JPH111464A - Dicarboxylic acid compounds and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compounds capable of being a manufacturing intermediate for a dyestuff with a high brightness by reacting a nitro carboxylic acid compound with an aqueous solution of a reducing sugar. SOLUTION: This compound is a dicarboxylic acid compound of formula I (R<1> -R<6> are each independently H, a halogen, a cyano, a hydroxyl, an amino, a sulfonic acid group, an alkyl, an aryl, etc.; X<1> and X<2> are each independently a halogen or a hydroxyl), for example, azoxybiphenylcarboxylic acid of formula H. The compound of formula I is obtained by reacting a nitrocarboxylic acid compound of formula III and/or a nitrocarboxylic acid compound of formula IV with an aqueous solution of a reducing sugar in the presence of an alkali preferably at 20-80 deg.C. A glucose, a mannose, etc., are used as the reducing sugar used for the reaction, and used as an aqueous solution having 1-50%, preferably 5-50% concentration. The molar ratio of the reducing sugar to the nitrocarboxylic acid of formulas III and/or IV is preferably 0.3-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel compound suitable for a dye intermediate and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, when dyes are dyed on yarn or cloth, sharpness (brightness) is required. As anthraquinone yellow dyes, C.I. I. Bat Yellow 10 and C.I.
I. Compounds such as Bat Yellow 33 are known,
It was not always satisfactory.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found that the general formula (1)

Embedded image

[In the formula (1), R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an amino group, a sulfonic acid group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group; Alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted N-alkylamino, substituted or unsubstituted N, N-dialkylamino, substituted or unsubstituted N-arylamino, substituted or unsubstituted N , N-diarylamino group, a substituted or unsubstituted N-alkyl-N-arylamino group,
X ¹ and X ² each independently represent a halogen atom or a hydroxyl group. The following formula (7) synthesized from the dicarboxylic acid compound represented by the following formula:

[0005]

Embedded image [In the formula (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
^{R 8, R 9, R 10} , R 11, R 12, R 13, R 14, R 15, R 16
Represents the same meaning as described above. It has been found that the anthraquinone dye represented by the formula (1) has a sharper hue than the conventionally known anthraquinone dyes and has a high value as a dye.

An object of the present invention is to provide a novel compound useful as an intermediate for producing the dye, and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have the following general formula (1):

Embedded image

[In the formula (1), R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ , R ¹⁶ , X ¹ and X ² each have the same meaning as described above. The dicarboxylic acid compound represented by the following general formula (4) is suitable for the dye and pigment intermediates described above.

[0009]

Embedded image

[In the formula (4), R ^{1 to} R ⁸ have the same meaning as described above. A nitrocarboxylic acid compound represented by the formula
Or the following general formula (5)

Embedded image

[In the formula (4), R ^{9 to} R ¹⁶ have the same meaning as described above. A nitrocarboxylic acid compound represented by
It was found that it can be produced by reacting with a reducing sugar aqueous solution in the presence of an alkali.

That is, the present invention provides the following general formula (1)

Embedded image

[In the formula (1), R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an amino group, a sulfonic acid group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group; Alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted N-alkylamino, substituted or unsubstituted N, N-dialkylamino, substituted or unsubstituted N-arylamino, substituted or unsubstituted N , N-diarylamino group, a substituted or unsubstituted N-alkyl-N-arylamino group,
X ¹ and X ² each independently represent a halogen atom or a hydroxyl group. And a process for producing the same.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
According to a specific embodiment of the present invention, a target compound can be obtained by reacting a nitrocarboxylic acid compound represented by the general formula (4) or (5) with an aqueous reducing sugar solution in the presence of an alkali. . Further, by reacting with a halogenating agent, a carboxylic acid halide which is a derivative thereof can be obtained.

