JP2000281680A - Production of 7-azolyl-1h-pyrazolo-triazoles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a 7-azolyl-1H-pyrazolo-triazoles useful as a coupler for photographs in a simple step and in a high yield by reacting specific halogenopyrazolotriazoles with azoles in the presence of an oxidizing agent and a base. SOLUTION: (A) A compound of formula I [X1 and X2 are each a group of the formula =C(R2)- or =N-; R1 and R2 are each H or a substituent group; X is a halogen] (e.g. a compound of formula II) is reacted with (B) an azole (e.g. a compound of formula III), preferably at a molar ratio of (1:1) to (1:10) in the presence of (C) an oxidizing agent (preferably hydrogen peroxide) and (D) a base (e.g. sodium carbonate), preferably at a temp. of 20-80 deg.C for 1-8 hr to provide the objective compound (e.g. a compound of formula V) of formula IV (A is non-metallic atomic group necessary for forming an azole ring together with N). Preferable amount of the components C and D used are each 0.01-0.1 mol and 1.1-10 mol based on 1 mol component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing 7-azolyl-1H-pyrazolo-triazoles useful as photographic couplers.

[0002]

2. Description of the Related Art 1H-pyrazolo-triazoles are useful compounds as couplers for silver salt color photography, and the like.
In particular, those having an azolyl group at the 7-position are couplers exhibiting excellent characteristics such as little generation of stains due to long-term storage after development and exposure to light, and not deteriorating the light resistance of a photographic color image formed by the development. . Therefore, in order to put this coupler compound into practical use in a color photographic light-sensitive material, it has been strongly desired to develop a production method suitable for industrial production. As a method for producing the 7-azolyl-1H-pyrazolo-triazoles, for example, a method in which a base such as a metal carbonate or a metal bicarbonate is used as a catalyst is disclosed in JP-A-5-294971. However, 1. 1. A purification step is essential for removing by-products. It was not satisfactory in that the yield was not always high.

[0003]

Accordingly, the present invention provides
It is an object of the present invention to provide a method for producing 7-azolyl-1H-pyrazolo-triazoles by a simple process and in a high yield.

[0004]

Means for Solving the Problems The present inventor has proposed a reaction of synthesizing 7-azolyl-1H-pyrazolo-triazoles from 7-halogeno-1H-pyrazolo-triazoles and azoles by using an oxidizing agent and a base. The present inventors have found that the above problem can be solved by performing a reaction in the presence of the compound, and have accomplished the present invention based on this finding. That is, the present invention provides: (1) a compound represented by the following general formula (I), which comprises reacting a compound represented by the following general formula (II) with an azole in the presence of an oxidizing agent and a base. -Azolyl-1H
Method for producing pyrazolo-triazoles, general formula (I)

[0005]

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Wherein X ₁ and X ₂ are each ＝ C (R ₂ )
— Or ＮN—, and R ₁ and R ₂ represent a hydrogen atom or a substituent. A represents a nonmetallic atomic group necessary for forming an azole ring together with a nitrogen atom. ) General formula (II)

[0007]

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Wherein X ₁ and X ₂ are each ＝ C (R ₂ )
— Or ＮN—, and R ₁ and R ₂ represent a hydrogen atom or a substituent. And (2) a method for producing 7-azolyl-1H-pyrazolo-triazoles according to item (1), wherein the oxidizing agent is hydrogen peroxide.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the formula (II) will be described in detail. In the general formula (II), X ₁ and X ₂ are each =
C (R ₂ ) — or ＮN—. R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, Ring oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arelesulfonyloxy group, acyl group , Alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, alkoxycarbonylamino group, aryloxyca Rubonylamino group, ureido group, sulfonamide group,
Represents a sulfamoylamino group, an imide group, an azo group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfinyl group, a sulfo group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, and a phosphonyl group. Alternatively, a bis-form may be formed with a divalent group. Further, it may be linked to the main chain of the polymer to form a polymer coupler. The above-mentioned alkyl group (residue), cycloalkyl group, aryl group (residue), heterocyclic group (residue), and the like may be further substituted with a substituent (such as a ballast group). Preferably, at least one of the substituents on the pyrazoloazole ring nucleus contains a ballast group.

