JP2892772B2 - Method for producing acid amide compound having pyrazoloazole skeleton or pyrazolone skeleton - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing an acid amide compound by reacting a primary amine compound with an acid halide, and more specifically, an acid useful especially as a photographic coupler. The present invention relates to a method for producing an acid amide compound having a pyrazoloazole skeleton or a pyrazolone skeleton which is particularly suitable for an amide compound.

(Prior Art) In a conventional method for producing an acid amide, a two-stage reaction of a deprotection reaction of an amino group and an acid amidation reaction with an acid halide is performed using a compound in which an amino group is protected by phthalimidation or the like as a starting material. Consists of

For example, such an acid amidation reaction is disclosed in
-65246, 61-65248, 63-25246, Tokubo Sho63
No. 22573, JP-A-2-6949, U.S. Pat. No. 4,443,536, etc., which carry out an acid amidation reaction in a homogeneous solvent using DMF / acetonitrile solvent, acetic acid / sodium acetate solvent and the like. The purpose is to produce magenta couplers.

(Problems to be Solved by the Invention) However, in such a conventional method, removal of unreacted components, crystallization, and filtration for purification of a primary amine compound when the amino group deprotection reaction proceeds to an acid amidation reaction. A process was required, and the manufacturing process was long and inefficient. Further, if the purification in the first stage is insufficient, there is a disadvantage that impurities and the reaction raw material, such as acid chloride, react with each other to cause a side reaction, resulting in a decrease in purity. Therefore, the conventional method is not sufficient as an industrial production method, and its improvement has been desired.

(Means for Solving the Problems) The object of the present invention is to react a phthalimide compound, which is a reaction product of a primary amine compound having a pyrazoloazole skeleton or a pyrazolone skeleton as a mother nucleus with a phthalic acid compound, with hydrazine. After the phthaloyl hydrazide salt of the primary amine compound is formed, the pH of the aqueous phase is adjusted to 7-1 by adding an aqueous solution of an organic acid or an inorganic acid to the reaction mixture. Aliphatic hydrocarbons, an organic acid halide dissolved in an ester having 4 or more carbon atoms or an ether having 8 or more carbon atoms are added, and the organic acid halide and the phthaloyl hydrazide salt of the primary amine compound are mixed in a heterogeneous system. This has been achieved by a method for producing an acid amide compound having a pyrazoloazole skeleton or a pyrazolone skeleton, which is characterized by reacting. In the method of the present invention, hydroxylamine may be used instead of the above hydrazine.

In the method of the present invention, a phthalimide compound obtained by protecting a primary amine compound with phthalic acid is used as a starting material.

Here, the primary amine compound is a primary amine compound having a pyrazoloazole skeleton or a pyrazolone skeleton as a mother nucleus.

 This pyrazoloazole compound is represented by the following formula.

formula Here, R ₁ represents a hydrogen atom or a substituent. Z represents a group of nonmetal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). L represents a single bond or a divalent group, and is bonded to a carbon atom of an azole ring containing Z. X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent.

Hereinafter, the formula (I) will be described in detail. A preferred skeleton of the pyrazoloazole skeleton represented by the formula (I) is
1H-imidazo [1,2- b ] pyrazole, 1H-pyrazolo [1,5- b ] [1,2,4] triazole, 1H-pyrazolo [5,
1- c ] [1,2,4] triazole and 1H-pyrazolo [1,5
-D ] tetrazole, each having the formula [MI],
[M-II], [M-III] and [M-IV].

The substituents R ₁₁ , R ₁₂ , R ₁₃ and X in these formulas will be described in detail.