R ¹ , R ² , and R ³ represented by the substituents of the general formulas (1) and (6) which are the compounds of the present invention and the general formulas (4) and (5) which are intermediates R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an amino group, a sulfonic acid group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group; Alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted N-alkylamino, substituted or unsubstituted N, N-dialkylamino, substituted or unsubstituted N-arylamino, substituted or unsubstituted N , N-diarylamino group, a substituted or unsubstituted N-alkyl-N-arylamino group,
X ¹ and X ² each independently represent a halogen atom or a hydroxyl group. As a specific example, as the halogen atom,
Examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the substituted or unsubstituted alkyl group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group and an iso-propyl group. , N-butyl group, iso-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, tert-pentyl group, sec-pentyl group, cyclopentyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group,
1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2
-Trimethylpropyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, methylcyclopentyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group,
3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 1,2
-Dimethylpentyl group, 1,3-dimethylpentyl group,
1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 1- Ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group,
1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 2,
3,3-trimethylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3- Methylbutyl group, 1-n-propylbutyl group, 1-iso-propylbutyl group 1-i
so-propyl-2-methylpropyl group, methylcyclohexyl group, n-octyl group, 1-methylheptyl group,
2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3- Dimethylhexyl group, 1,4
-Dimethylhexyl group, 1,5-dimethylhexyl group,
2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3, 5-dimethylhexyl group, 4,
4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3
-Ethylhexyl group 4-ethylhexyl group, 1-n-
Propylpentyl group, 2-n-propylpentyl group, 1
-Iso-propylpentyl group, 2-iso-propylpentyl group, 1-ethyl-1-methylpentyl group, 1-
Ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2
-Ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group,
2-ethyl-4-methylpentyl group, 3-ethyl-1-
Methylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-
4-methylpentyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4
-Trimethylpentyl, 1,2,2-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,2
4-trimethylpentyl group, 1,3,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2,
2,4-trimethylpentyl group, 2,3,4-trimethylpentyl group, 1,3,3-trimethylpentyl group,
2,3,3-trimethylpentyl group, 3,3,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 3,4,4-
Trimethylpentyl group, 1-n-butylbutyl group, 1-
iso-butylbutyl group, 1-sec-butylbutyl group, 1-tert-butylbutyl group, 2-tert-butylbutyl group, 1-n-propyl-1-methylbutyl group, 1-n-propyl-2-methylbutyl group, 1- n-
Propyl-3-methylbutyl group, 1-iso-propyl-1-methylbutyl group, 1-iso-propyl-2-methylbutyl group, 1-iso-propyl-3-methylbutyl group, 1,1-diethylbutyl group, 2-diethylbutyl group, 1-ethyl-1,2-dimethylbutyl group, 1-
Ethyl-1,3-dimethylbutyl group, 1-ethyl-2,
3-dimethylbutyl group, 2-ethyl-1,1-dimethylbutyl group, 2-ethyl-1,2-dimethylbutyl group, 2
-Ethyl-1,3-dimethylbutyl group, 2-ethyl-
2,3-dimethylbutyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4
-A dimethylcyclohexyl group, an ethylcyclohexyl group, an n-nonyl group, a 3,5,5-trimethylhexyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as an n-decyl group, a fluoromethyl group, Trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoroethyl group, chloroethyl group,
Bromoethyl group, trifluoroethyl group, pentafluoroethyl group, tetrachloroethyl group, hexafluoro-
A straight-chain, branched or cyclic halogenated hydrocarbon having 1 to 10 carbon atoms in which 1 to 21 halogen atoms such as an isopropyl group are substituted, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pen Toxicmethyl group, hexyloxymethyl group, cyclohexyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentoxyethyl group, hexyloxyethyl group, cyclohexyloxyethyl group, methoxyethoxyethyl group, A methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, a butoxypropyl group, a pentoxypropyl group, a hexyloxypropyl group, a cyclohexyloxypropyl group, a methoxyethoxypropyl group, etc. Arco Shi alkyl group group is substituted, methylthiomethyl group, ethylthiomethyl group, propyl thio methyl group, butylthiomethyl group, pentylthio methyl group,
Hexylthiomethyl group, cyclohexylthiomethyl group,
Methylthioethyl, ethylthioethyl, propylthioethyl, butylthioethyl, pentylthioethyl, hexylthioethyl, cyclohexylthioethyl, methoxyethylthioethyl, methylthiopropyl, ethylthiopropyl, propyl Thiopropyl group,
Butylthiopropyl group, pentylthiopropyl group, hexylthiopropyl group, cyclohexylthiopropyl group,
An alkyl group substituted by a linear, branched or cyclic alkylthio group having 1 to 10 carbon atoms such as methoxyethylthiopropyl group, N-methylaminomethyl group, N, N-dimethylaminomethyl group, N-ethylaminomethyl group , N, N-diethylaminomethyl group, N-propylaminomethyl group,
N, N-dipropylaminomethyl group, N-methyl-N-
An ethylaminomethyl group, an N-methylaminoethyl group,
N, N-dimethylaminoethyl group, N-ethylaminoethyl group, N, N-diethylaminoethyl group, N-propylaminoethyl group, N, N-dipropylaminoethyl group, N-methyl-N-ethylaminoethyl Group, N-methylaminopropyl group, N, N-dimethylaminopropyl group, N-ethylaminopropyl group, N, N-diethylaminopropyl group, N-propylaminopropyl group, N,
Examples thereof include a linear, branched or cyclic alkylamino group having 1 to 10 carbon atoms such as an N-dipropylaminopropyl group and an N-ethyl-N-butylaminopropyl group, or an alkyl group substituted with a dialkylamino group.

