JPH11199568A - Production of halogen compound of triazole derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply and inexpensively obtain the subject compound useful as a synthetic intermediate, etc., of dyes in photochemical field by a halogenating agent excellent in handleability by using a specific N-substituted-1,2,4-triazole derivative as a raw material. SOLUTION: (A) A compound of formula I [R1 is a (substituted)aliphatic group or a (substituted)aryl; R3 is an electron-attracting group in which a value of Hamet substituent group constant σρ is 0.2-1.0; R4 is a group substitutable for nitrogen atom of triazole ring (e.g. acetyl or benzoyl)] (e.g. derivatized from a compound of formula II) is halogenated with (B) a halogenating agent such as 1,3-dibromo-5,5-dimethyl-hydantoin to provide the objective compound of formula III (X is a halogen such as Br).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a halogen compound of a triazole derivative useful as an intermediate for synthesizing a dye or an intermediate for synthesizing a dye-forming coupler in the field of photographic chemistry.

[0002]

2. Description of the Related Art Regarding the synthesis of 1H-1,2,4-triazole derivative halogen compounds, see JP-A-8-1091.
No. 72 describes 1H-1,2,4 represented by the aforementioned general formula (I).
-Synthesis methods using triazole derivatives as starting materials. However, in this method, expensive pyridinium bromide perbromide is used, a simple halogen which is industrially difficult to handle is used at a high temperature, and expensive pyridine is used to suppress by-products such as dihalides. There is a disadvantage that the base of the derivative must be used in combination.

[0003]

The object of the present invention is to provide an industrially available, easy and inexpensive method for producing a halogen compound of an industrial triazole derivative using a halogenating agent having excellent handleability. It is assumed that.

[0004]

The present inventors have conducted studies to achieve the above object, and as a result, have found that a 1H-1,2,4-triazole derivative is a novel N-substituted-1,2,4-triazole derivative. It has been found that by using a derivative, halogenation proceeds and a new triazole derivative halogen compound can be efficiently led. That is, the present invention provides (1) a triazole represented by the following general formula (III), which comprises halogenating an N-substituted-1,2,4-triazole derivative represented by the following general formula (II). Method for producing derivative halogen compound.

[0005]

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In the formula, R1: an aliphatic group which may have a substituent or an aryl group which may have a substituent; R3: a value of Hammett's substituent constant σρ of 0.2 or more;
0 or less, an electron-withdrawing group, R4: a group that can be substituted on a nitrogen atom of a triazole ring, X: a halogen atom, (2) N-substituted-1,2,2, described in (1) above.
The method for producing a halogenated triazole derivative according to the above (1), wherein the 4-triazole derivative is obtained from a 1H-1,2,4-triazole derivative represented by the following general formula (I):

[0007]

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R2 represents an electron-withdrawing group having a Hammett's substituent constant σρ value of 0.2 or more and 1.0 or less, and R1 is as defined in claim 1.

[0009]

Next, the compounds represented by formulas (I), (II) and (III) used in the present invention will be described in detail. In these formulas, R1 represents an aliphatic group which may have a substituent or an aryl group which may have a substituent. The aliphatic group represented by R1 is a linear or branched alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group or cycloalkenyl group having 1 to 36 carbon atoms, for example, methyl, ethyl, propyl , Isopropyl, t-butyl, tridecyl, t-amyl, t-octyl, octadecyl,
Oleyl, propargyl, cyclohexyl, cyclopentyl, 4-butylcyclohexyl and the like can be mentioned.

The aliphatic group may be substituted with a substituent. Preferred substituents are a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group,
Nitro group, aryl group (for example, phenyl, naphthyl),
Alkoxy groups (eg, methoxy, ethoxy, n-butoxy), aryloxy groups (eg, phenoxy, naphthyloxy), alkylthio groups (eg, methylthio, n-propylthio), arylthio groups (eg, phenylthio), alkylsulfonyl groups (eg, methanesulfonyl, Ethanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl), formyl group, acyl group (eg, acetyl, benzoyl, propionyl), acyloxy group (eg, acetyloxy, benzoyloxy), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl, n -Octyloxycarbonyl),
Aryloxycarbonyl group (eg, phenoxycarbonyl), carbonamido group (eg, acetylamino, propionylamino, benzoylamino), sulfonamide group (eg, methanesulfonylamide, ethanesulfonylamide, benzenesulfonylamide), carbamoyl group (eg, dimethylaminocarbonyl) , Ethylaminocarbonyl, dioctylaminocarbonyl), sulfamoyl group (eg, methylaminosulfonyl, diethylaminosulfonyl, n-butylaminosulfonyl), ureido group (eg, dimethylaminocarbonylamino, anilinocarbonylamino), alkoxycarbonylamino group (eg, methoxy Carbonylamino, i-butoxycarbonylamino), amino group (eg, amino, diethylamino, dihexyl) Mino), an imido group (e.g. phthalimido), a Hajime Tamaki (e.g. furyl, thienyl, morpholino), with capable replacement of these substituents may be further substituted by these substituents.

