JPH03110554A - Production of amidophenols - Google Patents

Abstract

PURPOSE:To obtain the amidophenols of high purity at a high yield by a simple precipitation method by effecting an amidization reaction in a heterogeneous system of an org. solvent added with an org. solvent which is not miscible with water and an aq. alkaline soln., then adding a lean solvent to an org. solvent layer in the reaction liquid separated to two layers. CONSTITUTION:The 2-amino phenols or the 5-amino-2-amide phenols and carboxylic acid halide are brought into reaction in the heterogeneous system consisting of the polar solvent added with the org. solvent which is not miscible with water and the aq. alkaline soln. to form the amidephenols; thereafter, the lean solvent is added to the separated org. solvent layer to settle the amidephenols. Thus, the amidephenols formed by the reaction of the aminophenols and the carboxylic acid halide are obtd. with the high purity at the high yield. In addition, the reaction time is short and the amidephenols are obtd. with the simple operation without using a special reaction vessel.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing amide phenols used in photographic chemicals, and more specifically, to a method for producing amide phenols used in photographic chemicals, and more specifically, a method for producing a highly purified target product in a simple manner and in a high yield. The present invention relates to a method for producing amidophenols.

[Conventional technology]

When producing amide phenol compounds, which are generally used as chemicals for color photography, it is common to utilize a reaction between an amino compound and an acid halide. For example, JP-A No. 60-24547 describes an example of the reaction between 5-amino-2-amidophenol and an acid halide.
5-amino 2-amidophenol was suspended in acetonitrile and ethyl acetate, and acid halide was added dropwise over 1 hour. The mixture was heated under reflux for 4 hours, cooled, and the crystals were collected by filtration. The desired amide compound was obtained by recrystallization. Furthermore, in JP-A No. 61-69065, 5-amino-2-amidophenol is dissolved in dimethylacetamide, carboxylic acid halide is added dropwise to react it, and after stirring the reaction product at room temperature, water and ethyl acetate are dissolved. The desired amide phenol compound was extracted with ethyl acetate, and the ethyl acetate layer was washed with water and then soaked with N.
The desired amide phenol compound is obtained by condensing the mixture, heating and dissolving this concentrate in methanol, and crystallizing it.

However, the production method described in JP-A No. 60-24547 requires a long reaction time and a high temperature reaction, so impurities are produced as by-products and the content of the target product decreases, requiring recrystallization. Since the HCI gas produced as a by-product is not neutralized or removed, corrosion of equipment becomes a problem in post-processing steps such as crystallization, filtration, and drying, and the yield of the target product is also 60%.
The degree is low.

In addition, the production method described in JP-A No. 61-69065 involves extracting and washing the reaction product with water and ethyl acetate to first remove dimethylacetamide, a good solvent, and the acid component, and then concentrating the ethyl acetate layer. The target amide compound is obtained by substitutional crystallization with methanol, which is a poor solvent. However, this production method does not perform neutralization during extraction, so acid content remains and corrosion of equipment occurs in the post-processing process. In addition, it is complicated in terms of work because it requires concentration of the ethyl acetate layer and replacement with a poor solvent. Also, there is a large loss to the crystallization filtrate, and the yield is 84%.
and low.

[Problem that the invention seeks to solve]

The present invention aims to obtain amide phenols produced by the reaction of aminophenols and carboxylic acid halides with high purity and high yield, and moreover, requires a short reaction time, and uses simple operation and a special reaction vessel. To provide a manufacturing method suitable for mass production by boat fishing, to obtain amide phenols without having to do so.

[Means to solve the problem]

The method for producing amidophenols of the present invention is to prepare 2-aminophenols or 5-amino-2-amidophenols and a carboxylic acid halide from a polar solvent and an alkaline aqueous solution to which a water-immiscible solvent is added. The method is characterized in that after reacting in a heterogeneous system to produce amide phenols, a poor solvent is added to the separated organic solvent layer to precipitate the amide phenols.

The present invention will be explained in detail below.

