JPH0860010A - Production of two-equivalent yellow coupler - Google Patents

Abstract

PURPOSE: To obtain a highly pure two-equivalent yellow coupler by reacting a bromide solution obtained by reacting a four-equivalent yellow coupler with Bv2 in a specified solvent with a solution obtained by dissolving a two-equivalent eliminable group and a base in the same solvent. CONSTITUTION: A four-equivalent yellow coupler represented by formula I (wherein R1 is Cl or alkyl2 and R,, is acylamino or the like) is dissolved in a halogenated solvent such as dichloromethane or an ester solvent such as ethyl acetate, a solution containing a specified amount of dissolved Bv2 is added dropwise to the solution to replace the hydrogen atoms of an active methylene group with Bv, and the obtained reaction product is washed with water and subjected to liquid separation to obtain a bromide solution. This solution is added dropwise to a solution prepared by dissolving a two- equivalent eliminable group represented by formula II (wherein R11 is II or alkyl; and R2 and /R3 are each H, alkyl or alkoxyl) and a base such as a tert. organic amine in a halogenated solvent or an ester solvent and having a temperature of about 10-45 deg.C. After the reaction, alkaline water or the like is added to the reaction mixture to extract excess two-equivalent eliminable group in the water layer, the organic layer is neutralized with e.g. hydrochloric acid and washed with water, concentrated by removing the solvent, and the concentrate is crystallized to obtain a highly pure two- equivalent yellow coupler.

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 a yellow coupler as a photographic chemical, and more particularly to a method for producing a 2-equivalent yellow coupler which is simple and has a high yield and a high purity.

[0002]

2. Description of the Related Art Two-equivalent yellow couplers as color photographic chemicals generally have a structure in which one of the hydrogen atoms of the active methylene group is replaced with a cleavable group. Among such 2-equivalent leaving groups, hydantoins are classified into Japanese Patent Publication No.
No. 1-10783 and Japanese Patent Publication No. 56-45135. In the specific methods for synthesizing the corresponding 2-equivalent yellow couplers described therein, a compound in which one hydrogen atom of an active methylene group is replaced by a chlorine atom or a bromine atom, an alkali metal salt of hydantoins or hydantoin and water are used. The desired 2-equivalent yellow coupler is synthesized by reacting potassium oxide or triethylamine, washing with water in a conventional manner, concentrating the solvent, and crystallizing the residue.

However, in this synthetic method, the chloro atom-substituted compound (chlorinated compound) and the bromine atom-substituted compound (brominated compound) used are isolated ones, and the yield loss in the isolation step is also caused. There is no economical manufacturing method. In addition, the yield of the obtained 2-equivalent coupler is also low, which causes an increase in manufacturing cost.

For example, in Japanese Patent Publication No. 56-45135, α-pivaloyl-α- (1-benzyl-5-methoxy-3-hydantoinyl) -2-chloro-5- [γ-
Synthesis examples of (2,4-di-tert-amylphenoxy) butyramide] acetanilide are described. However, in this synthesis example, a methanol solution of potassium hydroxide was prepared, a solution of 1-benzyl-5-methoxyhydantoin dissolved in dimethylformamide was added to the solution, and α-pivaloyl-α-chloro-2 was further added. -Chloro-5- [γ- (2,4-di-tert-amylphenoxy)
Butylamido] acetanilide in dimethylformamide was added dropwise, and the mixture was reacted at 25 ° C. for 2 hours, then,
After adding ethyl acetate and extracting and washing with water according to a conventional method, the ethyl acetate layer was concentrated and the residue was crystallized from a mixed solvent of hexane and ethyl acetate to obtain the desired 2 equivalent coupler in a yield of 55.2%.

On the other hand, a method of synthesizing a 2-equivalent yellow coupler by reacting a 4-equivalent yellow coupler with a bromine (non-diluted) bromine atom-substituted compound and washing and extracting a bromine-substituted compound solution with a 2-equivalent leaving group in the presence of a base. , RESEAR
CH DISCLOSURE, 1979, 18053. As a specific synthetic example in this report, α-pivaloyl-α-
(1-benzyl-5-ethoxy-3-hydantoinyl)
The synthesis of 2-chloro-5-tetradecyloxycarbonyl-acetanilide is shown. That is, bromine was added dropwise to a solution in which a 4-equivalent coupler corresponding to a 2-equivalent coupler was dissolved in chloroform while being cooled to 10 ° C or lower.
After 0 minutes of reaction, the mixture is washed with water and separated until it becomes neutral. This brominated solution was added dropwise to a chloroform solution of 1-benzyl-5-ethoxy-hydantoin and triethylamine in 1 hour, and the mixture was further reacted for 2 hours. After removing excess 1-benzyl-5-ethoxyhydantoin with alkaline water, a conventional method was used. According to the procedure described above, the product is washed with water and neutralized, then chloroform is concentrated, and the residue is crystallized from methanol to obtain 80% of the desired product.