The aryl group represented by R1 is an aryl group having 6 to 36 carbon atoms, such as phenyl, 1-naphthyl and 2-naphthyl. The aryl group may be substituted with a substituent. Preferred examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, a nitro group, and an aliphatic group as described above. (Eg, methyl, t-butyl, t-amyl,
Octyl), an aryl group (eg, phenyl, naphthyl), an alkoxy group (eg, methoxy, ethoxy, n-
Butoxy), an aryloxy group (eg, phenoxy, phenyloxy), an alkylthio group (eg, methylthio,
n-propylthio), an arylthio group (eg, phenylthio), an alkylsulfonyl group (eg, methanesulfonyl, ethanesulfonyl), an arylsulfonyl group (eg, benzenesulfonyl), a formyl group, an acyl group (eg, acetyl, benzoyl, propionyl), an acyloxy group ( Acetyloxy, benzoyloxy), alkoxycarbonyl groups (eg, methoxycarbonyl, butoxycarbonyl, n-octyloxycarbonyl),
Aryloxycarbonyl group (eg, phenoxycarbonyl), carbonamido group (eg, acetylamino, propionylamino, benzoylamino), sulfonamide group (eg, methanesulfonylamide, ethanesulfonylamide, benzenesulfonylamide), carbamoyl group (eg, dimethylaminocarbonyl) , Ethylaminocarbonyl, dioctylaminocarbonyl), sulfamoyl group (eg, methylaminosulfonyl, diethylaminosulfonyl, n-butylaminosulfonyl), ureido group (eg, dimethylaminocarbonylamino, anilinocarbonylamino), alkoxycarbonylamino group (eg, methoxy Carbonylamino, i-butoxycarbonylamino), amino group (eg, amino, diethylamino, dihexyl) Mino), an imido group (e.g. phthalimido), a Hajime Tamaki (e.g. furyl, thienyl, morpholino), with capable replacement of these substituents may be further substituted by these substituents.

R2 and R3 are electron-withdrawing groups having a Hammett's substituent constant σρ value (hereinafter simply referred to as σρ value) of 0.2 to 1.0. Preferably, the electron-withdrawing group has a σρ value of 0.3 or more and 0.8 or less. Hammett's rule was published in 1935 in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. Hammett
Empirical rule, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σρ value and a σm value, and these values are described in many general books. A. Dea
ned. , “Lange's Handbook of
Chemistry ", 12th ed., McGra
w-Hill (1979) and the special edition of Chemistry 122 , 9
6-103, (1979), Chemical Rev
eews, 91 , 165-195 (1991). In the present invention, R2 is defined by Hammett's substituent constant σρ value, but it is not limited to only those substituents having a known value in the literature described in these books, but the value is unknown in the literature. Is naturally included as long as it is within the range when measured based on the Hammett's rule.

A typical σρ value of an electron-withdrawing group having a typical σρ value of 0.2 to 1.0 is bromine atom (0.2
3), chlorine atom (0.23), cyano group (0.66),
Nitro group (0.78), trifluoromethyl group (0.5
4), tribromomethyl group (0.29), carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.43), acetyloxy group (0.31), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.7
0), a methanesulfinyl group (0.49), a carbamoyl group (0.36), a methoxycarbonyl group (0.45),
Ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0. 57).

Specific examples of the electron-withdrawing groups R2 and R3 having a σρ value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, Cyano group,
Nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group,
An arylsulfonyl group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanate group, a thiocarbonyl group, an alkyl group substituted with at least two or more halogen atoms, an aryloxy group substituted with at least two or more halogen atoms, An alkylthio group substituted with at least two or more halogen atoms, at least 2
An alkylamino group substituted with one or more halogen atoms,
Examples include a heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a selenocyanate group. Among these substituents, the group which may have a substituent may further have a substituent as described in the above-mentioned substituent which the aliphatic group and the aryl group of R1 may have. .

