JP3462895B2 - Method for producing polyvalent metal salt of benzoic acid derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing crystals of a polyvalent metal salt of a benzoic acid derivative useful as an electron-accepting compound for recording materials.

[0002]

2. Description of the Related Art Conventionally, a heat-sensitive recording material utilizing a color reaction between an electron-donating color-forming compound and an electron-accepting compound (developing agent) is well known (for example, JP-B-43-4).
160, JP-B-45-14039). The heat-sensitive recording material is relatively inexpensive and has the advantage that the recording device is compact and maintenance-free, and is therefore widely used in the fields of facsimiles, recorders, printers and the like. In recent years, the fields of use of thermal recording materials have further expanded and diversified, and have expanded to applications (eg, labels, prepaid cards, etc.) under more severe environments. Conventionally, phenolic compounds have been widely used as electron-accepting compounds. Among them, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 4-hydroxybenzoic acid esters (JP-A-56-144193, JP-B-1-306
No. 40) is known as an electron-accepting compound. However, a heat-sensitive recording material using bisphenol A, 4-hydroxybenzoic acid benzyl ester or the like as an electron-accepting compound is, for example, in a harsh environment (for example, oil, solvent, plasticizer, oil and fat,
Under contact with a writing instrument such as a highlighter pen or in an environment of high temperature and high humidity), the uncolored part is significantly contaminated (ground stain).
There is a defect that the colored image is discolored or the color image is discolored.

In order to improve these drawbacks, the present inventors have used an amide group-substituted benzoic acid derivative or a polyvalent metal salt of the derivative as an electron-accepting compound to obtain an uncolored portion and a colored portion. It was found that a heat-sensitive recording material excellent in image storage stability (for example, oil resistance, wet heat resistance, writing instrument resistance) was obtained, and the application was filed earlier (Japanese Patent Application No. 5-219559). This polyvalent metal salt of a benzoic acid derivative having an amide group (for example, a zinc salt) is a polyvalent metal compound that is soluble in an aqueous solution of a corresponding alkali metal salt of a benzoic acid derivative (for example, a sodium salt) at room temperature. It can be produced by a so-called metathesis production method in which (for example, zinc sulfate) acts. But,
In this method, when the resulting polyvalent metal salt of a benzoic acid derivative is separated and isolated by filtration, the filterability is poor, the filtration step requires a long time, and the work efficiency and the production efficiency are deteriorated. .

The polyvalent metal salt of the benzoic acid derivative (for example, zinc salt) may vary depending on production conditions, drying conditions, etc.
It has been found that sometimes an amorphous body is produced. Furthermore, since this amorphous material has a low bulk density, it has a problem in workability in handling when it is used as an electron-accepting material for a heat-sensitive recording material, for example, it scatters in the air during weighing or transportation. was there. Therefore, an efficient method for converting the polyvalent metal salt from an amorphous form into crystals has been desired.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems and provide a recording material (for example, a heat-sensitive recording material).
To provide a method for producing a polyvalent metal salt of a benzoic acid derivative useful as an electron-accepting compound for use and a method for producing a crystal of the polyvalent metal salt.

[0006]

Means for Solving the Problems The present inventors have arrived at the present invention as a result of extensive studies on a method for producing a polyvalent metal salt of a benzoic acid derivative in order to meet the above-mentioned demand. That is, the present invention comprises at least an alkali metal salt of a benzoic acid derivative represented by the general formula (1) and a polyvalent metal compound.
The present invention relates to a method for producing a polyvalent metal salt of a benzoic acid derivative represented by the general formula (1), which comprises reacting in an aqueous medium containing 40% by weight of water and then heat-treating. Further, the amorphous body of the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) contains at least 40% by weight of water.
General formula (1) characterized by heat treatment in an aqueous medium
The present invention relates to a method for producing crystals of a benzoic acid derivative polyvalent metal salt represented by:

[0007]

[Chemical 3] (In the formula, X1 and X2 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a nitro group, Y represents an oxygen atom or a sulfur atom, and R1 represents a hydrogen atom, an alkyl group or an aralkyl. Represents a group or aryl group, R2 is an alkyl group, an alkenyl group,
In the benzoic acid derivative represented by the general formula (1) according to the present invention, X1 and X2 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, or an aralkyl group or an aryl group. Represents a nitro group, preferably a hydrogen atom, a fluorine atom, a chlorine atom,
Bromine atom, C1-C20 chain alkyl group, C5
To 14 cyclic alkyl groups, C1 to C20 alkoxy groups, C7 to C20 aralkyl groups, C5 to C20 aryl groups or nitro groups, and more preferably hydrogen atoms, chlorine atoms, and carbon atoms. It is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenyl group or a nitro group, and a hydrogen atom is particularly preferable.

In the general formula (1), Y represents an oxygen atom or a sulfur atom, and preferably an oxygen atom.

In the benzoic acid derivative represented by the general formula (1), R1 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, preferably a hydrogen atom, a chain alkyl group having 1 to 20 carbon atoms, Cyclic alkyl group having 5 to 14 carbon atoms, aralkyl group having 7 to 20 carbon atoms or 5 carbon atoms
To 20 aryl groups, more preferably a hydrogen atom, a chain alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a benzyl group or a phenyl group which may have a substituent. Yes, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group is more preferable, and a hydrogen atom is particularly preferable.

In the benzoic acid derivative represented by the general formula (1), R2 represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, preferably a chain alkyl group which may have a substituent, or a substituted group. A cyclic alkyl group which may have a group, a chain alkenyl group which may have a substituent, a cyclic alkenyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent It is a phenyl group which may have, a naphthyl group which may have a substituent, or a heteroaromatic ring group which may have a substituent.

The alkyl group and alkenyl group represented by R2 may have a substituent, and examples thereof include an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyloxy group having 2 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. Oxy group, carbon number 7
-20 aralkyloxy groups, C8-20 aralkyloxyalkoxy groups, C6-20 aryloxy groups, C7-20 aryloxyalkoxy groups, C8-20 arylalkenyl groups, carbon Number 9
To aralkylalkenyl group having 20 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkoxyalkylthio group having 2 to 20 carbon atoms, alkylthioalkylthio group having 2 to 20 carbon atoms,
Alkenylthio group having 2 to 20 carbon atoms, aralkylthio group having 7 to 20 carbon atoms, aralkyloxyalkylthio group having 8 to 20 carbon atoms, aralkylthioalkylthio group having 8 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms , An aryloxyalkylthio group having 7 to 20 carbon atoms, and 7 to carbon atoms
It may be mono-substituted or poly-substituted with a substituent such as 20 arylthioalkylthio groups, a heteroalkyl-containing cyclic alkyl group, and a halogen atom.

Further, the aryl group contained in these substituents is further an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms.
And an alkylthio group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aralkyloxy group having 7 to 10 carbon atoms, a hydroxyl group, a halogen atom and the like.

The aryl group in the aralkyl group and the aryl group of R2 may have a substituent, for example,
Alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, and 6 to 2 carbon atoms
0 aryl group, C1-20 alkoxy group, C2-20 alkoxyalkyl group, C2-20 alkoxyalkyloxy group, C2-20 alkenyloxy group, C3-20 Alkenyloxyalkyl group, C3-20 alkenyloxyalkyloxy group, C7-20 aralkyloxy group, C8-20 aralkyloxyalkyl group, C8-2
0 aralkyloxyalkyloxy group, 6 to 2 carbon atoms
0 aryloxy group, C7-20 aryloxyalkyl group, C7-20 aryloxyalkyloxy group, C2-20 alkylcarbonyl group,
C3-C20 alkenylcarbonyl group, C8-
An aralkylcarbonyl group having 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkenyloxycarbonyl group having 3 to 20 carbon atoms, an aralkyloxycarbonyl group having 8 to 20 carbon atoms,
C 7-20 aryloxycarbonyl group, C 2-20 alkylcarbonyloxy group, C 3-2
0 alkenylcarbonyloxy group, C8-20 aralkylcarbonyloxy group, C7-20 arylcarbonyloxy group, C14-20 aralkyloxyaralkyl group, C1-20 alkylthio group, carbon Aralkylthio group having 7 to 20 carbon atoms and 6 to 2 carbon atoms
It may be mono- or poly-substituted with a substituent such as an arylthio group, a nitro group, a formyl group, a halogen atom, a hydroxyl group, a cyano group or the like.

