-chloro-2-methylphenyl) ) Propane, 2,2-bis (4-benzoylamino-3-chloro-2-methylphenyl) propane, 2,2-bis (4-acetylamino-3-chloro-5-ethylphenyl) propane, 2,2 -Bis (4-tert-butyrylamino-3-chloro-5-ethylphenyl) propane, 2,2-bis (4-benzoylamino-3-chloro- -Ethylphenyl) propane, 2,2-bis (4-acetylamino-3-chloro-5-propylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-chloro-5-propylphenyl) propane 2,2-bis (4-benzoylamino-3-chloro-5-propylphenyl) propane, 2,2-bis (4-acetylamino-3-chloro-5-iso-propylphenyl) propane, 2,2 -Bis (4-tert-butyrylamino-3-chloro-5-iso-propylphenyl) propane, 2,2-bis (4-benzoylamino-3-chloro-5-iso-propylphenyl) propane, 2,2- Bis (4-acetylamino-3-chloro-5-butylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3) -Chloro-5-butylphenyl) propane, 2,2-bis (4-benzoylamino-3-chloro-5-butylphenyl) propane, 2,2-bis (4-acetylamino-3-chloro-2,5) -Dimethylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-chloro-2,5-dimethylphenyl) propane, 2,2-bis (4-benzoylamino-3-chloro-2,5- Dimethylphenyl) propane, 2,2-bis (4-acetylamino-3,5-dichlorophenyl) propane, 2,2-bis (4-tert-butyrylamino-3,5-dichlorophenyl) propane, 2,2-bis ( 4-benzoylamino-3,5-dichlorophenyl) propane, 2,2-bis (3-bromo-4-formylaminophenyl) propane, 2, -Bis (4-acetylamino-3-bromophenyl) propane, 2,2-bis (3-bromophenyl-4-propionylamino) propane, 2,2-bis (3-bromophenyl-4-iso-propionylamino) ) Propane, 2,2-bis (4-butyrylamino-3-bromophenyl) propane, 2,2-bis (4-sec-butyrylamino-3-bromophenyl) propane, 2,2-bis (4-tert-butyrylamino) -3-bromophenyl) propane, 2,2-bis (4-pentanoylamino-3-bromophenyl) propane, 2,2-bis (3-bromophenyl-4-hexanoylamino) propane, 2,2 -Bis (3-bromophenyl-4-octanoylamino) propane, 2,2-bis (4-benzoylamino-3-bromophene) ) Propane, 2,2-bis (3-bromo-4- (2'-methyl) benzoylaminophenyl) propane, 2,2-bis (3-bromo-4- (3'-methyl) benzoylaminophenyl) Propane, 2,2-bis (3-bromo-4- (4′-methyl) benzoylaminophenyl) propane, 2,2-bis (3-bromo-4- (2′-methoxy) benzoylaminophenyl) propane, 2,2-bis (3-bromo-4- (3′-methoxy) benzoylaminophenyl) propane, 2,2-bis (3-bromo-4- (4′-methoxy) benzoylaminophenyl) propane, 2, 2-bis (3-bromo-4- (2′-chloro) benzoylamino-phenyl) propane, 2,2-bis (3-bromo-4- (3′-chloro) benzoylamino-phenyl) propa 2,2-bis (3-bromo-4- (4′-chloro) benzoylaminophenyl) propane, 2,2-bis (3-bromo-4- (2 ′, 4′dichloro-) benzoylaminophenyl ) Propane, 2,2-bis (3-bromo-4- (3′-nitro) benzoylaminophenyl) propane, 2,2-bis (3-bromo-4- (4′-nitro) benzoylaminophenyl) propane 2,2-bis (4-acetylamino-3-bromo-5-methylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-methylphenyl) propane, 2,2- Bis (4-benzoylamino-3-bromo-5-methylphenyl) propane, 2,2-bis (4-acetylamino-3-bromo-6-methylphenyl) propane, 2,2-bis (4 tert-butyrylamino-3-bromo-6-methylphenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-6-methylphenyl) propane, 2,2-bis (4-acetylamino-3-) Bromo-2-methylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-2-methylphenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-2-methyl) Phenyl) propane, 2,2-bis (4-acetylamino-3-bromo-5-ethylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-ethylphenyl) propane, 2 , 2-bis (4-benzoylamino-3-bromo-5-ethylphenyl) propane, 2,2-bis (4-acetylamino-3-butyl) Lomo-5-propylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-propylphenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-5-propyl) Phenyl) propane, 2,2-bis (4-acetylamino-3-bromo-5-iso-propylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-iso-propylphenyl) ) Propane, 2,2-bis (4-benzoylamino-3-bromo-5-iso-propylphenyl) propane, 2,2-bis (4-acetylamino-3-bromo-5-butylphenyl) propane, 2 , 2-bis (4-tert-butyrylamino-3-bromo-5-butylphenyl) propane, 2,2-bis (4-benzoyl) Mino-3-bromo-5-butylphenyl) propane, 2,2-bis (4-acetylamino-3-bromo-2,5-dimethylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3) -Bromo-2,5-dimethylphenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-2,5-dimethylphenyl) propane, 2,2-bis (4-acetylamino-3-bromo) -5-chlorophenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-chlorophenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-5-chlorophenyl) propane, 2,2-bis (4-acetylamino-3,5-dibromophenyl) propane, 2,2-bis (4-tert-butyrylamino-3, -Dibromophenyl) propane, 2,2-bis (4-benzoylamino-3,5-dibromophenyl) propane, 2,2-bis (4-acetylamino-3-bromo-5-fluorophenyl) propane, 2, 2-bis (4-tert-butyrylamino-3-bromo-5-fluorophenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-5-fluorophenyl) propane, 2,2-bis (4 -Acetylamino-3-bromo-5-trifluoromethylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-trifluoromethylphenyl) propane, 2,2-bis (4- Benzoylamino-3-bromo-5-trifluoromethylphenyl) propane, 2,2-bis (4-tert-butyrylamino) -3-bromo-5-cyc-pentylphenyl) propane, 2,2-bis (3-bromo-4-tert-butyrylamino-5-cyc-pentylphenyl) propane, 2,2-bis (4-tert-butyrylamino) -3-bromo-5-cyc-pentylphenyl) propane, 2,2-bis (4-acetylamino-3-bromo-5-cyc-hexylphenyl) propane, 2,2-bis (4-tert-butyrylamino-) 3-bromo-5-cyc-hexylphenyl) propane, 2,2-bis (4-benzoylamino-3-bromo-5-cyc-hexylphenyl) propane, 2,2-bis (4-acetylamino-3-) Bromo-5-phenylphenyl) propane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-phenylphenol) Propane, 2,2-bis (4-benzoylamino-3-bromo-5-phenylphenyl) propane, 2,2-bis (3-chloro-4-formylaminophenyl) -1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chlorophenyl) -4-propionylamino) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chlorophenyl-4-iso-propionylamino) -1,1,1,3,3 , 3-hexafluoropropane, 2,2-bis (4-butyrylamino-3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-sec-butyryl) No-3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chlorophenyl) -1,1,1,3,3 3-hexafluoropropane, 2,2-bis (4
-Pentanoylamino-3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chlorophenyl-4-hexanoylamino) -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis (3-chlorophenyl-4-octanoylamino) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4 -Benzoylamino-3-chlorophenyl) 1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (2'-methyl) benzoylaminophenyl) -1,1 , 1,3,3,3-, hexafluoropropane, 2,2-bis (3-chloro-4- (3′-methyl) benzoylaminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2,2-bi (3-Chloro-4- (4′-methyl) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (2′- Methoxy) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (3′-methoxy) benzoylaminophenyl) -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (4′-methoxy) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane 2,2-bis (3-chloro-4- (2'-chloro) benzoylamino-phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro -4- (3'-chloro) benzoylamino-phen Nyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (4′-chloro) benzoylaminophenyl) -1,1,1,3 3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (2 ′, 4′dichloro-) benzoylaminophenyl) 1,1,1,3,3,3-hexafluoropropane, 2, , 2-bis (3-chloro-4- (3′-nitro) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4- (4′-nitro) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-chloro-5-methylphenyl) -1, 1,1,3,3,3-hexafluoropropane, 2,2 Bis (4-tert-butyrylamino-3-chloro-5-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-chloro-5) -Methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-chloro-6-methylphenyl) -1,1,1,3 3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chloro-6-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Bis (4-benzoylamino-3-chloro-6-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-chloro-2-) Methylphenyl) -1 , 1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chloro-2-methylphenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis (4-benzoylamino-3-chloro-2-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino) -3-chloro-5-ethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chloro-5-ethylphenyl) -1 , 1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-chloro-5-ethylphenyl) -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis (4 Acetylamino-3-chloro-5-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chloro-5-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-chloro-5-propylphenyl) -1,1,1,3,3,3- Hexafluoropropane, 2,2-bis (4-acetylamino-3-chloro-5-iso-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4 Tert-butyrylamino-3-chloro-5-iso-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-chloro-5- i o-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-chloro-5-butylphenyl) -1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chloro-5-butylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis (4-benzoylamino-3-chloro-5-butylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-chloro-2) , 5-dimethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-chloro-2,5-dimethylphenyl) -1,1 , 1,3,3,3-hex Safluoropropane, 2,2-bis (4-benzoylamino-3-chloro-2,5-dimethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4 -Acetylamino-3,5-dichlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3,5-dichlorophenyl) -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3,5-dichlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Bis (3-bromo-4-formylaminophenyl) -1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromophenyl-4-propionylamino)- 1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromophenyl-4-iso-propionylamino) -1,1,1,3,3,3-hexafluoropropane 2,2-bis (4-butyrylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-sec-butyrylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane , 2,2-bi (4-pentanoylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromophenyl-4-hexanoylamino) -1 , 1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromophenyl-4-octanoylamino) -1,1,1,3,3,3-hexafluoropropane, 2, , 2-bis (4-benzoylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (2′-methyl) Benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (3′-methyl) benzoylaminophenyl) -1,1,1, 3,3,3-hexafluoropropane, 2, -Bis (3-bromo-4- (4'-methyl) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (2 '-Methoxy) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (3'-methoxy) benzoylaminophenyl) -1, 1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (4′-methoxy) benzoylaminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis (3-bromo-4- (2′-chloro) benzoylamino-phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3 -Bromo-4- (3'-chloro) benzoylamino -Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (4'-chloro) benzoylaminophenyl) -1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis (3-bromo-4- (2 ′, 4′dichloro-) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane 2,2-bis (3-bromo-4- (3′-nitro) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo- 4- (4′-nitro) benzoylaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-5-methylphenyl)- 1,1,1,3,3,3-hexafluoropropane 2,2-bis (4-tert-butyrylamino-3-bromo-5-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3) -Bromo-5-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-6-methylphenyl) -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-6-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-6-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3- Bromo-2-methylpheny ) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-2-methylphenyl) -1,1,1,3,3 , 3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-2-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis ( 4-acetylamino-3-bromo-5-ethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-ethyl) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-5-ethylphenyl) -1,1,1,3,3 3-hexafluoropropane, 2,2- (4-acetylamino-3-bromo-5-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5) -Propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-5-propylphenyl) -1,1,1,3 3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-5-iso-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis (4-tert-butyrylamino-3-bromo-5-iso-propylphenyl) -1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-benzoylamino-3-bromo-5-iso-propylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino- 3-bromo-5-butylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-butylphenyl) -1, 1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-5-butylphenyl) -1,1,1,3,3,3-hexafluoropropane 2,2-bis (4-acetylamino-3-bromo-2,5-dimethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert- Butyrylamino-3-bromo- , 5-dimethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-2,5-dimethylphenyl) -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-5-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis (4-tert-butyrylamino-3-bromo-5-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-) 5-chlorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3,5-dibromophenyl) -1,1,1,3,3 3-hexafluoropropaprop 2,2-bis (4-tert-butyrylamino-3,5-dibromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3, 5-Dibromophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-5-fluorophenyl) -1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-fluorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis (4-benzoylamino-3-bromo-5-fluorophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-5) -Trifluoromethyl Ruphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-trifluoromethylphenyl) -1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-5-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis (4-tert-butyrylamino-3-bromo-5-cyc-pentylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-bromo-4- tert-Butyrylamino-5-cyc-pentylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-cy -Pentylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino-3-bromo-5-cyc-hexylphenyl) -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-cyc-hexylphenyl) -1,1,1,3,3,3-hexafluororopane, 2,2-bis (4-benzoylamino-3-bromo-5-cyc-hexylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-acetylamino- 3-bromo-5-phenylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-tert-butyrylamino-3-bromo-5-phenylphenyl) -1, 1, , 3,3,3-hexafluoropropane, 2,2-bis (4-benzoylamino-3-bromo-5-phenylphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. I can do it.