Examples of the substituted or unsubstituted aryl group include a phenyl group, a naphthyl group, an anthranyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group and a 2,3-dimethylphenyl group. , 2,4-
Dimethylphenyl group, 2,5-dimethylphenyl group,
2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group,
2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, hexylphenyl group, cyclohexylphenyl group, octylphenyl group, 2-methyl- 1-naphthyl group, 3-methyl-1-naphthyl group,
4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-
Naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-
Methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, 2-ethyl-
An aryl group substituted by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as 1-naphthyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,3-dimethoxyphenyl group, 2,4 -Dimethoxyphenyl group, 2,5
-Dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,6-dimethoxyphenyl group, 2,
3,4-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,6-trimethoxyphenyl group, 2,4,5-trimethoxyphenyl group, 2,4,6
-Trimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, octyloxyphenyl group, 2-methoxy- 1-naphthyl group, 3-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1
-Naphthyl group, 7-methoxy-1-naphthyl group, 8-methoxy-1-naphthyl group, 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group, 4-methoxy-2
-Naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group, 2-ethoxy-1
An aryl group substituted by a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms such as a naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, iodophenyl group, fluorophenyl An aryl group substituted with a halogen atom such as a trifluoromethylphenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group or a pentafluorophenyl group; an aryl group substituted with a halogenated alkyl group such as a trifluoromethylphenyl group; -Dimethylaminophenyl group, N, N-diethylaminophenyl group,
N-monosubstituted amino substitution such as N-phenyl-N-methylaminophenyl group, N-tolyl-N-ethylaminophenyl group, N-chlorophenyl-N-cyclohexylaminophenyl group, N, N-ditolylaminophenyl group Aryl groups, N, N-disubstituted aminoaryl groups,
Other examples include an alkylthioaryl group such as a methylthiophenyl group, an ethylthiophenyl group, a methylthionaphthyl group, and a phenylthiophenyl group, and an arylthioaryl group.

Examples of the substituted or unsubstituted alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1 and -Dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1-ethylpropoxy group, 2-ethylpropoxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, methylcyclohexyloxy group, Octyloxy, ethylcyclohexyl, dimethylcyclohexyloxy, nonyloxy, 2-
A linear, branched or cyclic C1-C10 alkoxy group such as ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, decyloxy group, fluoromethoxy group, trifluoromethoxy group, fluoroethoxy group, trifluoro Straight chain in which 1 to 21 halogen atoms such as ethoxy group, hexafluoroethoxy group, fluoropropoxy group, trifluoropropoxy group, hexafluoropropoxy group, chloromethoxy group, trichloromethoxy group, chloroethoxy group and trichloroethoxy group are substituted A branched or cyclic halogenated alkoxy group having 1 to 10 carbon atoms,
Methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, butoxymethoxy group, cyclohexyloxymethoxy group, methoxymethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, cyclohexyloxyethoxy group, methoxyethoxyethoxy Group, ethoxyethoxyethoxy group, propoxyethoxyethoxy group, butoxyethoxyethoxy group, methoxymethylethoxy group, ethoxymethylethoxy group, propoxymethylethoxy group,
Butoxymethylethoxy, cyclohexyloxymethylethoxy, methoxyethoxymethylethoxy, ethoxyethoxymethylethoxy, propoxyethoxymethylethoxy, butoxyethoxymethylethoxy, 2-[(2′-methoxy) propoxy] propoxy, methoxy A propoxy group, an ethoxypropoxy group, a linear, branched or cyclic C1-C10 alkoxyalkoxy group such as a propoxypropoxy group, an alkoxyalkoxyalkoxy group, an N-methylaminomethoxy group,
N, N-dimethylaminomethoxy group, N-ethylaminomethoxy group, N, N-diethylaminomethoxy group, N-
Methylaminoethoxy group, N, N-dimethylaminoethoxy group, N-ethylaminoethoxy group, N, N-diethylaminoethoxy group, N-methylaminopropoxy group,
A linear, branched or cyclic C1-C1 group such as an N, N-dibutylaminopropoxy group or an N-methylaminobutoxy group;
0 alkylaminoalkoxy group, methylthiomethoxy group, ethylthiomethoxy group, propylthiomethoxy group,
Straight-chain, branched or cyclic carbon atoms such as methylthioethoxy, ethylthioethoxy, propylthioethoxy, etc.
And 10 aryloxyalkoxy groups such as an alkylthioalkoxy group, a phenoxyethoxy group, a naphthyloxyethoxy group, a tolyloxyethoxy group, and an ethylphenoxyethoxy group.