More specifically, R ₁ and R ₂ are a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 32 carbon atoms,
A straight-chain or branched-chain alkyl group such as methyl,
Ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl), a cycloalkyl group (preferably a secondary or tertiary cycloalkyl group or a bicycloalkyl group, for example, cyclopropyl, cyclopentyl, cyclohexylbicyclooctyl) , Adamantyl), alkenyl group (preferably having 2 to 32 carbon atoms)
Alkenyl groups such as vinyl, allyl, 3-buten-1-yl) and aryl groups (preferably having 6 to 3 carbon atoms)
2 aryl groups such as phenyl, 1-naphthyl,
2-naphthyl), a heterocyclic group (preferably a 5- to 8-membered heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl , 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, halogen atom (for example, fluorine atom,
Chlorine atom, bromine atom, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 3 carbon atoms)
2 alkoxy groups such as methoxy, ethoxy, 1
-Butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy), a cycloalkyloxy group (preferably a cycloalkyloxy group having 3 to 8 carbon atoms,
For example, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 32 carbon atoms such as phenoxy and 2-naphthoxy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms)
A heterocyclic oxy group such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy,
2-furyloxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably having 2 to 32 carbon atoms) Acyloxy groups, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), alkoxycarbonyloxy groups (preferably alkoxycarboyloxy groups having 2 to 32 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy) , Cycloalkyloxycarboyloxy (preferably a cycloalkyloxycarbonyloxy group having 4 to 9 carbon atoms, for example, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably carbon Aryloxycarbonyloxy groups having 7 to 32, for example, phenoxycarbonyloxy),

A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 32 carbon atoms, for example, N, N-
Dimethylcarbamoyloxy, N-butylcarbamoyloxy), sulfamoyloxy group (preferably a sulfomoyloxy group having 1 to 32 carbon atoms, for example, N, N
-Diethylsulfamoyloxy, N-propylsulfamoyloxy), alkanesulfonyloxy group (preferably an alkanesulfonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy), arenesulfonyloxy ( Preferably an arenesulfonyloxy group having 6 to 32 carbon atoms,
For example, benzenesulfonyloxy), an acyl group (preferably an acyl group having 1 to 32 carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl), an alkoxycarbonyl group (preferably having 2 carbon atoms)
To 32 alkoxycarbonyl groups, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl), cycloalkyloxycarbonyl group (preferably a cycloalkyloxycarbonyl group having 2 to 32 carbon atoms, for example, cyclohexyloxycarbonyl), aryl An oxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, for example,

Phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms, such as carbamoyl, N, N-dibutylcarbamoyl,
-Ethyl-N-octylcarbamoyl, N-propylcarbamoyl), an amino group (preferably an amino group having 32 or less carbon atoms, for example, amino, methylamino, N, N-
Dioctylamino, tetradecylamino, octadecylamino), anilino group (preferably anilino group having 6 to 32 carbon atoms, for example, anilino, N-methylanilino), heterocyclic amino group (preferably heterocyclic ring having 1 to 32 carbon atoms) An amino group such as 4-pyridylamino),
A carbonamide group (preferably a carbonamide group having 2 to 32 carbon atoms, for example, acetamido, benzamido,
Tetradecanamide), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, for example, ureido, N, N-
Dimethylureide, N-phenylureide), imide group (preferably an imide group having 10 or less carbon atoms, for example, N
-Succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), aryl An oxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms such as phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 32 carbon atoms such as methanesulfonamide, Butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 32 carbon atoms, for example, N,
N-dipropylsulfamoylamino, N-ethyl-N
-Dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, e.g., phenylazo), an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms, e.g., ethylthio, octylthio),