Further, the aryl group contained in these substituents is further an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms.
And an alkylthio group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aralkyloxy group having 7 to 10 carbon atoms, a hydroxyl group, a halogen atom and the like.

Preferably, R 2 has an alkyl group having 1 to 24 carbon atoms which may have a substituent, an alkenyl group having 2 to 24 carbon atoms which may have a substituent, and a substituent. Is an aralkyl group having 7 to 24 carbon atoms or an aryl group having 6 to 24 carbon atoms which may have a substituent.

Specific examples of R2 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
-Pentyl group, isopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1- Methylheptyl group, 2-ethylhexyl group, n-nonyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group , 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group,

Cyclopentyl group, cyclohexyl group, 4-
Methylcyclohexyl group, 3-methylcyclohexyl group,
2-methylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3,
5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group,
Cycloheptyl group, cyclooctyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, bornel group, isobornene group, 2-norbornanemethyl group, 1-adamantylmethyl group,

Vinyl group, allyl group, 2-butenyl group, 3-butenyl group, 1-methyl-4-pentenyl group, 2-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-hexenyl group Group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-heptenyl group, 1-vinylhexyl group, 3-nonenyl group, 6-nonenyl group, 9-decenyl group, 10-undecenyl group, 1- A cyclohexenyl group,

2-methoxyethyl group, 2-ethoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-cyclohexyloxyethyl group, 3-methoxypropyl group, 3-ethoxy Propyl group, 3-
n-propoxypropyl group, 3-n-butoxypropyl group, 3-
n-hexyloxypropyl group, 3-n-octyloxyopropyl group, 3-cyclohexyloxypropyl group, 4-ethoxybutyl group, 5-methoxypentyl group, 6-ethoxyhexyl group, 2-methoxyethoxyethyl group, 2 -Ethoxyethoxyethyl group, 2-n-butoxyethoxyethyl group, 3-ethoxyethoxypropyl group,

2-allyloxyethyl group, 2- (4'-pentenyl) oxyethyl group, 3-allyloxypropyl group, 4-
Allyloxybutyl group,

2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4'-methylbenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 4-benzyloxybutyl group,
2-benzyloxymethoxyethyl group, 2- (4'-methylbenzyl) oxymethoxyethyl group,

Phenoxymethyl group, 2-phenoxyethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-
Methylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 3-phenoxypropyl group, 4-
Phenoxybutyl group, 6- (2'-chlorophenyloxy)
Hexyl group, 2-phenoxyethoxyethyl group, 2- (1'-
Naphthyloxy) ethyl group, 2- (2'-naphthyloxy)
Ethyl group, 3- (2'-naphthyloxy) propyl group,

Cinnamyl group, 2-methylthioethyl group, 2-
Ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octylthioethyl group, 2-n-
Decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group, 4-n-butylthiobutyl group Group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, 2-methoxyethylthioethyl group, 2-ethylthioethyl Thioethyl group,
2-allylthioethyl group, 2-benzylthioethyl group, 3-
(4'-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2-benzyloxyethylthioethyl group, 3-
Benzylthiopropylthiopropyl group, 2-phenylthioethyl group, 2- (4'-methoxyphenylthio) ethyl group, 2
-Phenoxyethylthioethyl group, 3- (2'-chlorophenylthio) ethylthiopropyl group,

2-tetrahydrofurfuryl group, 2-chloroethyl group, 3-chloropropyl group, 2,2,2-trichloroethyl group, 7-chloroheptyl group, 8-chlorooctyl group, 8-fluorooctyl group,

Benzyl group, α-methylbenzyl group, α-ethylbenzyl group, phenethyl group, α-methylphenethyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methyl group Benzyl group, 2-methylbenzyl group, 4-isopropylbenzyl group, 4-allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group, 4- (4'-methylphenyl)
Benzyl group, 4-methoxybenzyl group, 4-n-butoxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-allyloxybenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyl Oxybenzyl group, 4-
Phenethyloxybenzyl group, 4-phenoxybenzyl group, 3-phenoxybenzyl group, 4-hydroxybenzyl group, 3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 4-chlorobenzyl group , 3-chlorobenzyl group, 2-chlorobenzyl group,
2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group,

Phenyl group, 1-naphthyl group, 2-naphthyl group, 3-freel group, 3-thienyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group , 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-tert-octylphenyl group, 4- n-decylphenyl group, 4-n-dodecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-allylphenyl group, 2-allylphenyl group, 4-benzylphenyl group, 2-be Jirufeniru group, a 4-cumylphenyl group, 4
(4'-methoxycumyl) phenyl group, 4- (4'-benzyloxy) cumylphenyl group, 4- (4'-chlorobenzyl) phenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-
Phenylphenyl group, 4- (4'-methoxyphenyl) phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 2- (2'-
(Methoxyphenyl) phenyl group, 4- (4'-chlorophenyl)
Phenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group,
2-ethoxyphenyl group, 3-n-propoxyphenyl group, 4-
Isopropoxyphenyl group, 4-n-butoxyphenyl group,
4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-n-octyloxyphenyl group, 4-
n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-ethyl-1
-Naphthyl group, 6-n-butyl-2-naphthyl group, 2-methoxy-1
-Naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butoxy
-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-ethoxy
-2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group,
7-n-butoxy-2-naphthyl group, 4-methoxymethylphenyl group, 4-ethoxymethylphenyl group, 4-n-butoxymethylphenyl group, 3-methoxymethylphenyl group, 4- (2'-methoxyethyl) Phenyl group, 4- (2'-ethoxyethyloxy) phenyl group, 4- (2'-n-butoxyethyloxy) phenyl group, 4- (3'-ethoxypropyloxy) phenyl group, 4-
Vinyloxyphenyl group, 4-allyloxyphenyl group,
3-allyloxyphenyl group, 4- (4'-pentenyloxy)
Phenyl group, 4-allyloxy-1-naphthyl group, 4-allyloxymethylphenyl group, 4- (2'-allyloxyethyloxy) phenyl group, 4-benzyloxyphenyl group, 2-benzyloxyphenyl group, 4- Phenethyloxyphenyl group, 4- (4'-chlorobenzyloxy) phenyl group, 4- (4'-
Methylbenzyloxy) phenyl group, 4- (4'-methoxybenzyloxy) phenyl group, 4- (3'-ethoxybenzyloxy) phenyl group, 4-benzyloxy-1-naphthyl group, 5-
(4'-methylbenzyloxy) -1-naphthyl group, 6-benzyloxy-2-naphthyl group, 6- (4'-methylbenzyloxy) -2
-Naphthyl group, 7-benzyloxy-2-naphthyl group, 4- (benzyloxymethyl) phenyl group, 4- (2'-benzyloxyethyloxy) phenyl group,

4-phenoxyphenyl group, 3-phenoxyphenyl group, 2-phenoxyphenyl group, 4- (4'-methylphenoxy) phenyl group, 4- (4'-methoxyphenoxy) phenyl group, 4- (4 ' -Chlorophenoxy) phenyl group, 4-phenoxy-1-naphthyl group, 6-phenoxy-2-naphthyl group,

4-phenoxymethylphenyl group, 4- (2'-phenoxyethyloxy) phenyl group, 4- [2 '-(4'-methylphenyl) oxyethyloxy] phenyl group, 4- [2'-( Four'-
Methoxyphenyl) oxyethyloxy] phenyl group, 4-
[2 '-(4'-chlorophenyl) oxyethyloxy] phenyl group,