Examples of substituted or unsubstituted aryloxy groups include phenyloxy, naphthyloxy, anthranyloxy, 2-methylphenyloxy, and 3-
Methylphenyloxy group, 4-methylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3, 4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,6-dimethylphenyloxy group, 2,3
4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group , 3,
4,5-trimethylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group, butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, octylphenyloxy group, 2
-Methyl-1-naphthyloxy group, 3-methyl-1-naphthyloxy group, 4-methyl-1-naphthyloxy group,
5-methyl-1-naphthyloxy group, 6-methyl-1-
Naphthyloxy group, 7-methyl-1-naphthyloxy group, 8-methyl-1-naphthyloxy group, 1-methyl-
2-naphthyloxy group, 3-methyl-2-naphthyloxy group, 4-methyl-2-naphthyloxy group, 5-methyl-2-naphthyloxy group, 6-methyl-2-naphthyloxy group, 7-methyl- An aryloxy group substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as a 2-naphthyloxy group, an 8-methyl-2-naphthyloxy group, and a 2-ethyl-1-naphthyloxy group. And a 3-methoxyphenyloxy group, a 4-methoxyphenyloxy group, a 2,3-dimethoxyphenyloxy group,
2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 2,6-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5
-Dimethoxyphenyloxy group, 3,6-dimethoxyphenyloxy group, 2,3,4-trimethoxyphenyloxy group, 2,3,5-trimethoxyphenyloxy group,
2,3,6-trimethoxyphenyloxy group, 2,4
5-trimethoxyphenyloxy group, 2,4,6-trimethoxyphenyloxy group, 3,4,5-trimethoxyphenyloxy group, 2-ethoxyphenyloxy group, propoxyphenyloxy group, butoxyphenyloxy group, hexyl Oxyphenyloxy group, cyclohexyloxyphenyloxy group, octyloxyphenyloxy group, 2-methoxy-1-naphthyloxy group, 3-methoxy-1-naphthyloxy group, 4-methoxy-1-naphthyloxy group, 5-methoxy -1-naphthyloxy group,
6-methoxy-1-naphthyloxy group, 7-methoxy-
1-naphthyloxy group, 8-methoxy-1-naphthyloxy group, 1-methoxy-2-naphthyloxy group, 3-methoxy-2-naphthyloxy group, 4-methoxy-2-naphthyloxy group, 5-methoxy- Carbon number 1 such as 2-naphthyloxy group, 6-methoxy-2-naphthyloxy group, 7-methoxy-2-naphthyloxy group, 8-methoxy-2-naphthyloxy group, 2-ethoxy-1-naphthyloxy group, etc. And aryloxy groups substituted with a linear, branched or cyclic alkoxy group of 10 to 10, such as chlorophenyloxy, dichlorophenyloxy, trichlorophenyloxy, bromophenyloxy, dibromophenyloxy, and iodophenyloxy. , Fluorophenyloxy group, difluorophenyloxy group, trifluorophenyloxy An aryloxy group substituted with a halogen atom such as a trifluoromethylphenyloxy group, a trifluoromethylphenyloxy group, or the like; -Dimethylaminophenyloxy group, N, N-diethylaminophenyloxy group, N-phenyl-N-methylaminophenyloxy group, N-tolyl-N-ethylaminophenyloxy group, N-chlorophenyl-N-cyclohexylaminophenyloxy N-monosubstituted aminoaryloxy group such as N, N-ditolylaminophenyloxy group, N, N
An alkylthioaryloxy group such as a methylthiophenyloxy group, an ethylthiophenyloxy group, a methylthionaphthyloxy group, a cyclohexylthiophenyloxy group, a phenylthiophenyloxy group, a naphthylthiophenyloxy group; And an arylthioaryloxy group such as a phenylthionaphthyloxy group.

Examples of the substituted or unsubstituted N-alkylamino groups include methylamino, ethylamino, n-propylamino, iso-propylamino, n-butylamino, iso-butylamino, sec- -Butylamino group, n-pentylamino group, 1-methylbutylamino group, 2-methylbutylamino group, 3-methylbutylamino group, 1,1-dimethylbutylamino group, 1,2-dimethylbutylamino group, 2,2-dimethylbutylamino group, 1-ethylpropylamino group, 2-ethylpropylamino group, n-hexylamino group, cyclohexylamino group, n-heptylamino group, methylcyclohexylamino group, n-octylamino group, 2-ethylhexylamino group, ethylcyclohexylamino group, dimethylcyclohexylamino , N- nonylamino group, 3,5,5
A straight-chain, branched or cyclic alkylamino group having 1 to 10 carbon atoms such as a trimethylhexylamino group, an n-decylamino group, a methoxymethylamino group, an ethoxymethylamino group, a methoxyethylamino group, an ethoxyethylamino group, n -Propoxyethylamino group, iso-propoxyethylamino group, n-butoxyethylamino group, is
o-butoxyethylamino group, tert-butoxyethylamino group, n-hexyloxy-ethylamino group, cyclohexyloxyethylamino group, 2-methoxypropylamino group, methoxy-iso-propylamino group,
C1-C1 such as 2-ethoxypropylamino group, ethoxy-iso-propylamino group, 2-propoxypropylamino group, propoxy-iso-propylamino group, etc.
0 linear, branched or cyclic alkoxyalkylamino group, methylthiomethylamino group, ethylthiomethylamino group, methylthioethylamino group, ethylthioethylamino group, n-propylthioethylamino group, iso-propylthioethylamino Group, n-butylthioethylamino group, iso-butylthioethylamino group, tert-
Butylthioethylamino group, n-hexylthioethylamino group, cyclohexylthioethylamino group, 2-methylthiopropylamino group, methylthio-iso-propylamino group, 2-ethylthiopropylamino group, ethylthio-iso-propylamino group A straight chain having 1 to 10 carbon atoms such as a 2-propylthiopropylamino group, a propylthio-iso-propylamino group, a methylthioethoxyethylamino group, an ethylthioethylthioethylamino group,
A branched or cyclic alkylthioalkylamino group, N-
Methylaminomethylamino group, N-methylaminoethylamino group, N-ethylaminomethylamino group, N-ethylaminoethylamino group, N, N-dimethylaminomethylamino group, N, N-diethylaminomethylamino group,
A linear chain having 1 to 10 carbon atoms such as an N, N-dimethylaminoethylamino group, an N, N-diethylaminoethylamino group,
Examples thereof include a branched or cyclic N-alkylaminoalkylamino group and an N, N-dialkylaminoalkylamino group.

