JPH0959197A - Production of halogen-substituted phenolic compound using 1,3-dihalo-5,5-dimethylhydantoin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain the subject compound at low cost without using any halogen-based solvent harmful to the environment, useful as an organic material for color photographs, a photographic coupler or intermediate thereof, by using a specific compound. SOLUTION: The objective compound of formula II (R1 is a substitutable group; (n) is 1-4; X is X1 or X2 ; (m) is 1-3) is obtained by using a 1,3-dihalo-5,5- dimethylhydantoin of formula I (X1 and X2 are each Cl or Br) (pref. 1,3- dichlolro-5,5-dimethylhydantoin). The reaction solvent is pref. a solvent except halogen-based solvents (e.g. ethyl acetate, toluene, acetone, N,N- dimethylacetamide, acetic acid).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 1,3-dihalo-
The present invention relates to a method for producing halogenated substituted phenols using 5,5-dimethylhydantoin. Particularly, the present invention relates to a method for producing halogenated substituted phenols using 1,3-dihalo-5,5-dimethylhydantoin, which is effective when phenols are organic materials for photography and the reaction solvent is other than halogen type.

[0002]

2. Description of the Related Art In silver salt color photographic light-sensitive materials, silver halide which is sensed by light oxidizes a developing agent as an oxidant, and the oxidant thereof and a color-forming agent which is three kinds of organic materials contained in a film ( The so-called coupler is called "coupler" to form an image by forming a yellow, magenta and cyan dye image in the film by a coupling reaction. Of these photographic couplers, many cyan couplers have a substituted phenol structure. Phenolic cyan couplers have long been used as a 2-equivalent coupler capable of forming a dye image with at least two silver ions in order to form a dye image by coupling with an oxidized product of a developing agent. Therefore, a group called a coupling-off group is always substituted in the dye forming position.

As the coupling-off group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group is generally used. In the case of a leaving group other than a halogen atom, the introduction method thereof is the coupling position. A method of replacing a halogen atom by a nucleophilic substitution reaction is general. Therefore, halogenation is a very important step in the synthesis of phenol-based 2-equivalent cyan couplers, and the development of an inexpensive and safe halogenation method is due to recent regulations on the use of halogen-based solvents for environmental protection. Strongly desired. Some of the synthetic methods disclosed so far of 2-acylamino-5-alkyl-4,6-dichlorophenol, which is a typical photographic cyan coupler, are specifically exemplified below.

[0004]

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4-chloro-3-methyl or ethylphenol, which is a starting material in the above synthetic method and in the above synthetic method, is industrially available, and these are also obtained by chlorination of 3-methyl or ethylphenol or its analogs. can get. As can be seen from this example, halogenation (chlorination) of phenols is an important step in photographic cyan couplers.

As the halogenation method disclosed so far, a method of reacting with chlorine, sulfuryl chloride or hydrochloric acid / hydrogen peroxide in a halogen-based solvent such as dichloroethane or chlorobenzene (Japanese Patent Laid-Open No. 61-57536).
No. 3, JP-A-3-223235, and JP-A-4-29966).
Or a method of reacting with sulfuryl chloride in an organic acid such as acetic acid (Japanese Patent Laid-Open No. 1-271749, US Pat.
No. 4,194). Recently, the halogen-based solvent used in these methods has become extremely strict in terms of emission control in terms of environmental protection, and it is becoming difficult to use it on a commercial scale without special equipment. Sulfuryl chloride has a wider range of usable solvents than chlorine, but it produces sulfur dioxide, which is a toxic gas, and is similar to chlorine, but it produces hydrochloric acid and is unstable to acids. It cannot be applied to a substrate having such a group, and when an ester-based or amide-based solvent is used, the solvent is partially decomposed to make it difficult to recover the solvent.

As a method for solving these problems, imide-based halogenating agents such as N-chlorosuccinimide (NCS) can be considered, but these are expensive and it is not costly to replace chlorine or sulfuryl chloride with them. It was difficult.

[0008]

Thus, the halogenation step of substituted phenols is an important step in the production of, for example, photographic cyan couplers, but the halogenation step of chlorination or bromination is environmentally friendly. It is conceivable that the method of carrying out the method in a halogen-based solvent will not be industrially applicable in the near future because the restriction of No. 1 is strengthened. Therefore, an object of the present invention is to provide a low-cost halogenated substituted phenol which does not use a halogen-based solvent that is harmful to the environment, does not generate a harmful by-product, and enables recovery and reuse of the solvent. In the future, where environmental protection is becoming more and more important, it is possible to fully meet the requirements of environmental protection, and to provide cyan couplers for photography, which are important as color photographic organic materials, at low cost and with stability. It is to provide a method of supplying to.