An arylthio group (preferably having 6 to 3 carbon atoms)
2 arylthio groups, for example, phenylthio) and heterocyclic thio groups (preferably 1 to 32 carbon atoms, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio) An alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms such as dodecanesulfinyl), an arenesulfinyl (preferably an arenesulfinyl group having 6 to 32 carbon atoms such as benzenesulfinyl), an alkanesulfonyl group (preferably Has 1 to 3 carbon atoms
2, alkane sulfonyl groups such as methanesulfonyl and octanesulfonyl), arenesulfonyl groups (preferably 6 to 32 carbon atoms such as benzenesulfonyl and 1-naphthalenesulfonyl), and sulfamoyl groups (preferably carbon Sulfamoyl groups of the number 32 or less, for example, sulfamoyl, N, N
-Dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl) ). These groups may further have a substituent.

The substituents of the groups represented by R ₁ and R ₂ may be any groups capable of substituting these groups, and preferred substituents are a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group,
Aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, Anilino group, heterocyclic amino group, carbonamide group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group,
Examples include a sulfamoylamino group, an imide group, an azo group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfinyl group, a sulfo group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, and a phosphonyl group. . X represents a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a bromine atom, a chlorine atom, and most preferably a bromine atom.

R₁Represents an alkyl group, a cycloalkyl group,
Reel group, alkoxy group, aryloxy group, alkyl
Thio group, arylthio group, ureido group, oxycarboni
Is preferably an amino group or an amide group.
Kill group, cycloalkyl group, aryl group, alkoxy
And an aryloxy group. R
₁Is an alkyl group, R₁Is a methyl group, ethyl
Group, isopropyl group and t-butyl group are preferred.
And a tertiary alkyl group is most preferred. Also, R₁
Is a cycloalkyl group,₁Is second grade
Is preferably a tertiary cycloalkyl group or a bicycloalkyl group.
Good. These groups have further substituents as described above.
May be.

When X ₁ is ＮN— and X ₂ is ＣC (R ₂ ) —, R ₂ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkyloxycarbonyl group, a carbamoyl group, a sulfamoyl group. , An acyl group or a cyano group is preferable, an alkyl group or an aryl group is more preferable, and a secondary or tertiary alkyl group or a phenyl group is most preferable. These groups may further have a substituent as described above.

When X ₁ is ＝ C (R ₂ ) — and X ₂ is ＮN—, R ₂ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, It is preferably a carbamoyl group, a sulfamoyl group, an acyl group or a cyano group, and more preferably an alkyl group or an aryl group. R ₂
Is an alkyl group, R ₂ is a group which substitutes a carbon atom directly bonded to a pyrazoloazole mother nucleus with a nitrogen atom such as a carbonamide group, a sulfonamide group, a ureido group or an oxycarbonylamino group, or an alkoxy group or A primary or secondary alkyl group having a group substituted with an oxygen atom such as an aryloxy group is particularly preferred, and the above-mentioned secondary or tertiary alkyl group having no substituent is also preferred. When R ₂ is an alkyl group, a substituted alkyl group such as an alkyl group having an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group is also preferable. When R ₂ is an aryl group, R ₂ is preferably a phenyl group, and most preferably a phenyl group having the above-mentioned substituents at the 2- and 6-positions.

Of the compounds represented by the general formula (II), R ₁ preferably represents an alkyl group, an alkoxy group or an aryloxy group.

The compound represented by formula (II) used in the present invention is disclosed in US Pat. Nos. 4,500,630 and 4,5,630.
No. 40,654, No. 4-79349, No. 4-79
Nos. 350, 4-79351, European Patent Nos. 0173256, 0217353, and 02268.
The compound can be synthesized by the method described in the specification such as No. 49. The compound represented by the general formula (II) used in the present invention is specifically represented by the general formula (II-a) or (II-b).

[0020]

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In the formula, R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formula (II). In the present invention, a compound represented by the general formula (II-a) is preferable, and a case where R ₁ is an aryloxy group and R ₂ is an aryl group is particularly preferable.