4-acetylphenyl group, 3-acetylphenyl group, 2-acetylphenyl group, 4-ethylcarbonylphenyl group, 4-n-butylcarbonylphenyl group, 4-n-hexylcarbonylphenyl group, 4-n- Octylcarbonylphenyl group, 4-cyclohexylcarbonylphenyl group, 4-acetyl-1-naphthyl group, 6-acetyl-2-naphthyl group, 6-n-
Butylcarbonyl-2-naphthyl group, 4-allylcarbonylphenyl group, 4-benzylcarbonylphenyl group, 4- (4'-
Methylbenzyl) carbonylphenyl group, 4-phenylcarbonylphenyl group, 4- (4'-methylphenyl) carbonylphenyl group, 4- (4'-chlorophenyl) carbonylphenyl group, 4-phenylcarbonyl-1-naphthyl group,

4-methoxycarbonylphenyl group, 2-methoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-n-propoxycarbonylphenyl group, 4-n-butoxycarbonylphenyl group, 4 -n-hexyloxycarbonylphenyl group,
4-n-decyloxycarbonylphenyl group, 4-cyclohexyloxycarbonylphenyl group, 4-ethoxycarbonyl-1-naphthyl group, 6-methoxycarbonyl-2-naphthyl group, 6-n-butoxycarbonyl-2-naphthyl group, 4-allyloxycarbonylphenyl group, 4-benzyloxycarbonylphenyl group, 4- (4'-chlorobenzyl) oxycarbonylphenyl group, 4-phenethyloxycarbonylphenyl group, 6-benzyloxycarbonyl-2-naphthyl group, 4 -
Phenyloxycarbonylphenyl group, 4- (4'-ethylphenyl) oxycarbonylphenyl group, 4- (4'-chlorophenyl) oxycarbonylphenyl group, 4- (4'-ethoxyphenyl) oxycarbonylphenyl group, 6-phenyl Oxycarbonyl-2-naphthyl group,

4-acetyloxyphenyl group, 3-acetyloxyphenyl group, 4-ethylcarbonyloxyphenyl group, 2-ethylcarbonyloxyphenyl group, 4-n-propylcarbonyloxyphenyl group, 4-n-pentylcarbonyloxy Phenyl group, 4-n-octylcarbonyloxyphenyl group, 4-cyclohexylcarbonyloxyphenyl group, 4-acetyloxy-1-naphthyl group, 4-n-butylcarbonyloxy-1-naphthyl group, 5-acetyloxy-1 -Naphthyl group, 6-ethylcarbonyloxy-2-naphthyl group, 7-
Acetyloxy-2-naphthyl group, 4-allylcarbonyloxyphenyl group, 4-benzylcarbonyloxyphenyl group, 4-phenethylcarbonyloxyphenyl group, 6-benzylcarbonyloxy-2-naphthyl group, 4-phenylcarbonyloxyphenyl group , 4- (4'-methylphenyl) carbonyloxyphenyl group, 4- (2'-methylphenyl) carbonyloxyphenyl group, 4- (4'-chlorophenyl) carbonyloxyphenyl group, 4- (2'-chlorophenyl) Carbonyloxyphenyl group, 4-phenylcarbonyloxy
-1-naphthyl group, 6-phenylcarbonyloxy-2-naphthyl group, 7-phenylcarbonyloxy-2-naphthyl group,

4-methylthiophenyl group, 2-methylthiophenyl group, 4-ethylthiophenyl group, 3-ethylthiophenyl group, 4-n-propylthiophenyl group, 4-n-butylthiophenyl group, 4-n -Hexylthiophenyl group, 4-n-octylthiophenyl group, 4-cyclohexylthiophenyl group,
4-benzylthiophenyl group, 3-benzylthiophenyl group, 4- (4'-chlorobenzylthio) phenyl group, 4-phenylthiophenyl, 3-phenylthiophenyl group, 4- (4'-methylphenylthio) Phenyl group, 4- (4'-methoxyphenylthio) phenyl group, 4- (4'-chlorophenylthio) phenyl group, 2-ethylthio-1-naphthyl group, 4-methylthio-1-naphthyl group, 6-ethylthio- 2-naphthyl group, 6-phenylthio-2-naphthyl group,

4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3-
Chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 4-nitrophenyl group, 3-
Nitrophenyl group, 4-formylphenyl group, 3-formylphenyl group, 2-formylphenyl group, 4-formyl-1-naphthyl group, 1-formyl-2-naphthyl group, 4-hydroxyphenyl group, 3-hydroxyphenyl group Group, 2-hydroxyphenyl group, 4-hydroxy-1-naphthyl group, 6-hydroxy-2-
Naphthyl group, 4-cyanophenyl group, 2-cyanophenyl group, 4-cyano-1-naphthyl group, 6-cyano-2-naphthyl group,
2-chloro-4-nitrophenyl group, 4-chloro-2-nitrophenyl group, 6-chloro-3-methylphenyl group, 2-chloro-6-methylphenyl group, 4-chloro-2-methylphenyl group, 4-chloro-3-methylphenyl group, 2,4-dimethylphenyl group,
2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,
5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4-
Diethylphenyl group, 2,3,5-trimethylphenyl group, 2,
3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4- Dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2-methoxy-4-methylphenyl group, 2,6-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5- Diethoxyphenyl group, 3,5-di-n
Examples thereof include -butoxyphenyl group, 3,4,5-trimethoxyphenyl group, 2,4-dichloro-1-naphthyl group and 1,6-dichloro-2-naphthyl group.

The compound represented by the general formula (1) according to the present invention has an amide group in the benzoic acid skeleton,
The substitution position of the amide group is an ortho position, a meta position or a para position with respect to the carboxylic acid group, and specifically,
A benzoic acid derivative represented by the following general formula (1-a), general formula (1-b) or general formula (1-c).

[0035]

[Chemical 4] (In the formula, X1, X2, Y, R1 and R2 are the same as above)

The benzoic acid derivative represented by the general formula (1) according to the present invention is produced by a known method, for example, Journal of o.
It can be produced by the method described in rganic chemistry, 9 , 396-399, (1944). That is, for example, in the aminobenzoic acid derivative represented by the general formula (2), in the presence of a base (for example, sodium hydroxide or sodium hydrogen carbonate), in an aqueous solution or in an organic solvent (for example, a hydrocarbon-based solvent, a halogen-based It can be preferably produced by reacting the compound represented by the general formula (3) with a solvent or an ester solvent.

[0037]

[Chemical 5] (In the formula, X1, X2 and R1 are the same as above)

[0038]

[Chemical 6] (In the formula, Z represents a halogen atom, and Y and R2 are the same as above)

Exemplified Compound No. 1.2- (Methylcarbonylamino) benzoic acid 2.2- (Ethylcarbonylamino) benzoic acid 3.2- (Ethylcarbonylamino) -3-methylbenzoic acid 4.2- (Ethylcarbonyl) Amino) -5-methylbenzoic acid 5.2- (ethylcarbonylamino) -4-nitrobenzoic acid 6.2- (n-propylcarbonylamino) benzoic acid 7.2- (n-propylcarbonylamino) -6- Ethylbenzoic acid 8.2- (Isopropylcarbonylamino) benzoic acid 9.2- (Isopropylcarbonylamino) -5-chlorobenzoic acid 10.2- (n-Butylcarbonylamino) benzoic acid

11.2- (Isobutylcarbonylamino) benzoic acid 12.2- (tert-Butylcarbonylamino) benzoic acid 13.2- (tert-Butylcarbonylamino) -4-chlorobenzoic acid 14.2- (2 -Ethylbutylcarbonylamino) benzoic acid 15.2- (2-ethylhexylcarbonylamino) benzoic acid 16.2- (n-octylcarbonylamino) benzoic acid 17.2- (n-decylcarbonylamino) benzoic acid 18.2 -(Cyclohexylcarbonylamino) benzoic acid 19.2-[(2'-cyclohexylethyl) carbonylamino] benzoic acid 20.2- (allylcarbonylamino) benzoic acid