However, the synthetic method introduced in this report is described in, for example, α-pivaloyl-α-chloro-2-chloro-5- [γ- (2,4-di-tert-amylphenoxy) butyramide] acetanilide. When a 2-equivalent coupler was synthesized by a bromination reaction using bromine that did not dilute, 4-equivalent coupler as a raw material and 4-Br corresponding to the following structure
The amount of the compound (Chemical Formula 2) is increased as a by-product, resulting in a decrease in the purity of the 2-equivalent coupler and a decrease in the yield due to the purification, which causes an increase in manufacturing cost.

[0007]

Embedded image (In the formula, R ₁ represents a chloro atom or an alkoxy group, and R _1
2 represents an acylamino group or an alkoxycarbonyl group, R ₁₁ represents a hydrogen atom or an alkyl group, R ₁₂ and R ₁₃
Represents a hydrogen atom, an alkyl group or an alkoxy group. However, R ₁₂ and R ₁₃ may be the same or different. )

[0008]

The object of the present invention is to eliminate the disadvantages of the conventional production method, namely, the isolation step and the loss due to the isolation of the bromine atom substitution product at the active position of the 4-equivalent coupler,
An object of the present invention is to provide a method for producing a 2-equivalent yellow coupler in which the yield and purity of the desired 2-equivalent yellow coupler are improved.

[0009]

In order to achieve the above object, the present invention provides a method for producing a bromide of a 4-equivalent yellow coupler after dissolving the 4-equivalent yellow coupler in a halogen solvent or an ester solvent. By adding bromine diluted with the same solvent as these solvents, one hydrogen atom of the active methylene group of the 4-equivalent yellow coupler is replaced with bromine, and the resulting bromide solution is washed with water and separated. Is characterized by.

In the present invention, a solution of 4 equivalents of an active methylene bromide of 4 equivalents of a yellow coupler is dissolved in a halogen-based solvent or an ester-based solvent after dissolving 2 equivalents of a leaving group and a base in the same solvent. It is characterized by adding and reacting.

Further, preferably, the halogen-based solvent or the ester-based solvent comprises dichloromethane or ethyl acetate.

The present invention will be described in more detail below. The 4-equivalent yellow coupler used in the present invention is preferably represented by the following formula (1).

[0013]

[Chemical 3] (In the formula, R ₁ represents a chlorine atom or an alkoxy group (eg, methoxy, ethoxy, octoxy, hexadecyloxy), and R ₂ represents an acylamino group (eg, α-
(2,4-di-tert-amylphenoxy) butyramide, γ- (2,4-di-tert-amylphenoxy) butyramide, octadecanoylamide, 2-octyldecanoylamide), alkoxycarbonyl group (for example, dodecyl Oxycarbonyl, tetradecyloxycarbonyl).

Further, a preferable 2-equivalent leaving group includes a group represented by the following formula (2).

[0015]

[Chemical 4] (In the formula, R ₁₁ represents a hydrogen atom or an alkyl group (eg, methyl, benzyl), and R ₁₂ and R ₁₃ represent a hydrogen atom, an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy, Hexyloxy), and R ₁₂ and R ₁₃ may be the same or different.) After brominating the compound of formula (1) with bromine diluted with a solvent, the following formula The 2-equivalent yellow coupler produced by the reaction with the compound (2) is represented by the following formula (3).

[0016]

[Chemical 5] (In the formula, R ₁ represents a chloro atom or an alkoxy group, and R _1
2 represents an acylamino group or an alkoxycarbonyl group, R ₁₁ represents a hydrogen atom or an alkyl group, R ₁₂ and R ₁₃
Represents a hydrogen atom, an alkyl group or an alkoxy group. However, R ₁₁ and R ₁₂ may be the same or different. ) The method of the present invention is a step of introducing a substituent into the active methylene position in the production process of a 2-equivalent yellow coupler. When the compounds of the above formulas (1), (2) and (3) are used, It is represented by a scheme.