  Including these, bis (3-halogeno-4-acylaminophenyl) compounds represented by the general formula (1) that can be used as raw materials for the methods [1] to [30] of the present invention (Table 1) to (Table 13) However, the raw materials used in the methods [1] to [30] of the present invention are not limited to these exemplified compounds, and if present, include optical isomers, diastereomers, salt compounds and the like. Including all compounds represented by general formula (1)

Here, the meanings of the abbreviations used in the tables of this specification will be described. Each abbreviation in the table has the following meaning.

Me: methyl group Et: ethyl group Pr: n-propyl group iso-Pr: isopropyl group iso-Bu: isobutyl group sec-Bu: sec-butyl group tert-Bu: tert-butyl group Pen: n-pentyl group Hex: n-hexyl group Oct: n-octyl group cyc-Pen: cyclopentyl group cyc-Hex: cyclohexyl group Ph: phenyl group 1-naphthyl: 1-naphthyl group 2-naphthyl group: 2-naphthyl group MeO: methoxy group iso-PrO: isopropoxy BuO: n-butoxy group NHMe: methylamino group NMe _2: dimethylamino group

For example, in the case of a 2-methylphenyl group, this is described as Ph (2-Me), and in the case of a 2,4-dichlorophenyl group, this is described as Ph (2,4-Cl ₂ ). did.

  The bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) used as a raw material in the methods [1] to [30] of the present invention is a compound per se known or General formula (a) which can be produced according to a known method (for example, see US Pat. No. US3670024)

(In the formula, R ₁ , R ₂ , R ₃ , and A have the same meaning as described above.)

Bis (4-aminophenyl) compound represented by formula (1), for example, carboxylic acid such as formic acid, acetic acid and propionic acid according to a conventional method; or acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, etc. Acid anhydrides; or acylating agents such as acid halides such as acetyl chloride, propionyl chloride, butyryl chloride, and benzoyl chloride, 1.0 to 10.0 equivalents, preferably 1.0 to 1.5 equivalents (corresponding general formula A suitable solvent (for example, dichloromethane, 1,2-dichloroethane) is used in an amount of 2.0 to 20 mol, preferably 2.0 to 3.0 mol, based on the bis (4-aminophenyl) compound represented by (a). Aliphatic halogenated hydrocarbons including chlorobenzene, o-dichlorobenzene, etc .: Aromatic halogenated hydrocarbons including benzene, xylene, etc. And an acid base (for example, an inorganic acid such as hydrochloric acid and sulfuric acid) or a base (for example, an organic base such as pyridine and triethylamine: sodium bicarbonate and the like). Bis (4-aminophenyl) compound represented by the general formula (a) obtained by N-acylation by reaction in the temperature range of 0 ° C. to the boiling point of the solvent. The compound in which the amino group is N-acylated is further added with a halogenating agent represented by chlorine, thionyl chloride, sulfuryl chloride, bromine and the like in an amount of 1.0 to 25 equivalents, preferably 1.0 to 2.5 equivalents ( The bis (4-aminophenyl) compound represented by the general formula (a) can be obtained by halogenation at 2.0 to 50 mol, preferably 2 to 5 mol). In this halogenation, an oxidizing agent such as hydrogen peroxide can be used together (SU2058302) or a base such as sodium acetate can be used in combination in order to smoothly promote halogenation with bromine or the like.

  Specifically, for example, 2,2-bis (4-aminophenyl) propane is produced by reacting aniline with acetone or bisphenol-A in the presence of an acid catalyst, and N-acylation according to the above. 2,2-bis (3-halogeno-4-acylaminophenyl) propane can be produced by the halogenating method.

  In addition, the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) is a compound known per se or manufactured according to a known method (for example, see SU664957). General formula (b) to be obtained

(In the formula, R ₁ , R ₂ , R ₃ , A, and X have the same meaning as described above.)