R ₁₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group , Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyl Oxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
R ₁₁ represents a phosphonyl group, an aryloxycarbonyl group, an acyl group, or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), an alkyl group (eg, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl). Groups, cycloalkyl groups and cycloalkenyl groups, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- ｛4 − ｛2-
[4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3- (2,4-di-t-amylphenoxy) propyl),
An aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (e.g., 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy,
2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, tetradecaneamido, 2- (2,4-
Di-t-amylphenoxy) butanamide, 4- (3-
t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecaneamide), an alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5
-Dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {α- (3-t-butyl-4
-Hydroxyphenoxy) dodecaneamide @ alinino), a ureido group (eg, phenylureido, methylureide, N, N-dibutylureide), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl) -N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,
3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example,
Phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonyl) Amino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide), a carbamoyl group (eg, , N-
Ethylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl @ carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-
Dodecyloxyethyl sulfamoyl, N-ethyl-
N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl,
Octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (eg, 1-phenyltetrazole-5)
-Oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo,
4-pivaloylaminophenylazo, 2-hydroxy-
4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg,
N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N -Phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl,
Octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group (for example, imidazolyl, Pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Among these substituents, preferred R ₁₁ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Examples thereof include an alkylthio group, a ureido group, a urethane group, and an acylamino group.

R ₁₂ and R ₁₃ are the same as the substituents exemplified for R ₁₁ , and are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group. And cyano groups.

However, at least one of R ₁₂ and R ₁₃ is -L-
It is NH _2. L is preferably X represents a hydrogen atom or a group capable of leaving in the reaction with an oxidized form of an aromatic primary amine color developing agent, and when the group capable of leaving is specifically described, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl Or an arylsulfonyloxy group, an acylamino group, an alkyl or arylsulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl, aryl or heterocyclic thio group, a carbamoylamino group, a 5- or 6-membered nitrogen-containing heterocyclic ring group, an imido group, include arylazo groups, these groups may be further substituted with allowed group as a substituent of R _11.

More specifically, a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy) , 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy),
Acyloxy groups (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino) An alkyl or aryl sulfonamide group (for example, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, Phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (e.g. dodecylthio, 1-carboxydodecylthio, Niruchio, 2- butoxy-5
-T-octylphenylthio, tetrazolylthio), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl,
Pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (for example, succinimide, hydantoinyl), arylazo group (for example, phenylazo, 4-methoxyphenylazo) and the like. X may be in the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group bonded via a carbon atom. X may contain a photographically useful group such as a development inhibitor and a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site with a nitrogen atom.

 The pyrazolone-based amine compound is represented by the following formula.

(Wherein, R ₁₂ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. Ar represents a phenyl group or one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Z ₁ represents a hydrogen atom or aromatic 1
Represents a group which can be eliminated in the reaction with an oxidized form of a secondary amine color developing agent. Hereinafter, the present invention will be described in detail. In formula (II), R
₂₁ represents H or an alkyl group having an amino group at the terminal, an aryl group, an acyl group or a carbamoyl group. Specifically, the alkyl group is a linear or branched alkyl group having 1 to 42 carbon atoms, an aralkyl group, an alkenyl group. A alkynyl group, a cycloalkyl group or a cycloalkenyl group; an aryl group represents an aryl group having 6 to 46 carbon atoms;
The acyl group is an aliphatic acyl group having 2 to 32 carbon atoms or 7 carbon atoms.
A carbamoyl group is an aliphatic carbamoyl group having 2 to 32 carbon atoms or an aromatic carbamoyl group having 7 to 46 carbon atoms. These groups may have a substituent, and they are an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