Examples of the substituted or unsubstituted N, N-dialkylamino group include N, N-dimethylamino group,
N, N-diethylamino group, N, N-di (n-propyl) amino group, N, N-di (iso-propyl) amino group, N, N-di (n-butyl) amino group, N, N- Di (iso-butyl) amino group, N, N-di (sec-butyl) amino group, N, N-di (n-pentyl) amino group, N, N-di (1-methylbutyl) amino group, N, N
-Di (2-methylbutyl) amino group, N, N-di (3-
Methylbutyl) amino group, N, N-di (1,1-dimethylbutyl) amino group, N, N-di (1,2-dimethylbutyl) amino group, N, N-di (2,2-dimethylbutyl) An amino group, an N, N-di (1-ethylpropyl) amino group, an N, N-di (2-ethylpropyl) amino group,
N, N-di (n-hexyl) amino group, N, N-di (cyclohexyl) amino group, N, N-di (n-heptyl)
Amino group, N, N-di (methylcyclohexyl) amino group, N, N-di (n-octyl) amino group, N, N-di (2-ethylhexyl) amino group, N, N-di (dimethylcyclohexyl) Amino group, N, N-di (n-nonyl) amino group, N, N-di (3,5,5-trimethylhexyl) amino group, N, N-di (n-decyl) amino group, N-methyl -N-ethylamino group, N-propyl-
C1-C10 linear, branched or branched such as N-ethylamino group, N-hexyl-N-ethylamino group, N-octyl-N-ethylamino group, N- (cyclohexyl) -N-ethylamino group, etc. A cyclic alkyldisubstituted amino group, N,
N-di (methoxymethyl) amino group, N, N-di (ethoxymethyl) amino group, N, N-di (methoxyethyl)
Amino group, N, N-di (ethoxyethyl) amino group,
N, N-di (n-propoxyethyl) amino group, N, N
-Di (iso-propoxyethyl) amino group, N, N-
Di (n-butoxyethyl) amino group, N, N-di (is
o-butoxyethyl) amino group, N, N-di (tert
-Butoxyethyl) amino group, N, N-di (n-hexyloxyethyl) amino group, N, N-di (cyclohexyloxyethyl) amino group, N, N-di (2-methoxypropyl) amino group, N , N-di (methoxy-iso-
Propyl) amino group, N, N-di (2-ethoxypropyl) amino group, N, N-di (ethoxy-iso-propyl) amino group, N, N-di (2-propoxypropyl)
Amino group, N, N-di (propoxy-iso-propyl) amino group, N, N-di (methoxyethoxyethyl)
Amino group, N, N-di (ethoxyethoxyethyl) amino group, N-methyl-N- (methoxyethyl) amino group,
An N- (propyloxyethyl) -N-ethylamino group,
N-hexyloxyethyl-N-ethylamino group, N-
(Ethoxyethoxyethyl) -N-ethylamino group, N
A dialkylamino group substituted with a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms such as-(cyclohexyloxyethyl) -N-ethylamino group, an N, N-di (methylthiomethyl) amino group, N , N-di (ethylthiomethyl) amino group, N, N-di (methylthioethyl)
An amino group, an N, N-di (ethylthioethyl) amino group,
An N, N-di (n-propylthioethyl) amino group,
N-di (iso-propylthioethyl) amino group, N,
N-di (n-butylthioethyl) amino group, N, N-di (iso-butylthioethyl) amino group, N, N-di (tert-butylthioethyl) amino group, N, N-di (n -Hexylthioethyl) amino group, N, N-di (cyclohexylthioethyl) amino group, N, N-di (2-
Methylthiopropyl) amino group, N, N-di (methylthio-iso-propyl) amino group, N, N-di (2-ethylthiopropyl) amino group, N, N-di (ethylthio-iso-propyl) amino group N, N-di (2-propylthiopropyl) amino group, N, N-di (propylthio-iso-propyl) amino group, N, N-di (methylthioethoxyethyl) amino group, N, N-di ( N, N substituted with a linear, branched or cyclic alkylthio group having 1 to 10 carbon atoms such as an ethylthioethylthioethyl) amino group
-Dialkylthioalkylamino group, N, N-di (N-
Methylaminomethyl) amino group, N, N-di (N-methylaminoethyl) amino group, N, N-di (N-ethylaminomethyl) amino group, N, N-di (N-ethylaminoethyl) amino Group, N, N-di (N, N-dimethylaminomethyl) amino group, N, N-di (N, N-diethylaminomethyl) amino group, N, N-di (N, N-dimethylaminoethyl) amino A linear group having 1 to 10 carbon atoms such as a group, N, N-di (N, N-diethylaminoethyl) amino group,
Examples thereof include a branched or cyclic N, N-di (N-alkylaminoalkyl) amino group and an N, N-di (N, N-dialkylaminoalkyl) amino group.

Examples of the substituted or unsubstituted N-arylamino group include N-phenylamino group, N-tolylamino group, N-chlorophenylamino group, N-trifluorophenylamino group, N-naphthylamino group, -Methylnaphthylamino group, N-chloronaphthylamino group and the like.

