JPH0959250A - Production of compound having aromatic 5-membered ring structure containing nitrogen using 1,3-dihalo-5,5-dimethylhydantoin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply produce a compound, usable as a disinfectant for water in pools or cooling towers and useful as a photographic organic material by using a specific amount of a readily available dihalo-dimethylhydantoin at a low cost. SOLUTION: (A) A 1,3-dihalo-5,5-dimethylhydantoin of formula I (X1 and X2 are each Cl or Br) is used to halogenate (B) a compound having an aromatic 5-membered ring structure containing nitrogen (e.g. an aromatic 5-5 condensed ring compound such as a pyrazoloazole or a pyrroloazole, pyrrole, pyrazole or imidazole) is halogenated with X1 or X2 which is the halogen in the compound of formula I to afford (C) a compound of the formula A(X)n [A is the compound of the component (B)]; X is X1 or X2 ; (n) is an integer of 0-4]. A reactional solvent other than a halogen-based one is preferably used. A pyrazolon-5-one-based coupler, etc., are preferred as the compound of the formula which is the component (C).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 1,3-dihalo-
Nitrogen-containing aromatic 5 using 5,5-dimethylhydantoin
The present invention relates to a method for producing a halide of a compound having a member ring structure. Particularly, a halide using 1,3-dihalo-5,5-dimethylhydantoin, which is effective when the compound having a nitrogen-containing aromatic 5-membered ring structure is an organic material for photography and the reaction solvent is other than a halogen type. Manufacturing method.

[0002]

2. Description of the Related Art In silver salt color photographic light-sensitive materials, light-sensitive silver halide oxidizes a developing agent as an oxidant, and an oxidant thereof and a color-forming agent (coupler) which is three kinds of organic materials contained in a film. (Referred to as) is formed by forming a yellow, magenta, and cyan dye image in the film through a coupling reaction.

A compound having a nitrogen-containing aromatic 5-membered ring structure is often used for this photographic coupler. In particular, couplers that form magenta and cyan dyes (hereinafter referred to as magenta couplers and cyan couplers) often have such a structure.

In the past, as a magenta coupler, a 4-equivalent coupler which requires at least 4 silver ions to form a magenta dye image has been used, but in recent years, at least 2 has been used for the purpose of protecting silver resources. Two-equivalent couplers have been used which are capable of forming a dye image with a single silver ion. The feature of the 2-equivalent coupler is that it has a structure having a coupling-off group at the position where the oxidized product of the developing agent is coupled.

As the coupling-off group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an azolyl group or the like is generally used. The introduction method is a 4-equivalent coupler (the coupling position is unsubstituted). Introduction to a methylene group) is common. When the halogen atom is a coupling-off group, it is customary to introduce a coupling-off group by halogenating the 4-equivalent coupler, and for other leaving groups, halogenating the 4-equivalent coupler and subsequent nucleophilic substitution reaction. Is.

In any case, it is difficult to avoid the halogenation step for making the two equivalents. Halogenation is often performed in a halogen-based solvent. However, recently, due to environmental protection, the use of halogen-based solvents has been restricted, which makes it difficult to halogenate with a high reaction yield and at a low cost, compared with before.

As a method of solving this problem, for example, a method of enabling bromination using bromine in ethyl acetate is disclosed in JP-A-6-234666. Further, a method of performing chlorination with sulfuryl chloride in a solvent other than a halogen-based solvent such as ethyl acetate is disclosed in JP-A-4-230638.

However, these methods have the following problems. In halogenation using bromine or sulfuryl chloride, a strong acid gas such as HBr or HCl is generated. These acids decompose not a little acetic acid ester solvent, and lead to the formation of acetic acid and the like after the treatment. Since couplers are produced in large quantities as organic materials for photography, solvent recovery / reuse is essential from the viewpoint of cost reduction and environmental protection, but the inclusion of acetic acid makes recovery / reuse difficult. In other words, in simple distillation, acetic acid is inevitably mixed in the recovery solvent, so precision distillation is necessary.
The benefits of reuse are significantly reduced.

Further, the latter use of sulfuryl halide such as sulfuryl chloride has a problem of solvent decomposition,
As a problem before that, there was an essential defect that the generation of SO ₂ which is a toxic gas is accompanied, and there was a problem that it is desired to avoid the use from the viewpoint of environmental protection. A special device is required to prevent SO ₂ from being released into the atmosphere, which is also a factor of cost increase.