[0009]

As a result of intensive studies to solve the above problems, the present inventors have used 1,3-, which is available as a disinfectant for pool water and cooling tower water, at low cost. It was found that halogenation of phenols proceeded smoothly by using a predetermined amount of dihalo-5,5-dimethylhydantoin and all of the above problems could be solved, and the present invention was completed based on this finding.

That is, the present invention provides (1) general formula (I)
A method for producing a halogenated substituted phenol represented by the general formula (II) using 1,3-dihalo-5,5-dimethylhydantoin represented by

[0011]

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(In the formula, X ₁ and X ₂ represent a chlorine atom or a bromine atom.)

[0013]

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(In the formula, R ₁ represents a substitutable group, and n
Represents an integer of 1 to 4. When n is 2 or more, they may be the same or different. X represents X ₁ or X ₂ . m represents an integer of 1 to 3. (2) The production method according to item (1), wherein the halogenated substituted phenol is an organic material for photography.
(4) The production method according to item (2), wherein the photographic organic material is a photographic coupler or a synthetic intermediate thereof.
A reaction solvent other than a halogen-based solvent is used, and the production method according to (1), (2) or (3), and (5) 1,3-dihalo-5 represented by the general formula (I). ，
5-dimethylhydantoin is 1,3-dichloro-5,5
-Dimethylhydantoin is provided, which provides the production method described in (1), (2), (3) or (4).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
1,3-dihalo-5,5-dimethylhydantoin is a compound represented by the following general formula (I), wherein X ₁ and X ₂
May be the same or different. Preferably X ₁ and X
₂ are the same. Particularly preferably, both X ₁ and X ₂ are chlorine atoms.

The substituted phenols will be described in detail.

Explaining the substituent R ₁ in detail, R ₁ represents an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aryloxy group, an acylamino group, a disubstituted amino group, a nitro group, a silyl group or a hydroxyl group. Except for nitro group and hydroxyl group, aliphatic hydrocarbon group has 1 carbon atom.
To 32 linear or branched alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl groups, wherein the aliphatic hydrocarbon oxy group has 1 to 1 carbon atoms.
32 represents a linear or branched alkoxy, cycloalkyloxy, aralkyloxy, alkenyloxy, cycloalkenyloxy or alkynyloxy group, the aryloxy group represents a phenoxy or naphthoxy group having 6 to 23 carbon atoms, and an acylamino group. Represents an alkanoylamino group having 1 to 32 carbon atoms, aryloylamino group, alkanesulfonylamino group or allenesulfonylamino group,
The di-substituted amino group is a C2-C32 N, N-dialkylamino, N-alkyl-N-arylamino, N, N-
Diarylamino, N-alkyl-N-acylamino,
It represents an N-aryl-N-acylamino group, and the silyl group represents a 3-substituted silyl group having 3 to 32 carbon atoms. These groups may have a substituent, and they are organic substituents or halogen atoms linked by a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom or a sulfur atom. These substituents are described in detail, for example, an alkyl group, an alkenyl group,
Alkynyl group, aryl group, heterocyclic group, cyano group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, Silyl group, aryloxycarbonylamino group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, A sulfonyl group, a sulfinyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