21.2-[(2'-Hexenyl) carbonylamino] benzoic acid 22.2-[(2'-ethoxyethyl) carbonylamino] benzoic acid 23.2-[(3'-n-hexyloxypropyl) ) Carbonylamino] benzoic acid 24.2-[(2'-benzyloxyethyl) carbonylamino] benzoic acid 25.2- (phenoxymethylcarbonylamino) benzoic acid 26.2-[(2'-phenoxyethyl) carbonylamino ] Benzoic acid 27.2- [2 '-(4-chlorophenyl) ethyloxycarbonylamino] benzoic acid 28.2- [2'-(4-Methoxyphenyl) ethyloxycarbonylamino] benzoic acid 29.2-[( 2'-phenoxyethoxyethyl) carbonylamino] benzoic acid 30.2- (cinnamylcarbonylamino) benzoic acid

31.2-[(2'-n-butylthioethyl) carbonylamino] benzoic acid 32.2-[(2'-methoxyethylthioethyl) carbonylamino] benzoic acid 33.2-[(2 ' -Allylthioethyl) carbonylamino] benzoic acid 34.2-[(2'-benzylthioethyl) carbonylamino]
Benzoic acid 35.2-[(2'-phenylthioethyl) carbonylamino]
Benzoic acid 36.2-[(7'-chloroheptyl) carbonylamino] benzoic acid 37.2- (benzylcarbonylamino) benzoic acid 38.2- (benzylcarbonylamino) -4-chlorobenzoic acid 39.2- [ (4'-Methylbenzyl) carbonylamino] benzoic acid 40.2-[(4'-Chlorobenzyl) carbonylamino] benzoic acid

41.2-[(3'-phenoxybenzyl) carbonylamino] benzoic acid 42.2- (phenylcarbonylamino) benzoic acid 43.2- (phenylcarbonylamino) -4-methylbenzoic acid 44.2- (Phenylcarbonylamino) -4-phenylbenzoic acid 45.2- (phenylcarbonylamino) -5-nitrobenzoic acid 46.2- (phenylcarbonylamino) -4-chlorobenzoic acid 47.2- (phenylcarbonylamino) -5-Chlorobenzoic acid 48.2-[(2'-naphthyl) carbonylamino] benzoic acid 49.2-[(3'-Freel) carbonylamino] benzoic acid 50.2-[(3'-phenylphenyl) Carbonylamino] benzoic acid

51.2-[(4'-Methylphenyl) carbonylamino] benzoic acid 52.2-[(4'-n-butylphenyl) carbonylamino] benzoic acid 53.2-[(4'-tert- Butylphenyl) carbonylamino]
Benzoic acid 54.2-[(4'-cyclohexylphenyl) carbonylamino] benzoic acid 55.2-[(3'-methoxyphenyl) carbonylamino] benzoic acid 56.2-[(4'-n-butoxyphenyl) Carbonylamino]
Benzoic acid 57.2-[(4'-n-octyloxyphenyl) carbonylamino] benzoic acid 58.2-[(4'-phenoxyphenyl) carbonylamino]
Benzoic acid 59.2-[(2'-acetylphenyl) carbonylamino] benzoic acid 60.2-[(4'-allylcarbonylphenyl) carbonylamino] benzoic acid

61.2-[(4'-phenylcarbonylphenyl) carbonylamino] benzoic acid 62.2-[(4'-n-butoxycarbonylphenyl) carbonylamino] benzoic acid 63.2-[(4'- Benzyloxyphenyl) carbonylamino] benzoic acid 64.2-[(4'-acetyloxyphenyl) carbonylamino] benzoic acid 65.2-[(4'-ethylthiophenyl) carbonylamino]
Benzoic acid 66.2-[(4'-fluorophenyl) carbonylamino] benzoic acid 67.2-[(4'-chlorophenyl) carbonylamino] benzoic acid 68.2-[(3'-chlorophenyl) carbonylamino] benzoic acid Acid 69.2-[(4'-Nitrophenyl) carbonylamino] benzoic acid 70.2-[(4'-Formylphenyl) carbonylamino] benzoic acid

71.2-[(4'-Hydroxyphenyl) carbonylamino] benzoic acid 72.2-[(4'-Cyanophenyl) carbonylamino] benzoic acid 73.2-[(2 ', 4'-dimethyl) Phenyl) carbonylamino]
Benzoic acid 74.2-[(3 ', 5'-dichlorophenyl) carbonylamino]
Benzoic acid 75.2- (n-butylthiocarbonylamino) benzoic acid 76.2- (n-octylthiocarbonylamino) benzoic acid 77.2-[(4'-chlorobenzyl) carbonylamino] benzoic acid 78.2 -[(3'-Methylphenyl) carbonylamino] benzoic acid 79.2- (phenylthiocarbonylamino) benzoic acid 80.2-[(4'-ethoxyphenyl) thiocarbonylamino] benzoic acid

81.2- (N-phenyl-N-phenyloxycarbonylamino) benzoic acid 82.3- (ethylcarbonylamino) benzoic acid 83.3- (n-propylcarbonylamino) benzoic acid 84.3- ( Isopropylcarbonylamino) benzoic acid 85.3- (n-butylcarbonylamino) benzoic acid 86.3- (isobutylcarbonylamino) benzoic acid 87.3- (tert-butylcarbonylamino) benzoic acid 88.3- (n- Pentylcarbonylamino) benzoic acid 89.3- (Isopentylcarbonylamino) benzoic acid 90.3- (n-hexylcarbonylamino) benzoic acid

91.3- (n-heptylcarbonylamino) benzoic acid 92.3- (n-octylcarbonylamino) benzoic acid 93.3-[(2'-ethylhexyl) carbonylamino] benzoic acid 94.3- ( n-nonylcarbonylamino) benzoic acid 95.3- (n-decylcarbonylamino) benzoic acid 96.3- (n-undecylcarbonylamino) benzoic acid 97.3- (n-dodecylcarbonylamino) benzoic acid 98. 3- (n-Tridecylcarbonylamino) benzoic acid 99.3 3- (n-Tetradecylcarbonylamino) benzoic acid 100.3- (n-Pentadecylcarbonylamino) benzoic acid

101.3- (n-hexadecylcarbonylamino) benzoic acid 102.3- (n-heptadecylcarbonylamino) benzoic acid 103.3- (n-octadecylcarbonylamino) benzoic acid 104.3- (cyclopentyl) Carbonylamino) benzoic acid 105.3- (cyclohexylcarbonylamino) benzoic acid 106.3-[(4'-tert-butylcyclohexyl) carbonylamino] benzoic acid 107.3- (Cycloheptylcarbonylamino) benzoic acid 108.3 -(Cyclooctylcarbonylamino) benzoic acid 109.3- (Cyclohexylmethylcarbonylamino) benzoic acid 110.3-[(2'-Tetrahydrofurfuryl) carbonylamino] benzoic acid

111.3-[(2'-Methoxyethyl) carbonylamino] benzoic acid 112.3-[(2'-n-hexyloxyethyl) carbonylamino] benzoic acid 113.3-[(2'-n) -Octyloxyethyl) carbonylamino] benzoic acid 114.3-[(3'-ethoxypropyl) carbonylamino]
Benzoic acid 115.3-[(3'-n-butoxypropyl) carbonylamino] benzoic acid 116.3-[(3'-n-octyloxypropyl) carbonylamino] benzoic acid 117.3-[(2'- n-Butoxyethoxyethyl) carbonylamino] benzoic acid 118.3-[(2′-benzyloxyethyl) carbonylamino] benzoic acid 119.3-[(phenoxymethyl) carbonylamino] benzoic acid 120.3-[(2 '-Phenoxyethyl) carbonylamino]
benzoic acid