N-chlorosuccinic acid isides (NCS) and N-bromosuccinic acid are halogenating agents which do not have the above-mentioned problems and have few side reactions even when a halogen-based solvent is not used and which can be halogenated in a high yield. N-halosuccinic acid isides such as isid (NBS) are known, but these halogenating agents are expensive, and it is difficult to use them for mass production of photographic organic materials such as couplers.

[0011]

DISCLOSURE OF THE INVENTION The problem to be solved by the present invention is halogenation which is an essential step in the step of halogenating a compound having a nitrogen-containing aromatic 5-membered ring structure, for example, in the production of a photographic 2-equivalent coupler. The chemical process is to cope with the situation where environmental protection restrictions are tightened and may not be affordable in the near future. That is, an object of the present invention is to use an inexpensive nitrogen-containing aromatic compound 5 which does not use a halogen-based solvent which is unfavorable to the environment, does not generate harmful by-products, and can also recover and reuse the solvent. Providing a halogenation method for compounds having a membered ring structure, and supplying environmentally important magenta couplers or cyan couplers, which are important as organic materials for color photography, inexpensively and stably, even in the future when environmental conservation becomes more important To provide a method.

[0012]

As a result of intensive studies to solve the above problems, the inventors of the present invention used as a disinfectant for pool water and cooling tower water, and were available at low cost 1,3 -By using a predetermined amount of dihalo-5,5-dimethylhydantoin, it was found that halogenation of a compound having a nitrogen-containing aromatic 5-membered ring structure proceeds smoothly, and that all of the above problems are solved, Based on this, the present invention has been completed.

That is, the present invention provides (1) a process for producing a compound represented by the general formula (II), which comprises using 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I).

[0014]

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(Wherein, X ₁ and X ₂ represent a chlorine atom or a bromine atom, A represents a compound having a nitrogen-containing aromatic 5-membered ring structure, X represents X ₁ or X _2, and n is 0. Represents an integer of 1 to 4, preferably 1 to 4, particularly preferably an integer of 1, 2 or 3.), (2) nitrogen-containing aromatic 5
The method according to item (1), wherein the compound having a member ring structure is an organic material for photography, and (3) the organic material for photography is a coupler for photography. (4) The photographic coupler is pyrazoline-
A production method according to (3), which is a 5-one coupler or a pyrazolotriazole coupler.
(5) A method other than halogen type reaction solvent is used, (1), (2), (3) or (4) described in the production method, and (6) represented by the general formula (I) 1 , 3-Dihalo-5,5-dimethylhydantoin is 1,3-dichloro-5,5-dimethylhydantoin (1), (2), (3), (4) or (5). The present invention provides a manufacturing method described in the above item.

[0016]

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), and X ₁ and X ₂ may be the same or different, but preferably the same halogen atom. Particularly preferably, both X ₁ and X ₂ are chloro atoms.

In the reaction of the present invention, the compound A having a nitrogen-containing aromatic 5-membered ring structure is a halogen of 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I), X ₁ and X _2. Halogenated with A- (X) _n of the general formula (II)
It is to make it a halogen. The compound represented by the general formula (II) will be described in detail. A is a nitrogen-containing aromatic compound 5-5 such as pyrazoloazole or pyrroloazole.
A condensed ring compound and a benzene ring condensate thereof, or a nitrogen-containing aromatic 5-membered ring compound such as pyrrole, pyrazole or imidazole and a benzene ring condensate thereof.

Preferably, the compound represented by the general formula (II) is a photographic organic material, and when explained in detail, a pyrazoloazole-based nitrogen-containing aromatic 5-5 condensed ring compound or a pyrazole-based nitrogen-containing aromatic compound is used. The couplers for photographic use are 5-membered ring compounds, and the former are pyrazolotriazole, imidazopyrazole or pyrazolotetrazole couplers, and the latter are pyrazolin-5-one couplers.

Particularly preferably, the photographic coupler is a pyrazolotriazole or pyrazolin-5-one type coupler.