More specifically, R ₁ other than nitro group and hydroxyl group
For example, R ₁ is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, 3-cyclohexenyl, 2-propenyl, 2-propynyl, benzyl, methoxyethyl, ethoxy. Ethyl, t-butoxyethyl, phenoxyethyl, methanesulfonylethyl,
2-hydroxyethyl, 3- (3-pentadecylphenoxy) propyl, 4,4,4-trifluorobutyl, 3
An aliphatic hydrocarbon group such as-(2,4-di-aminophenoxy) propyl; for example, methoxy, ethoxy, isopropoxy, n-butyloxy, t-butyloxy, octyloxy, dodecyloxy, hexadecyloxy, 2-
Methoxyethoxy, 2-ethoxyethoxy, 2-dodecyloxyethoxy, 2-phenoxyethoxy, 3-cyclohexenyloxy, 2-propenyloxy, 2-propynyloxy, benzyloxy, 2- (4-t-amylphenoxy) ethoxy, 2- (4-nitrophenoxy)
Aliphatic hydrocarbon oxy groups such as ethoxy and 2- (2,4-dichlorophenoxy) ethoxy; for example, phenoxy,
2-methoxyphenoxy, 2-methylphenoxy, 3-
Methoxyphenoxy, 3-methylphenoxy, 4-methoxyphenoxy, 4-methylphenoxy, 2,4-dimethoxyphenoxy, 2,4-dimethylphenoxy, 4-
Methoxycarbonylphenoxy, 1-naphthyloxy,
An aryloxy group such as 2-naphthyloxy, 1-methoxy-2-naphthyloxy, 2-methoxy-1-naphthyloxy, 4-methoxy-1-naphthyloxy; for example, acetylamino, propionylamino, butyrylamino, isobutyrylamino. , Pivaloylamino, octanoylamino, palmitoylamino, stearoylamino, oleylamino, 3- (4-nitrophenyl) butanoyl, 2- (2,4-di- t -amylphenoxy) hexanoylamino, 2- (2,4 -Di- t- amylphenoxy) butyrylamino, 2- (2-chlorophenoxy) tetradecanoylamino, 2- (2-chloro-4-)
t -amylphenoxy) octanoylamino, 2- (2
-Cyanophenoxy) octanoylamino, 2- (2,2
4-di- t -amylphenoxy) -2-methylbutyrylamino, 2- (hexadecanesulfonyl) -2-methylbutyrylamino, methanesulfonylamino, ethanesulfonylamino, hexadecanesulfonylamino, benzenesulfonylamino, 2-octyl Acylamino groups such as oxy-5- t -octylbenzenesulfonylamino and 4-dodecyloxybenzenesulfonylamino; for example, dimethylamino, diethylamino, dioctylamino, octylmethylamino, dodecylmethylamino, N
-Methylphenylamino, N-methylacetylamino,
Di-substituted amino groups such as N-methyloctanoylamino, N-methylbenzoylamino; for example, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, dimethylphenylsilyl, t-butyldiphenylsilyl,
A silyl group such as triphenylsilyl.

R ₁ is preferably an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an acylamino group, a nitro group or a hydroxyl group, more preferably an alkyl or alkoxy group having 2 to 20 carbon atoms. Particularly preferred is an alkyl group having 2 to 9 carbon atoms, and of these, the most preferred is ethyl group.

N represents an integer of 1 to 4, preferably 2.

Preferred combinations of the substituents R ₁ when n is 2 are an alkyl group and an acylamino group, an alkyl group and a nitro group, or both acylamino groups.

The preferred substitution position of R ₁ is the ortho position or the meta position. In the compound represented by the general formula (II) obtained by the present invention, m is 1 to 3, but preferably 1 or 2. The substitution position of X is 2, with respect to the hydroxy group.
It is at least one of the 4th or 6th positions.

The halogenated substituted phenols represented by the general formula (II) are preferably photographic organic materials (including synthetic raw materials and intermediates). Substituted phenol-based organic materials for photography include dispersed oils, color-enhancing agents, color-mixing inhibitors,
The anti-fading agent or the photographic coupler, and their synthetic raw materials and intermediates are preferable, and the photographic couplers and their synthetic raw materials and intermediates are particularly preferable.

When the phenol represented by the general formula (II) is a photographic coupler or a synthetic raw material or intermediate thereof,
Specifically, they are 2-acylamino-5-alkylphenols or 2,5-diacylaminophenols, 3-
Alkylphenol, 3-alkyl-4-chlorophenol or 2-nitro-4-chloro-5-alkylphenol, 2-nitro-5-alkylphenol.

Specific examples of 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I) are shown below.

[0026]

[Chemical 6]

Specific examples of photographic organic materials represented by the general formula (II), particularly substituted phenols containing photographic couplers and synthetic raw materials / intermediates thereof are shown below, but are not limited thereto. is not.

[0028]

[Chemical 7]

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

[Chemical 12]

[0034]

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The conditions of the halogenation reaction with 1,3-dihalo-5,5-dimethylhydantoin of the present invention will be described in detail below. 1,3-Dihalo-5,5-dimethylhydantoin is industrially produced by halogenating 5,5-dimethylhydantoin, and is easily and inexpensively available as a disinfectant for pools and cooling towers. When X ₁ = X ₂ in the general formula (I), usually two halogens can be used. However, in the case of X ₁ ≠ X ₂ , a halogenated coupler using only the halogen on the imide nitrogen can be used. It is necessary to adjust so that it does not become a mixture, but this does not apply if it does not matter if it becomes a mixture. Generally, 1,3-dibromo- in which X ₁ = X _2.
5,5-Dimethylhydantoin (DMH-Br), 1,
3-dichloro-5,5-dimethylhydantoin (DMH
It is preferable to react with -Cl).

