JPH0463341A - Production of yellow coupler or intermediate thereof - Google Patents

Abstract

PURPOSE:To facilitate the production of benzamides and to enhance the yield and purity thereof by specifying the process for producing the benzamides. CONSTITUTION:The yellow coupler or the intermediate thereof is produced by bringing anilines and acid halide into reaction in a heterogeneous system consisting of a polar solvent added with an org. solvent which is not miscible with water and an aq. alkaline soln. to form the benzamides, then concentrating the org. solvent layer and taking out the benzamides or adding a poor solvent to the org. solvent layer to settle and separate the benzamides. The compd. of formula I is preferably used as the anilines. In the formula, R11 denotes halogen, alkyl group, etc.; R12 denotes a nitro group or the group of formula II; R13 denotes an aryl group or secondary or ternary alkyl, etc.; Z denotes hydrogen or elimination group.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing yellow couplers and intermediates thereof as photographic chemicals, and more specifically, a method for producing high-purity benzamides in a simple and high yield. The present invention relates to a method for producing a yellow coupler or an intermediate thereof.

(Prior art) When producing benzamide compounds, which are generally used as chemicals for color photography, it is common to use a reaction between an amino compound and an acid halide.
-249150 describes a reaction example of α-pivaloyl-(2-chloro-5-amino)acetanilide hydrochloride and an acid halide, but α-pivaloyl=(2
-Chloro-5-amino)acetanilide hydrochloride was suspended in acetonitrile, and acid halide was added dropwise under heating to reflux to react for 2 hours, then cooled and collected by filtration to obtain the desired amide compound in 90% yield. ing. Also, JP-A-2-616
In Publication No. 37, a solution of acid halide dissolved in dimethylacetamide is dissolved in α-pivaloyl-(2-chloro-5-
Add amino)acetanilide dropwise to a solution of acetonitrile at 80°C, react for 1 hour, cool on ice, extract with ethyl acetate/water, wash with water, dry the organic layer over magnesium sulfate, and concentrate under reduced pressure to obtain a residue. Later, isoproper tool/
The desired amide compound was crystallized using an n-hexane mixed solvent with a yield of 89%.

(Problems to be Solved by the Invention) However, the production method described in JP-A No. 60-249150 has a long reaction time (and is a high-temperature reaction, so impurities are produced as by-products and the content of the target product is reduced). Furthermore, since the hydrochloric acid gas produced as a by-product in the reaction is not neutralized or removed, equipment corrosion becomes a problem during post-processing steps such as crystallization, filtration, and drying.

In addition, in the production method described in JP-A-2-61637, the reaction product is extracted and washed with water and ethyl acetate to first remove the good solvent dimethylacetamide and the acid component, and then the ethyl acetate layer is concentrated. The desired amide compound is obtained by displacement crystallization using the poor solvent Impropatol/n-hexane, but as this production method does not perform neutralization during extraction, acid content remains and is removed in the post-processing step. corrosion of equipment;
Furthermore, the process is complicated because it requires concentrating the ethyl acetate layer and replacing it with a poor solvent. Further, there was a large loss to the crystallization filtrate, and the yield was still not sufficient.

Therefore, it is an object of the present invention to provide a process for producing benzamides that overcomes the drawbacks of these conventional methods.

(Means for Solving the Problems) The above object of the present invention is to react an aniline with an acid halide in a heterogeneous system consisting of a polar solvent and an alkaline aqueous solution to which an organic solvent that is immiscible with water is added, thereby producing a benzamide. A method for producing a yellow coupler or an intermediate thereof, which is characterized in that after producing a compound, the organic solvent layer is concentrated to take out the benzamide, or a poor solvent is added to the organic solvent layer to precipitate and separate the benzamide. achieved.

The present invention will be explained in detail below.

The anilines used in the present invention are preferably those represented by the following formula.

Rl+ (wherein R11 is a halogen atom (chlorine, bromine, fluorine,
iodine), an alkyl group or an alkoxy group, and RI2
represents a nitro group or R, COCHCON H- (R, represents an aryl group, a secondary or tertiary alkyl group, or a cyclic alkyl group), and Z represents a hydrogen atom or a combination with an aromatic primary amine developing agent. Indicates a group that leaves due to a coupling reaction. Moreover, in the formula, the amino group may form a salt with an acid. ) Also, examples of acid halides include those represented by the following formula.

R, COX -(II-a) (In the formula, RI represents an alkyl group and X represents a halogen atom.) Produced by the reaction of the compound of formula (1) above and the compound of formula (I[-a) Benzamides are represented by formula (m-a).

NHCOR.