The pyrazolotriazole type coupler will be specifically described. 1 H -pyrazolo [1,5- b ] [1,2,4] triazole type coupler represented by the general formula (III) and the general formula (IV). 1 H -pyrazolo [5 represented by
1- c ] [1,2,4] triazole type coupler.

[0021]

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(In the general formula (III), R ₁ and R ₂ represent a hydrogen atom or a substituent. X represents X ₁ or X _2. )

[0023]

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In the general formula (IV), R ₃ and R ₄ represent a hydrogen atom or a substituent. X represents X ₁ or X ₂ . )

The substituent R ₁ in the general formulas (III) and (IV)
~ R ₄ will be described in detail below.

R _{1 to} R ₄ are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, Acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group Group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group, a silyl group or an azolyl group, and R _{1 to} R ₄ may be a divalent group to form a bis form.

More specifically, R _{1 to} R ₄ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, aralkyl). Group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy). Propyl,
3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamido} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl,
Cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), an aryl group (for example, phenyl, 4
-T-butylphenyl, 2,4-di-t-amylphenyl, 2,4,6-trimethylphenyl, 3-tridecanamide-2,4,6-trimethylphenyl, 4-tetradecanamidophenyl), heterocycle Group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2- Methoxyethoxy, 2-
Dodecylethoxy, 2-methanesulfonylethoxy),
Aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (eg, acetamide, benzamide, tetradecane) Amide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide) , An alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-). 5- Decyloxycarbonyl anilino, N- acetyl anilino, 2-chloro-5- {2-
(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipro). Pilsulfamoylamino, N-methyl-N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-t-butylphenoxy) propylthio), an arylthio group (eg, phenylthio, 2-butoxy-5-
t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, ,
Methanesulfonamide, hexadecanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5
t-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N
-{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (for example,
Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) , 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy). A carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryl Oxy carbonylamino group (e.g., phenoxycarbonylamino), an imido group (e.g., N- succinimido, N- phthalimido, 3
-Octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl), silyl group (eg trimethylsilyl, t-butyldimethylsilyl), azolyl group (eg imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁ and R ₂ are alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group,
Examples thereof include urethane group and acylamino group.

R ₃ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group,
Carbamoyl group, sulfamoyl group, sulfinyl group,
It is an acyl group or a cyano group. More preferably, it is an alkyl group, an aryl group or a heterocyclic group.

R ₄ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group or an acyl group, and more preferably , An alkyl group, an aryl group, a heterocyclic group,
It is an alkylthio group or an arylthio group.

More specifically, the pyrazolin-5-one type coupler is a pyrazolin-5-one type coupler represented by the following general formula (V).

[0032]

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In the general formula (V), R ₅ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group. A
r represents a phenyl group or a phenyl group substituted with one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. X represents X ₁ or X ₂ .

Each substituent in the general formula (V) will be described in detail. R ₅ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group. More specifically, the alkyl group is a linear or branched alkyl group having 1 to 42 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group or a cycloalkyl group. Group or cycloalkenyl group, the aryl group represents an aryl group having 6 to 46 carbon atoms, the acyl group represents an aliphatic acyl group having 2 to 32 carbon atoms or an aromatic acyl group having 7 to 46 carbon atoms, and carbamoyl The group has 2 to 32 carbon atoms
Represents an aliphatic carbamoyl group or an aromatic carbamoyl group having 7 to 46 carbon atoms. These groups may have a substituent, and they are an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