[0017]

[Chemical 6] (In the formula, R ₁ represents a chloro atom or an alkoxy group, and R _1
2 represents an acylamino group or an alkoxycarbonyl group, R ₁₁ represents a hydrogen atom or an alkyl group, R ₁₂ and R ₁₃
Represents a hydrogen atom, an alkyl group or an alkoxy group. However, R ₁₂ and R ₁₃ may be the same or different. ) The compounds of the above formulas (1) to (3) and the manufacturing process conditions of the present invention will be described in more detail.

In the above formula (1), R ₁ is preferably a chloro atom or a methoxy group. R ₂ is an acylamino group and is α- (2,4-di-tert-amylphenoxy) butyramide, γ- (2,4-di-tert-amylphenoxy) butyramide, octadecanoylamide, 2-octyldecadecane. Noylamide is preferable, and as the alkoxycarbonyl group, dodecyloxycarbonyl,
Tetradecyloxycarbonyl is preferred. As a more preferable compound of the above formula (1), α-pivaloyl-2-
Chloro-5- [α- (2,4-di-tert-amylphenoxy) butyramide] acetanilide, α-pivaloyl-2-methoxy-5-tetradecyloxycarbonyl-
Acetanilide, α-pivaloyl-2-chloro-5-
[Γ- (2,4-di-tert-amylphenoxy) butylamide] acetanilide, α-pivaloyl-2-chloro-5-octadecanoylamide acetanilide and the like can be mentioned.

Among the two equivalent leaving groups represented by the above formula (2), preferable compounds include, for example, 1-benzyl-5-methoxyhydantoin and 1-benzyl-5-.
Examples thereof include ethoxyhydantoin, 1-methyl-5-hexyloxyhydantoin and 5,5-dimethylhydantoin.

The solvent used in the present invention is a halogen solvent or an ester solvent. Halogen-based solvents and ester-based solvents are well known, for example, “Solvent Handbook” edited by Teruzo Asahara et al., Published by Kodansha Scientific (1976).
Year) EWFlick, "Industrial Solvents Handbook,
Fourth Edition ", published by Noyes Data Corporation (1991). That is, the halogen-based solvent is classified as Chapter 2 "halogenated hydrocarbon" in the above Asahara work,
It is a hydrocarbon having one or more halogen atoms. Examples of the halogen-based solvent that can be used in the present invention include methyl chloride, dichloromethane, chloroform, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane,
In addition to 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, allyl chloride, butyl chloride, chlorobenzene, 1,2-dibromoethane, 2 of the same book
The solvents described on pages 44 to 325 can be mentioned.

The ester solvent is a solvent having an ester bond, which is classified in Chapter 8 "Ester" by Asahara mentioned above. Examples of ester solvents that can be used in the present invention include methyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, and methyl propionate. In addition to these, the ester solvents exemplified in Chapter 8 of Asahara can also be used in the present invention. Further above
Solvents classified by Flick as Halogenated Hydrocarbons and also as Esters can also be used in the present invention.

These solvents are used for the dilution of bromine and the dissolution of the 4-equivalent coupler during the production of the 4-equivalent yellow coupler bromide, and the dissolution of the 2-equivalent leaving group and the base. Dichloromethane is preferable, and ethyl acetate is preferable as the ester solvent. Considering pollution and the like, an ester solvent is more preferable than a halogen solvent, and ethyl acetate is more preferable.

The amount of solvent used for diluting bromine is preferably 1 to 10 times the volume of bromine. When the amount of solvent used for diluting bromine is small, the amount of by-products increases, while when the amount of solvent is too large, the reaction efficiency decreases. A more preferable amount of solvent is 1 to 5 times the volume of bromine. For dissolving 4 equivalents of the yellow coupler, 1 to 10 parts by volume is preferable, and 1 is more preferable.
~ 4 parts by volume. When the brominated compound is reacted with the two-equivalent leaving group, an auxiliary solvent may be used, and dimethylformamide or dimethylacetamide is preferable, and the amount used is at least 10% by volume, preferably 15-100% by volume. .

The amount of bromine used in the present invention is 0.96 equivalents to 1.10 equivalents with respect to the 4-equivalent yellow coupler. More preferably, in the case of a dichloromethane solvent, 0.
98 equivalents to 1.03 equivalents, and in the case of an ethyl acetate solvent, 1.00 equivalents to 1.08 equivalents. In the bromination reaction, the diluting solution of bromine is preferably added dropwise in 5 minutes or more, preferably 10 minutes to 30 minutes. The reaction temperature is 35 ° C.
The following is good, and preferably 5 to 30 ° C.