Or a carboxylic acid such as formic acid, acetic acid, propionic acid or the like according to a conventional method; or acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, and a bis (3-halogeno-4-aminophenyl) compound represented by Acid anhydrides such as acids; or acylating agents such as acid halides such as acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, etc., preferably 1.0 to 10 equivalents, preferably 1.0 to 1.5 equivalents (corresponding general 2.0 to 20 mol, preferably 2.0 to 3.0 mol, based on the bis (4-aminophenyl) compound represented by the formula (a) is added to an appropriate solvent (for example, dichloromethane, 1,2 -Aliphatic halogenated hydrocarbons including dichloroethane: Aromatic halogenated hydrocarbons including chlorobenzene, o-dichlorobenzene, etc. ), An acid catalyst (for example, an acid catalyst (for example, an inorganic acid such as hydrochloric acid or sulfuric acid) as necessary) or a base (for example, an organic compound such as pyridine or triethylamine). It can also be produced / obtained by reacting in the temperature range of 0 ° C. to the boiling point of the solvent and N-acylating in the presence of a base: an inorganic base including sodium hydrogencarbonate and the like.

  Specifically, for example, orthohalogenoaniline such as 2-chloroaniline, 2-chloro-6-methylaniline and the like, and bis (3-halogeno-4-amino represented by general formula (b) from acetone or bisphenol-A A 2,2-bis (3-halogeno-4-acylaminophenyl) propane derivative can be obtained by producing a phenyl) derivative and N-acylating it.

R ₄ which is an acyl group on the nitrogen atom of these bis (3-halogeno-4-aminophenyl) compounds is preferably a hydrogen atom, an aliphatic hydrocarbon, or an aromatic hydrocarbon, and among these, a methyl group, ethyl Group, propyl group, butyl group, t-butyl group and phenyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable.

  A base is reacted with the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1), preferably in the presence of a copper catalyst, and the corresponding bis (benzoxazol-6-yl) compounds. The reaction conditions and the like of the step of obtaining (corresponding to the present invention [31] to [57]) will be described.

  Although the reaction proceeds even without a copper compound in this step, it is preferable to use a copper compound. Examples of the copper compound that can be used include metallic copper; copper oxide; or salts of organic and inorganic acids and copper; A complex in which a child is bonded can be mentioned, and the valence of copper can be monovalent or divalent, and can be selected according to reactivity, the magnitude of side reactions, and other reaction characteristics.

  Specific examples of copper compounds that can be used in this step include copper powder; copper is monovalent or divalent, copper oxide, cuprous oxide: copper sulfate, copper carbonate, copper hydroxide, copper chloride, odor Examples thereof include copper iodide, copper iodide, copper acetate, copper trifluoroacetate, and 8-hydroxyquinoline copper. These copper compounds may be used alone or in a mixture of any ratio.

  These copper compounds are known compounds.

  Of these copper compounds, copper (II) sulfate, copper bromide (copper bromide) (from the standpoints of catalytic activity in this step, difficulty in side reactions such as dehalogenation, ease of handling and availability, and production costs) I), copper iodide (I), 8-hydroxyquinoline copper (II) and the like are preferable, and copper iodide (I) and 8-hydroxyquinoline copper (II) (oxine copper) are particularly excellent. Moreover, although these copper catalysts can be used independently, they can be used in the presence of a compound serving as a ligand. At the same time, several catalysts and ligands may be used in combination.

  The molar ratio of the copper catalyst used in this step is usually 0.0001 to 1.0 mol, preferably 0.001 to 0.00 mol, based on 1 mol of these raw material compounds, relative to the compound represented by the general formula (1). A range of 3 mol, more preferably a range of 0.001 to 0.2 mol can be exemplified.

  Examples of copper ligands that can be used in the reaction of this step include 8-hydroxyquinoline, 1,8-bis (dimethylamino) naphthalene, 2,2′-bipyridine, 1,10-phenanthroline, ethylenediamine, N— Methylethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, trans-1,2-cyclohexanediamine, trans-N-methyl-1,2 -Cyclohexanediamine, trans-N, N'-dimethyl-1,2-cyclohexanediamine, cis-1,2-cyclohexanediamine, cis-N-methyl-1,2-cyclohexanediamine, cis-N, N'-dimethyl -1,2-cyclohexanediamine, 1,3-diaminopropane, 1,3- (N, N′-dimethylamino) propane, ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, 3-amino-1-propanol, 3- (N-methylamino) -1-propanol, Triphenylphosphine, tri (2-methylphenyl) phosphine, tricyclohexylphosphine, tri-t-butylphosphine, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis ( Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexylphos) (Fino) butane and the like.

  In this step, the ligand may or may not be used, but when used, the molar ratio used is usually based on 1 mol of these starting compounds relative to the compound represented by the general formula (1). A range of 0 to 3.0 mol, preferably 0.001 to 0.6 mol, more preferably a range of 0.001 to 0.4 mol can be exemplified.

  Moreover, addition of a base is essential in the ring-closing reaction of this step to the bis (benzoxazol-6-yl) compound represented by the general formula (2).

  Examples of the base added to the ring-closing reaction in this step include alkali metal hydrides such as sodium hydride, potassium hydride, lithium hydride; phenyl sodium, n-butyl lithium, t-butyl lithium, sec-butyl lithium, methyl lithium. Alkali metal organic compounds such as sodium methylate, sodium ethylate, potassium t-butoxy, sodium t-butoxy; alkali metal carboxylates such as sodium acetate, potassium acetate, sodium propionate; Inorganic bases such as sodium, potassium hydroxide, calcium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate; or pyridine, (4 Dimethylamino) pyridine (DMAP), triethylamine, N, N-diisopropylethylamine, diisopropylamine, 1,4-diazabicyclo [2.2.2] octane (Dabco), 1,8-diazabicyclo [5.4.0] undecene An organic base such as (DBU) can be used. The use of an inorganic base is preferable, and among them, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium phosphate, sodium acetate and the like are preferable.

  In order to smoothly proceed the ring-closing reaction to the bis (benzoxazol-6-yl) compound represented by the general formula (2) in this step, it is preferable to use a solvent. The solvent that can be used in this reaction is not particularly limited as long as it does not inhibit the reaction. For example, phenyl ether, anisole, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,4- Ethers such as dioxane; aromatic hydrocarbons such as toluene, xylene, mesitylene and tetralin, decalin and other alicyclic hydrocarbons; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Aprotic polar solvents such as lydinone, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane; aromatic nitro compounds such as nitrobenzene and p-nitrotoluene; aromatic halogen compounds such as chlorobenzene, o-dichlorobenzene and trichlorobenzene Etc. Of these, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane are particularly preferable. The solvent can be used alone or as a mixed solvent in an arbitrary ratio.

  The amount of solvent used in this step may be an amount that can sufficiently stir the reaction system, but 1 mol of the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1). On the other hand, it is usually 0.3 to 100 l, preferably 0.5 to 10 l.

  The reaction temperature of the ring closure reaction to the bis (benzoxazol-6-yl) compound represented by the general formula (2) in this step can be exemplified by the range of 50 ° C. to the reflux temperature of the solvent used, preferably 70 C. to 250.degree.

  Although the reaction time of the ring closure reaction to the bis (benzoxazol-6-yl) compound represented by the general formula (2) in this step is not particularly limited, it is preferably 1 hour to 40 hours from the viewpoint of byproduct suppression. Is good.

  The pressure of the ring closure reaction to the bis (benzoxazol-6-yl) compound represented by the general formula (2) in this step is not particularly limited, and can be any of under pressure, under reduced pressure, or normal pressure. Normal pressure is preferred for ease of operation and economy.

  Subsequently, a bis (3-hydroxy-4-aminophenyl) propane compound is produced by hydrolysis of the bis (benzoxazol-6-yl) compound represented by the general formula (2) in the production method of the present invention. The reaction conditions for the process will be described.

  This step can be carried out under either acidic conditions or basic conditions, but is preferably carried out under acidic conditions.

  As the acid used in this step, inorganic acids such as hydrochloric acid, nitric acid, hydrobromic acid and sulfuric acid are suitable. Of these, use of hydrochloric acid is most convenient.

  The molar ratio of the acid to the bis (benzoxazol-6-yl) compound represented by the general formula (2) in this step is 0.1 to 1000 times mol, preferably 0.1 to 50 times mol, more preferably It is 3-20 times mole.

  Examples of the base used in this step include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferably used. .

  The molar ratio of these bases to the bis (benzoxazol-6-yl) compound represented by the general formula (2) in this step is 0.1 to 1000 times mol, preferably 0.1 to 50 times mol, More preferably, it is 3-20 times mole.

  The solvent used in this step is water or alcohols such as methanol, ethanol, propanol and butanol; diols such as ethylene glycol, diethylene glycol and propylene glycol; ethers such as tetrahydrofuran and 1,4-dioxane; or dimethyl sulfoxide. Aprotic polar solvents such as sulfolane can be used, and among these, water; alcohols such as methanol and ethanol are preferred. These solvents can be used alone or in combination.