121.3- [2 '-(4-Chlorophenyl) oxyethylcarbonylamino] benzoic acid 122.3- [2'-(4-Methoxyphenyl) oxyethylcarbonylamino] benzoic acid 123.3-[( 2'-phenoxyethoxyethyl) carbonylamino] benzoic acid 124.3-[(3'-n-butylthiopropyl) carbonylamino] benzoic acid 125.3-[(6'-ethylthiohexyl) carbonylamino] benzoic acid 126.3-[(2'-Benzylthioethyl) carbonylamino] benzoic acid 127.3-[(2'-phenylthioethyl) carbonylamino] benzoic acid 128.3-[(2'-chloroethyl) carbonylamino] Benzoic acid 129.3-[(9'-decenyl) carbonylamino] benzoic acid 130.3- (benzylcarbonylamino) benzoic acid

131.3- (Benzylcarbonylamino)-
2,6-Dimethoxybenzoic acid 132.3-[(4'-methylbenzyl) carbonylamino] benzoic acid 133.3-[(4'-chlorobenzyl) carbonylamino] benzoic acid 134.3-[(2'- Phenylethyl) carbonylamino] benzoic acid 135.3- (phenylcarbonylamino) benzoic acid 136.3-[(1'-naphthyl) carbonylamino] benzoic acid 137.3-[(2'-naphthyl) carbonylamino] benzoic acid Acid 138.3-[(2'-furyl) carbonylamino] benzoic acid 139.3-[(4'-phenylphenyl) carbonylamino]
Benzoic acid 140.3-[(4'-methylphenyl) carbonylamino] benzoic acid

141.3-[(3'-Methylphenyl) carbonylamino] benzoic acid 142.3-[(2'-methylphenyl) carbonylamino] benzoic acid 143.3-[(4'-ethylphenyl) carbonyl Amino] benzoic acid 144.3-[(4'-tert-butylphenyl) carbonylamino] benzoic acid 145.3-[(4'-cyclohexylphenyl) carbonylamino] benzoic acid 146.3-[(2'-cyclohexyl) Phenyl) carbonylamino] benzoic acid 147.3-[(4'-cumylphenyl) carbonylamino] benzoic acid 148.3-[(4'-methoxyphenyl) carbonylamino]
Benzoic acid 149.3-[(3'-methoxyphenyl) carbonylamino]
Benzoic acid 150.3-[(2'-ethoxyphenyl) carbonylamino]
benzoic acid

151.3-[(4'-n-Butoxyphenyl) carbonylamino] benzoic acid 152.3-[(4'-n-hexyloxyphenyl) carbonylamino] benzoic acid 153.3-[(4 ' -Benzyloxyphenyl) carbonylamino] benzoic acid 154.3- [4 '-(4-benzyloxycumyl) phenylcarbonylamino] benzoic acid 155.3-[(4'-phenoxyphenyl) carbonylamino] benzoic acid 156 3- [2 '-(6-benzyloxy) naphthylcarbonylamino] benzoic acid 157.3-[(4'-phenylcarbonylphenyl) carbonylamino] benzoic acid 158.3-[(4'-acetylphenyl) carbonyl amino]
Benzoic acid 159.3-[(4'-ethoxycarbonylphenyl) carbonylamino] benzoic acid 160.3-[(4'-cyclohexyloxycarbonylphenyl) carbonylamino] benzoic acid

161.3-[(4'-n-propylcarbonyloxyphenyl) carbonylamino] benzoic acid 162.3-[(4'-methylthiophenyl) carbonylamino] benzoic acid 163.3-[(4'- Benzylthiophenyl) carbonylamino] benzoic acid 164.3-[(4'-fluorophenyl) carbonylamino]
Benzoic acid 165.3-[(2'-fluorophenyl) carbonylamino]
Benzoic acid 166.3-[(4'-chlorophenyl) carbonylamino] benzoic acid 167.3-[(3'-chlorophenyl) carbonylamino] benzoic acid 168.3-[(4'-bromophenyl) carbonylamino] benzoic acid Acid 169.3-[(4'-nitrophenyl) carbonylamino] benzoic acid 170.3-[(4'-formylphenyl) carbonylamino]
benzoic acid

171.3-[(4'-Cyanophenyl) carbonylamino] benzoic acid 172.3-[(2 ', 4'-Dimethylphenyl) carbonylamino] benzoic acid 173.3-[(3', 5) '-Dimethylphenyl) carbonylamino] benzoic acid 174.3-[(2', 4'-dichlorophenyl) carbonylamino] benzoic acid 175.3-[(3 ', 5'-dimethoxyphenyl) carbonylamino] benzoic acid 176 3-[(3'-nitro-4'-chlorophenyl) carbonylamino] benzoic acid 177.3-[(4'-chloro-2'-methylphenyl) carbonylamino] benzoic acid 178.3- (n-propyl) Thiocarbonylamino) benzoic acid 179.3- (n-hexylthiocarbonylamino) benzoic acid 180.3- (n-decylthiocarbonylamino) benzoic acid

181.3- (phenylthiocarbonylamino) benzoic acid 182.3-[(4'-methylphenyl) thiocarbonylamino] benzoic acid 183.3-[(4'-ethoxyphenyl) thiocarbonylamino] benzoic acid Acid 184.3- (Nn-butyl-N-heptylcarbonylamino)
Benzoic acid 185.4- (methylcarbonylamino) benzoic acid 186.4- (methylcarbonylamino) -6-methylbenzoic acid 187.4- (methylcarbonylamino) -6-chlorobenzoic acid 188.4- (ethylcarbonyl) Amino) benzoic acid 189.4- (Ethylcarbonylamino) -6-nitrobenzoic acid 190.4- (n-Propylcarbonylamino) benzoic acid

191.4- (n-Propylcarbonylamino)
-5-Benzylbenzoic acid 192.4- (n-Butylcarbonylamino) benzoic acid 193.4- (Isobutylcarbonylamino) benzoic acid 194.4- (sec-Butylcarbonylamino) benzoic acid 195.4- (n- Pentylcarbonylamino) benzoic acid 196.4- (Isopentylcarbonylamino) benzoic acid 197.4- (n-hexylcarbonylamino) benzoic acid 198.4- (n-heptylcarbonylamino) benzoic acid 199.4- (n -Octylcarbonylamino) benzoic acid 200.4-[(2'-ethylhexyl) carbonylamino] benzoic acid

201.4- (n-Nonylcarbonylamino) benzoic acid 202.4- (n-decylcarbonylamino) benzoic acid 203.4- (n-undecylcarbonylamino) benzoic acid 204.4- (n- Dodecylcarbonylamino) benzoic acid 205.4- (n-tetradecylcarbonylamino) benzoic acid 206.4- (n-hexadecylcarbonylamino) benzoic acid 207.4- (Cyclopentylcarbonylamino) benzoic acid 208.4- ( Cyclohexylcarbonylamino) benzoic acid 209.4-[(2'-methylcyclohexyl) carbonylamino] benzoic acid 210.4-[(4'-Methylcyclohexyl) carbonylamino] benzoic acid

211.4-[(4'-tert-Butylcyclohexyl) carbonylamino] benzoic acid 212.4-[(2'-Cyclohexylethyl) carbonylamino] benzoic acid 213.4- (Cyclooctylcarbonylamino) benzoic acid Acid 214.4-[(2'-Tetrahydrofurfuryl) carbonylamino] benzoic acid 215.4-[(2'-Methoxyethyl) carbonylamino] benzoic acid 216.4-[(2'-n-hexyloxyethyl) ) Carbonylamino] benzoic acid 217.4-[(3'-ethoxypropyl) carbonylamino]
Benzoic acid 218.4-[(3'-isopropoxypropyl) carbonylamino] benzoic acid 219.4-[(2'-methoxyethoxyethyl) carbonylamino] benzoic acid 220.4- (phenoxymethylcarbonylamino) benzoic acid