2-aminophenols or 5-amino-2-amidophenols are represented by the following formula (1) X (wherein R is -NH!(・M)n or -N HCORt
W is a hydrogen atom; (・M),.

Z is hydrogen or a halogen atom; Rz and Rx may be the same or different and each represents an alkyl group, an aryl group, or a heterocycle; M is an acid capable of forming a salt with an amino group; n is 0 or 1 ) Aminophenols have one hydroxyl group and one free amino group, in addition to 1OH, which can be substituted on the benzene nucleus.
-NH! It may have any substituent other than. The amino group may also be in the form of a salt, and M is a mineral or organic acid.

Further, the carboxylic acid halide is represented by the following formula (n).

R, COX...(I[)(
In the formula, R1 represents an alkyl group, and X represents a halogen atom. ) The number of carbon atoms contained in the carboxylic acid halide is 1 to 30, preferably represented by the formula (U>), and the halogen atom constituting the halide is preferably chlorine.

The alkyl group of R8 may have a substituent.

The substituent is preferably a substituent that hardly reacts with carboxylic acid halide. Examples of these preferred substituents are an aryoloxy group, an arylthio group, an arylthio group, a halogen atom, and a hydroxyl group.

The generated amide phenols have the following formula (I[[)% formula% (in the formula, R' is -NHCOR, or -NHCORt
Y'' is -NHCO when the above R'' is -NHCOR.
When R or the lower alkyl group R is -NHCORl, it represents -NHCOR, and the others are the same as in formulas (+) and (II) above. ) is a compound represented by

Formulas (1) to (I[I) will be explained in more detail. In these formulas, the alkyl group represented by Rt, Rj or R2 may be linear, branched or cyclic, and also includes N-substituted alkyl groups. Here, substituents include halogen atoms (e.g. 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-butyldecanamide, cyamylphenoxyacetamide, octadecyloxybenzamide, pentadecylphenoxybutanamide) ), carbamoyl group (e.g. N
, N-diethylcarbamoyl, N-hexadecylcarbamoyl, N-tetradecyloxyphenylcarbamoyl, N-butyl-N-dodecylcarbamoyl, N-cyamylphenoxyphenylcarbamoyl), alkoxycarbonyl groups (e.g. ethoxycarbonyl, dodecyloxycarbonyl, ethoxycarbonylpentadecyloxycarbonyl), oryl groups (e.g. phenyl, tridecylcarbonylphenyl, N-tetradecylsulfonylphenyl, cyamylphenoxyacetamidophenyl, hexadecyloxyphenyl, ethoxycarbonyldodecyloxyphenyl, methoxycarponylheneico) Sanamidophenyl, octadecylsuccinimidophenyl)
, heterocyclic groups (for example, N-dodecyl phenylsuccinimide, dodecylsuccinimide, octadecylcarbamoylphthalimide), and the like.

The aryl group represented by R2 or R4 in the above-mentioned -spelling allowance (f) or (il+) also includes a substituted -l group. 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 ( For example, amylphenoxybutanamide, amylphenoxybenzamide, di(methoxycarbonyl)phenylcarbamoylpentanamide, di(methoxycarbonylmethoxy)benzamide), sulfamoyl group (e.g. di(methoxycarbonyl)phenylsulfamoyl, octadecylsulf 1 moyl), etc. can be mentioned.

In the above-mentioned binding allowance (1) or (I[l), W.