  Although the reaction temperature of the hydrolysis of this process can illustrate the range of 0 degreeC-the reflux temperature of the solvent to be used, Preferably it is 10 to 250 degreeC.

  The hydrolysis reaction time in this step is not particularly limited, but preferably 1 hour to 40 hours from the viewpoint of suppressing by-products.

  The hydrolysis pressure in this step is not particularly limited and can be any of increased pressure, reduced pressure or normal pressure, but normal pressure is preferred from the viewpoint of simplicity of operation and economy.

  Subsequently, the bis (benzoxazol-6-yl) compound represented by the general formula (2) corresponding to the present invention [58] to [82] will be described.

  The bis (benzoxazol-6-yl) compound represented by the general formula (2) of the present invention can be produced according to the method of the present invention.

  Next, specific examples of the bis (benzoxazol-6-yl) compound represented by the general formula (2) of the present invention are illustrated in (Table 14) to (Table 22). It is not limited to, but includes all compounds represented by the general formula (2) including optical isomers and geometric isomers, and also includes these salts.

  Subsequently, the bis (3-halogeno-4-acylaminophenyl) methane compound represented by the general formula (4) corresponding to the present invention [83] to [94] will be described.

  The bis (3-halogeno-4-acylaminophenyl) methane compound represented by the general formula (4) of the present invention is a bis (3-halogeno-4-acylamino) represented by the above general formula (1). It can be produced according to a method for producing a phenyl) compound.

  Next, specific examples of the bis (3-halogeno-4-acylaminophenyl) propane compound represented by the general formula (4) of the present invention are illustrated in (Table 23) to (Table 29). It is not limited to these exemplified compounds, but includes all compounds represented by the general formula (4).

  Subsequently, the bis (3-hydroxy-4-aminophenyl) compound of the present invention represented by the general formula (5) (the present invention [95] to [99]) will be described.

  The bis (3-hydroxy-4-aminophenyl) compound represented by the general formula (5) of the present invention is the bis (3-halogeno-4-acylaminophenyl) represented by the general formula (3). It can manufacture according to the manufacturing method (invention method) of a compound.

  Next, specific examples of the bis (3-hydroxy-4-aminophenyl) compound represented by the general formula (5) of the present invention are illustrated in (Table 30), but the present compound is limited to these exemplary compounds. It is not intended to include all compounds represented by the general formula (5) including optical isomers and geometric isomers, and also includes salts thereof.

  Next, although a reference example and an Example are given and the manufacturing method of this invention compound is demonstrated concretely, this invention is not limited at all by these Examples. Further, the melting points described in the following Reference Examples and Examples are values measured by a Mettler melting point measuring device in air unless otherwise specified.

Reference example 1
A 500 ml four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 225.1 g (2.0 mol) of 2-chloroaniline and cooled in an ice bath with stirring at 35 ° C. or lower and 35% hydrochloric acid 68. 8 g (0.66 mol) was added dropwise. Thereafter, the temperature was raised to 158 ° C. to distill water. Thereafter, 45.7 g (0.2 mol) of bisphenol-A and 27.3 g (0.2 mol) of zinc chloride were added and the mixture was heated and stirred at 155 ° C. for 12 hours. As a result, the total area ratio of 2,2-bis (3-chloro-4 -Aminophenyl) propane was 66.7%, 2- (3-chloro-4-aminophenyl) -2- (4-hydroxyphenyl) propane was 24.0%, and the raw material bisphenol-A was 1.6. %Met. Thereafter, unreacted 2-chloroaniline and produced phenol were recovered under reduced pressure (28 to 33 mmHg) (boiling point 101 to 104 ° C.). The residue was added to a mixture of 500 ml of toluene and 500 ml of water, and 166.7 g (2 mol) of 48% sodium hydroxide was added dropwise while cooling in an ice bath. The precipitated crystals were suction filtered on radiolite. The filter residue was washed with 550 ml of toluene and 400 ml of water, the filtrate was separated, the toluene layer was taken out, and 233.3 g of water was added thereto. Further, when 166.7 g (2 mol) of 48% sodium hydroxide was dropped again at 30 to 35 ° C., crystals were precipitated and removed by suction filtration on radiolite again. The filtrate residue was washed with 30 ml of toluene and the filtrate was separated. After concentrating the toluene layer, 2-chloroaniline and other low-boiling substances were recovered under reduced pressure (boiling point: 102 to 104 ° C./27 to 4 mmHg). Thereafter, 600 ml of toluene and 400 ml of water were added, 35% hydrochloric acid was added dropwise until the pH became 1 or less, the mixture was stirred for 25 minutes, and the precipitated tar was removed by decantation. The aqueous layer was separated, 500 ml of toluene was added, and 48% sodium hydroxide was added dropwise until pH = 11 or more, followed by liquid separation. The toluene layer was removed and washed with 400 ml of water. After adding 10 g of anhydrous sodium sulfate and 30 g of silica gel, the mixture was stirred for 25 minutes. After filtration, toluene was distilled off to obtain 34.8 g of 2,2-bis (4-amino-3-chlorophenyl) propane as a black-red viscous liquid. Obtained. Yield 59%.

GC / MS (EI): m / z = 294 (M ⁺ ), 279 (M ⁺ -CH ₃ )
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.55 (s, 6H), 3.92 (brs, 4H), 6.64 (d, 2H, J = 8.4 Hz), 6.87 ( dd, 2H, J = 2.1, 8.4 Hz), 7.11 (dd, 2H, J = 2.1 Hz)

Reference example 2
A 500 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 10.5 g (35.5 mmol) of 2,2-bis (4-amino-3-chlorophenyl) propane and 178 ml of dichloromethane. While cooling on a water bath, 6.14 g (78.2 mmol) of acetyl chloride was added dropwise at 25-30 ° C. to precipitate white crystals. After stirring for 10 minutes, 6.46 g (81.7 mmol) of pyridine was added dropwise at the same temperature to dissolve the crystals, resulting in a transparent red wine solution. After stirring at room temperature for 2.5 hours, the reaction solution was washed with 200 ml of water and further with 200 ml of 2% hydrochloric acid. Subsequently, it was washed with an aqueous sodium hydrogen carbonate solution and washed with 150 ml of saturated saline. The organic layer was taken out and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. To the obtained crystals, n-hexane containing a small amount of ethyl acetate and isopropyl ether was added, washed, filtered, and dried, and 10.62 g of 2,2-bis (4-acetylamino-3-chlorophenyl) propane was added to a light brown color. Obtained as crystals (yield 78.9%).

Melting point: 191-193 ° C
GC / MS (EI): m / z = 378 (M ⁺ ), 363 (M ⁺ -CH ₃ )

Reference example 3
In a 500 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 15.00 g of 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane ( 0.04488 mol) and 314 ml of dichloromethane were charged, and 7.75 g (0.09874 mol) of acetyl chloride was added dropwise at 22 to 29 ° C. while cooling on a water bath with stirring, whereby white crystals were precipitated. After stirring for 10 minutes, 8.17 g (0.1032 mol) of pyridine was added dropwise at the same temperature. As a result, the white crystals were dissolved, and then the white crystals were precipitated again. The mixture was further stirred at room temperature for 4 hours. Dichloromethane was distilled off, and the resulting white crystals were dissolved in 63 ml of methanol, and then 180 ml of water was added dropwise at 22-30 ° C. with stirring to precipitate white crystals. After aging at 21 ° C. for 30 minutes, the white crystals were filtered off, washed with 90 ml of water and dried, 18.44 g of 2,2-bis (4-acetylaminophenyl) -1,1,1,3,3,3 -Hexafluoropropane was obtained as white crystals (yield 98.2%).

Melting point: 236-237 ° C.
GC / MS (EI): m / z = 418 (M ⁺ ), 376,307

Reference example 4
A 300 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 34.24 g (0.15 mol) of bisphenol-A and 116.63 g (0.90 mol) of aniline hydrochloride and heated on an oil bath. And melted. After the inside of the flask became a solution, the mixture was heated and stirred at 185 to 190 ° C. for 9 hours. The reaction mixture was poured into 1 L of water and stirred to dissolve. Next, 60.4 g (0.43 mol) of 35% hydrochloric acid was added to make it acidic, and then extracted twice with 200 mL of toluene to remove neutral and acidic components. Thereafter, 470 g (2.94 mol) of 25% sodium hydroxide was added, and extracted twice with 300 mL of toluene. The toluene layer was separated and washed twice with 400 mL of water. Further, the toluene layer was concentrated with a rotary evaporator to obtain 67.9 g of a crude product. This was distilled under reduced pressure to recover 43.6 g of aniline (bp = 45 ° C., 5 mmHg). When the distillation residue was analyzed by gas chromatography, 96.37% of 2,2-bis (4-aminophenyl) propane was contained in the total area ratio of gas chromatography. 19.18 g (yield 56.5%) of crude 2,2-bis (4-aminophenyl) propane was obtained. Further, this was recrystallized from toluene to obtain 14.19 g of purified 2,2-bis (4-aminophenyl) propane (yield 41.8%, purity 99.07%).