More specifically, R ₂₁ is H or an alkyl group having an amino group at a terminal (eg, methyl, ethyl, butyl, propyl, octadecyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, methoxyethyl, ethoxyethyl, t-butoxyethyl, phenoxy) Ethyl, methanesulfonylethyl, 2- (2,4-di-tert-amylphenoxy) ethyl), an aryl group (for example, phenyl, 2
-Chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5-
(3-octadecenyl-1-succinimide) phenyl, 2-chloro-5-octadecylsulfonamidophenyl, 2-chloro-5- [2- (4-hydroxy-3-
tert-butylphenoxy) tetradecanoamidophenyl), an acyl group (eg, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-di-tert-pentylphenoxy) acetyl, 2- (2,4-di-tert-pentyl) Phenoxy) butanoyl, benzoyl, 3- (2,4-di-tert)
-Amylphenoxyacetamido) benzoyl), carbamoyl groups (e.g. N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-hexadecylcarbamoyl,
N-methyl-N-phenylcarbamoyl, N- [3-
{1- (2,4-di-tert-pentylphenoxy) butyramide}] phenylcarbamoyl). Specific examples of the substituents that these groups may have include, for example, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an acyl group, and an aryloxycarbonyl group. , Alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, acylamino group, alkylamino group, anilino group, ureido group, sulf Famoylamino group, alkoxycarbonylamino group, sulfonamide group, aryloxycarbonylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfonyl group, sulfinyl group, azo group, phosphonyl group, azo Group, a fluorine atom, a chlorine atom, a bromine atom. R ₂₁ is preferably _{-NH 2 -, - R 1 '} , −NH−RR ₁ ′, (R ₁ ′ is an amino-substituted aryl group), and Ar represents a phenyl group or a phenyl group substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups. Ar is, for example, a phenyl group, a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group, a 2,4-dimethyl-6-
A methoxyphenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 2,6-dichloro-4-ethoxycarbonylphenyl group, a 2,6-dichloro-4-cyanophenyl group, or 4-2 (2,4- Di-tert-amylphenoxy) butylamido] phenyl group. Preferably Ar is a 2,4,6-trichlorophenyl group or a 2,5-dichlorophenyl group.

Z ₁ represents a hydrogen atom or a coupling-off group, and details of the coupling-off group include, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an amide group, an alkoxycarbonyloxy group, an aryloxy group. Carbonyloxy group,
An alkyl, aryl or heterocyclic thio group, an imide group, a 5- or 6-membered nitrogen-containing heterocyclic group, or an arylazo group, and these groups may be further substituted with a group permitted as a substituent of R _1. Good. More specifically, the coupling-off group represented by Z ₁ is a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), an alkoxy group (eg, dodecyloxy, dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy, Methanesulfonyloxy), aryloxy groups (eg, 4-methylphenoxy, 4-
tert-butylphenoxy, 4-methoxyphenoxy, 4
-Methanesulfonylphenoxy, 4- (4-benzyloxyphenylsulfonyl) phenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), amide Groups (eg, dichloroacetylamino, methanesulfonylamino, triphenylphosphonamide), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy, 2,4,6 -Trimethylphenoxycarbonyl),
Alkyl, aryl or heterocyclic thio groups (e.g. dodecylthio, benzylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio, 2,5-dioctyloxyphenylthio,
2- (2-ethoxyethoxy) -5-tert-octylphenylthio, 2-pivaloylaminophenylthio, tetrazolylthio), imide group (for example, succinimide,
Hydantoinyl, 2,4-dioxooxazolidine-3-
Yl, 3-benzyl-4-ethoxyhydantoin-1-
Yl) 5- or 6-membered nitrogen-containing heterocyclic group (eg, 1-pyrazolyl, 1-benzotriazolyl, 5-chloro-1,2,4-triazol-1-yl, 1,2-dihydro-2
-Oxo-1-pyridyl), an arylazo group (for example,
Phenylazo, 4-methoxyphenylazo) and the like. Z ₁ may also take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group bonded via a carbon atom.
Further, Z ₁ may contain a development inhibitor, a photographically useful group such as a development accelerator. Preferred Z ₁ is a hydrogen atom, an alkyl,
An aryl or heterocyclic thio group or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site with a nitrogen atom.

The phthalimidated compound of this amine compound is represented by the following formula.

(In the formula, A represents a pyrazoloazole nucleus or a pyrazolone nucleus, and L ₁ has the same meaning as described above.) In the present invention, a pyrazoloazole-based phthalimidized compound represented by the following formula among the above phthalimidated compounds: Is preferred.