The 5,5-dimethylhydantoin produced as a by-product of the reaction is safe enough to be used as a feed for livestock (see “Fine Chemical Market Data '9
2 ", Vol. 2, 411, CMC), and no special precautions are required for disposal.

Of the two halogen atoms of 1,3-dihalo-5,5-dimethylhydantoin, the halogen atom on the imide group at the 3-position is generally more reactive, and both halogen atoms are halogenated. It is possible to use only the halogen atom at the 3-position without using it. At this time, 1-halo-5,5-dimethylhydantoin, which is a by-product, is reduced with sodium sulfite etc. before being discarded to give 5,5-dimethylhydantoin.
It is preferably discarded as dimethylhydantoin. 5,5-dimethylhydantoin, 1-halo-5,5
-Dimethylhydantoin is a compound that is almost neutral and has high water solubility, so if you want to remove it, you can easily remove it by washing with water and post-treatment.

The halogenation reaction conditions using DMH-Br and DMH-Cl will be described in detail. The amount used in the case of monohalogenation is 0.4 to 1.5 molar equivalents relative to 1 mol of the substituted phenols to be halogenated. And preferably 0.45 to 0.55 molar equivalents. General formula (I
In the production of the compound in which m is 2 or 3 in I), the reaction and the reaction may be carried out stepwise so as to introduce one halogen at a time, and in this case, the reaction is carried out at the same reaction ratio as the above monohalogenation. be able to. Also, 2 or 3 halogen atoms may be introduced onto the benzene ring in one reaction. In such a case, the amount of DMH-Br or DMH-Cl is 1.
Use 0 to 3.5 molar equivalents. As the reaction solvent, a halogen-based solvent, an ester-based solvent, an aromatic hydrocarbon-based solvent, a ketone-based solvent, an amide-based solvent, a carboxylic acid-based solvent, an alcohol-based solvent, water and the like can be used as a single solvent or a mixed solvent, and the remainder is used. Although not limited by the solvent, an ester solvent, an aromatic hydrocarbon solvent, a ketone solvent, an amide solvent and a carboxylic acid solvent are preferable from the viewpoint of environmental protection and a small number of side reactions. Particularly preferred solvents are ethyl acetate, toluene, acetone, N, N-dimethylacetamide (DMA
c) and acetic acid.

The amount of the reaction solvent used is such that DMH-Br or DMH-Cl which is a halogenating agent is first placed in a reaction vessel, and when a substrate such as a 4-equivalent coupler is dropped therein, the halogenating agent is not necessarily dissolved. It is not necessary that the amount is such that stirring is possible. Even if the halogenating agent is added, in the case of powder addition, an amount that can be stirred is sufficient. The solvent under such conditions is not a problem with any of the above solvents, but DMH-Br and DMH-C
When 1 is completely dissolved and it is desired to carry out the reaction by dropping it in a 4-equivalent coupler, it is preferable to use a ketone-based or amide-based solvent in view of the solubility of these halogenating agents.
In general, the method of dissolving in acetone or DMAc and dropping is often used because the amount of solvent is small.

It is known that the reactivity of DMH-Br with an aromatic ring compound is increased by an acid (Bull. C.
hem. Soc. Jpn. 67 1918 (199
4) In the case where the reaction is slow even in this reaction where there is no example of phenol, a Lewis acid or proton acid catalyst for promoting the reaction may be added. AlCl as Lewis acid
₃ , ZnCl ₂ or FeCl ₃ is preferable, and as the protic acid, sulfuric acid, perchloric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid or trifluoromethanesulfonic acid, trifluoroacetic acid, etc. Is preferred.
The amount used is 0.01 to 2.00 equivalents, preferably 0.1 to 1.0 equivalents, relative to the substrate.

The reaction temperature is -20 ° C to 120 ° C, preferably 10 ° C to 100 ° C, particularly preferably 1 ° C.
It is 0 to 40 ° C.