GC / MS (EI): m / z = 226 (M ⁺ ), 211 (M ⁺ —CH ₃ ), 195 (M ⁺ —CH ₃ —NH ₂ )

Example 1
In a 200 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 5.00 g (13.2 mmol) of 2,2-bis (4-acetylamino-3-chlorophenyl) propane and 5.59 g of sodium carbonate ( 52.7 mmol), 0.93 g (2.6 mmol) of 8-hydroxyquinoline copper, and 105 ml of N, N-dimethylacetamide were charged and heated to reflux at 164 ° C. for 35 hours in a nitrogen stream. As a result of analysis of the reaction solution, the target 2,2-bis (2-methylbenzoxazol-6-yl) propane was 64.9%, 2- (4-acetylamino-3-chlorophenyl) -2- (2- 27.8% of methylbenzoxazol-6-yl) propane and 0.9% of 2,2-bis (4-acetylamino-3-chlorophenyl) propane as raw materials were contained in the total area ratio of gas chromatography . After cooling the reaction mixture, N, N-dimethylacetamide was concentrated under reduced pressure. Subsequently, 250 ml of ethyl acetate and 200 ml of water were added and mixed, and the precipitated insoluble matter was removed by suction filtration. The organic layer was separated, washed with 300 ml of water twice, and further washed with 200 ml of saturated brine. The organic layer was concentrated and separated and purified by silica gel chromatography to obtain 2.10 g of 2,2-bis (2-methylbenzoxazol-6-yl) propane as a yellow viscous liquid. Yield 52.0%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.77 (s, 6H), 2.60 (s, 6H), 7.15 (dd, 2H, J = 1.8, 8.4 Hz), 7.38 (d, 2H, J = 1.8 Hz) 7.51 (d, 2H, J = 8.4 Hz)
GC / MS (EI): m / z = 306 (M ⁺ ), 291 (M ⁺ -CH ₃ )

Example 2
To a 25 ml round bottom flask equipped with a magnetic stir bar, 1.40 g (2.99 mmol) of 2,2-bis (4-acetylamino-3-bromophenyl) propane, 0.87 g (6.28 mmol) of potassium carbonate, 8 -0.053 g (0.15 mmol) of hydroxyquinoline copper and 6 ml of N, N-dimethylformamide were charged, and the mixture was heated and stirred at 145 ° C. for 4.5 hours under a nitrogen stream. The reaction mixture was cooled, and N, N-dimethylformamide as a solvent was recovered under reduced pressure in the container. The residue was poured into 20 ml of water and 20 ml of toluene and stirred, insoluble matter was suction filtered on a glass fiber filter paper, and the filtrate was separated. The toluene layer was taken out and washed with 3.5% hydrochloric acid and 20 ml of water, followed by washing with 20 ml of an aqueous sodium hydrogen carbonate solution and 20 ml of saturated brine. When the toluene layer was analyzed by gas chromatography using n-dodecane as an internal standard substance, the yield of the product 2,2-bis (2-methylbenzoxazol-6-yl) propane was 69.2%. there were.

Example 3
In a 25 ml round bottom flask equipped with a magnetic stir bar, 1.40 g (2.99 mmol) of 2,2-bis (4-acetylamino-3-bromophenyl) propane, 0.87 g (6.28 mmol) of potassium carbonate, iodine Copper (I) 0.029 g (0.15 mmol) and N, N-dimethylformamide 6 ml were charged and heated under reflux for 12 hours under a nitrogen stream. The reaction mixture was poured into 100 ml of water and 150 ml of ethyl acetate and stirred, and then the insoluble material was suction filtered on a glass fiber filter paper, and the filtrate was separated. The organic layer was washed with 50 ml of saturated brine. When the obtained ethyl acetate solution was analyzed by gas chromatography using n-dodecane as an internal standard substance, the yield of the product 2,2-bis (2-methylbenzoxazol-6-yl) propane was 70. It was 8%.

Example 4
In a 25 ml round bottom flask equipped with a magnetic stir bar, 1.60 g (3.19 mmol) of 2,2-bis (4-benzoylamino-3-chlorophenyl) propane, 0.92 g (6.67 mmol) of potassium carbonate, iodinated Copper (I) 0.061g (0.32mmol) and N, N- dimethylformamide 12.7ml were prepared, and it heated and refluxed for 11 hours under nitrogen stream. The reaction mixture was poured into 300 ml of water and 200 ml of ethyl acetate, stirred and separated, and the organic layer was washed twice with 200 ml of water, and further washed with 200 ml of 3.5% hydrochloric acid and 200 ml of water. Subsequently, it was washed with 200 ml of an aqueous sodium hydrogen carbonate solution and 150 ml of saturated brine, and then dried over anhydrous magnesium sulfate. After distilling off ethyl acetate, 20 ml of toluene and 1 g of silica gel were added and stirred at room temperature for 1 hour. After filtering the mixture, toluene was distilled off to obtain 1.20 g of 2,2-bis (2-phenylbenzoxazol-6-yl) propane, which was the target product, as a brown viscous liquid. Yield 87.4%. This was allowed to stand for 3 days and solidified to obtain the target brown crystals.

Melting point: 53-62 ° C.
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.83 (s, 6H), 7.24 (dd, 2H, J = 8.4, 1.8 Hz), 7.47 to 7.52 (m 6H), 7.53 (d, 2H, J = 1.8 Hz), 7.66 (d, 2H, J = 8.4 Hz), 8.20-8.24 (m, 4H)
LC / MS: m / z = 430 (M ⁺ ), 415 (M ⁺ -CH ₃ )

Example 5
A 100 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 4.53 g (20 mmol) of 2,2-bis (4-aminophenyl) propane and 18 mL of acetic acid and heated at 114 to 116 ° C. for 7 hours. Refluxed. When the reaction solution was analyzed by gas chromatography, 96.1% of 2,2-bis (4-acetylaminophenyl) propane was produced. The reaction mixture was cooled to room temperature and then slightly cooled with water, and 7.99 g (50 mmol) of bromine was added dropwise at 30 to 32 ° C. over 20 minutes with stirring. Thereafter, in the analysis after stirring at room temperature for 2 hours, 10.0% of 2,2-bis (4-acetylaminophenyl) propane remained, and 2- (4-acetylaminophenyl) -2- (4-acetylamino- 3-bromophenyl) propane was 34.9%, and the desired 2,2-bis (4-acetylamino-3-bromophenyl) propane was 50.3%. Further, after stirring for 1.5 hours at room temperature, 2.84 g (25 mmol) of 30% aqueous hydrogen peroxide was added dropwise at 32 to 37 ° C. under water cooling, and the reaction mixture changed from a yellow slurry to a dark red solution. In the later analysis, the production rate of the target 2,2-bis (4-acetylamino-3-bromophenyl) propane reached 94.4%. Further, after stirring at the same temperature for 1 hour, when the reaction solution was slowly added to 40 ml of water, a small amount of bromine was generated and crystals were deposited. Thereafter, an aqueous sodium sulfite solution was added until the bromine color disappeared, and then 24% sodium hydroxide was added dropwise to adjust the pH of the solution to 4. Next, the mixture was stirred for 15 minutes, filtered, washed with water, and dried under reduced pressure to obtain 2,2-bis (4-acetylamino-3-bromophenyl) propane. The yield was 99.9% and the purity was 92.3% (Gas Chromium total area method).