Examples of the substituted or unsubstituted N, N-diarylamino group include N, N-diphenylamino group, N, N
-Ditolylamino group, N, N-dichlorophenylamino group, N, N-ditrifluorophenylamino group, N, N
-Dinaphthylamino group, N, N-dimethylnaphthylamino group, N, N-dichloronaphthylamino group and the like.

Examples of the substituted or unsubstituted N-alkyl-N-arylamino group include N-methyl-N-phenylamino group, N-ethyl-N-tolylamino group, N-methoxyethyl-N-chlorophenylamino group. , N-ethyl-
N-trifluorophenylamino group, N-cyclohexyl-N-naphthylamino group, N-ethyl-N-naphthylamino group, N-2-ethylhexyl-N-methylnaphthylamino group, N-methyl-N-chloronaphthylamino And the like.

Preferred examples of the substituent of R ^{1 to} R ¹⁶ include a hydrogen atom, a chlorine atom, a hydroxyl group and a sulfonic acid group. Preferred examples of X ¹ and X ² include a chlorine atom and a hydroxyl group.

In the method of the present invention, the general formula (1):
The compounds represented by (2) and (3) have (E)-and (Z) -isomers. Its abundance ratio is
(E): (Z) is 0: 100 to 100: 0.

In the method of the present invention, examples of the reducing sugar used include glucose, mannose, arabinose and the like. Preferably, it is glucose. The reducing sugar to be used is charged into the reaction system in the form of an aqueous solution, and the concentration is usually 1 to 50%, preferably 5 to 50%.

In the method of the present invention, the amount of reducing sugar to be used is 0.1 to 10 mole ratio to the compounds represented by the general formulas (4) and (5). Preferably, 0.3
５5 mole ratio, more preferably 0.7-2.1 mole ratio.

In the method of the present invention, the temperature for charging the reducing sugar is 10 ° C. or higher. Preferably, 20 to 80 ° C
It is. The charging time is usually 0.1 to 20 hours.

In the method of the present invention, the stirring temperature after charging the reducing sugar is 10 ° C. or higher. Preferably, 20 to
80 ° C. The time is usually 1 to 20 hours.

In the method of the present invention, the synthesis reaction of the compound represented by the general formula (1) is carried out in water or an organic solvent. Specific examples include water, methanol, ethanol, propanol, N, N-dimethylformamide,
1,3-dimethyl-2-imidazolidinone and the like. Preferred are water, methanol and ethanol.
The amount of use is 1 to 50 parts by weight, preferably 5 to 200 parts by weight, based on 1 part by weight of the compound represented by the general formula (4) and / or the general formula (5) as a raw material.

In the method of the present invention, the reduction reaction is carried out in the presence of an alkali. As the alkali used, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, Calcium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, rubidium bicarbonate, cesium bicarbonate, preferably sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like can be mentioned. More preferably, they are sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. As the alkali, an aqueous solution is usually used, but an alkali which is charged and dissolved in water or an organic solvent in a solid state may be used. Its concentration is 0.1-20% by weight, preferably 0.5-10% by weight.

The amount of the alkali used is 1.0 to 100 mole ratio to the compounds of the general formulas (4) and (5).
Preferably, 1.5 to 50 molar ratio, more preferably,
The molar ratio is 4.9 to 14.6. After using these alkalis, neutralization is performed with an aqueous solution of a mineral acid such as hydrochloric acid or sulfuric acid.

The acid halides of the present invention can be produced by reacting a carboxylic acid in an organic solvent with a commonly known halogenating agent. As the halogenating agent, for example, thionyl chloride, thionyl bromide, phosgene, phosphorus trichloride, phosphorus pentachloride and the like can be used. Preferably, thionyl chloride and phosgene are used.

The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 10 mol, based on the carboxylic acid. Examples of the organic solvent include aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as benzene and toluene.

When a halogenating agent which is liquid at the reaction temperature is used, a solvent may be used. The reaction temperature is 40 to 2
00 ° C, preferably 50 to 180 ° C. When an organic nitrogen compound such as picoline, pyridine or DMF is added, the reaction is accelerated.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. "Ε" means gram extinction coefficient. Absorption analysis was performed using a 1 cm wide quartz cell with a visible ultraviolet absorption spectrophotometer (manufactured by Shimadzu Corporation).
The absorbance at 00 nm was measured and determined. The measurement sample is
Azoxybiphenylcarboxylic acid is weighed and 97-98%
The one dissolved in sulfuric acid (manufactured by Wako Pure Chemical) was used.

The term "yield" refers to the yield of azoxybiphenylcarboxylic acid relative to nitrobiphenylcarboxylic acid. The content of nitrobiphenylcarboxylic acid contained in axizobiphenylcarboxylic acid was analyzed by HPLC.