As the base used in the present invention, organic 3
Primary amine bases and metal alkoxides are preferred, triethylamine is preferred as the organic tertiary amine base, and sodium methoxide is preferred as the metal alkoxide. The amount of base used is from 0.90 to 2 equivalents of leaving group.
1.10 equivalents are preferred.

The amount of 2 equivalent leaving groups used in the present invention is
It is preferably 1.2 equivalents or more, more preferably 1.3 to 2.0 equivalents, relative to 4 equivalents of the yellow coupler. The reaction between the bromide and the 2 equivalent leaving group is preferably carried out by dropping a solution of the bromide into a solution in which a predetermined amount of the 2 equivalent leaving group and a base are dissolved, and the reaction temperature is 10 ° C to Four
5 ° C is preferred.

In the present invention, first, a 4-equivalent yellow coupler represented by the above formula (1) is dissolved in a halogen-based solvent such as dichloromethane or an ester-based solvent such as ethyl acetate to prepare 5 to 5 parts thereof.
Bromine obtained by diluting bromine in a liquid cooled to 20 ° C. with a solvent is 0.98 to 1.03 equivalents when the solvent is, for example, dichloromethane, and 1.00 to 1.10 equivalents when the solvent is ethyl acetate. The liquid is added dropwise over 10 to 30 minutes. After the reaction is completed for 1 to 15 minutes after the completion of dropping, the solution is washed with water and separated to collect the bromide solution in a container. In the case of ethyl acetate, washing with water is preferably performed once or twice.

Next, a base is added to the solution of 2 equivalent leaving groups represented by the above formula (2) and the solvent while stirring, and the mixture is kept at 10 to 45 ° C., and the bromide solution prepared above is added to this solution for 30 minutes or more. Drop by. The reaction is carried out until the bromide disappears, and the reaction temperature is usually 18 to 45 ° C. and the reaction time is preferably 1 hour or more. After completion, add water or excess alkaline water to add excess 2
Equivalent leaving groups are extracted into the aqueous layer. The organic layer is neutralized with an acid such as hydrochloric acid and washed with water, and the solvent is concentrated and then crystallized or taken out as a concentrate solid to obtain the desired high-purity 2-equivalent yellow coupler. The concentrate having a high 2-equivalent yellow coupler purity in the concentrate (about 96% or more, preferably 98% or more) can be directly used as a photographic coupler.

On the other hand, excess 2 extracted in the alkaline water layer
Among the equivalent leaving groups, for 1-benzyl-5-methoxyhydantoin, 1-benzyl-5-ethoxyhydantoin and 1-methyl-5-hexyloxyhydantoin, neutralize the alkali extract with acetic acid or hydrochloric acid. Can be collected and reused.

Examples of specific compounds of the 2-equivalent yellow coupler produced by the method of the present invention are shown in Table 1 below. However, the present invention is not limited to only these compounds. In Table 1 below, A and B in R ₂
Are shown in Chemical formula 7, respectively.

[0031]

[Table 1]

[0032]

[Chemical 7] Among the 4-equivalent yellow couplers represented by the above formula (1) used in the present invention, compounds in which R ₁ is an acylamino group can be synthesized by the synthetic method described in JP-A-4-63341, that is, The method of synthesizing by the reaction represented by the formula (4) is particularly preferable.

[0033]

Embedded image (In the formula, R ₁ represents a chloro atom or an alkoxy group, and R _1
3 represents a residue obtained by removing NHCO- from an acylamino group or an alkoxycarbonyl group. ) In particular, when dichloromethane or ethyl acetate is used as the reaction solvent, the 4-equivalent coupler can be used in the state of a solution in the bromination step of the present invention without being isolated by crystallization. This is an effective manufacturing method that can reduce costs without loss due to analysis.

As a concrete synthesis example, α-pivaloyl-2
A method for synthesizing -chloro-5- [2- (2,4-di-tert-amylphenoxy) butyramide] -acetanilide is shown below.

50 g (0.186 mol) of α-pivaloyl-2-
Chloro-5-amino-acetanilide was added to toluene 120
Dissolve in ml, and add 10.38 g (0.1
(100 mol) was added to 100 ml of water, and the mixture was stirred well at room temperature. 67.4 g (0.196 mol) of 2- (2,4-di-tert-amylphenoxy) butyryl chloride was added dropwise over 1 hour, washed with 20 ml of toluene and further stirred for 2 hours.
I continued for hours. Concentrated hydrochloric acid (21 ml) and water (10 ml) were added dropwise to neutralize, and the layers were separated. The organic layer was washed with 120 ml of water and separated.
The organic layer was concentrated under reduced pressure, and 276 ml of methanol was added to the residue.
Was added and dissolved by heating.