(Wherein, R ₃₁ is a hydrogen atom, an alkyl group, an aryl group,
An alkoxy group, an aryloxy group, an anilino group, a ureido group or a carbamoyl group, and specific examples thereof are represented by the formula [M-
I] are the same as those mentioned in R ₁₁ to [M-IV]. X
And L have the same meaning as described above. In the present invention, a phthalimide compound having a pyrazoloazole skeleton or a pyrazolone skeleton is reacted with hydrazine to form a phthaloyl hydrazide salt of a primary amine compound. The amount of hydrazine used is usually 0.8 to 3.0, preferably 1.0 to 1.5, in molar ratio to the phthalimide compound.
More preferably, it is 1.0 to 1.2. If the amount of hydrazine is too large, a large amount of by-products will be generated during the subsequent reaction with acid chloride, leading to a decrease in yield and a decrease in purity. If the amount is too small, a large amount of by-products such as residual phthalimide and its decomposed products, and the generated amine, phthalimide and reaction products are generated, and the yield in the next step is reduced.

This deprotection reaction is usually performed in a solvent. Examples of the solvent include alcohols, water, acetonitrile, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyridine (NM
P), pyridine, ethyl acetate, acetic acid and the like are used, but water, alcohols and a mixed solvent thereof are preferable, and methanol, ethanol and a mixed solvent containing 40% or more thereof are more preferable.

The reaction temperature is usually from 0 to 120 ° C, preferably from the reflux temperature of the solvent to a temperature lower by 10 ° C. The reaction time is not particularly limited, but is preferably from 10 minutes to 5 hours.

Further, a catalyst is not necessarily required in this reaction, but an organic amine or the like may be used as a catalyst.

Next, when performing the second step, an aqueous solution of an organic acid or an inorganic acid is added to the reaction mixture of the first step in advance to adjust the pH of the aqueous phase to 7.
To 1. As the acid used at this time, preferably acetic acid,
Hydrochloric acid, sulfuric acid, nitric acid, formic acid, propionic acid, phosphoric acid, carbonic acid (carbon dioxide) and the like are used, and acetic acid and sulfuric acid are more preferably used. The amount used is preferably at least 0.8 times the molar amount of the primary amine compound in the reaction mixture,
Twice mole is more preferred. Thus, the pH of the aqueous phase is adjusted to 7
By the following, the dissociation of the phthaloyl hydrazide salt is promoted, and the reaction rate is increased.

It is preferable that the phthaloyl hydrazide precipitated after the treatment with the acid is filtered and the second step is performed in order to reduce the post-treatment step, but the present invention is not limited thereto.

Next, an organic acid halide is added to the reaction mixture whose pH has been adjusted as described above, and the mixture is reacted in a heterogeneous system.

As the organic acid halide used here, aryloxyalkylene carboxylic acid chloride (for example, (Ar: aryl group such as substituted phenyl group, R: alkyl group), carboxylic acid chloride (eg, CH ₃ (CH ₂ ) _n COCl, A
rCH ₂ COCl (Ar: substituted and unsubstituted phenyl group, n = 1 to 1
9), alkyl carboxylic acid chlorides having 5 to 20 carbon atoms are preferred. ), Benzoyl chloride, benzenesulfonyl chloride, acrylic acid chloride, methacrylic acid chloride, and the like, but are not limited thereto. These include not only unsubstituted ones but also those having a substituent.

In this reaction, the ratio between the phthaloyl hydrazide salt of the primary amine compound and the organic acid halide is not particularly limited, and either one may be used in a large excess, but it is preferably represented by the molar ratio of the primary amine compound to the organic acid halide. 0.6-3.
0: 1, more preferably 0.7 to 1.3: 1.

This reaction can be carried out by dissolving the organic acid halide in the organic phase, and causing a heterogeneous reaction between the organic phase and the aqueous phase in which the phthaloyl hydrazide salt of the primary amine compound is dissolved. . As the solvent for the organic acid halide, the aforementioned aromatic or aliphatic hydrocarbons, esters or ethers are used, and aromatic or aliphatic hydrocarbons are preferred. The amount of the solvent used is preferably 1/3 or more of the organic phase.

The reaction temperature is usually −30 to 100 ° C., preferably −10 to 50 ° C.
° C, more preferably 0 to 40 ° C, and the reaction time is not particularly limited, and is preferably 10 minutes or more, and usually 5 hours or less is sufficient.