Melting point: 183-189 ° C. (decomposition)
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.61 (s, 6H), 2.22 (s, 6H), 7.14 (dd, 2H, J = 2.1, 8.7 Hz), 7.35 (d, 2H, J = 2.1 Hz) 7.57 (brs, 2H), 8.17 (d, 2H, J = 8.7 Hz)
GC / MS (EI): m / z = 467,468,469 (1: 2: 1, M ⁺ )

Example 6
0.70 g (2.3 mol) of 2,2-bis (2-methylbenzoxazol-6-yl) propane synthesized in Example 1 in a 25 ml round bottom flask equipped with a magnetic stir bar, 12 ml of degassed methanol Then, 1.2 ml of 35% hydrochloric acid was added dropwise while cooling on a water bath. Thereafter, the temperature was raised to 67 to 68 ° C. and stirred for 5 hours. Thereafter, methanol was distilled off to obtain white crystals. This was dissolved in 50 ml of degassed water and placed in a 50 ml four-necked flask purged with nitrogen. When 24% sodium hydroxide and saturated sodium hydrogen carbonate solution were added dropwise to the aqueous solution to adjust the pH of the solution to 8.7, white crystals were precipitated. The obtained crystals were filtered and washed with water to obtain 0.45 g (yield 76%) of 2,2-bis (4-amino-3-hydroxy) propane.

Melting point: 213-219 ° C. (decomposition)
¹ H-NMR (300 MHz, DMSO-d ₆ ) δ = 1.43 (s, 6H), 4.25 (brs, 4H), 6.43 to 6.45 (m, 6H), 8.70 (brs) , 2H)
LC / MS: m / z = 258 (M ⁺ ), 243 (M ⁺ -CH ₃ )

Example 7
The inside of a 10 ml round bottom flask equipped with a magnetic stir bar was replaced with nitrogen gas, and 1.20 g of 2,2-bis (2-phenylbenzoxazol-6-yl) propane synthesized in Example 4 and 30% sulfuric acid (desorbed). After gas), 5 g was charged and heated to reflux on an oil bath at 125 to 130 ° C. for 20 hours. Thereafter, 5 g of acetic acid was added and the mixture was further heated to reflux for 80 hours. When the reaction solution was analyzed by high performance liquid chromatography (detector; UV, 280 nm), it was found that 75.3% of 2,2-bis (4-amino-3-hydroxy) propane was produced. The liquid chromatographic retention time and LC / MS cleavage pattern of this product coincided with those obtained in Example 6.

Example 8
The inside of a 50 ml four-necked flask equipped with a magnetic stirring bar was replaced with nitrogen gas, and 0.134 g (0.52 mmol) of 2,2-bis (4-amino-3-hydroxy) propane obtained in Example 6 was replaced. Then, 0.18 g of 35% hydrochloric acid was dissolved in 5 ml of water and added dropwise. After stirring for 10 seconds, the solution became clear and colored pale purple. This was allowed to stand for 5 minutes and then evaporated to dryness to obtain white crystals slightly colored in purple. The obtained crystals were azeotropically dehydrated twice with 25 ml of toluene and further dried under reduced pressure at 50 to 55 ° C. with an oil pump to give 0.071 g of 2,2-bis (4-amino-3-hydroxy) propane dihydrochloride. Got.

Melting point: 188-195 ° C (decomposition)
¹ H NMR (300 MHz, DMSO-d ₆ ): δ = 1.55 (s, 6H), 6.75 (dd, 2H, J = 2.1, 8.1 Hz), 6.90 (d, 2H, J = 2.1 Hz), 7.32 (d, 2H, J = 8.1 Hz), 10.04 (brs, 6H), 10.60 (brs, 2H)

Example 9
In a 100 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 7.02 g (15.0 mmol) of 2,2-bis (4-acetylamino-3-bromophenyl) propane and 4.35 g of potassium carbonate. (31.5 mmol), 0.26 g (0.75 mmol) of 8-hydroxyquinoline copper, and 30.0 ml of N, N-dimethylformamide were charged, and the mixture was heated and stirred at 136 to 146 ° C. for 6 hours in a nitrogen stream. After cooling the reaction mixture and reducing the pressure in the container, N, N-dimethylformamide as a solvent was recovered. Boiling point 66 ° C./27 mmHg, recovery amount 27 ml. The residue was poured into 30 ml of water and 50 ml of toluene and stirred, and then 1 ml of 35% hydrochloric acid was added. Since insoluble matter was precipitated, the solution was suction filtered on diatomaceous earth, and the residue was washed with water and toluene. After separating the filtrate, the toluene layer was taken out and washed with 100 ml of water, and further washed with 100 ml of 3% aqueous sodium hydrogen carbonate solution. The toluene layer was distilled off to obtain 4.00 g of 2,2-bis (2-methylbenzoxazol-6-yl) propane. Yield 87.0%, purity 84.6%.

Example 10
A 100 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 1.98 g (6.7 mmol) of 2,2-bis (4-amino-3-chlorophenyl) propane and 30 ml of dichloromethane. When 2.07 g (14.7 mmol) of benzoyl chloride was added dropwise at 22 to 28 ° C. while cooling on a water bath, white crystals were precipitated. After stirring for 15 minutes, 1.22 g (15.4 mmol) of pyridine was added dropwise at the same temperature. The mixture was further stirred at room temperature for 6 hours. Dichloromethane was distilled off, followed by extraction with ethyl acetate and water, and the ethyl acetate layer was separated and washed with water and dilute hydrochloric acid. Further, it was washed with an aqueous sodium hydrogen carbonate solution and saturated brine. The organic layer was taken out and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. N-hexane containing a small amount of ethyl acetate and isopropyl ether was added to the obtained crystals, washed, filtered and dried, and 2.75 g of 2,2-bis (4-benzoylamino-3-chlorophenyl) propane was added to a light brown Obtained as crystals (yield 81.6%).

Melting point: 188-190 ° C.
LC / MS (EI): m / z = 502 (M ⁺ ), 487 (M ⁺ -CH ₃ )

Example 11
16.94 g of 2,2-bis (4-acetylaminophenyl) -1,1,1,3,3,3-hexafluoropropane was added to a 100 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer. (0.0405 mol) and 42 mL of acetic acid were added, and 16.18 g (0.1013 mol) of bromine was added dropwise at 23 to 35 ° C. over 10 minutes with stirring, and then stirred at room temperature for 2 hours and 45 minutes. Thereafter, 5.74 g (0.0506 mol) of 30% hydrogen peroxide solution was added dropwise at 24 to 35 ° C. over 5 minutes, then aged at 30 to 38 ° C. for 40 minutes under appropriate water cooling, and further aged at room temperature for 1 hour and 35 minutes. did. After pouring the reaction liquid into 200 ml of water, 200 ml of ethyl acetate was added to dissolve the precipitated crystals. Further, 50 g of saturated brine was added and the layers were separated, and the organic layer was washed with 200 ml of water and 200 g of a saturated aqueous sodium bicarbonate solution. When 100 g of an 8% aqueous sodium sulfite solution was added dropwise at 20 to 25 ° C. with stirring under ice-cooling, the bromine coloration disappeared. Furthermore, when the organic layer was separated and washed with 200 ml of water, white crystals were precipitated. Precipitated white crystals were separated by filtration, washed with 200 ml of ethyl acetate and 100 ml of water, dried and dried to give 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3- 6.57 g of hexafluoropropane was obtained (yield 28.2%).
After adding 300 ml of ethyl acetate to the filtrate and dissolving the gradually precipitated white crystals, the organic layer was separated, washed with saturated brine, dried over magnesium sulfate and concentrated, and a small amount of isopropyl ether was added to the obtained white crystals. The n-hexane containing was added, washed, filtered and dried to obtain 13.55 g of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane. Obtained (yield 58.1%). In this step, a total of 20.12 g of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane is obtained in a yield of 86.2%. I was able to.

Melting point: 180-181 ° C
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 2.27 (s, 6H), 7.29 (dd, J = 1.2, 9.3 Hz, 2H), 7.55 (d, J = 1) .2 Hz, 2H), 7.68 (brs, 2H), 8.42 (d, J = 9.3 Hz, 2H)
GC / MS (EI): m / z = 574, 576, 578 (1: 2: 1, M ⁺ ), 532, 534, 536 (1: 2: 1), 495,497 (100: 95)

Example 12
2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoro was added to a 100 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer. Propane 12.10 g (0.021 mol), potassium carbonate 6.10 g (0.0441 mmol), 8-hydroxyquinoline copper 0.369 g (0.00105 mol), N, N-formamide 63 ml were charged, and 139-141 under nitrogen atmosphere The mixture was heated and stirred at 0 ° C. for 4 hours. Analysis of the reaction mixture revealed that the desired product 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane was 52.6%, 2- ( 4-Acetylaminophenyl) -2- (2-methylbenzoxazol-6-yl) propane was included in 26.1% of each in a total area ratio of gas chromatography. After cooling the reaction mixture, 400 ml of toluene and 400 ml of water were added and mixed, and the precipitated insoluble matter was removed by filtration. The organic layer was separated, and the precipitated insoluble matter was filtered off, washed twice with 400 ml of water, further washed with 300 ml of saturated brine, and dried over magnesium sulfate. The organic layer was concentrated, separated and purified by silica gel chromatography, and 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane (2,75 g) was pale yellow. Obtained as a viscous liquid. Yield 52.0%. The resulting pale yellow viscous liquid was suspended in methanol and crystallized or allowed to solidify by standing for one week to give 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1, White to slightly brown crystals of 3,3,3-hexafluoropropane were obtained.