R2 and R3 may be the same or different, and examples of these substituents are preferably an aliphatic oxycarbonyl group (a linear or branched alkoxycarbonyl group having 2 to 36 carbon atoms, an aralkyl group). An oxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, a cycloalkoxycarbonyl group or a cycloalkenyloxycarbonyl group, such as methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl,
Ethyloxycarbonyl, sec-butyloxycarbonyl, oleyloxycarbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl,
2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), a carbamoyl group (a carbamoyl group having 1 to 36 carbon atoms, for example, diethylcarbamoyl,
Dioctylcarbamoyl), a sulfamoyl group (a sulfamoyl group having 1 to 36 carbon atoms, such as dimethylsulfamoyl and dibutylsulfamoyl), and a dialkylphosphono group (a dialkylphosphono group having 2 to 36 carbon atoms). For example, diethylphosphono, dioctylphosphono) and a diarylphosphono group (a diarylphosphono group having 12 to 50 carbon atoms, for example, diphenylphosphono, di (p-tolyl) phosphono). R 2 and R 3 are more preferably an aliphatic oxycarbonyl group, and particularly preferably an aliphatic oxycarbonyl group represented by the following formula (IV). Note that R
As for 2, those which can form a metal salt (eg, lithium salt, sodium salt, potassium salt) among these substituents may be salts.

[0016]

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In the formula, R 1 ′ and R 2 ′ represent an aliphatic group, R 3 ′, R 4 ′ and R 5 ′ represent a hydrogen atom or an aliphatic group, and Z is necessary to form a 5- to 8-membered ring. Represents a non-metallic atomic group. Here, examples of the aliphatic group in R1 ′ to R5 ′ include a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and a cycloalkenyl group. Represents, for example, methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl. R3 '
, R4 'and R5' are preferably hydrogen atoms. In the group of nonmetallic atoms represented by Z, preferred nonmetallic atoms include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and more preferred is a carbon atom. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a piperazine ring, an oxane ring, and a thiane ring. It may be substituted with such a substituent. Preferred as the ring formed by Z is a cyclohexane ring which may be substituted, and more preferred is an alkyl group having 1 to 24 carbon atoms at the 4-position (substituted with the substituent described for R1 above). A cyclohexane ring substituted with

R4 represents a group that can be substituted on the N of the triazole ring, for example, acetyl, chloroacetyl, benzoyl, methanesulfonyl, alkyl (methyl, benzyl,
Methoxymethyl), trimethylsilyl and the like,
Preferably, acetyl and benzoyl are mentioned. X represents a halogen atom. X is preferably a bromine atom or a chlorine atom, particularly preferably a bromine atom.

Next, the present invention will be described in detail. In the present invention, the desired compound of the general formula (III) is obtained by halogenating the compound of the general formula (II) using a halogenating agent. Examples of the halogenating agent used in this reaction include 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, N-bromosuccinimide and N-chlorosuccinimide. And preferred is 1,
3-dibromo-5,5-dimethylhydantoin, 1,3
-Dichloro-5,5-dimethylhydantoin, particularly preferred is 1,3-dibromo-5,5-dimethylhydantoin.

In the method of the present invention, the halogenation reaction is preferably carried out in the presence of an acid. Examples of such an acid include methanesulfonic acid, hydrobromic acid, p-toluenesulfonic acid, sulfuric acid and the like, and preferred is methanesulfonic acid. As the solvent, a non-polar solvent is preferable, and usually, a solvent such as toluene, ethyl acetate, or methylene chloride is used. The amount of the halogenating agent to be used is suitably from 1.0 to 1.3 equivalents, preferably from 1.03 to 1.05 equivalents, based on the compound of the formula (II). The amount of the acid used is appropriately from 0 to 1.0 equivalent, preferably from 0.0 to 1.0 equivalent.
It is 1 to 0.1 equivalent. The reaction temperature is usually from 0 to 80C, preferably from 20 to 60C. Reaction time is usually 1
Minutes to 72 hours, preferably 15 to 60 minutes.

In the present invention, the compound of the general formula (II) can be obtained by acylating the compound of the general formula (I) using a generally known acylating agent. Examples of such an acylating agent include industrially useful acetyl chloride, benzoyl chloride, acetic anhydride and the like. These are used in an amount of 1.1 to 1. 1 based on the starting compound of the general formula (I). Used in a 2 molar ratio.
The acylation reaction is usually performed at 25 to 40 ° C for 0.5 to 1.0 hour. At this time, ethyl acetate, toluene and the like can be used as a reaction solvent. The resulting N-acyl-1,
The 2,4-triazole derivative is once taken out and subsequently halogenated.