This reaction can be carried out either without a catalyst or in the presence of a catalyst. When a catalyst is used, an organic or inorganic base such as sodium (or potassium) bicarbonate, borax, potassium silicate, tertiary phosphorus Sodium acid, sodium acetate (or potassium), sodium dihydrogen phosphate (or potassium) + NaOH (or KOH), boric acid + NaOH (or KOH) and the like are used.

The reaction can be carried out with stirring, and after the reaction is completed, preferably, the aqueous phase is completely or partially removed by liquid separation or the like, and then the organic phase is appropriately extracted and washed with water to obtain the desired acid amide compound in a usual manner. Separation by the method. Separation method is not particularly limited, but crystallizes by adding an appropriate solvent as necessary, after concentrating or distilling the reaction solvent, crystallizing by adding another solvent,
Any method such as dropping into a poor solvent to precipitate and filtering, concentrating the reaction solution to dryness, and taking out may be used,
As a result, a highly pure target compound can be obtained, and if the primary amine compound / acid halide molar ratio is 0.9 or more, a highly pure product is obtained.

In the present invention, the first step may be performed using hydroxylamine instead of hydrazine. In this method, a phthalimide compound having a pyrazoloazole skeleton or a pyrazolone skeleton is reacted with hydroxyamine to form a hydroxyphthalimide salt of a primary amine compound having a pyrazoloazole skeleton or a pyrazolone skeleton as a mother nucleus. , An aromatic or aliphatic hydrocarbon, an ester having 4 or more carbon atoms, or an organic acid halide dissolved in an ether having 8 or more carbon atoms is added, and the reaction is performed in a heterogeneous system. The method using hydroxylamine can be performed in exactly the same manner as in the case of using hydrazine except that the pH of the aqueous phase is not specifically adjusted by adding an organic acid or an inorganic acid as described above, and the reaction components and reaction conditions are the same. it can.

Specific examples of the primary amine compound used in the present invention are shown below, but are not limited thereto.

Further, specific examples of the organic acid halide used in the present invention are shown below, but the present invention is not limited thereto.

Next, examples of the acid amide compound obtained by the method of the present invention, particularly a compound useful as a magenta coupler, will be illustrated below, but it should not be construed that the invention is limited thereto.

(Examples) Next, the present invention will be described in more detail based on examples.

Example 1 In a 300 ml three-necked flask equipped with a stirring device, 45.38 g (0.132 mol), 82.5 ml of methanol and DMAc 2
Charge 2ml, After dissolving, hydrated hydrazine (80% aqueous solution) 9.
5 g (0.152 mol) was added together with 6 ml of methanol, and the solution was stirred under reflux (71 to 72 ° C.) for 3 hours while stirring. As a result, crystals were precipitated 2 to 4 minutes after the start of reflux. Then, the reaction solution was cooled to 40 ° C., and 11.32 ml of acetic acid was added to water 1
After addition with 00 ml, the mixture was adjusted to pH 5.4 and stirred at 30 ° C. for 30 minutes to form a salt. Then, after adding 66 ml of water, the precipitated phthaloyl hydrazide was removed by filtration. About 283 ml of an aqueous solution (concentration: about 9%) was obtained.

Next, about 283 ml of the salt-forming solution and 165 ml of toluene were charged into a one-volume three-necked flask equipped with a stirrer. Then dissolved in 30 ml of toluene 47.4 g (0.12 mol) was added dropwise with stirring at 20 ° C. over 30 minutes, and the mixture was further reacted at 30 ° C. for 2 hours with stirring. After standing for 30 minutes, the aqueous phase was separated, and toluene was added to the organic phase.
90 ml, 2.1 ml of acetic acid and 180 ml of warm water (40 ° C.) were added, and the mixture was stirred for 5 minutes, allowed to stand for 30 minutes, then separated, and the organic phase was removed at 55 ° C. using an evaporator to remove the solvent. 67.94 g (98.5% yield) was obtained with a purity of 95%. The target compound was identified by IR and NMR. The same applies hereinafter.