Y and Z may be the same or different, and each represents a hydrogen atom,
Halogen atoms (e.g. chlorine atom, bromine atom), alkyl groups (e.g. methyl, octyl, pentadecyl), aryl groups (e.g. phenyl, amyl phenyl), alkoxy groups (e.g. methoxy, dodecyloxy), carbonamide groups (e.g. acetamide, benzamide) , dodecaneamide, cyamylphenoxyacetamide, chlorosulfonylbenzamide, amylbenzamide, furylamide, di(methoxycarbonyl)phenylcarbamoylpentanamide, pentadecylphenoxybutanamide, tetrafluoropropanamide, perfluorooctaneamide, butylhydroxyphenoxytetradecanamide, dodecyloxyphenoxyacetamide, dodecafluorohebutanamide benzamide), sulfonamide groups (e.g. methylsulfonamide, dodecylsulfonamide, phenylsulfonamide, N-dodecanamide phenylsulfonamide), carbamoyl groups (e.g. N,N
-diethylcarbamoyl group, N-butyl-N-dodecylcarbamoyl, phenylcarbamoyl), or sulfamoyl (methylsulfamoyl, octylsulfamoyl, N,N-diethylsulfamoyl, phenylsulfamoyl).

In addition, in the above-mentioned (1) or (II), X represents a hydrogen atom or a Campling leaving group.

Here, the term "campling separation group" is a term commonly used in the field of photographic color-forming couplers.
Photographic color-forming couplers include atoms or groups that can be dissociated upon campling with the oxidation products of color developing agents (e.g., aromatic-grade amine developing agents). Examples of campling leaving groups include halogen atoms (e.g. chlorine atoms,
fluorine atom, iodine atom), alkoxy groups (e.g. methoxy, propoxy, methoxyethoxy, methylsulfamoylethoxy, N-propylaminopropoxy), aryloxy groups (e.g. phenoxy, ethylphenoxy, chlorophenoxy, nitrophenoxy, aminophenoxy, butyloxy) carbonyloxy groups (e.g. acedeloxy, butyroyloxy, benzoyloxy, amylbenzoyloxy, stearoyloxy, ethoxycarbonyloxy, phenoxycarbonyloxy, carbamoyloxy, methylcarbamoyloxy) , phenylcarbamoyloxy), sulfonyloxy groups (e.g. methylsulfonyloxy, ethoxyethylsulfonyloxy,
N-methylaminoethylsulfonyloxy, methylsulfonylpropylsulfonyloxy), sulfonamide groups (e.g. ethylsulfonamide, butylsulfonamide, nonylsulfonamide, phenylsulfonamide, naphthylsulfonamide), arylazo groups (e.g. phenylazo, naphthylazo), Alkylthio groups (e.g. methylthio, ocdylthio), arylthio groups (e.g. phenylthio, nitrophenylthio), heterocyclic thio groups (
Examples include tetrazolylthio, benzthiazolylthio, benzoxazolylthio), heterocyclic groups (eg, triazolyl, benztriazolyl), and cyclic imide groups (eg, succinimide, phthalimide).

2N), the preferred combination is R=N+(z
(-M), 1 W=H X=01, or leaving group Y=methyl or ethyl group z=x=c I! or R= -N HCORz W=H X=CZ, or leaving group Y=NH leaving at O or N
, (-M).

-H be.

A compound in which R+ and Rz in the above-mentioned binding margin are an unsubstituted alkyl group, an alkyl group partially or completely substituted with a fluorine atom, or a group represented by the following general formula (IV) or (V). Especially on Yoigetsu.

(In the formula, A is an alkyl group, R8 is a hydrogen atom or an alkyl group, R2 and R1 may be the same or different and each represents a hydrogen atom, an alkyl group, or an alkoxy group, and n represents 0 or 1. )(V) (In the formula, R4 and R1 may be the same or different and each represents an alkyl group.) The polar solvent used in the present invention is a liquid that has an electronic dipole fixedly inside the molecule. , which has a fairly large dielectric constant, and is preferably one that can dissolve the compound represented by the -C formula (I). Preferably, the liquid has a dielectric constant ε of 10 to 200 at 25°C. These liquids are
For example, Chemistry Handbook (revised 3rd edition, basic edition, pages 11-502) J, A.

Riddick[“Organic 5olvent
s (John Wiley & 5ons
.

(1986) can be easily identified. More preferable ε is 30-40. Dimethylformamide (No. 44)
2>DMF ε=36.71 and dimethylacetamide (No, 445) DMAC ε=37.78 are 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 used in an amount of at least 10% by volume, preferably 5-100% by volume.