More specifically, R ₅ is an alkyl group (for example, methyl, ethyl, butyl, propyl, octadecyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, methoxyethyl, ethoxyethyl, t-butoxyethyl, phenoxyethyl, methanesulfonylethyl). Two
-(2,4-di-tert-amylphenoxy) ethyl), an aryl group (for example, phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-). Octadecenyl-1-succinimido) phenyl, 2-chloro-
5-octadecylsulfonamidophenyl, 5-hexadecanoamidophenyl, 2-chloro-5- [2- (4-
Hydroxy-3-tert-butylphenoxy) tetradecanamidophenyl]), an acyl group (eg acetyl, pivaloyl, tetradecanoyl, 2- (2,4-di-tert-pentylphenoxy) acetyl, 2-
(2,4-di-tert-pentylphenoxy) butanoyl, benzoyl, 3- (2,4-di-tert-amylphenoxyacetamido) bayzoyl), a carbamoyl group (for example, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-hexadecylcarbamoyl, N-
Methyl-N-phenylcarbamoyl, N- [3- {1-
(2,4-di-tert-pentylphenoxy) butyramide}] phenylcarbamoyl). Specific examples of the substituents that these groups may further have include, for example, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an acyl group, an aryloxycarbonyl group, Alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, acylamino group, alkylamino group, anilino group, ureido group, sulfa Moylamino group, alkoxycarbonylamino group, sulfonamide group, aryloxycarbonylamino group, imide group, alkylthio group,
Arylthio group, heterocyclic thio group, sulfamoyl group,
A sulfonyl group, a sulfinyl group, an azo group, a phosphonyl group, an azolyl group, a fluorine atom, a chlorine atom and a bromine atom. R ₅ is preferably an aryl group or an acyl group. A
r represents a phenyl group or a phenyl group substituted with one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group or an acylamino group. Specifically, Ar is, for example, a phenyl group, 2,
4,6-trichlorophenyl group, 2,5-dichlorophenyl group, 2,4-dimethyl-6-methoxyphenyl group,
2,6-dichloro-4-methoxyphenyl group, 2,6-
Dichloro-4-ethoxycarbonylphenyl group, 2,6
-Dichloro-4-cyanophenyl group, 2,3,4,5-
Tetrachlorophenyl group, pentachlorophenyl group, 4
-Cyano-2,3,5,6-tetrachlorophenyl group,
4-ethoxycarbonyl-2,3,5,6-tetrachlorophenyl group or 4- [2- (2,4-di-tert)
-Amylphenoxy) butylamido] phenyl group. Preferably Ar is a 2,4,6-trichlorophenyl group, a pentachlorophenyl group or a 2,5-dichlorophenyl group.

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

[0037]

[Chemical 6]

Specific examples of the compound represented by the general formula (II) are shown below, but the invention is not limited thereto. Incidentally, 1,3-dihalo-represented by the general formula (I)
A specific example of a compound which is reacted with dimethylhydantoin to give a compound represented by the general formula (II) is a compound in which X is H.

[0039]

[Chemical 7]

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

[Chemical 12]

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

[Chemical 21]

[0054]

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[0055]

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[0056]

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How the halogenation reaction of the present invention is involved in the synthesis of a photographic coupler will be described below. The halogenation reaction is generally carried out on a coupler having no substituent on the active methylene group, that is, a 4-equivalent coupler. The main synthesis method of 4-equivalent coupler is disclosed in JP-A-60-197.
No. 688, No. 59-162548, and Japanese Patent Publication No. 46-43
No. 947, No. 58-1098, No. 54-17772.
No. 49-24080 and the like, and can be easily performed by those methods.

When the halogen atom is a coupling-off group, a 4-equivalent magenta coupler is added to 1,3-dihalo-5,5.
-Halogenation with a hydantoin completes the synthesis of the 2-equivalent coupler, but in the case of other coupling-off groups, halogenation is followed by a nucleophilic substitution reaction which introduces the desired leaving group. These methods are described in JP-A Nos. 61-53644, 55-118034,
55-29805, JP-A-2-135443, and JP-A-3-135443.
No. 284747, No. 5-294971 and the like are disclosed in detail.

A halogenation reaction scheme of a 4-equivalent coupler with 1,3-dihalo-5,5-dimethylhydantoin is shown below by taking 1 H -pyrazolo [1,5- b ] [1,2,4] triazole as an example. Indicated.

[0060]

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1,3-Dihalo-5,5-dimethylhydantoin is industrially produced by halogenating 5,5-dimethylhydantoin (a), and can be easily and inexpensively used as a disinfectant for water in pools and cooling towers. It is available. When X ₁ = X ₂ , usually two halogens can be used, but when X ₁ ≠ X ₂ , only the halogen on the imide nitrogen is used in the reaction so that the halogenated coupler is not mixed. However, this does not apply if a mixture is acceptable. Generally, reacting with 1,3-dibromo-5,5-dimethylhydantoin (DMH-Br) and 1,3-dichloro-5,5-dimethylhydantoin (DMH-Cl) in which X ₁ = X _2. Is preferred. Compound (A) is safe enough to be used as livestock feed ("Fine Chemical Market Data '92", Volume 2, 411).
Page, CMC), so no special precautions are required for disposal. The compound (B) is reduced with sodium sulfite or the like before being discarded and is discarded as the compound (a).
Since (a) and (b) are almost neutral compounds and have high water solubility, they can be easily removed by extraction and washing with water when they are desired to be removed, and post-treatment is easy.