Example 2 In a 300 ml three-necked flask equipped with a stirrer, 45.0 g (0.13 mol), 82.0 ml of ethanol and 22 ml of ethylene glycol were charged, After dissolving, hydrated hydrazine (80% aqueous solution) 9.
42 g (0.15 mol) was added together with 5.5 ml of ethanol, and the solution was reacted under reflux (71-72 ° C.) for 3 hours while stirring. Then, the reaction solution was cooled to 20 ° C., and 8.0 ml of acetic acid was added together with 108 ml of water. Then, the mixture was adjusted to pH 6.0 and stirred at 30 ° C. for 30 minutes to form a salt. Then, after adding 65 ml of water, the precipitated phthaloyl hydrazide was removed by filtration. About 319 ml of an aqueous solution (concentration: about 8%) was obtained.

Next, 49.5 ml of n-hexane and 132 ml of ethyl acetate were added to about 319 ml of this aqueous solution, and potassium bicarbonate 3 was added at an internal temperature of 5 ° C or less.
3 g was added with 33 ml of water. Then in 33 ml of ethyl acetate 55.6 g (0.14 mol) was added dropwise while stirring the reaction solution at 20 ° C. over 30 minutes, and further reacted at 30 ° C. for 2 hours. Next, after standing for 30 minutes, the aqueous phase was separated, and 90 ml of ethyl acetate, 2.6 ml of acetic acid, and 213 ml of water were added to the obtained organic phase, and the mixture was stirred for 5 minutes, subjected to extraction treatment, allowed to stand for 30 minutes, and then separated. Then, the solvent was removed from the organic phase at 80 ° C. using an evaporator, 100 ml of the solvent was removed, then cooled to 25 ° C., and left overnight for crystallization, 63.1 g (yield 84.3%) was obtained. The purity was 98%.

Example 3 In a 300 ml three-necked flask equipped with a stirring device, 45.3 g (0.10 mol), 100 ml of methanol were charged, After dissolution, add hydrated hydrazine (80% aqueous solution) to this solution.
9 g (0.11 mol) are added and the solution is refluxed (67-68).
C) for 3 hours while stirring.
After cooling to 20 ° C. and adding 9.5 ml of acetic acid together with 108 ml of water, the mixture was adjusted to pH 5.5 and stirred at 30 ° C. for 30 minutes to form a salt. Then, after adding 65 ml of water, the precipitated phthaloyl hydrazide was removed by filtration. About 310 ml of an aqueous solution (concentration: about 8%) was obtained.

Next, about 310 ml of aqueous solution and 50 ml of cyclohexane,
After adding 30 ml, 50 g of borax was added together with 33 ml of water at an internal temperature of 5 ° C. or less. Then in 35 ml of toluene 48.5 g (0.10 mol) of the reaction solution was added dropwise with stirring at 20 ° C. over 30 minutes, and the mixture was further reacted at 30 ° C. for 2 hours. Then, after standing for 30 minutes, the aqueous phase was separated, and the obtained organic phase was treated with acetic acid 5 m.
l and 500 ml of water were added, stirred for 5 minutes, subjected to extraction treatment, allowed to stand for 30 minutes, then separated, and the organic phase was removed at 80 ° C. using an evaporator at 80 ° C. and dissolved in 100 ml of methanol. When this is dripped slowly into water, 525.3 g of powder (yield 97.5%) was obtained. The purity was 95%.

Example 4 In a 300 ml three-necked flask equipped with a stirring device, 45.0 g (1.05 mol), 75 ml of methanol and 20 ml of acetonitrile were charged, After dissolution, add hydrated hydrazine (80% aqueous solution) to this solution.
1 g (0.13 mol) was added together with 10 ml of methanol, and the solution was reacted under reflux (68-71 ° C.) for 3 hours while stirring. Then, the reaction solution was cooled to 20 ° C. and 3 ml of concentrated hydrochloric acid was added to 1 ml of water.
After adding with 08 ml, the mixture was adjusted to pH 4.2 and stirred at 30 ° C. for 30 minutes to form a salt. Then, after adding 65 ml of water, the precipitated phthaloyl hydrazide was removed by filtration. About 320 ml of an aqueous solution (concentration: about 8%) was obtained.