At an external temperature of 60 ° C., 148 ml of methanol and 32 ml of water were added, then the external temperature was set to 22 ° C., and stirring was performed for about 4 minutes.
It continued for hours. Furthermore, after stirring for 1 hour at an external temperature of 15 ° C., a mixed solution of 10 ml of methanol and 20 ml of water was added and stirred for 30 minutes. Next, the internal temperature was cooled to 0 to -5 ° C, and the produced crystals were collected by filtration. The crystals are washed with 175 ml of methanol and 12 ml of water cooled to 5 ° C or lower,
The crystals obtained were dried. Yield 102.3 g (96.3
%) To obtain the desired product having a melting point of 86 to 91 ° C.

In the above reaction, the desired product can be obtained in almost the same manner by using ethyl acetate or dichloromethane as a reaction solvent.

[0038]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited to these.

Example 1 α-pivaloyl-α- (1-benzyl-5-ethoxy-
3-Hydantoinyl) -2-chloro-5- [2- (2,
Synthesis of 4-di-tert-amylphenoxy) butyramide] -acetanilide (Compound 2) α-pivaloyl-2-chloro-5- [2- (2,4-di-tert-amyl-phenoxy) butyramide] -acetanilide ( Compound 1-A) 100 g (0.175 mol) is dissolved in 132 ml of dichloromethane and the internal temperature is 8 to 8
Stir at 20 ° C. 28.2 g of bromine (0.176 mol, 1.007 equivalent with respect to 4 equivalent coupler) was added to 52 ml of dichloromethane.
And added dropwise over 10 to 20 minutes. The dropping funnel was washed with 10 ml of dichloromethane and further reacted for 1 minute. After 352 ml of water was added, the mixture was extracted, washed with water, and then separated, and the organic layer containing bromide was collected in a dropping funnel.

74 g (0.316 mol, 1.
80 equivalents) of 1-benzyl-5-ethoxyhydantoin,
64 ml of dichloromethane and 30.2 g of triethylamine
(0.298 mol) was stirred and dissolved at an external temperature of 16 to 22 ° C., and a bromide solution was added dropwise over 2 hours while keeping the internal temperature at 30 ° C. or lower.
The dropping funnel was washed with 1 and reacted for 3 hours. Dissolve 15.8 g of sodium hydroxide in 480 ml of water to prepare an alkaline solution.

300 ml of this alkaline solution was added to the reaction solution, and after 5 minutes of stirring and 20 minutes of standing, the solution was separated. Save the aqueous layer to recover the excess of 2 equivalent leaving groups. 180 ml of alkaline water was added to the organic layer for extraction and liquid separation. The aqueous layer was combined with the first aqueous layer and used in the recovery step of a 2-equivalent leaving group described later. Subsequently, the organic layer was extracted and washed with 176 ml of water, 32 ml of concentrated hydrochloric acid, 350 ml of water, and 350 ml of water in this order.

The organic layer subjected to the above treatment was concentrated under reduced pressure, dried, pulverized, and taken out to obtain 137.1 g (yield 97) of the target coupler concentrate powder (mp. 76 to 87 ° C.). .5%). When the obtained target product was analyzed by high performance liquid chromatography, the results shown below were obtained.

Raw material (Compound 1-A) 1.2% Target product 97.0% By-product (4-bromo compound) 0.9% <Step of recovering excess 2 equivalent leaving group> Excess 2 equivalent leaving The base can be recovered and replenished to make up the shortage for reuse. This recovery method is shown below.

The alkaline aqueous layer containing the excess 1-benzyl-5-ethoxyhydantoin extracted with alkali is added to 46 ml of dichloromethane and 7 ml of acetic acid.
Furthermore, acetic acid (about 1.5 ml) was added to neutralize the solution to pH = 6.7, and the solution was extracted and separated. The organic layer is 70 ml, and a part of it is concentrated to dryness and the solid content is measured.
It was 1.9 g (collection rate 97%).

65 ml of a recovered liquid of 1-benzyl-5-ethoxyhydantoin recovered here (2 equivalent leaving group 29.
6g) new crystals 44.4g and dichloromethane 18ml
And 30.2 g of triethylamine were added to the solution,
The reaction and post-treatment steps were performed in the same manner as the bromide solution synthesized according to the bromination reaction described above to obtain a coupler concentrate. Purity analysis with a yield of 139.4 g (yield 99.1%) gave the following results.