The post-treatment after the reaction is carried out by a method in which a usual organic reaction is carried out, and no special precautions are required. However, when the residual of the excess halogenating agent is not preferable, it is generally treated with sodium sulfite water. Target. It may be effective to treat with a small amount of a sodium salt solution in methanol. When performing extraction operation, by-product of washing with water
Dimethylhydantoin can be easily removed.

Isolation and purification of the halogenated compound is carried out by any one of column chromatography method, crystallization method or extraction method or a combination thereof depending on the nature.

[0044]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 3-Ethylphenol (Exemplified Compound (P-5)) 12.
3 g of 1,3-dichloro-5,5-dimethylhydantoin (DMH-Cl, Exemplified Compound (H-1)) (9.9 g, 0.05 mol) was added to 2 g (0.1 mol) of a toluene solution.
The mixture was divided into portions and added at room temperature. After stirring for 2 hours, extraction, washing with water, drying and concentration, the residue was purified to give 4-chloro-3.
-13.3 g of ethylphenol could be obtained. When the purity of the recovered toluene was examined by gas chromatography, it was 99% or more.

Example 2 In the same manner as in Example 1, 17.8 g of 2-t-butyl-5-ethylphenol (exemplified compound (P-12)) was chlorinated, and 2-t-butyl-4-chloro was obtained. It was possible to obtain 19.1 g of -5-ethylphenol.

Example 3 2-Amino-5-ethylphenol obtained by catalytic reduction of 5-ethyl-2-nitrophenol and chloritone palmitate were reacted by the Schotten-Baumann method,
Exemplified compound (P-21) was obtained. 200 ml of ethyl acetate
Disperse 26 g (0.133 mol) of DMH-Cl in
Stir, and in it, 50 g of (P-21) (0.133 mo
l) was added at room temperature. After stirring at room temperature for about 30 minutes, about 1
The reaction solution became pale yellow when heated under reflux for hours. Extraction
2,4-dichloro-
53 g (yield 90%) of 3-ethyl-6-n-hexadecanoylaminophenol could be obtained.

Example 4 Exemplified Compound (P-25) (US Pat. No. 5,214,194)
(Synthesized from 4-nitroaniline based on the method of No. 20) 20
In a solution of g (0.032 mol) in toluene (40 ml), 4.6 g (0.016 mol) of 1,3-dibromo-5,5-dimethylhydantoin (DMH-Br) was added.
It was dissolved in 5 ml of N-dimethylacetamide, and the mixture was stirred dropwise at room temperature. The product was extracted, dried, and concentrated by a conventional method, and the product was measured by NMR. As a result, almost pure (P-25) 4-bromo compound could be quantitatively obtained.

Example 5 4-chloro-5-ethylphenol (157 g, 1.0 m)
ol) is dissolved in 90% sulfuric acid 75 g, 90 g of mixed acid (98% nitric acid 40 g, 98% sulfuric acid 50 g) is added dropwise at 0 to 10 ° C., and 4-chloro-5-ethyl-2-nitrophenol (exemplified compound (P- 33)) was synthesized. Thus synthesized (P-33) was added to the reaction solution without isolation.
MH-Cl 118g (0.6 mol) was added, and 60-
Stirred at 70 ° C. By thin layer chromatography (P-3
After confirming the disappearance of 3), the reaction solution was poured into water, and the precipitate was filtered and isolated and purified, or the product crystallized after extraction with ethyl acetate or toluene was tested by NMR to find pure 2,4 180 g of -dichloro-3-ethyl-6-nitrophenol could be obtained.

Example 6 Exemplified compound (P-34) (2-amino-4-chloro-5 by nitration / reduction of 4-chloro-3-ethylphenol)
-Synthesizing ethylphenol and synthesizing it by acylation) 410 g (1.0 mol) of ethyl acetate 500
Dissolve in ml, in which DMH-Cl 98.5 g
(0.5 mol) was added and the mixture was heated under reflux for 1 hour. The reaction solution was washed twice with water, ethyl acetate was concentrated under reduced pressure, and the residue was tested by NMR to find that it was almost pure 2,4-dichloro-3-ethyl-6-n-hexadecanoylaminophenol. confirmed. When the purity of the distilled ethyl acetate was examined by gas chromatography, the presence of hydrolyzed acetic acid was hardly observed, and the purity was 99%.
It was found that more than% of ethyl acetate was recovered.

Example 7 237 g of the exemplified compound (P-35) (synthesized by sulfonating 4-chloro-3-ethylphenol)
(1.0 mol) was dissolved in acetic acid, and DMH-C was added therein.
102.5 g (0.52 mol) was added and heated to 50 ° C. When the reaction solution was concentrated under reduced pressure, the residue was 4,6-dichloro-5-ethyl-2-sulfophenol and 5,5-
It was a mixture of dimethylhydantoins.