(In the formula, R++, II2 and R1 have the same meanings as above.) The method of the present invention is an amidation reaction for connecting a ballast group in the production process of a yellow coupler or an intermediate thereof,
When the compounds of the above formulas (I), (II), and (m) are used, they are represented by the following scheme, and the yellow coupler core formulas (1) to (IllF) will be explained in more detail.

In formula (I), the halogen atom of R11 is preferably a chlorine atom, the alkoxy group is preferably a lower alkoxy group, more preferably methoxy or ethoxy, and the alkyl group is preferably a lower alkyl group, more preferably methyl, It is ethyl. Note that the term "lower" as used herein refers to a carbon number of 1 to 5.

R+s is preferably a phenyl group, tertiary alkyl or cyclic alkyl, more preferably (methoxy), t-
They are a butyl group and an optionally substituted cyclopropyl group. ).

The number of carbon atoms contained in the acid halide is 1 to 30, preferably represented by formula (II-a), and the halogen atom constituting the halide is preferably chlorine.

The alkyl group of R1 may have a substituent. The substituent is preferably a substituent that does not react with the carboxylic acid halide. Examples of these preferable substituents are an aryloxy group, an aryl group, an arylthio group, a halogen atom, and a hydroxy group.

The alkyl group represented by R1 in these formulas may be linear, branched, or cyclic, and also includes substituted alkyl groups.

Here, the substituent is a halogen atom (for example, a chlorine atom,
fluorine atom), alkoxy groups (e.g. methoxy, propoxy, amyloxymethoxy, octoxy, dodecyloxy, cyamylcyclohexyloxy, octadecyloxy), alkylthio groups (e.g. methylthio, butylthio, octylthio, dodecylthio, octadecylthio)
, aryloxy groups (e.g. phenoxy, amylphenoxy, cyamylphenoxy, pentadecylphenoxy,
Dodecyloxyphenoxy, chlorotetradecylphenoxy, octadecaneamidophenoxy, N-methyl-N
-octadecylsulfamoylphenoxy, di(methoxycarbonyl)phenoxy, dodecylsuccinimidophenoxy), carbonamide groups (e.g. N-butyldecaneamide, diamylphenoxyacetamide, octadecyloxybenzamide, pentadecylphenoxybutanamide), carbamoyl groups (e.g. N,N-diethylcarbamoyl, N-hexadecylcarbamoyl, N-tetradecyloxyphenylcarbamoyl, N-butyl-
N-dodecylcarbamoyl, N-cyamylphenoxyphenylcarbamoyl), alkoxycarbonyl groups (e.g. ethoxycarbonyl, dodecyloxycarbonyl, ethoxycarbonylpentadecyloxycarbonyl), aryl groups (e.g. phenyl, tridecylcarbonylphenyl, N-tetradecylsulfonyl) Phenyl, cyamylphenoxyacetamidophenyl, hexadecyloxyphenyl, ethoxycarbonyldodecyloxyphenyl, methoxylponylheneicosanamidophenyl,
octadecylsuccinimidophenyl), heterocyclic groups (eg, N-dodecylphenylsuccinimide, dodecylsuccinimide, octadecylcarbamoylphthalimide), and the like.

In the formula (I) or (I[I), when R13 is a phenyl group, substituted phenyl groups are also included. Examples of substituents here include alkyl groups (e.g. amyl, octadecyl), aryl groups (e.g. phenyl, tolyl), alkoxy groups (e.g. amyloxy), aryloxy groups (e.g.
phenoxy, amylphenoxy, cyamylphenoxy), carbonamide groups (e.g. amylphenoxybutanamide, amylphenoxybenzamide, di(methoxycarbonyl)phenylcarbamoylpentanamide, di(methoxycarbonylmethoxy)benzamide),
Sulfamoyl group (e.g. di(methoxycarbonyl)phenylsulfamoyl, octadecylsulfamoyl)
etc.