221.4- (2'-phenoxyethylcarbonylamino) benzoic acid 222.4- [2 '-(4-chlorophenyl) oxyethylcarbonylamino] benzoic acid 223.4- [2'-(4-methoxy) Phenyl) oxyethylcarbonylamino] benzoic acid 224.4-[(2'-phenoxyethoxyethyl) carbonylamino] benzoic acid 225.4-[(2'-n-hexylthioethyl) carbonylamino] benzoic acid 226.4 -[(2'-Phenylthioethyl) carbonylamino] benzoic acid 227.4- (2'-chloroethylcarbonylamino) benzoic acid 228.4- (5'-hexenylcarbonylamino) benzoic acid 229.4- (benzyl) Carbonylamino) benzoic acid 230.4- (benzylcarbonylamino) -5-ethylbenzoic acid

231.4-[(4'-Methylbenzyl) carbonylamino] benzoic acid 232.4-[(4'-chlorobenzyl) carbonylamino] benzoic acid 233.4-[(2'-phenylethyl) carbonyl Amino] benzoic acid 234.4- (phenylcarbonylamino) benzoic acid 235.4-[(2'-naphthyl) carbonylamino] benzoic acid 236.4-[(4'-phenylphenyl) carbonylamino]
Benzoic acid 237.4-[(3'-methylphenyl) carbonylamino] benzoic acid 238.4-[(4'-ethylphenyl) carbonylamino] benzoic acid 239.4-[(4'-cyclohexylphenyl) carbonylamino ] Benzoic acid 240.4-[(4'-cumylphenyl) carbonylamino] benzoic acid

241.4-[(4'-Methoxyphenyl) carbonylamino] benzoic acid 242.4-[(3'-Ethoxyphenyl) carbonylamino]
Benzoic acid 243.4-[(4'-n-butoxyphenyl) carbonylamino] benzoic acid 244.4-[(4'-phenoxyphenyl) carbonylamino] benzoic acid 245.4-[(4'-acetylphenyl) Carbonylamino]
Benzoic acid 246.4-[(4'-methoxycarbonylphenyl) carbonylamino] benzoic acid 247.4-[(4'-ethylcarbonyloxyphenyl) carbonylamino] benzoic acid 248.4-[(4'-ethylthio) Phenyl) carbonylamino] benzoic acid 249.4-[(4'-phenylthiophenyl) carbonylamino] benzoic acid 250.4-[(4'-fluorophenyl) carbonylamino]
benzoic acid

251.4-[(3'-Fluorophenyl) carbonylamino] benzoic acid 252.4-[(4'-chlorophenyl) carbonylamino] benzoic acid 253.4-[(3'-chlorophenyl) carbonylamino] Benzoic acid 254.4-[(2'-chlorophenyl) carbonylamino] benzoic acid 255.4-[(2'-formylphenyl) carbonylamino]
Benzoic acid 256.4-[(2'-cyanophenyl) carbonylamino] benzoic acid 257.4-[(2 ', 4'-Dimethylphenyl) carbonylamino] benzoic acid 258.4-[(3', 5 ' -Dimethylphenyl) carbonylamino] benzoic acid 259.4-[(3'-nitro-4'-chlorophenyl) carbonylamino] benzoic acid 260.4- (n-butylthiocarbonylamino) benzoic acid

261.4- (n-heptylthiocarbonylamino) benzoic acid 262.4- (n-dodecylthiocarbonylamino) benzoic acid 263.4- (phenylthiocarbonylamino) benzoic acid 264.4-[(4 '-Methylphenyl) thiocarbonylamino] benzoic acid 265.4-[(2'-naphthyl) thiocarbonylamino] benzoic acid 266.4-[(4'-chlorophenyl) thiocarbonylamino] benzoic acid 267.4- ( N-methyl-N-phenylcarbonylamino) benzoic acid

The polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) of the present invention is obtained by adding the alkali metal salt of the benzoic acid derivative represented by the general formula (1) and the polyvalent metal compound to water. It can be obtained by acting in a medium .

The polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) according to the present invention is preferably a sparingly water-soluble or water-insoluble divalent, trivalent or tetravalent metal salt, More preferably, it is a divalent metal salt. Specific examples of the polyvalent metal salt include zinc, magnesium, calcium, barium, nickel, tin, copper, manganese, cobalt, titanium, aluminum, and iron salts, preferably zinc, magnesium, calcium, It is a salt of barium, nickel, manganese, cobalt or aluminum, more preferably a salt of zinc, calcium or manganese, and a zinc salt is a preferable metal salt.

Examples of the alkali metal salt of the benzoic acid derivative represented by the general formula (1) according to the present invention include sodium, potassium and lithium salts, more preferably sodium and potassium salts. . These alkali metal salts can be produced by a known method, and are usually 0.8 to 1.2 equivalents, preferably 1. to 1 equivalent to 1 equivalent of the benzoic acid derivative represented by the general formula (1). 0 to
1.1 equivalents of an alkali metal hydroxide compound, an alkali metal carbonate compound, and an alkali metal hydrogen carbonate compound (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate) are treated with water. It can be produced by reacting in the presence of.

The amount of water used for preparing the alkali metal salt represented by the general formula (1) may be such that a part of the alkali metal salt is dissolved, but preferably, the alkali metal salt is preferably used. 50% by weight or more of the metal salt, more preferably 80%
It is desirable to use an amount that dissolves by weight or more. At this time, in addition to water, water-soluble organic solvents, for example, methanol, isopropanol, alcohol solvents such as methyl cellosolve, dioxane, ether solvents such as tethydrofuran, N, N-dimethyl imidazolidinium. An aprotic polar solvent such as non- or N-methyl-2-pyrrolidone may coexist. However, when the proportion of these water-soluble organic solvents is high, the yield of the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) produced decreases, so that the water content in all the media is reduced. The proportion of the organic solvent soluble in is preferably 60% by weight or less, and more preferably 40% by weight or less.

The temperature for preparing the alkali metal salt is preferably about 0 to about 50 ° C, more preferably about 10 to about 40 ° C.

Further, as a suitable polyvalent metal compound used when preparing the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) according to the present invention, a water-soluble polyvalent metal compound is used. Preferably, for example, sulfates such as zinc sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc chloride, magnesium chloride, calcium chloride, chlorides such as barium chloride, nickel chloride, cobalt chloride, aluminum chloride, zinc acetate, manganese acetate. And the like. These polyvalent metal compounds may be used as a solid as they are, or may be used as an aqueous solution.

The amount of these polyvalent metal compounds used is such that the alkali metal salt of the benzoic acid derivative represented by the general formula (1) is 1
0.8 to 1.5 equivalents relative to equivalents, preferably 1.0
~ 1.2 equivalents. The equivalent weight in this case means the alkali metal salt 1 of the benzoic acid derivative represented by the general formula (1).
When the polyvalent metal compound is, for example, a divalent metal compound (eg, zinc sulfate), 0.5 mol of 2
A valent polyvalent metal compound corresponds to one equivalent.

As a method of reacting the alkali metal salt of the benzoic acid derivative represented by the general formula (1) with the polyvalent metal compound in the presence of water, an alkali of the benzoic acid derivative represented by the general formula (1) is used. A method of adding a polyvalent metal compound to an aqueous solution of a metal salt may be used, or a method of adding an aqueous solution of an alkali metal salt of a benzoic acid derivative represented by the general formula (1) to the polyvalent metal compound may be used.

The temperature at which the alkali metal salt of the benzoic acid derivative represented by the general formula (1) is reacted with the polyvalent metal compound is preferably about 0 to about 50 ° C., more preferably about 1
0 to about 40 ° C.