The reaction conditions for halogenation using DMH-Br and DMH-Cl will be described in detail. The amount used is 0.4 with respect to the substrate such as a 4-equivalent coupler to be halogenated.
~ 1.5 molar equivalents, preferably 0.45-0.5
It is 5 molar equivalents. When _n of A- (X) _{n in} the general formula (II) represents an integer of 2 or more, it goes without saying that DMH-B
The amounts of r and DMH-Cl used are equivalent numbers. 0.9 to 1.1 equivalents when n = 2, 1.4 to 1.6 equivalents when n = 3, and 1.9 to 2.1 when n = 4.
Equivalent weights are preferred. If only X ₁ is used for halogenation, use this double amount. 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 or mixed solvent. However, the solvent is not limited so much, but from the viewpoint of environmental protection and few side reactions, ester solvents, aromatic hydrocarbon solvents,
Ketone-based solvents, amide-based solvents and carboxylic acid-based solvents are preferred. Particularly preferred solvents are ethyl acetate, toluene,
Acetone, N, N-dimethylacetamide (DMAc)
And acetic acid.

The amount of the reaction solvent used is such that when DMH-Br or DMH-Cl, which is a halogenating agent, is first placed in a reaction vessel and a substrate such as a 4-equivalent coupler is dropped therein, the halogenating agent is not necessarily dissolved. You don't have to
An amount that allows stirring is sufficient. Even when the halogenating agent is added, in the case of powder addition, an amount that allows stirring is sufficient. The solvent under such conditions is not a problem for any of the above solvents, but DMH-Br and DMH
When -Cl 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 the solution is often used because the amount of solvent is small.

It is known that the reactivity of DMH-Br with an aromatic ring compound (there is no example of a compound having a nitrogen-containing aromatic 5-membered ring structure) is increased by an acid (Bull. C.
hem. Soc. Jpn. 67 (1918 (199
4)), In the case where the reaction also proceeds slowly in this reaction, a Lewis acid or proton acid catalyst for promoting the reaction may be added. The Lewis acid is preferably AlCl ₃ , ZnCl ₃ or FeCl ₃ , and the protic acid is sulfuric acid, perchloric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, or the like. 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 10 ° C to 40 ° C.

The post-treatment after the reaction is carried out by a method which is usually carried out by an organic reaction, and no special precautions are required. However, when the excess halogenating agent is not preferable to remain, it may be treated with sodium sulfite water. It is common. It may be effective to treat with a small amount of sodium methylate in methanol. When the extraction operation is performed, the by-produced 5,5-dimethylhydantoin can be easily removed by washing with water.

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 its nature.

[0068]

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 41.8 g (0.1 mol) of a precursor (derived from compound 6 described in JP-A-64-6274) having a hydrogen atom in place of X in Exemplified Compound (A-1) was added to toluene. 100m
It was dissolved in 1 and stirred at room temperature. In it, 1,3-dichloro-5,5-dimethylhydantoin (DMH-Cl)
When 19.7 g (0.1 mol) was added and stirred for about 30 minutes, a 7,7-dichloro compound was obtained as a product. This 7,7-dichloro compound can be isolated, but it can be easily reduced to the 7-chloro compound by adding an aqueous solution of sodium hydrogen sulfite to the reaction solution without isolation and stirring it for extraction, drying and concentration. 7-chloro-2-
[1-Methyl-2-((2- (2,4-di-t-pentylphenoxy) octanoyl) amino) propyl] -1
H-pyrazolo [1,5-b] [1,2,4) triazole could be quantitatively obtained as an NMR-pure crystalline compound.