Example 1 12.4 g of nitrobiphenylcarboxylic acid was added to 420 g of a 4.7% aqueous sodium hydroxide solution, the temperature was raised to 80 ° C, the mixture was stirred for 30 minutes, and then cooled to 60 ° C. Separately, a solution prepared by dissolving 12.6 g of glucose in 30 g of water was dropped at 60 ° C. over 3 hours. The mixture was stirred for 4 hours while maintaining the temperature. After cooling, the mixture was filtered and 3% saline 2
Washed with 60 g. This wet cake was added to 410 g of 2.6% sulfuric acid and stirred at 60 ° C. for 2 hours. The solid is collected by filtration, washed with warm water, and dried to obtain the desired formula (2)

[0040]

Embedded image 9.9 g of azoxybiphenylcarboxylic acid was obtained.
As a result of HPLC analysis, nitrobiphenylcarboxylic acid
It was 0%. The ¹ H-NMR spectrum is shown in FIG.
FIG. 2 shows the R spectrum, FIG. 3 shows the Raman spectrum, and FIG. 4 shows the MS spectrum.

Example 2 The same procedure as in Example 1 was carried out except that the temperature at which the glucose aqueous solution was dropped and the subsequent stirring temperature were 100 ° C. 9.9 g of azoxybiphenylcarboxylic acid of the formula (2)
was gotten. ε was 115. As a result of HPLC analysis, the content of nitrobiphenylcarboxylic acid was 0%.

Example 3 12.4 g of nitrobiphenylcarboxylic acid was added to 420 g of a 4.7% aqueous sodium hydroxide solution, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes. Separately, glucose6.
What melt | dissolved 3 g in 15 g of water was dripped at 80 degreeC over 3 hours. The mixture was stirred for 4 hours while maintaining the temperature. After cooling, the mixture was filtered and washed with 260 g of 3% saline.
This wet cake is added to 410 g of 2.6% sulfuric acid,
Stirred at 0 ° C. for 2 hours. The solid is collected by filtration and washed with warm water.
Upon drying, 10.0 g of azoxybiphenylcarboxylic acid of formula (2) was obtained. ε was 116. HPLC
As a result of the analysis, the content of nitrobiphenylcarboxylic acid was 1%.

Example 4 The procedure of Example 3 was repeated, except that 18.9 g of glucose was dissolved in 45 g of water and added dropwise. 9.9 g of azoxybiphenylcarboxylic acid of the formula (2) were obtained. ε was 118. As a result of HPLC analysis, the content of nitrobiphenylcarboxylic acid was 0%.

Example 5 12.4 g of nitrobiphenylcarboxylic acid was added to 410 g of a 2.5% aqueous sodium hydroxide solution, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes. Separately, glucose6.
What melt | dissolved 3 g in 15 g of water was dripped at 80 degreeC over 3 hours. The mixture was stirred for 4 hours while maintaining the temperature. After cooling, the mixture was filtered and washed with 260 g of 3% saline.
This wet cake is added to 410 g of 2.6% sulfuric acid,
Stirred at 0 ° C. for 2 hours. The solid is collected by filtration and washed with warm water.
Upon drying, 9.8 g of azoxybiphenylcarboxylic acid of formula (2) was obtained. ε was 118. As a result of HPLC analysis, the content of nitrobiphenylcarboxylic acid was 1%.

Example 6 The procedure of Example 5 was repeated except that 431 g of a 7.1% aqueous sodium hydroxide solution was used. 9.9 g of azoxybiphenylcarboxylic acid of the formula (2) were obtained. ε was 118. As a result of HPLC analysis, the content of nitrobiphenylcarboxylic acid was 0%.

Example 7 28.4 g of the azoxybiphenylcarboxylic acid of the formula (2) produced in Example 1 was suspended in 723 g of o-dichlorobenzene. After adding 0.2 g of picoline, 30 g of thionyl chloride was added dropwise at 60 ° C. over 1.5 hours, and the temperature was raised to 145 ° C. After stirring at 145 ° C for 3 hours, the mixture was cooled to 20 ° C. The precipitated crystals are collected by filtration, washed with toluene, and dried to obtain the formula (3)

[0047]

Embedded image 24 g of azoxybiphenylcarboxylic acid chloride were obtained. The ¹ H-NMR spectrum is shown in FIG. 5, the IR spectrum is shown in FIG. 6, the Raman spectrum is shown in FIG. 7, and the MS spectrum is shown in FIG.

Usage Example At room temperature, 28.4 g of the carboxylic acid compound of the formula (2) and 0.2 g of picoline were added to 723 g of o-dichlorobenzene, and the temperature was raised to 60 ° C. Then 30.0 g of thionyl chloride
(3.7 times mol / azoxybiphenylcarboxylic acid) was added dropwise over 1.5 hours, and then the temperature was raised to 145 ° C over 3 hours. After stirring at 145 ° C. for 3 hours, thionyl chloride was distilled out of the system while flowing nitrogen through the gas phase. Furthermore,
Cooled to 100 ° C. and stirred for 30 minutes. 28.6 g of 1-aminoanthraquinone and 119 of o-dichlorobenzene
g were previously mixed at room temperature and added. 14 again
The temperature was raised to 5 ° C, and after stirring for 3 hours, the mixture was cooled to 80 ° C. The o-dichlorobenzene was distilled off from the reaction mixture by steam distillation, and the crystal part was filtered and washed with water to obtain 182.0 g of a target wet cake. When this is dried and the water is distilled off, the formula (8) is obtained.

[0049]

Embedded image 49.7 g of the anthraquinone compound was obtained.