In the formula (I) above, Z represents a hydrogen atom or a coupling-off group. The term "coupling-off group" as used herein is a term commonly used in the field of photographic color-forming couplers, and is a term commonly used in the field of photographic color-forming couplers. It includes atoms or groups that can be separated upon coupling with. Examples of coupling-off groups include halogen atoms (e.g. chlorine, fluorine, iodine), alkoxy groups (e.g. methoxy, propoxy, methoxyethoxy, methylsulfamoylethoxy, N-propylaminopropoxy), aryloxy groups. (e.g. phenoxy, ethylphenoxy, chlorophenoxy, nitrophenoxy, amylphenoxy, butylcarbamoylphenoxy, ethylsulfamoylphenoxy, phenylsulfonylphenoxy, naphthyloxy), carbonyloxy groups (e.g. acetyloxy, butyroyloxy, benzoyloxy, amylbenzoyloxy) , stearoyloxy, ethoxycarbonyloxy, phenoxycarbonyloxy, carbamoyloxy, methylcarbamoyloxy, phenylcarbamoyloxy), sulfonyloxy groups (e.g. methylsulfonyloxy, ethoxyethylsulfonyloxy, N-methylaminoethylsulfonyloxy, methylsulfonylpropylsulfonyl) oxy), sulfonamide groups (e.g. ethylsulfonamide, butylsulfonamide, nonylsulfonamide, phenylsulfonamide, naphthylsulfonamide), arylazo groups (e.g. phenylazo, naphthylazo), alkylthio groups (e.g. methylthio, octylthio), arylthio groups ( (e.g. phenylthio, nitrophenylthio), 'heterocyclic thio groups (e.g. tetrazolylthio, penzthiazolylthio, penzoxalylthio), heterocyclic groups (e.g. triazolyl, penztriazolyl), cyclic imide groups (e.g. succinimide, phthalimide) etc.

Among formula (J), preferred compounds are nCIzHz, sOtC(2 In addition, in the method of the present invention, the following formula (n
-b) sulfonyl halides can be used.

R2So□X...(n-b) (In the formula, R2 represents an alkyl group, and X represents a herogen atom.

) The number of carbon atoms in R2, the type of halide, the fact that the alkyl group of R2 may have a substituent, examples of the substituent, etc. are the same as R2.

Preferred compounds in formula (n-b) are as follows.

O2 Ox The polar solvent used in the present invention is a liquid that has an electronic dipole fixed inside its molecules, has a fairly large dielectric constant, and dissolves the compound represented by formula (I). Something is desirable. Preferably, the liquid has a dielectric constant ε of 10 to 200 at 25°C. These liquids are described, for example, in the Chemical Handbook (revised 3rd edition, basic edition, page n-502) J,
A. Riddick edition “Organic 5olven”
ts-(John Wiley & 5ons, 198
6) can be easily identified. More preferable C is 30~
It is 40. Dimethylformamide (No. 442) D
MF t=36.71, and dimethylacetamide (
No, 445) DMACε=37.78 is most preferred.

Further, one or more types of polar solvents can be used as a mixture, and in this case, it is sufficient that ε of the mixture is within a specified range. The polar solvent is at least 10% by volume, preferably 15-100% by volume.
use.

The amount used is 0.1 to 100 parts by weight of the compound of formula (r), preferably 0.1 to 10 parts by weight, particularly preferably 0.3 to 2 parts by weight.

The organic solvent to be added is preferably a solvent that is immiscible with water, such as toluene or ethyl acetate, and the amount used is 0.1 to 100 parts by weight, preferably 1 part by weight, based on the compound represented by formula (I). ~10 parts by weight, particularly preferably 1
．． It is 5 to 5 parts by weight.

The alkaline compound used in the reaction may be either sodium hydrogen carbonate or potassium hydrogen carbonate (it may or may not be dissolved in water. The amount of the alkaline compound used is shown in formula (I). 0.5-2 for the compound
equivalent, preferably equivalent.

Furthermore, if the compound represented by formula (I) is an amine salt, it is desirable to add an amount of hydrogen carbonate to free it. This aqueous hydrogen carbonate solution may be added in batches or dropwise.

A poor solvent is a solvent that does not dissolve or hardly dissolves the amide, which is the target compound of the reaction.

Examples include lower alcohols, petroleum solvents such as n-hexane, acetonitrile, water, and the like. The lower alcohols have 1 to 10 carbon atoms, preferably methanol, ethanol, and impropatol, particularly preferably methanol. When used, it is preferable to use it in the form of hydrous alcohol or acetonitrile, and the amount of alcohol and water is 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight of the acetic acid ester, which is an organic solvent that is immiscible with water.
The amount is 3 to 4 parts by weight, particularly preferably 0.3 to 2 parts by weight.

In the present invention, first, the aminophenol represented by formula (I) or its mineral acid salt is added to a heterogeneous system in which a water-immiscible organic solvent and an alkaline aqueous solution are added to a polar solvent, and the mixture is stirred. Then, formula (II-a) or (n-b)
Add the acid halide shown and react. The amount of acid halide is 0.5 to 2.0 equivalent to aminophenol, but considering cost merit and reactivity, it is 1.0 to 2.0 equivalent.
1.2 equivalents, particularly preferably "substantially equimolar"
1,0 to 1.02 equivalents.

Moreover, the reaction temperature is -20°C to 40°C (preferably 0°C to 30°C).

Although there is no problem with the reaction time up to about 10 hours immediately after the addition of the acid halide, in consideration of productivity it is preferably within 1 hour.