As the aqueous solution of the alkali metal salt of the benzoic acid derivative represented by the general formula (1), a plurality of different alkali metal salts of the benzoic acid derivative represented by the general formula (1) may be used. , For example, a mixed salt of alkali metal salts of 4- (n-octylcarbonylamino) benzoic acid and 4- (phenylcarbonylamino) benzoic acid, or 2-
(Phenyloxymethylcarbonylamino) benzoic acid and 4-
A polyvalent metal compound may be reacted with a mixed salt of respective alkali metal salts of (benzylcarbonylamino) benzoic acid. In this case, it goes without saying that polyvalent metal salts of the benzoic acid derivative represented by the general formula (1) having corresponding structures are produced.

The method for producing a polyvalent metal salt of a benzoic acid derivative of the present invention is characterized in that the polyvalent metal salt of a benzoic acid derivative represented by the general formula (1) produced by the above-mentioned method is further heat-treated. It is what

Usually, when an alkali metal salt of a benzoic acid derivative represented by the general formula (1) is reacted with a polyvalent metal compound in an aqueous medium , most of the general formula (1) can be obtained in a short time. The polyvalent metal salt of the benzoic acid derivative represented is precipitated in the aqueous medium. As the method of heat treatment, an aqueous medium containing the solid is used as it is, or further, a mixed solution of water or a water-soluble organic solvent and water is added to enhance stirring efficiency, and the temperature is adjusted to about 50 to about 100. C, more preferably about 6
It is a method of heating to 0 to about 95 ° C. and stirring.

If the heat treatment time is about 30 minutes or more, the effect of the present invention can be obtained. Although the heat treatment for a long time does not hinder the effect of the present invention, spending a long time itself only lowers the work efficiency, the production efficiency and the like. Generally, a heat treatment time of about 30 minutes to about 15 hours, more preferably about 1 hour to about 10 hours is sufficient.
The stirring device is not particularly limited, but the stirring required for maintaining the state in which the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) is dispersed in the aqueous medium. It is preferable to use a device that is capable.

Although the use capacity of the aqueous medium does not hinder the effects of the present invention even if used in a large amount, use of an unnecessarily large amount itself requires a large device and a container, which causes a reduction in production efficiency. It is obvious that the amount is usually 1 to 200 times (volume / weight) with respect to the weight of the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1), and more preferably 2 to 150 times (volume / weight).

General formula (1) produced as described above
The polyvalent metal salt of the benzoic acid derivative represented by
Depending on the kind of the benzoic acid derivative represented by the general formula (1) or the kind of the polyvalent metal, a hydrate may sometimes be formed. The hydrate also has the general formula (1) according to the present invention. The polyvalent metal salt of the benzoic acid derivative represented by

These polyvalent metal salts are often obtained in an amorphous (amorphous) state or may change from a crystalline state to an amorphous state depending on the production conditions or post-production conditions such as drying. . Since such a polyvalent metal salt in an amorphous form has a low bulk density as compared with the crystal of the polyvalent metal salt, when it is used as an electron-accepting compound for a recording material, for example, a heat-sensitive recording material, it is, for example, It was found that there is a problem in workability in handling, such as scattering in the air during transportation or transportation.

The change from a crystal to an amorphous substance is carried out under strictly controlled conditions by producing a polyvalent metal salt of the benzoic acid derivative represented by the general formula (1), or by changing the polyvalent metal salt of the polyvalent metal salt. Although it is possible to prevent it by handling the crystal, it is often the case that the crystal is often changed to an amorphous body due to unforeseen circumstances, causing a considerable amount of trouble.

The method for producing the crystal of the present invention is represented by the general formula (1)
By heat-treating an amorphous form of a polyvalent metal salt of a benzoic acid derivative in an aqueous medium, a crystal of a polyvalent metal salt of a benzoic acid derivative is produced, which is a simple operation. Provide a method for converting an amorphous body into a useful crystal.

The crystals of the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) according to the present invention are produced under the production conditions, the kind of the benzoic acid derivative represented by the general formula (1) or the polyvalent metal salt. A hydrate may sometimes be formed depending on the kind of the metal, and the hydrate crystal is also a crystal of a polyvalent metal salt of a benzoic acid derivative represented by the general formula (1) according to the present invention. Are included in.

The amorphous form of the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) according to the present invention is hardly soluble or insoluble in water and is substantially insoluble in an aqueous medium. It is dispersed. As a method of heat treatment, a method of heating an aqueous medium containing the amorphous body to about 50 to about 100 ° C. and stirring it can be applied.

Also, most of the amorphous body can be converted into crystals by carrying out the heat treatment for about 30 minutes or more. Whether or not the amorphous body has been converted into crystals can be easily determined by known analysis means such as X-ray diffraction spectrum and infrared spectrum, and thus the heat treatment time can be determined by these analysis means. The long-time heat treatment does not have any adverse effect, but spending a long time itself only causes a decrease in work efficiency, production efficiency, etc., and is usually about 30 minutes to about 20.
Times of heat treatment, more preferably from about 1 to about 15 hours, are sufficient.

The method for producing a crystal of the present invention is represented by the general formula (1)
Is characterized in that the amorphous body of a polyvalent metal salt of a benzoic acid derivative represented by is heat-treated in an aqueous medium, in addition to water, a water-soluble organic solvent, for example, methanol, isopropanol, Alcohol solvents such as methyl cellosolve, ether solvents such as dioxane and tethydrofuran, N, N-dimethylimidazolidinone, N-methyl
An aprotic polar solvent such as -2-pyrrolidone may coexist. However, when the proportion of these water-soluble organic solvents is high, the recovery rate of the crystals of the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) to be produced is lowered, and therefore, in all the media. The proportion of the water-soluble organic solvent is preferably 60% by weight or less, and more preferably 40% by weight or less.

The stirring device is not particularly limited, but an amorphous body or crystal of a polyvalent metal salt of a benzoic acid derivative represented by the general formula (1) is dispersed in an aqueous medium. It is preferred to use a device with the necessary stirring capacity to maintain the.

Although the use capacity of the aqueous medium does not impede the effect of the present invention even if used in a large amount, use of an excessively large amount itself requires a large apparatus and container, which causes a reduction in production efficiency. It is obvious that the amount is usually 1 to 200 times (volume / weight) based on the weight of the amorphous polyvalent metal salt, and more preferably 2 to 15 times.
It is 0 times (volume / weight).

The polyvalent metal salt and the crystal thereof produced by the method of the present invention have extremely excellent filterability and can be easily filtered from the reaction system by known means and devices without using a special device. , Can be isolated. After filtration, it is dried (drying temperature is preferably about 20 to about 90 ° C.) and dispersed by a known means or method, or directly dispersed after filtration to obtain a recording material (for example, a heat-sensitive recording material). It is also possible to prepare a dispersion liquid of the electron-accepting compound for).

[0091]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (Production of zinc salt of 2-n-nonylcarbonylaminobenzoic acid) 22.4 g of 2-n-nonylcarbonylaminobenzoic acid in a methanol suspension (100 ml) was added with 6 parts of sodium hydrogen carbonate. 200 ml of an aqueous solution in which 0.4 g was dissolved was added dropwise at room temperature over 15 minutes, and the mixture was further stirred at room temperature for 2 hours. 100 ml of an aqueous solution in which 11.0 g of zinc sulfate heptahydrate was dissolved was added dropwise to the sodium 2-n-nonylcarbonylaminobenzoate aqueous solution at room temperature over 30 minutes. After the dropping, stirring was performed for 30 minutes. A colorless zinc salt of 2-n-nonylcarbonylaminobenzoic acid was precipitated. The zinc salt dispersion was further heated to 80 ° C. and stirred at 80 ° C. for 2 hours. After cooling to room temperature, the crystals were filtered and washed with water, and then 5
After drying at 0 ° C. for 24 hours, 24.5 g of zinc salt of 2-n-nonylcarbonylaminobenzoic acid as colorless crystals was obtained.