Raw Material (Compound 1-A) 0.8% Target 97.6% By-product (4-Bromide) 0.6% Example 2 Synthesis of compound 2 in ethyl acetate solvent 100 g (0.175 mol) Compound 1-A from ethyl acetate 300
Add to ml and stir the internal temperature to 8-20 ° C. Bromine 2
9.9 g (0.187 mol, 1.07 equivalent to 4 equivalent coupler) was mixed with 52 ml of ethyl acetate and added dropwise over 10 to 20 minutes.

Wash the dropping funnel with 5 ml of ethyl acetate,
The reaction was continued for another 30 minutes. 350 ml of water was added, and the mixture was extracted and washed with water, followed by liquid separation, followed by washing with 6 g of sodium bicarbonate and 350 ml of water, followed by liquid separation, and then the organic layer was washed with 350 ml of water and separated to obtain an organic layer. Collected in funnel.

74 g (0.316 mol, relative to Compound 1-A)
1.80 equivalents of 1-benzyl-5-ethoxy-hydantoin and 66 ml of ethyl acetate to 30.2 g of triethylamine.
(0.298 mol) was added dropwise to the liquid stirred at an external temperature of 16 to 22 ° C. over 2 hours while maintaining the internal temperature of 30 ° C. or lower. After completion of the dropwise addition, the dropping funnel was washed with 10 ml of ethyl acetate, and Reacted for 4 hours.

15.8 g of sodium hydroxide and 480 m of water
Dissolve in 1 and adjust the alkaline solution. 300 ml of this alkaline solution was added to the reaction solution, and after 5 minutes of stirring and 20 minutes of standing, the layers were separated. Save the aqueous layer to collect 1-benzyl-5-ethoxyhydantoin. 180 ml of alkaline water was added to the organic layer for extraction and liquid separation. Next, the organic layer is 180 ml of water, 32 ml of concentrated hydrochloric acid and 350 ml of water,
Further, 350 ml of water was sequentially used for washing with water.

The organic layer subjected to the above treatment was concentrated under reduced pressure and dried to obtain the desired coupler concentrate. Yield 139.
The results of the purity analysis with 9 g (yield 99.5%) were as follows.

Raw material (Compound 1-A) 1.2% Target 96.8% By-product (4-bromo compound) 0.8% Example 3 4 equivalent coupler compound 1-A was converted to aniline and carboxylic acid chloride. Was directly synthesized and brominated from the extracted solution
An example of synthesizing an equivalent yellow coupler compound 2.

50 g (0.186 mol) of α-pivaloyl-2-
Chloro-5-amino-acetanilide was dissolved in 60 ml of dichloromethane and to this solution was added sodium carbonate 10.38.
An aqueous solution prepared by dissolving g (0.1 mol) in 100 ml of water was added, and the mixture was vigorously stirred at an external temperature of 16 to 20 ° C. 67.4g (0.196
Mol) 2- (2,4-di-tert-amylphenoxy) butyryl chloride is added dropwise over 1 hour and dichloromethane 10
It was rinsed with ml and stirring was continued for 2 hours. Concentrated hydrochloric acid 21
ml and 10 ml of water were added dropwise to neutralize and the layers were separated. The organic layer was extracted with 120 ml of water, washed with water and separated to obtain an organic layer of compound 1-A.

The organic layer was stirred at an internal temperature of 8 to 20 ° C., 30.6 g of bromine (0.191 mol, 1.03 equivalent to 4 equivalent coupler) was mixed with 60 ml of dichloromethane and added dropwise over 10 to 20 minutes. The dropping funnel was washed with 10 ml of dichloromethane and further reacted for 1 minute. After 352 ml of water was added, the mixture was extracted, washed with water, and then separated, and the organic layer containing bromide was collected in a dropping funnel.

74 g (0.316 mol, 1.
80 equivalents) of 1-benzyl-5-ethoxyhydantoin,
64 ml of dichloro-methane and 30.2 of triethylamine
g (0.298 mol) was stirred and dissolved at an external temperature of 16 to 22 ° C, and the bromide solution was added dropwise over 2 hours while keeping the internal temperature at 30 ° C or lower.
The dropping funnel was washed with 1 and further reacted for 2.5 hours or more. Dissolve 15.8 g of sodium hydroxide in 480 ml of water to prepare an alkaline solution.

300 ml of this alkaline solution was added to the reaction solution, and after stirring for 5 minutes and standing 20 minutes, the solution was separated. 180 ml of alkaline water was added to the organic layer for extraction and liquid separation. Continuing,
The organic layer is 176 ml of water, 32 ml of concentrated hydrochloric acid and 350 m of water.
1, and then 350 ml of water were successively used to wash with water.