After the reaction is complete, stirring is stopped and the aqueous layer that is separated into two layers is removed, concentrated and taken out, or an alcohol and water are added to the organic solvent layer to precipitate the desired amide compound.

Specific compound examples of benzamides produced by the method of the present invention are shown below. However, in the present invention, n indicates the number of carbon atoms in the alkyl group, and C (n
, z) is the substituent Z in the C(n,z) group
represents.

Also, specific examples of the above R3 are -C15Hs+, and L -CaFs, -(CF mountain H, etc.) can also be mentioned.

(Operations and effects of the invention) Generally, this type of amidation reaction proceeds almost quantitatively in a short time, but the reaction is carried out in a heterogeneous system of an organic solvent to which an organic solvent immiscible with water is added and an aqueous alkaline solution. Then, by concentrating and extracting the organic solvent layer of the reaction solution separated into two layers or adding a poor solvent, there is no need to remove side reaction products by recrystallization, and a simple precipitation method can be used with high purity and high yield. You can get what you want. In addition, extraction, neutralization, and liquid separation operations for deacidification and the associated extraction solvent concentration steps are no longer necessary, resulting in a significant cost reduction effect and making it a manufacturing method suitable for mass production of benzamide yellow couplers. It is.

(Examples) Hereinafter, the present invention will be explained by examples, but the embodiments of the present invention are not limited thereto.

Example 1 Synthesis of 4-[α-(2,4-di-tert-amylphenoxy)butyramide go-6-nidrochlorobenzene (Compound 1).

4-amino-6-nitro-chlorobenzene 34.4g
(0.2 mol), 110 ml of ethyl acetate, and 5 ml of dimethylacetamide were added to a 500 ml flask, followed by 126 d of an aqueous solution of 16.8 g of sodium hydrogen carbonate, and the mixture was stirred at room temperature. Next, 67.7 g (0
, 2 mol) was added dropwise over 30 minutes at a temperature below 10°C. After this, dissolve by heating, discard the aqueous layer, add 220 ml of methanol to the ethyl acetate layer, cool at 25°C for 30 minutes, and add 50 ml of methanol.
ml and 32ml of water were added and crystallized at 0℃ to obtain 90% of the target compound.
．． 1 g (y=95.1%) was obtained.

Elemental analysis value: Calculated value H: 7.43%C: 65.7
4% N: 5.90% Cρ near, 46% Actual value H: 7.50% C: 65.61% N: 5.82% C near, 55% Example 2 α-pivaloyl-[2-chloro −5−(α〜(2,4−
tert-amylphenoxy)butylaminode)]
Synthesis of acetanilide (compound 2).

26.8 g (0.1 mol) of α-pivaloyl-(2-chloro-5-amino)acetanilide was mixed with 80 ml of ethyl acetate.
1. Dimethylacetamide 5Tn [! was added to a 500 ml flask, and 63 ml of an aqueous solution of 8.4 g of sodium hydrogen carbonate was added and stirred at room temperature.
33.9 g (0.1 mol) of -di-tert-amylphenoxy)butanoyl chloride was added dropwise at 10° C. or lower over 30 minutes. Thereafter, the aqueous layer was discarded, the ethyl acetate layer was concentrated to dryness, and 57.0 g of the target compound (y=10
0%) was obtained.

Elemental analysis value: Calculated value H: 8.13% C: 69.51% N: 4.91% Cρ: 6.22% Actual value H: 8.15% C: 69.61% N = 4.89% Cρ: 6.20%

Claims (3)

[Claims] (1) Anilines and acid halides are reacted in a heterogeneous system consisting of a polar solvent containing an organic solvent that is immiscible with water and an alkaline aqueous solution to produce benzamides, and then the organic solvent layer is concentrated. Take out benzamides or
Alternatively, a method for producing a yellow coupler or an intermediate thereof, which comprises adding a poor solvent to an organic solvent layer to precipitate and separate benzamides. (2) The method for producing a yellow coupler or an intermediate thereof according to claim 1, wherein the polar solvent is dimethylacetamide or dimethylformamide, the organic solvent is ethyl acetate or toluene, and the poor solvent is a hydrous alcohol. (3) The method for producing a yellow coupler or an intermediate thereof according to claim 1, wherein the aniline is represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1_1 represents a halogen atom, an alkyl group, or an alkoxy group, and R_1_2 is a nitro group or ▲Mathical formula,
There are chemical formulas, tables, etc. ▼ (R_1_3 represents an aryl group, secondary or tertiary alkyl, or cyclic alkyl group), and Z is separated by a coupling reaction with a hydrogen atom or an aromatic primary amine developing agent. Indicates a group that Moreover, in the formula, the amino group may form a salt with an acid. )