Next, about 320 ml of aqueous solution and 150 ml of n-hexane and ethyl acetate
After adding 200 ml, 10 g of triethylamine was added together with 33 ml of water at an internal temperature of 5 ° C. or lower. Then 40.8 g (0.10 mol) of the reaction solution was added dropwise with stirring at 20 ° C. over 30 minutes, and further reacted at 30 ° C. for 2 hours. Then, after standing still for 30 minutes, the aqueous phase was separated, and 90 ml of ethyl acetate, 1.5 ml of acetic acid and 400 ml of water were added to the obtained organic phase, and the mixture was stirred for 5 minutes, subjected to extraction treatment, allowed to stand for 30 minutes, and then separated. Then, the solvent was removed from the organic phase at 80 ° C. using an evaporator, and after removing the entire amount of the solvent, 500 ml of acetonitrile was added to the organic phase at 25 ° C.
And left overnight for crystallization, To give 590.3 g (92.3% yield). The purity was 98%.

Example 5 In a 300 ml three-necked flask equipped with a stirring device, 45.38 g (0.132 mol), 100 ml of water were charged, After dissolution, add hydrated hydrazine (80% aqueous solution) to this solution.
75 g (0.14 mol) was added together with 20 ml of water, and the solution was reacted for 3 hours while stirring under reflux (100 ° C.). Then, the reaction solution was cooled to 20 ° C., and 10 ml of acetic acid was added.
The pH was adjusted to 5.0, and the mixture was stirred at 30 ° C. for 30 minutes to form a salt. Then, after adding 65 ml of water, the precipitated phthaloyl hydrazide was removed by filtration. About 130 ml of an aqueous solution (concentration: about 18%) was obtained.

Next, 250 ml of toluene was added to about 130 ml of the aqueous solution, and then the internal temperature was 5
Below 40 ° C., 45 g of potassium bicarbonate were added along with 33 ml of water. Then 84.0 (0.12 mol) was added dropwise while stirring the reaction solution at 20 ° C over 30 minutes, and further reacted at 30 ° C for 2 hours. Then, after standing still for 30 minutes, the aqueous phase was separated, and 200 ml of n-hexane, 30 ml of methanol and 100 ml of water were added to the obtained organic phase, and the mixture was stirred for 5 minutes, subjected to extraction treatment, allowed to stand for 30 minutes, and then separated. And
Add the organic phase and cool to -10 ° C, 90.4 g (yield: 89.8%) of crystals were obtained. The purity was 98%.

Example 6 In a 1000 ml three-necked flask equipped with a stirrer 70 g (0.186 mol), ethyl acetate 210 ml, DMAc 46.5 ml,
230 ml of water and 47.0 g of sodium bicarbonate are charged to pH 10.5 and then in 5 ml of DMAc and 60 ml of ethyl acetate. While stirring the reaction mixture, 77.3 g (0.196 mol) of internal temperature 5 ° C
For 30 minutes, and further reacted at 30 ° C. for 30 minutes. Next, 18.8 g of triethylamine was added to the reaction solution,
The reaction was further performed at 30 ° C. for 60 minutes. After separating the aqueous phase from the reaction solution, the organic phase was extracted with ethyl acetate, concentrated and crystallized. 390 g (95% yield) with a purity of 98%.

Example 7 In a 300 ml three-necked flask equipped with a stirring device, 34.4 g (0.1 mol), 100 ml of methanol were charged, After dissolving, 79.2 g (0.12 mol) of hydroxylamine (50% aqueous solution) was added to the solution, and the solution was refluxed (6%).
(8-69 ° C) with stirring for 5 hours, and the reaction solution is cooled to 20 ° C.