[0022]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1: Synthesis of compound (III-1) The following compound (I-1) (46.78 g, 0.1 mol)
And potassium acetate (9.81 g, 0.1 mol) were suspended in a solvent of 100 ml of ethyl acetate and stirred. While maintaining the internal temperature of this solution at 15 to 25 ° C, acetic anhydride (12.25
g, 0.12 mol) over 20 minutes.
The reaction was performed at a temperature of 1 ° C. for 1 hour. Thereafter, the mixture was cooled, and the precipitate was filtered by suction to collect the following compound (II-1) (46.89 g in yield, yield 9).
2%). Compound (II-1) (76.46) obtained
g, 0.15 mol) and the following compound (A) (22.09)
g, 0.077 mol) was suspended in 112.5 ml of ethyl acetate and stirred. Methanesulfonic acid (0.144 g, 0.0015 mol) was added thereto, and the solution was stirred for 30 minutes while maintaining the internal temperature of the solution at 40 ° C. Thereafter, the mixture was cooled and the precipitate was filtered by suction to give the following compound (III-
1) (84.76 g of yield, 96% of yield) was obtained.

[0023]

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Example 2 Synthesis of compound (III-2) The following compound (I-2) (47.06 g, 0.1 mol)
And potassium acetate (9.81 g, 0.1 mol) were suspended in a solvent of 100 ml of ethyl acetate and stirred. While maintaining the internal temperature of this solution at 15 to 25 ° C, acetic anhydride (12.25
g, 0.12 mol) over 20 minutes.
The reaction was performed at a temperature of 1 ° C. for 1 hour. Thereafter, the mixture was cooled, and the precipitate was filtered with suction to obtain the following compound (II-2) (44.60 g, yield 8).
7%). Compound (II-2) (76.90) obtained
g, 0.15 mol) and the following compound (B) (15.52)
g, 0.079 mol) was suspended in a solvent of 150 ml of toluene and stirred. Add methanesulfonic acid (0.28
8 g, 0.005 mol), and the internal temperature of the solution was adjusted to 8
The mixture was stirred for 30 minutes while maintaining the temperature at 0 ° C. Thereafter, the mixture is cooled and the precipitate is filtered by suction to give Exemplified Compound (III-2) (yield 7).
(7.14 g, 94% yield).

[0025]

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Example 3 Synthesis of Compound (III-3) The following compound (I-3) (42.56 g, 0.1 mol)
And pyridine (7.91 g, 0.1 mol) in toluene 1
Dissolved in 00 ml of solvent and stirred. The internal temperature of this solution
Acetyl chloride (8.64 g,
0.11 mol) was added dropwise over 20 minutes and reacted at an internal temperature of 25 ° C. for 30 minutes. Thereafter, 50 ml of acetonitrile was added and the mixture was cooled, and the precipitate was filtered by suction and the following compound (II-3)
(39.75 g, 85% yield). The obtained compound (II-3) (70.15 g, 0.15 mol) and the following compound (C) (29.37 g, 0.165 mol) were suspended in a solvent of 80 ml of ethyl acetate, and stirred. Methanesulfonic acid (1.44 g, 0.015 mol) was added thereto, and the solution was stirred for 30 minutes while keeping the internal temperature of the solution at 20 ° C. Thereafter, the mixture was cooled and the precipitate was filtered by suction to obtain Exemplified Compound (III-3) (amount obtained: 68.54 g, yield: 91%).

[0027]

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[0028]

According to the present invention, a halogen compound of a triazole derivative can be synthesized from the triazole derivative by a simple and inexpensive industrial method.

Claims (2)

[Claims] An N-substituted compound represented by the following general formula (II):
A method for producing a halogenated triazole derivative represented by the following general formula (III), comprising halogenating a 1,2,4-triazole derivative. Embedded image In the formula, R1: an aliphatic group which may have a substituent or an aryl group which may have a substituent; R3: a value of Hammett's substituent constant σρ of 0.2 or more;
0 or less, an electron-withdrawing group, R4: a group that can be substituted on a nitrogen atom of a triazole ring, X: a halogen atom. 2. The method of claim 1, wherein the N-substituted-1,2,4-triazole derivative is represented by the following general formula (I):
The method for producing a halogenated triazole derivative according to claim 1, wherein the method is obtained from a 2,4-triazole derivative. Embedded image R2: The value of Hammett's substituent constant σρ is 0.2 or more.
It represents an electron-withdrawing group of 0 or less, and R1 has the same meaning as in claim 1.