The organic layer subjected to the above treatment was concentrated under reduced pressure and dried to obtain the desired coupler concentrate. Yield 136.
It was 4 g (yield 97.0%). The analysis results by high performance liquid chromatography were as follows.

Starting Material (Compound 1-A) 1.4% Target 97.1% By-product (4-bromo) 0.7% Example 4 α-pivaloyl-α- (5-dimethyl-3-hydantoinyl) ) -2-Chloro-5- [2- (2,4-di-tert-
Synthesis of amylphenoxy) butyramide] -acetanilide (Compound 4) Compound 1-A 100 g (0.175 mol) was added to dichloromethane 13
Dissolve in 2 ml and stir at an internal temperature of 8-20 ° C. Bromine 2
8.2 g (0.176 mol, 1.007 equivalent to 4 equivalent coupler) was mixed with 52 ml dichloromethane and added dropwise over 10 to 20 minutes.

The dropping funnel was washed with 10 ml of dichloromethane and further reacted for 1 minute. After 352 ml of water was added and the mixture was washed with water and separated, the organic layer containing bromide was collected in a dropping funnel. 40.2 g (0.316 mol, 1.80 equivalents relative to compound 1-A) 5,5-dimethylhydantoin, 28% NaOMe in 66 ml dichloromethane 57.
4 g (0.298 mol) are added and stirred at an external temperature of 16-26 ° C. A bromide solution was added dropwise to this solution over 2 hours while maintaining the internal temperature at 30 ° C. or lower. After the completion of the addition, the dropping funnel was washed with 10 ml of dichloromethane and the reaction was continued for 4 hours.

A solution prepared by dissolving 2 g of sodium hydroxide in 300 ml of water is added to the reaction solution, and the solution is extracted and separated. Next, concentrated hydrochloric acid 3
2 ml, 300 ml of water, and then 300 ml of water were successively used for washing with water. 150 ml of ethanol was added to the residue obtained by concentrating the organic layer subjected to the above treatment under reduced pressure, and the mixture was heated and dissolved, then cooled and crystallized. After further cooling to an internal temperature of 5 ° C or lower to precipitate crystals, the crystals were filtered and dried. The target compound 4 has a melting point of 102 to 109 ° C. and a crystal yield of 112.3.
g (yield 92%).

When the obtained target product was analyzed by high performance liquid chromatography, the following results were obtained.

Starting Material (Compound 1-A) 1.5% Target 97.4% By-product (4-Bromide) 0.9% Example 5 α-pivaloyl-α- (1-methyl-5-hexyl) Synthesis of oxy-3-hydantoinyl) -2-methoxy-5-tetradecyloxycarbonylacetanilide (Compound 8) 60 g (0.123 mol) of α-pivaloyl-2-methoxy-5-tetradecyloxycarbonylacetanilide was dissolved in 120 ml of dichloromethane. Stir at an internal temperature of 8-20 ° C. Bromine (19.5 g, 0.122 mol, 0.99 equivalents based on 4 equivalent coupler) was mixed with 20 ml of dichloromethane and added dropwise over 20 minutes. The dropping funnel was washed with 10 ml of dichloromethane and further reacted for 1 minute. After 330 ml of water was added and the mixture was extracted, washed with water, and separated, the organic layer containing bromide was collected in a dropping funnel.

35 g (0.163 mol, relative to 4 equivalent coupler)
1.35 equivalents) of 1-methyl-5-hexyloxyhydantoin, 45 ml of dichloromethane and 1 of triethylamine
A solution of 6.7 g (0.165 mol) dissolved with stirring at an external temperature of 16 to 22 ° C. was added dropwise with a bromide solution over 1 hour, and after completion of the dropping, the dropping funnel was washed with 10 ml of dichloro-methane,
The reaction was continued at an external temperature of 45 ° C. for 2.5 hours.

An alkaline solution prepared by dissolving 4 g of sodium hydroxide in 260 ml of water was added to the reaction solution, and after stirring for 5 minutes, 15 ml of concentrated hydrochloric acid was added, and the mixture was extracted and separated. Furthermore, 250m of water
1 was added and washed with water. 220 ml of methanol was added to and dissolved in the residue obtained by concentrating the organic layer subjected to the above treatment under reduced pressure, and cooled while stirring to precipitate crystals. After cooling to an internal temperature of 0 ° C. or lower for 1 hour, the precipitated crystal was filtered, and the obtained crystal was washed with 30 ml of cooled methanol and dried. The target compound 8 was obtained as crystals with a melting point of 88 to 90 ° C. and a yield of 76.9 g (yield 89.4%).