The factor used is 0.1 to 100 parts by weight of the compound of general formula (+), preferably 0.1 to 100 parts by weight. 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 10% based on the compound represented by general formula (1).
0 parts by weight, preferably 1 to 10 parts by weight, particularly preferably 1.5 to 5 parts by weight.

The alkaline compound used in the reaction may be either sodium hydrogen carbonate or potassium hydrogen carbonate, and may or may not be dissolved in water.

The amount of the alkali compound to be used is 0.5 to 2 equivalents, preferably equivalent, to the compound represented by (1).

Moreover, if the compound represented by - Tsuzuriyo (1) 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 target amide.

Examples include lower alcohols, petroleum solvents such as n-hexane, acetonitrile, water, and the like. The lower alcohol has 1 to 10 carbon atoms, preferably methanol, ethanol, and isopropanol, particularly preferably methanol.

When using it, it is best to use it in the form of hydrous alcohol or acetonitrile, and the amount of alcohol and water is determined by the amount of O,1 to acetic acid esters, which are aqueous solvents that are immiscible with water.
The amount is 10 parts by weight, preferably 0.3 to 4 parts by weight, particularly preferably 0.3 to 2 parts by weight.

In the present invention, first, the aminophenol or its mineral acid salt shown in (1) 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. Next, an acid halide represented by (II) is added and reacted. The amount of acid halide is 0.5 to 2.0 equivalents relative to the aminophenol, but considering cost merit and reactivity, it is 1.0 to 1.2 equivalents, and particularly preferably ``substantially equimolar amount''. ” 1,
It is 0 to 1.02 points.

Further, the reaction temperature is preferably -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 completed, stirring is stopped, the aqueous layer is separated into two layers, and an alcohol and water are added to the aqueous medium layer to precipitate the desired amide compound.

Specific examples of aminophenols produced by the method of the present invention are shown below. However, the present invention is not limited only to these compounds.

(Margin below) however, In the table below (t) CsH lower shows.

() n is the number of carbon atoms in the alkyl group, Also (n.

2) 2 in is, (n.

2) Based on represents a substituent Z.

[Operation and effect of the invention]

Generally, this type of amidation reaction proceeds almost quantitatively in a short time, but the reaction was carried out in a heterogeneous system of an aqueous alkaline solution and an organic solvent to which an organic solvent immiscible with water was added, and then separated into two layers. By adding a poor solvent to the organic solvent layer in the reaction solution, the removal of side reaction products by recrystallization becomes unnecessary, and the target product can be obtained with high purity and good yield by a simple precipitation method. 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 phenolic cyan couplers. It is.

EXAMPLES The present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

[Example 1] Synthesis of 5-methyl-4,6-dichloro-2-[α(2,4-di-tert-amylphenoxy)butyramide]phenol (Compound 1).

17.2 g of 5-methyl-4,6-dichloro-2-aminophenol hydrochloride, 10-end β of dimethylacetamide,
Fifty percent of ethyl acetate was added to 20% aqueous sodium bicarbonate solution 74-1 to adjust the pH to 5.7, followed by stirring under a nitrogen atmosphere.

Then α-(2,4-di-tert-amylphenoxy)
25.4 g (1 equivalent) of butanoyl chloride was added at 10°C.
The mixture was added dropwise over a period of 30 minutes.

After this, dissolve by heating, discard the aqueous layer left standing, and methanol 8
0 ml of water was added thereto, and further 40 ml of water was added at 35°C, cooled at 5°C for 1 hour, filtered, and 36 g of white crystals of Compound 1 (
y=97%) was obtained.