Example 2 A precursor having a hydrogen atom instead of X in Exemplified Compound (A-4) (synthesized by the method described in JP-A-6-43611).
55.2 g (0.1 mol) was stirred in 70 ml of toluene at room temperature, and 118 g of DMH-Cl (0.0
6 mol) to dimethylacetamide (DMAc) 300
It was dissolved in ml and added dropwise. In order to reduce the partially formed 7,7-dichloro compound, an alkaline aqueous solution (pH 10) containing ethanol was added and stirred, and the disappearance of the 7,7-dichloro compound was confirmed by thin-layer chromatography. An extraction operation was performed. The extract was concentrated under reduced pressure and the toluene was distilled off to give 6-t-butyl-7-chloro-2- [4- (2
-(N-Tetradecanoxycarbonyl) propanoyl)
Amino) phenyl] -1H-pyrazolo [1,5- b ]
[1,2,4] triazole is almost pure in terms of NMR,
And it could be obtained quantitatively. When the purity of the recovered toluene used in this reaction was examined by gas chromatography, almost no chlorination of toluene was confirmed, and it was found that the purity was 99% or more.

Example 3 71.6 g (0.1 mol) of a precursor (synthesized according to the method described in JP-A-2-149582) having a hydrogen atom in place of X of Exemplified Compound (A-11) was added to ethyl acetate. 1
It was dissolved in 00 ml and stirred. After ice cooling, DMH-Br
14.3 g (0.05 mol) was added and the temperature was returned to room temperature with gradual stirring (the addition method may be reversed. That is, DMH-Br was added to ethyl acetate and stirred, and (A-1
You may add the said precursor of 1). ). After stirring at room temperature for about 1 hour, the mixture was extracted and dried by a conventional method, and ethyl acetate was distilled off under reduced pressure to quantitatively obtain a 7-bromo derivative which was almost pure by NMR. When the purity of ethyl acetate recovered by distillation under reduced pressure was examined by gas chromatography,
The presence of acetic acid was hardly observed, and the purity was 99% or more.

Example 4 43.1 g (0.1 mol) of a precursor having a hydrogen atom in place of X of the exemplified compound (A-13) (synthesized by the method described in JP-A-5-66536) was added to 100 parts of ethyl acetate.
The mixture was added to the mixture and stirred at room temperature. Among them, 1,3-dibromo-5,5-dimethylhydantoin (DMH-Br) 1
4.3 g (0.05 mol) was dissolved in 72 ml of acetone and added dropwise. The mixture is stirred for about 30 minutes, extracted by a conventional method, washed with water, dried, and concentrated to give an NMR-purified compound.
-Bromo form could be obtained.

Example 5 2,6-Dimethyl-1H-pyrazolo [1,5- b ]
[1,2,4] triazole (Exemplified compound (A-15)
Having a hydrogen atom in place of X in JP-A-60-
Synthesized by the method described in 197688) 13.6 g
Dissolve (0.1 mol) in methanol and add DM
14.3 g (0.05 mol) of H-Br was added in portions. After stirring at room temperature for about 1 hour, the solvent methanol was about 2/3.
It was distilled off under reduced pressure, and then ethyl acetate was added to precipitate 7-bromo-2,6-dimethyl-1H-pyrazolo [1,5-
The crystals of b ] [1,2,4] triazole were filtered off. The yield was 14.5 g.

Example 6 Precursor having a hydrogen atom in place of X in Exemplified Compound (B-4) (synthesized based on JP-A-3-258780) 4
3.9 g (0.1 mole) was dissolved in ethyl acetate, and a DMAc (25 ml) solution of DMH-Cl 9.9 g (0.05 mole) was added dropwise thereto. Extraction, drying, and concentration operations were carried out by a conventional method, and the obtained residue was column-purified to obtain 42.5 g of 7-chloro compound.

Example 7 70.0 g of a precursor having a hydrogen atom in place of X in the exemplified compound (D-1) (Japanese Patent Publication No. 54-17772) (0.
A solution of 1 mol) in toluene (100 ml) was added to DMH-B.
r 14.3 g of a toluene (50 ml) solution was added dropwise at room temperature, and the mixture was stirred for about 1 hour after the addition. Then, water was added and the mixture was washed with water (twice), and the obtained toluene solution was concentrated under reduced pressure at 50 ° C. or lower. As a result, 77.0 g of an NMR pure 4-bromo compound could be obtained. Example 8 68 g (1.0 mol) of pyrazole (a precursor having a hydrogen atom in place of X of Exemplified Compound (E-2)) was added to acetic acid 2
Dissolve in 00 ml, DMH-Br143g in it
(0.5 mol) was added, and the mixture was stirred at room temperature for about 30 minutes, and then 6
It was heated to 0 ° C. and stirred for about 1 hour. Then, acetic acid was distilled off under reduced pressure, and column purification was performed to obtain 118 g of 4-bromopyrazole.