The target product thus obtained was analyzed by high performance liquid chromatography. The results were as follows: raw material (4 equivalent coupler) 1.1% target product 98.9% by-product (4-bromo compound) ) 0.0% Comparative Example 1 Compound 2 was synthesized according to Example 1 without diluting bromine Compound 1-A 100 g (0.175 mol) was added to dichloromethane 1
Dissolve in 32 ml and stir at an internal temperature of 8-20 ° C. 28.2 g of bromine (0.176 mol, 1.007 equivalent to 4 equivalent coupler) was added dropwise from the dropping funnel over 10 to 20 minutes. The dropping funnel was washed with 5 ml of dichloromethane and further reacted for 1 minute. After 352 ml of water was added, the mixture was extracted, washed with water, and then separated, and the brominated organic layer was collected in a dropping funnel.

74 g (0.316 mol, 1.
80 equivalents) of 1-benzyl-5-ethoxyhydantoin,
64 ml of dichloromethane and 30.2 g of triethylamine
(0.298 mol) was stirred and dissolved at an external temperature of 16 to 22 ° C, and the bromide solution was added dropwise over 2 hours while keeping the internal temperature at 30 ° C or lower.
The dropping funnel was washed with 1 and reacted for 3 hours.

15.8 g of sodium hydroxide and 480 m of water
The alkaline solution dissolved in 1 is prepared in advance. 300 ml of this alkaline solution was added to the reaction solution, and after stirring for 5 minutes, the solution was allowed to stand for 20 minutes for partitioning. 180 ml of alkaline water was added to the organic layer for extraction and liquid separation. Subsequently, the organic layer is 176 m of water.
1, 32 ml of concentrated hydrochloric acid and 350 ml of water, 350 m of water
1 was sequentially used and washed with water. The organic layer subjected to the above treatment was concentrated under reduced pressure, dried, pulverized, and taken out to obtain 138.6 g (yield 98.6 g) of a concentrate powder of a target coupler.
%).

The target product thus obtained was analyzed by high performance liquid chromatography.
The raw materials and the by-product 4-bromo compound increased, and the purity of the target product decreased.

Raw Material (Compound 1-A) 3.1% Target 92.6% By-product (4-Bromide) 3.9% As is apparent from the above comparative examples, the bromination reaction without diluting bromine. In the case of carrying out, the amount of 4-bromo compound as a raw material or by-product was increased, resulting in a decrease in purity and a decrease in yield as compared with the examples of the present invention.

[0069]

As described above, according to the present invention, a solution of a bromide obtained by substituting one hydrogen atom of an active methylene group of a 4-equivalent yellow coupler with bromine is washed with water, and an isolation step is required. It can be used as it is for the production of a 2 equivalent yellow coupler, and since bromine diluted in a solvent is added dropwise to the reaction system, a high yield of a high purity 2 equivalent yellow coupler with few by-products is obtained. Obtainable.

Claims (5)

[Claims] 1. A hydrogen atom of an active methylene group of the 4-equivalent yellow coupler is prepared by dissolving 4-equivalent yellow coupler in a halogen solvent or an ester solvent, and then adding bromine diluted with the same solvent as these solvents. A method for producing a 4-equivalent yellow coupler bromide, characterized in that one atom is replaced with bromine, and the resulting bromide solution is washed and separated. 2. A method in which a 2-equivalent leaving group and a base are dissolved in a halogen-based solvent or an ester-based solvent and then a solution of 4-equivalent yellow coupler active methylene bromide dissolved in the same solvent as these solvents is added and reacted. Characterized by 2
Equivalent yellow coupler manufacturing method. 3. The method according to claim 1, wherein the halogen-based solvent or ester-based solvent is dichloromethane or ethyl acetate. 4. A method for producing a 2-equivalent yellow coupler, wherein a solution of an active methylene bromide of a 4-equivalent coupler obtained by the production method according to claim 1 is used in the production method according to claim 2. 5. A 2-equivalent yellow coupler has the following formula (1):
The method for producing a 2-equivalent yellow coupler according to claim 2 or 4, wherein Embedded image (In the formula, R ₁ represents a chloro atom or an alkoxy group, and R _1
2 represents an acylamino group or an alkoxycarbonyl group, R ₁₁ represents a hydrogen atom or an alkyl group, R ₁₂ and R ₁₃
Represents a hydrogen atom, an alkyl group or an alkoxy group. However, R ₁₂ and R ₁₃ may be the same or different. )