Melting point: 99-105 ° C. For filtration, use a Kiriyama-type funnel with a diameter of 95 mm and N
o. 5 Filter paper (manufactured by Nippon Rikagaku Kikai Co., Ltd.) was used. The time required for filtration was 7 minutes, the liquid was well drained, and the filterability was very good.

Example 2 (Production of Zinc Salt of 2-Phenyloxymethylcarbonylaminobenzoic Acid) 2-Phenyloxymethylcarbonylaminobenzoic Acid 1
For 5.0 g of methanol suspension solution (50 ml),
Aqueous solution 100 in which 4.6 g of sodium hydrogen carbonate was dissolved
ml at room temperature for 15 minutes, and then 2 more at room temperature.
Stir for hours. 7. Zinc sulfate heptahydrate in the sodium 2-phenyloxymethylcarbonylaminobenzoate aqueous solution 8.
100 ml of an aqueous solution in which 0 g was dissolved was added dropwise at room temperature over 30 minutes. After the dropping, stirring was performed for 30 minutes. Colorless
A zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid was deposited. This zinc salt dispersion is further added with 9
The mixture was warmed to 0 ° C and stirred at 90 ° C for 2 hours. After cooling to room temperature, the crystals were filtered, washed with water and dried at 50 ° C. for 24 hours to obtain 15.8 g of zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid as colorless crystals.

Melting point: 135 to 155 ° C. The filtration is carried out using a Kiriyama funnel with a diameter of 95 mm and N
o. 5 Filter paper (manufactured by Nippon Rikagaku Kikai Co., Ltd.) was used. The time required for filtration was 5 minutes, drainage was good, and filterability was very good.

Example 3 (Production of Zinc Salt of 2-Benzylcarbonylaminobenzoic Acid) Example 3 was repeated except that 2-benzylcarbonylaminobenzoic acid was used instead of 2-phenyloxycarbonylaminobenzoic acid. Following the method described in Example 2-
A zinc salt of benzylcarbonylaminobenzoic acid was prepared.

Melting point: 100 to 101 ° C. Note that filtration is performed using a Kiriyama funnel with a diameter of 95 mm and N
o. 5 Filter paper (manufactured by Nippon Rikagaku Kikai Co., Ltd.) was used. The time required for filtration was 5 minutes, drainage was good, and filterability was very good.

Example 4 [Preparation of zinc salt of 4- (4′-nitrophenylcarbonylamino) benzoic acid] In place of 2-phenyloxycarbonylaminobenzoic acid in Example 2, 4- (4′-nitrophenyl) was used. A zinc salt of 4- (4′-nitrophenylcarbonylamino) benzoic acid was produced according to the method described in Example 2 except that carbonylamino) benzoic acid was used.

Melting point> 300 ° C. Note that the filtration is performed with a Kiriyama funnel with a diameter of 95 mm and N
o. 5 Filter paper (manufactured by Nippon Rikagaku Kikai Co., Ltd.) was used. The time required for filtration was 5 minutes, drainage was good, and filterability was very good.

Comparative Example 1 (Production of Zinc Salt of 2-Phenyloxymethylcarbonylaminobenzoic Acid) 2-Phenyloxymethylcarbonylaminobenzoic Acid 1
For 5.0 g of methanol suspension solution (50 ml),
Aqueous solution 100 in which 4.6 g of sodium hydrogen carbonate was dissolved
ml at room temperature for 15 minutes, and then 2 more at room temperature.
Stir for hours. 7. Zinc sulfate heptahydrate in the sodium 2-phenyloxymethylcarbonylaminobenzoate aqueous solution 8.
100 ml of an aqueous solution in which 0 g was dissolved was added dropwise at room temperature over 30 minutes. After the dropping, stirring was performed for 30 minutes. Colorless
A zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid was deposited. The zinc salt dispersion was further stirred at room temperature for 2 hours. The precipitated solid is filtered, washed with water and dried at 50 ° C. for 24 hours to give colorless zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid 15.8.
g was obtained. For filtration, a Kiriyama funnel with a diameter of 95 mm is used.
No. 5 filter paper (manufactured by Nippon Rikagaku Kikai Co., Ltd.) was used. The time required for filtration was as long as 30 minutes, and the work efficiency was poor.

Example 5 (Production of Zinc Salt of 2-Phenyloxymethylcarbonylaminobenzoic Acid) 25.5 g of an amorphous form of zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid was added to an aqueous solution (200 m).
l), and the zinc salt dispersion was heated to 80 ° C. and stirred at 80 ° C. for 4 hours. After cooling to room temperature, the crystals were filtered, washed with water, and dried at 50 ° C. for 24 hours to obtain 25.5 g of crystals of zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid.

Melting point 135-155 ° C. This zinc salt crystal shows an X-ray diffraction pattern showing a strong peak at a diffraction angle (2θ) of 7.8 ° in a powder X-ray diffraction method using Cu-Kα radiation. The X-ray diffraction pattern is shown in FIG.

In displaying the diffraction angle (2θ),
Usually, there is an error of about ± 0.2 °.

Reference Example 1 (Production of Amorphous Zinc Salt of 2-Phenyloxymethylcarbonylaminobenzoic Acid) The zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid produced in Example 2 was heated at 110 ° C. for 1 hour. I left it. The powder X-ray diffraction pattern of the solid by Cu-Kα radiation is shown in FIG. From this diffractogram, it was found that the solid was substantially amorphous (amorphous).

The crystals of the zinc salt of benzoic acid represented by the general formula (1) produced by the method of the present invention are compared with the amorphous form of the zinc salt of benzoic acid produced by the method described in Reference Example. Since it has a high bulk density, when it is used as an electron-accepting compound of a heat-sensitive recording material, it does not scatter into the air during, for example, weighing or transporting, and it is easy to handle. Was good.

[0106]

INDUSTRIAL APPLICABILITY According to the present invention, a polyvalent metal salt of a benzoic acid derivative having a specific structure, which is useful as an electron-accepting compound for a recording material, can be efficiently produced, and a benzoic acid derivative having a specific structure can be efficiently produced. It has become possible to easily produce a crystal from the amorphous body of the polyvalent metal salt.

[Brief description of drawings]

FIG. 1 shows an X-ray diffraction pattern of crystals of a zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid.

FIG. 2 shows an X-ray diffraction pattern of an amorphous form of a zinc salt of 2-phenyloxymethylcarbonylaminobenzoic acid.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C07C 235/24 C07C 235/24 C (72) Inventor ▲ Jiro Taro 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical (72) Inventor Masakatsu Nakatsuka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (56) Reference JP-A-52-156830 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C07C 231/12 C07C 231/24 C07C 233/00-237/52 B41M 5/18

Claims (2)

(57) [Claims] 1. At least 4 parts of an alkali metal salt of a benzoic acid derivative represented by the general formula (1) and a polyvalent metal compound.
A method for producing a polyvalent metal salt of a benzoic acid derivative represented by the general formula (1), which comprises reacting in an aqueous medium containing 0% by weight of water and then heat-treating. [Chemical 1] (In the formula, X1 and X2 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a nitro group, Y represents an oxygen atom or a sulfur atom, and R1 represents a hydrogen atom, an alkyl group or an aralkyl. Represents a group or aryl group, R2 is an alkyl group, an alkenyl group,
Represents an aralkyl group or an aryl group) 2. At least 40 parts by weight of an amorphous body of a polyvalent metal salt of a benzoic acid derivative represented by the general formula (1).
%, And heat-treating it in an aqueous medium containing water to prepare a crystal of a polyvalent metal salt of a benzoic acid derivative represented by the general formula (1). [Chemical 2] (In the formula, X1 and X2 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a nitro group, Y represents an oxygen atom or a sulfur atom, and R1 represents a hydrogen atom, an alkyl group or an aralkyl. Represents a group or aryl group, R2 is an alkyl group, an alkenyl group,
Represents an aralkyl group or an aryl group)