Example 9 5-amino-3-methylpyrazole (exemplified compound (E-
3) A precursor having a hydrogen atom instead of X) 97.1
g (1.0 mol) was dissolved in 100 ml of concentrated hydrochloric acid, 108 g (0.55 mol) of DMH-Cl was added, and the mixture was stirred at room temperature for about 2 hours. The precipitated crystals were separated by filtration and dried to obtain 118 g of white crystals. The white crystals were the hydrochloride of 5-amino-4-chloro-3-methylpyrazole.

Example 10 Indole (11.7 g (0.1 mol) of a precursor having a hydrogen atom instead of X of Exemplified Compound (E-16)) was dissolved in 30 ml of DMAc, and DMH-Br1 was added thereto.
A solution of 4.3 g (0.05 mol) of DMAc (15 ml) was stirred dropwise. After 1 hour, water was added, and the precipitated crystals were separated by filtration and dried to give 3-bromoindole (18.2 g).
I was able to get it.

Comparative Example 1 In Example 2, the reaction was carried out using 0.12 mol of sulfuryl chloride instead of DMH-Cl, and the same post-treatment was carried out to obtain a crude 7-chloro compound having a purity of DMH-Cl. It was confirmed by NMR that it was inferior to the case of. Recrystallization from ethyl acetate gave 49.8 g (yield 85%) of pure 7-chloro compound. The purity of the recovered toluene was 96%, which was inferior to the case of using DMH-Cl.

Comparative Example 2 In Example 3, 0.1 m of bromine was used instead of DMH-Br.
When bromination was carried out using ol and the same post-treatment was carried out, the resulting crude 7-bromo compound was analyzed by NMR.
It turned out that the purity was rather low. Therefore, purification by silica gel chromatography yielded 57.5 g (yield 75%) of pure 7-bromo, but DMH-B
The yield was considerably lower than when r was used. Moreover, the purity of the recovered ethyl acetate was 95%, and DMH-Br
Gave inferior results.

[0080]

As described above in detail, according to the present invention, the halogenation step, which is an important reaction step in the synthesis of a photographic two-equivalent coupler, is simple and inexpensive without using an environmentally unfavorable halogen-based solvent. Will be able to do. Therefore, the present invention provides a solution to the problem of supplying a coupler, which is important as an organic material for color photography, inexpensively and safely, that is, reducing the cost while advancing measures to protect the environment. It can be achieved, and its effect is great both socially and economically. This method is not limited to photographic couplers and can be used for halogenation of all compounds having a nitrogen-containing aromatic 5-membered ring structure, and it is recognized that the effect on environmental protection is extremely large.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 231/44 C07D 231/44 231/56 231/56 Z 233/68 233/68 235/24 235 / 24 249/10 249/10 403/12 207 403/12 207 487/04 136 487/04 136 137 137 138 138 138 139 139 142 142 G03C 7/38 G03C 7/38 7/384 7/384

Claims (6)

[Claims] 1. A process for producing a compound represented by the general formula (II), which comprises using 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I). Embedded image (In the formula, X ₁ and X ₂ represent a chlorine atom or a bromine atom. A represents a compound having a nitrogen-containing aromatic 5-membered ring structure. X represents X ₁ or X _2. n represents 0 to 4). Represents an integer.) 2. The method according to claim 1, wherein the compound having a nitrogen-containing aromatic 5-membered ring structure is an organic material for photography. 3. The method according to claim 2, wherein the photographic organic material is a photographic coupler. 4. The method according to claim 3, wherein the photographic coupler is a pyrazolin-5-one type coupler or a pyrazolotriazole type coupler. 5. The production method according to claim 1, 2, 3 or 4, wherein a reaction solvent other than a halogen type solvent is used. 6. The 1,3-dihalo-5,5-dimethylhydantoin represented by the general formula (I) is 1,3-dichloro-5,5-dimethylhydantoin. The manufacturing method according to 3, 4, or 5.