Melting point: 129-130 ° C
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 2.66 (s, 6H), 7.31 (d, J = 8.4 Hz, 2H), 7.61 (s, 2H), 7.63 ( d, J = 8.4 Hz, 2H)
GC / MS (EI): m / z = 414 (M ⁺ ), 345, 304

Example 13
In a 50 ml round bottom flask equipped with a magnetic stirrer, 2.88 g of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane (0. 005 mol), 2.97 g (0.0215 mol) of potassium carbonate, 0.0476 g (0.00025 mol) of copper (I) iodide, and 30 ml of N, N-dimethylformamide were added and heated under reflux for 12 hours in a nitrogen atmosphere. Analysis of the reaction mixture revealed that the desired product 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane was 76.9%, 2- ( 4-Acetylaminophenyl) -2- (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane is contained in an amount of 10.5% in the total area ratio of gas chromatography It was. The reaction mixture was poured into 350 ml of water and 350 ml of ethyl acetate and stirred, and then insoluble matter was suction filtered on a glass fiber filter paper, and the filtrate was separated. The aqueous layer was extracted again with 100 ml of ethyl acetate, and all the organic layers were combined and washed with 400 ml of water three times and 300 ml of saturated brine while filtering out the insoluble matter that precipitated. The obtained ethyl acetate solution was analyzed by gas chromatography using n-dodecane as an internal standard substance. The product, 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1, The yield of 3,3,3-hexafluoropropane was 55.3%.

Example 14
In a 25 ml round bottom flask equipped with a magnetic stir bar, 1.44 g (0. 0. 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane). 0025 mol), potassium carbonate 1.49 g (0.0108 mol), copper iodide (I) 0.0476 g (0.00025 mol), N, N′-dimethylethylenediamine 0.0441 g (0.0005 mol), toluene 15 ml, The mixture was heated in a nitrogen atmosphere and gently refluxed for 24 hours. Analysis of the reaction mixture revealed that the desired product 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane was 70.0%, 2- ( 4-acetylaminophenyl) -2- (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane is 14.2%, 2- (4-acetylamino- 3-Bromophenyl) -2- (2-methylbenzooxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane was included in a gas chromatographic total area ratio of 4.1% each. .

Example 15
1.24 g of 2,2-bis (2-methylbenzoxazol-6-yl) propane synthesized in Example 12 in a 50 ml three-necked round bottom flask equipped with a reflux condenser, a thermometer, and a magnetic stirring bar ( 0.003 mol), 30 ml of degassed methanol was charged, and 3 ml of 35% hydrochloric acid was added dropwise while cooling on a water bath. Thereafter, the temperature was raised to 67 to 68 ° C. and stirred for 4 hours. Thereafter, methanol was distilled off and evaporated to dryness to obtain 0.97 g of pale yellow crystals.

  Under a nitrogen stream, charge 0.408 g (0.0009290 mol) of the pale yellow crystals obtained above into a 50 ml three-necked round bottom flask equipped with a magnetic stir bar, and dissolve by adding 7.5 g of degassed water. did. To this aqueous solution, 25% sodium hydroxide and saturated sodium hydrogen carbonate solution were added dropwise, and when the pH of the solution was adjusted to 8.4, white crystals were precipitated. The resulting crystals were filtered and washed with degassed water under a nitrogen stream, and then dried under reduced pressure to give 0.281 g (yield 60.8%, 2,2-bis (2-methylbenzoxazole-6). -Yl) propane basis) 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Melting point: 217.7-219.5 ° C. (measured with a Mettler melting point measuring instrument in air)
235-237 ° C. (decomposition, measurement by visual observation using a magnifying glass in air)
LC / MS (EI): m / z = 366 (M ⁺ ), 296, 280
GC / MS (EI): m / z = 366 (M ⁺ ), 297, 280

Example 16
2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane 2,2-bis (4-aminophenyl) -1,1,1, 334.26 g (1 mol) of 3,3,3-hexafluoropropane was dissolved in 1.5 L of acetic acid, and 224.2 g (2.2 mol) of acetic anhydride was added dropwise at 30 ° C. or less over 3 hours with stirring.
To this solution, 344.5 g (4.2 mol) of sodium acetate was added, and the temperature was raised to 65 ° C. with stirring. To this solution, 671.2 g (4.2 mol) of bromine was added dropwise over 8 hours. Thereafter, aging was performed for 16 hours, and the reaction was cooled after completion of the reaction. 891.9 g (3 mol) of 35% sodium bisulfite aqueous solution was dissolved in 2 L of water, and the reaction solution was dropped into a solution cooled to 20 ° C. with stirring at 30 ° C. or less over 3 hours. The solution was filtered, and the resulting crystals were dried and white crystals of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane 580 0.2 g (yield 100%) was obtained. The obtained crystals were recrystallized from 600 mL of ethyl acetate, and white crystals of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane 486 were obtained. .3 g (yield 85%) was obtained.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ = 9.60 (s, 2H), 7.86 (d, 2H, J = 8.7 Hz), 7.50 (s, 2H), 7. 37 (d, 2H, J = 8.7 Hz), 2.14 (s, 6H)
IR (KBr disk, cm ⁻¹ ): 3432.7, 1697.1
Melting point: 179.5-180.7 ° C

Example 17
2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane copper iodide 0.38 g (0.002 mol), 1,10-phenanthroline 0 A solution obtained by suspending 0.72 g (0.004 mol) and 14.3 g (0.044 mol) of cesium carbonate in 400 mL of toluene was heated to 60 ° C. with stirring and aged for 1 hour. To this solution was added 11.5 g (0.02 mol) of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane, and the temperature was raised. The mixture was refluxed, aged for 24 hours, and cooled after completion of the reaction. 20 mL of water was added to this solution, filtration and liquid separation were performed, and 20 mL of water was added again for liquid separation. The obtained organic layer was concentrated to obtain a black oily substance.
To this oily substance, 20 mL of ethanol and 20 mL of water were added for crystallization, filtration and drying, and 2,2-bis (2-methylbenzoxazole-6-)-1,1,1,3,3,3 in the form of brown crystals. -Obtained 6.1 g of hexafluoropropane (crude yield 73.6%). The obtained crystals were purified by column chromatography with ethyl acetate / n-hexane, and 2,2-bis (2-methylbenzoxazol-6-yl)-of white crystals having a total area of 100% by high performance liquid chromatography. 1,1,1,3,3,3-hexafluoropropane was obtained.
This was used as a standard, and the yield was calculated by the absolute calibration curve method.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ = 7.77 (d, 2H, J = 9.0 Hz), 7.66 (s, 2H), 7.28 (d, 2H, J = 9) .0Hz), 2.64 (s, 6H)
IR (KBr disk, cm ⁻¹ ): 1616.1
Melting point: 132.1-133.0 ° C

Example 18
2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane 0.48 g (0.0025 mol) of copper iodide, 1,10-phenanthroline 0 A solution obtained by suspending .90 g (0.005 mol) and 71.7 g (0.22 mol) of cesium carbonate in 400 mL of toluene was heated to 60 ° C. with stirring and aged for 1 hour. To this solution, 57.6 g (0.1 mol) of 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane was added, and the temperature was raised. The mixture was refluxed, aged for 24 hours, and cooled after completion of the reaction. 400 mL of water was added to this solution, followed by filtration and liquid separation, and 400 mL of water was added again for liquid separation. The obtained organic layer was concentrated to obtain a black oily substance. To this oily substance, 100 mL of ethanol and 200 mL of water were added for crystallization, filtration and drying, and 2,2-bis (2-methylbenzoxazol-6-yl) 1,1,1,3,3,3 in the form of brown crystals. -37.8 g (yield 79.2%) of hexafluoropropane was obtained.