Example 8 2-sec-tetradecanyl hydroquinone (P-3
9) 30.6 g (0.1 mol) was dissolved in a mixed solvent of 50 ml of acetic acid and 100 ml of ethyl acetate, and the mixture was stirred at room temperature. DMH-Cl 9.9g (0.5mol) in it
Was added in 3 portions, and the mixture was stirred for about 1 hour after the addition. Water was added for extraction, dried and concentrated. By purifying the residue by silica gel chromatography, 2-chloro-5-sec-tetradecanylhydroquinone was purified to give 2
It was possible to obtain 4.0 g.

Comparative Example 1 50 g (0.133 mol) of 5-ethyl-2-n-hexadecanoylamino-phenol (P-21) was stirred in 200 ml of ethyl acetate, and chlorine gas 1 was weighed therein.
8.9 g (0.266 mol) was slowly bubbled in below 25 ° C. After extraction, washing with water, drying, concentration, and recrystallization, 45 g of 2,4-dichloro-3-ethyl-6-n-hexadecanoylaminophenol was obtained (yield 76%).
I was able to get it. When the same reaction was carried out in dichloromethane, the yield was 88%. Thus, when chlorine was used as a chlorinating agent in ethyl acetate, the amount of by-products was large and the yield was low. The yield is DM shown in Example 3.
It is considerably lower than when H-Cl is used. On the other hand, D
When MH-Cl was used as the chlorinating agent, almost the same yield was shown regardless of whether ethyl acetate or dichloromethane was used as the solvent. Further, when ethyl acetate used in this comparative example was recovered, it had a considerable odor of acetic acid, and it was about 95% in purity test by gas chromatography. The recovered ethyl acetate in Example 3 had a purity of 99% or higher. The amount recovered was about 90% in this comparative example compared to the example.

Comparative Example 2 5.1 g (0.1% of bromine) was added to a solution of 20 g (0.032 mol) of the exemplified compound (P-25) in toluene (40 ml).
(032 mol) was slowly added dropwise at 0 ° C. The residue was extracted, dried, and concentrated by a conventional method, and the obtained residue was purified by column chromatography to obtain 17.8 g (yield 79%) of 4-bromo compound of (P-25). .
When the same reaction was carried out in 1,2-dichloroethane, the yield was 92%. Thus, the DM of the fourth embodiment
When brominating with bromine in toluene, a by-product was produced and the yield was lower than when H-Br was used. On the other hand, when DMH-Br was used, the quantitative reaction proceeded even when the reaction was carried out in 1,2-dichloroethane, and the same result as in toluene was obtained.

[0055]

INDUSTRIAL APPLICABILITY As described above in detail, according to the present invention, the halogenation step, which is an important reaction step in the synthesis of substituted phenols, especially the coupler of useful photographic organic material, is harmful to the environment. It became possible to carry out the process easily and at low cost without using a halogen-based solvent. Therefore, even in the future where environmental protection becomes more and more important, it is possible to inexpensively and stably supply an important coupler as an organic material for color photography, and the present invention is to solve a problem that is a trade-off in terms of environmental protection and cost reduction. It can be achieved, and its effect is great both socially and economically.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C07C 231/12 C07C 231/12 233/25 9547-4H 233/25 275/34 9451-4H 275/34 303 / 22 303/22 309/42 309/42 G03C 7/34 G03C 7/34

Claims (5)

[Claims] 1. A general formula (I) using 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I).
A method for producing a halogenated substituted phenol represented by I). Embedded image (In the formula, X ₁ and X ₂ represent a chlorine atom or a bromine atom.) (In the formula, R ₁ represents a substitutable group, n represents an integer of 1 to 4, and when n is 2 or more, they may be the same or different. X represents X ₁ or X _2. m Represents an integer of 1 to 3.) 2. The method according to claim 1, wherein the halogenated substituted phenols are photographic organic materials. 3. The method according to claim 2, wherein the photographic organic material is a photographic coupler or a synthetic intermediate thereof. 4. The production method according to claim 1, 2 or 3, wherein a reaction solvent other than a halogen-based solvent is used. 5. The 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I) is 1,3-dichloro-5,5-dimethylhydantoin. 3. The manufacturing method according to 3 or 4.