10. An anthraquinone compound (40 g) was mixed with 49.6 g of Vanilex RN (manufactured by Nippon Paper Co., Ltd.), 10.6 g of vaniole ODP (manufactured by Nippon Paper Co., Ltd.), and Vanirex RNAP Liquid (manufactured by Nippon Paper Industries). 2
g, Neocoll P (Daiichi Kogyo Seiyaku Co., Ltd.) (1.2 g) are mixed with water (183.7 g). When a wet cake of the anthraquinone compound of the formula (8) is used, the total amount of water is 1
83.7 g. 3 to 1 with 6-cylinder sand grinder
Disperse for 0 hour to obtain a dye solution. This dye solution is weighed into a dyeing pot of a laboratory master (manufactured by Tsujii Dyeing Machine Co., Ltd.), water, cotton cloth and hydrosulfite water are added, and the lid is closed. Stir at 40 ° C. for 10 minutes, then at 50 ° C. for 30 minutes. After cooling, the lid is opened, the cotton cloth is taken out, oxidized with sodium perborate water, washed with water, soaped, washed again with water, and dried. By this operation, a clear yellow dyed cotton cloth was obtained.

Examples 8 to 14 Nitrobiphenylcarboxylic acid of Example 1 (general formula (4)
The compound shown in Table 1 was replaced with a compound as shown in Table 1, and a dye intermediate was similarly synthesized. Furthermore, according to the usage example,
By reacting with 1-aminoanthraquinone, an anthraquinone dye was synthesized. Dye intermediate (dicarboxylic acid compound)
Table 1 shows the yield of the dye and the results of dyeing the anthraquinone dye.

[0052]

[Table 1]

Reference Example (Conventional Dye) At room temperature, 723 g of o-dichlorobenzene was added to the following formula (8)

Embedded image

28.4 g of the azocarboxylic acid compound and 0.2 g of picoline were added, and the temperature was raised to 60 ° C. Next, 30.0 g of thionyl chloride (3.7 times mol / azobiphenylcarboxylic acid) was added dropwise over 1.5 hours, and then 145 ° C.
Until 3 hours. After stirring at 145 ° C. for 3 hours, thionyl chloride was distilled out of the system while flowing nitrogen through the gas phase. Furthermore, it cooled to 100 degreeC and stirred for 30 minutes. 28.6 g of 1-aminoanthraquinone and 119 g of o-dichlorobenzene were previously mixed at room temperature and added. The temperature was raised again to 145 ° C, and after stirring for 3 hours, 80 ° C
And cooled. The o-dichlorobenzene was distilled off from the reaction mixture by steam distillation, and the crystal part was filtered and washed with water to obtain 182.0 g of a target wet cake. This was dried and water was distilled off to obtain C.I. I. Bat Yellow 33
Was obtained 49.7 g. When this was dyed on cotton cloth according to the usage example, it was dyed dark yellow.

[0055]

The novel compound of the present invention is a dye intermediate from which a dye having good definition can be obtained.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a compound synthesized in Example 1.

FIG. 2 is an IR spectrum of the compound synthesized in Example 1.

FIG. 3 is a Raman spectrum of the compound synthesized in Example 1.

FIG. 4 is an MS spectrum of the compound synthesized in Example 1.

FIG. 5 is a ¹ H-NMR spectrum of the compound synthesized in Example 7.

FIG. 6 is an IR spectrum of the compound synthesized in Example 7.

FIG. 7 is a Raman spectrum of the compound synthesized in Example 7.

FIG. 8 is an MS spectrum of the compound synthesized in Example 7.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoto Ito 30 Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] [Claim 1] The following general formula (1) [In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
^{R 8, R 9, R 10} , R 11, R 12, R 13, R 14, R 15, R 16
Is independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an amino group, a sulfonic acid group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted N-alkylamino group, a substituted or unsubstituted N, N-dialkylamino group, a substituted or unsubstituted N-arylamino group, Unsubstituted N, N-diarylamino group, substituted or unsubstituted N-
It represents an alkyl-N-arylamino group, and X ¹ and X ² each independently represent a halogen atom or a hydroxyl group. A dicarboxylic acid compound represented by the formula: 2. The following formula (2): A dicarboxylic acid represented by the formula: 3. The following formula (3): A dicarboxylic acid chloride represented by the formula: 4. The following general formula (4): [In the formula (4), R ^{1 to} R ⁸ have the same meaning as described above. ]
And / or a nitrocarboxylic acid compound represented by the following general formula (5): [In the formula (4), R ^{9 to} R ¹⁶ have the same meaning as described above. A nitrocarboxylic acid compound represented by the following general formula (6): [In the formula (6), R ^{1 to} R ¹⁶ have the same meaning as described above. ] A method for producing a dicarboxylic acid represented by the formula: 5. The molar ratio of the reducing sugar is represented by the general formula (4) and / or
Alternatively, 0.1 to the nitrocarboxylic acid compound of the general formula (5).
The method according to claim 4, wherein the number is from 3 to 5. 6. The method according to claim 4, wherein the reaction temperature with the reducing sugar is 20 to 80 ° C.