Melting point: 149.5-152°C Elemental analysis value: Actual value H: 7.51%C:
65.65% N: 2.81% C1l: 14.30% Calculated value H: 7.54% C: 65.58% N: 2° 83% CI: 14.34% [Example 2] 5-ethyl -Synthesis of 4,6-dichloro-2-hexatecanoylamidophenol (compound 5) 5-ethyl-4,
6-dichloro-2-aminophenol hydrochloride 18.2g
, dimethylacetamide 20I111, ethyl acetate 9
The mixture was added to 100 mff of a 1.8% sodium hydrogen carbonate aqueous solution and stirred under a nitrogen atmosphere.

Next, 20.6 g of hexadecanoyl chloride (1 portion was added dropwise over 15 minutes at 20°C or lower. After 30 minutes of reaction, it was heated and allowed to stand. After separating and removing the aqueous layer, the organic solvent layer Add 40 ml of methanol to the solution, then add 3 ml of water at 30°C.
01111 was added dropwise. The mixture was cooled to 5° C. and crystallized for 30 minutes to obtain 32.2 g of white crystals of Compound 5 (y=98%).

Melting point near 7.5-79°C Elemental analysis value: Actual fiH: 8.80%C: 6
5.01% N: 3.12% 01:15.90% Direct calculation H: 8.84 %C:
64.85% N: 3.15% C1: 15.95% [Example 3] 2-(4-cyanophenyl)ureido-5[α-(2,
Synthesis of 4-di-tert-amylphenoxy)hexylamidocyphenol (Compound 21).

2- (4-cyanophenyl)urei 1! -34.4 g of 5-aminophenol was added to 35 m of dimethylacetamide.
! , 120ml of ethyl acetate, added to 140*ffi of 20% aqueous sodium bicarbonate solution, stirred under nitrogen atmosphere,
Further α-(2,4-di-tert-amylphenoxy)
47.5 g (1.01 equivalents) of hexanoyl chloride was added dropwise at 25° C. or below over 30 minutes. After reacting for 30 minutes, the mixture was dissolved by heating, left to stand, and the aqueous layer was separated and removed, while 260 ml of methanol was added to the organic solvent layer, and then 155 mA of water was added dropwise at 35°C. After cooling with water, 1.
Separated by filtration, 71.3 g of white crystals of compound 21 (y = 91%
) was obtained.

Melting point: 185-189.5℃ Elemental analysis value: Actual value H near, 82% C: 12.05% N: 9.41% Calculated value H: 1.14% C near 2.21% N:9.35% Application to Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] (1) 2-aminophenols or 5-amino-2-
Amidophenols and carboxylic acid halides are reacted in a heterogeneous system consisting of a polar solvent containing an organic solvent immiscible with water and an alkaline aqueous solution to produce amidephenols, and then the separated organic solvent layer is A method for producing amide phenols, which comprises adding a poor solvent to precipitate amide phenols. (2) The method for producing amidophenols according to claim 1, wherein the polar solvent is dimethylacetamide or dimethylformamide, the organic solvent is ethyl acetate, and the poor solvent is hydrous alcohol. (3) The 2-aminophenols or 5-amino-
2-Amidophenols are represented by the following formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R is -NH_2(・M)_n or -NHCOR
_2, W is a hydrogen atom, X is hydrogen or a coupling-off group, Y is hydrogen, a lower alkyl group or -NHCOR_3 when the above R is -NH_2(M)_n group, Sometimes -NH_2(・M)_n, Z is a hydrogen or halogen atom, R_2 and R_3 may be the same or different, and each is an alkyl group, an aryl group or a heterocycle, M can form a salt with an amino group Acid, n represents 0 or 1. ) Furthermore, the carboxylic acid halide is represented by the following formula (II), R_1COX...(II) (In the formula, R_1 is an alkyl group, and X represents a halogen atom.) Furthermore, the amide phenol is represented by the following formula: 3. The method for producing amidophenols according to claim 1, wherein the compound is a compound represented by (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (R' in the formula is -NHCOR_1 or -NHCOR_2
Y' is -NHC when the above R' is -NHCOR_1
OR_3 or a lower alkyl group, When the above R' is -NHCOR_2, it represents -NHCOR_1, and the others are the same as the above formulas (I) and (II). )