Example 19
2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane copper bromide 0.36 g (0.0025 mol) 1,10-phenanthroline A solution obtained by suspending 90 g (0.005 mol) and 71.7 g (0.22 mol) of cesium carbonate in 400 mL of toluene was heated to 60 ° C. with stirring and aged for 1 hour. To this solution, 57.6 g (0.1 mol) of 2,2-bis (4-acetylamino-3-bromophenyl) 1,1,1,3,3,3-hexafluoropropane was added, and the temperature was raised to reflux. The mixture was aged for 24 hours and cooled after completion of the reaction. 400 mL of water was added to this solution, followed by filtration and liquid separation, and 400 mL of water was added again for liquid separation. The obtained organic layer was concentrated to obtain a black oily substance. Ethanol 100mL and water 200mL were added to this oily substance, and crystallization, filtration and drying were carried out, and 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3 in the form of brown crystals. 35.1 g (yield 74.6%) of 3-hexafluoropropane was obtained.

Example 20
2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3,3-hexafluoropropane copper bromide 0.07 g (0.0005 mol), 1,10-phenanthroline 0 A solution of .18 g (0.001 mol) and 6.1 g (0.044 mol) of potassium carbonate suspended in 400 mL of toluene was heated to 60 ° C. with stirring and aged for 1 hour. 2,2-bis (4-acetylamino-3-bromophenyl) -1,1,1,3,3,3-hexafluoropropane (11.5 g 0.02 mol) was added to this solution, and the temperature was raised to reflux. Aging was performed for 24 hours, and the reaction was cooled after completion of the reaction. 80 mL of water was added to this solution, followed by filtration and liquid separation, and then 80 mL of water was added again for liquid separation. The obtained organic layer was concentrated to obtain a black oily substance. To this oily substance, 20 mL of ethanol and 40 mL of water were added for crystallization, filtration and drying, and 2,2-bis (2-methylbenzoxazol-6-yl) -1,1,1,3,3 in the form of brown crystals. 6.7 g (yield 68.8%) of 3-hexafluoropropane was obtained.

Example 21
2,2-bis (4-amino-3-hydroxy) -1,1,1,3,3,3-hexafluoropropane 2,2-bis (2-methylbenzoxazol-6-yl) -1, 2.1 g of 1,1,3,3,3-hexafluoropropane was dissolved in 5 mL of 35% aqueous hydrochloric acid solution, heated and refluxed with stirring, aged for 4 hours, and cooled after completion of the reaction. 15 mL of water was added to this solution, and 10.6 g of 25% sodium hydroxide was added dropwise at 30 ° C. or lower to adjust the pH to 8. After the pH adjustment, filtration and drying were carried out to obtain 1.6 g of blue crystalline 2,2-bis (4-amino-3-hydroxy) 1,1,1,3,3,3-hexafluoropropane. . The obtained crystals were purified by column chromatography with ethyl acetate / n-hexane, and 2,2-bis (4-amino-3-hydroxy) -1, white crystals having a total area of 100% by high performance liquid chromatography. 1,1,3,3,3-hexafluoropropane was obtained. This was used as a standard, and the yield was calculated by the absolute calibration curve method.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ = 9.15 (s, 2H), 6.61-6.56 (m, 6H), 4.77 (s, 4H)

IR (KBr disk, cm ⁻¹ ): 3434.6, 3316.9
Melting point: 217.7-219.5 ° C. (decomposition)

Example 22
2,2-bis (4-amino-3-hydroxy) -1,1,1,3,3,3-hexafluoropropane 2,2, -bis (2-methylbenzoxazol-6-yl) 1,1 , 1,3,3,3-hexafluoropropane 74.6 g, 25% sodium hydroxide 288.0 g dissolved in 180 mL of ethanol, heated to reflux with stirring, aged for 4 hours, after completion of the reaction, Cooled down. 540 mL of water was added to this solution, and 150.0 g of 35% aqueous hydrochloric acid solution was added dropwise at 30 ° C. or lower to adjust the pH to 9. A solution prepared by previously dissolving 3.2 g of ascorbic acid in 18 mL of water was added dropwise to this solution so that the pH was 8. After completion of pH adjustment, filtration is performed, and the obtained crystals are dissolved by heating in 180 mL of ethanol, 360 mL of water is added, crystallized, filtered, freeze-dried, and light red crystals of 2,2-bis (4-amino- 3-Hydroxy) -1,1,1,3,3,3-hexafluoropropane 63.37 g (yield 93.4%) was obtained.

  According to the present invention, a bis (3-hydroxy-4-aminophenyl) compound useful as a raw material for a polymer or a functional material can be produced at an inexpensive and industrial scale.

Claims (14)

General formula (1)

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent,
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or a substituted group. An aryl group which may have a group,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )
A base is reacted with the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (2)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A represent the same meaning as described above.)
And then hydrolyzing the bis (benzoxazol-6-yl) compound represented by the general formula (3)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A represent the same meaning as described above.)
The manufacturing method of the bis (3-hydroxy-4-aminophenyl) compound represented by these. The bis (3-hydroxy) according to claim 1, wherein the reaction between the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) and the base is carried out in the presence of a copper compound. -4-aminophenyl) compound production method. The bis (3-hydroxy-4-aminophenyl) compound according to claim 1, wherein the bis (benzoxazol-6-yl) compound represented by the general formula (2) is hydrolyzed under acidic conditions. Manufacturing method. R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. The manufacturing method of the bis (3-hydroxy-4-aminophenyl) compound of Claim 1 thru | or 3 which is the C1-C8 substituted alkyl group substituted by group or one or more halogen atoms. General formula (1)

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent,
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or a substituted group. An aryl group which may have a group,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )
A base is reacted with a bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (2)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and A represent the same meaning as described above.)
The manufacturing method of the bis (benzoxazol-6-yl) compound represented by these. The bis (benzoxazole-) according to claim 5, wherein the reaction between the bis (3-halogeno-4-acylaminophenyl) compound represented by the general formula (1) and the base is carried out in the presence of a copper compound. 6-yl) A method for producing a compound. R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. The manufacturing method of the bis (benzoxazol-6-yl) compound of Claim 1 thru | or 6 which is the C1-C8 substituted alkyl group substituted by group or one or more halogen atoms. General formula (2)

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, one or more A C1-C8 alkyl group substituted with a halogen atom, a C1-C8 alkoxy group, a hydroxyl group, an amino group, a mono- or di (C1-C8 alkyl) amino group, or an aryl group which may have a substituent,
R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or a substituted group. An aryl group which may have a group,
A represents —CR ₅ R ₆ —, —O—, —NR ₅ —, —S—, —SO—, —SO ₂ —, or a single bond;
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )
The bis (benzoxazol-6-yl) compound represented by these. R ₁ , R ₂ and R ₃ are all hydrogen atoms, R ₄ is a C1-C8 alkyl group or aryl group, A is —CR ₅ R ₆ —, and R ₅ and R ₆ are C1-C8 alkyl. The bis (benzoxazol-6-yl) compound according to claim 8, which is a C1-C8 substituted alkyl group substituted with a group or one or more halogen atoms. General formula (4)

(R ₄ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 alkyl group substituted with one or more halogen atoms, or An aryl group which may have a substituent,
R ₅ and R ₆ may be the same or different and each independently represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkyl group substituted with one or more halogen atoms,
R ₅ and R ₆ may be bonded to each other to form a C ₃ to C 17 cycloalkyl group together with the carbon atom to which they are bonded, or a C 3 to C 17 cycloalkyl which may be substituted with any number of fluorine atoms. Often,
X represents chlorine, bromine or iodine. )
A bis (3-halogeno-4-acylaminophenyl) methane compound represented by the formula: 11. The bis (10) according to claim 10, wherein R ₄ is a C1-C8 alkyl group or an aryl group, and R ₅ and R ₆ are a C1-C8 alkyl group or a C1-C8 alkyl group substituted with one or more halogen atoms. 3-halogeno-4-acylaminophenyl) methane compound. General formula (5)

Wherein R ₇ and R ₈ may be the same or different and each independently represents a C1 to C8 alkyl group or a C1 to C8 alkyl group substituted with one or more halogen atoms, ₅ and R ₆ may be bonded to each other to form a C3-C17 cycloalkyl group together with the carbon atom to which they are bonded, or a C3-C17 cycloalkyl which may be substituted with any number of fluorine atoms. .)
A bis (3-hydroxy-4-aminophenyl) compound represented by the formula: R _{7, R 8} is C1-C8 alkyl group, bis claim 12, wherein (3-hydroxy-4-aminophenyl) compound. The bis (3-hydroxy-4-aminophenyl) compound according to claim 12, wherein R ₇ and R ₈ are C1-C8 alkyl groups substituted with one or more halogen atoms.