Next, 50 ml of n-hexane and 150 ml of ethyl acetate were added, and then 33 g of potassium bicarbonate was added together with 33 ml of water at an internal temperature of 5 ° C. or lower. Then in 33 ml of ethyl acetate 9.1 g (0.10 mol) of the reaction solution was added dropwise at 20 ° C. over 10 minutes while stirring, and the mixture was further reacted at 30 ° C. for 2 hours. Then, after standing still for 30 minutes, the aqueous phase was separated, and 90 ml of ethyl acetate, 30 ml of acetic acid and 200 ml of water were added to the obtained organic phase, and the mixture was stirred for 5 minutes, subjected to extraction treatment, left to stand for 30 minutes, and then separated. The solvent was removed from the organic phase at 80 ° C. using an evaporator, 100 ml of the solvent was removed, then cooled to 25 ° C., and left overnight for crystallization, 24.2 g (89% yield) was obtained. The purity was 99%.

(Action) The reason why the acid amide compound having a pyrazoloazole skeleton or a pyrazolone skeleton can be obtained in high yield and high purity in the present invention is not yet clear, but after the first step, the pH of the aqueous phase is adjusted to 7 or less in phthalo. It is considered that the dissociation of the ylhydrazide salt is promoted to increase the reaction rate. By separating the reaction system into two phases, it is considered that the reaction between the first-stage reaction solvent, hydrazine and the like and the organic acid halide is avoided, and the side reaction is minimized.

(Effect of the Invention) According to the method of the present invention, an acid amide compound having a pyrazoloazole skeleton or a pyrazolone skeleton can be synthesized in a heterogeneous system by a two-phase reaction, and a high-purity acid amide compound can be produced in a high yield. can do. In the method of the present invention, it is not particularly necessary to isolate the primary amine compound formed by the deprotection from the phthalimide compound in the first reaction, and the acid amide compound from the organic phase formed in the second reaction is not required. A sufficiently high purity can be synthesized by one extraction treatment, and the time required for producing the acid amide compound from the phthalimide compound can be greatly reduced.

Claims (4)

(57) [Claims] 1. A phthalimide compound which is a reaction product of a primary amine compound having a pyrazoloazole skeleton or a pyrazolone skeleton as a mother nucleus and a phthalic acid compound is reacted with hydrazine to produce a phthaloyl hydrazide salt of the primary amine compound. After the reaction, an aqueous solution of an organic acid or an inorganic acid is added to the reaction mixture to adjust the pH of the aqueous phase to 7 to 1. Then, the mixture is mixed with an aromatic or aliphatic hydrocarbon having 4 to 4 carbon atoms. A pyrazoloazole characterized by reacting the organic acid halide with the phthaloyl hydrazide salt of the primary amine compound in a heterogeneous system by adding an organic acid halide dissolved in the above ester or ether having 8 or more carbon atoms. A method for producing an acid amide compound having a skeleton or a pyrazolone skeleton. 2. The method for producing an acid amide compound according to claim 1, wherein the phthalimide compound is a phthalimide compound having a pyrazoloazole skeleton represented by the formula (IV). (Wherein, R ₃₁ is a hydrogen atom, an alkyl group, an aryl group,
X represents an alkoxy group, an aryloxy group, an anilino group, a ureido group or a carbamoyl group, X represents a hydrogen atom or a coupling-off group, and L represents a single bond or a divalent group. ) 3. The method for producing an acid amide compound according to claim 1, wherein the organic acid halide is aryloxyalkylene carboxylic acid chloride, benzoyl chloride, benzenesulfonyl chloride, acrylic acid chloride or methacrylic acid chloride. 4. A reaction of a phthalimide compound, which is a reaction product of a primary amine compound having a pyrazoloazole skeleton or a pyrazolone skeleton as a mother nucleus with a phthalic acid compound, and hydroxyamine to form a hydroxyphthalimide salt of the primary amine compound. After that, an aromatic or aliphatic hydrocarbon, an ester having 4 or more carbon atoms or an organic acid halide dissolved in an ether having 8 or more carbon atoms is added to the mixture, and the organic compound is mixed in a heterogeneous system. A method for producing an acid amide compound having a pyrazoloazole skeleton or a pyrazolone skeleton, which comprises reacting an acid halide with a hydroxyphthalimide salt of the primary amine compound.