The azoles used as the other starting material in the present invention include, for example, those represented by the general formula (III). General formula (III)

[0023]

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In the formula, Z ₁ , Z ₂ , Z ₃ and Z ₄ represent a nitrogen atom or a carbon atom, and at least one of Z ₁ , Z ₂ , Z ₃ and Z ₄ represents a carbon atom. When Z ₁ , Z ₂ , Z ₃ or Z ₄ is a carbon atom, Z ₁ , Z ₂ , Z ₃ or Z ₄ may be an unsubstituted methine group or a substituted methine group.
When Z ₁ , Z ₂ , Z ₃ or Z ₄ is a substituted methine group, preferred substituents are those described in the description of R ₁ and R ₂ and halogen atoms (fluorine atom, chlorine atom, bromine atom, or Iodine atom, etc.). When _{two of} Z ₁ , Z ₂ , Z ₃ or Z ₄ are carbon atoms, these are 5
A 7-membered ring may be formed. In the present invention, Z ₁ , Z ₂ ,
Z ₃ and Z ₄ are particularly preferably those in which Z ₁ and Z ₂ are a nitrogen atom and Z ₃ and Z ₄ are a carbon atom. The azoles represented by the general formula (III) are represented by Comprehens
live Organic Chemistry, Vo
l. 4 (Pergamom Pess, 1979) and The Chemistry of Heteroc
ycyclicCompounds (Williy Int
erscience, 1967). Hereinafter, specific examples of the azole represented by the general formula (III) are shown, but the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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The compound represented by the general formula (I) obtained by the production method of the present invention is represented by, for example, the general formula (IV).

[0029]

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In the formula, X ₁ and X ₂ are each ＝ C (R ₂ )-
Or = N-, wherein R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formula (II). Z ₁ , Z ₂ ,
Z ₃ and Z ₄ have the same meanings as Z ₁ , Z ₂ , Z ₃ and Z ₄ in formula (III). Hereinafter, specific compound examples of the compound represented by the general formula (IV) are shown, but the present invention is not limited thereto.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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In the present invention, the molar ratio of the compound represented by the general formula (II) to the azoles represented by the general formula (III) is in the range of 1: 1 to 1: 100, preferably 1: 1. : 1 to 1:10.

The oxidizing agent used in the present invention is not particularly limited. For example, hydrogen peroxide, sodium percarbonate (Na
₂ CO ₃ .3H ₂ O ₂ ), manganese (eg, KMnO ₄ ,
MnO ₂ ), halogens (eg, I ₂ , Br ₂ , Cl ₂ ),
Hypochlorous acids (eg, NaClO), hypobromous acids (eg, NaBrO), perchloric acids (eg, NaClO)
O ₄ ), periodic acids (eg, NaIO ₄ ), N-chlorosuccinimide, N-bromosuccinimide, 1,3-
Dichloro 5,5-dimethylhydantoin, 1,3-dibromo 5,5-dimethylhydantoin, m-CPBA (m
-Chloroperbenzoic acid) and the like. Preferred are aqueous hydrogen peroxide, sodium percarbonate, halogens, hypochlorous acids, and hypobromous acids which can be easily removed from the aqueous layer by washing with water. Among them, aqueous hydrogen peroxide is particularly preferable because it does not contain halogen in the wastewater. The oxidizing agent can be used in an amount of 0.001 to 10 times the number of moles of the compound represented by the general formula (II).
It is between 1 and 0.1 times.

The base used in the present invention is not particularly restricted but includes, for example, carbonate, bicarbonate, acetate, hydroxide, trialkylamine and DBU (diazabicycloundecene). Among them, sodium carbonate is preferred in terms of the rate of reaction formation. The base can be used in a mole number of 1 to 100 times the compound represented by the formula (II), and preferably in a range of 1.1 to 10 times.

The solvent used in the present invention is not particularly limited. For example, N, N-dimethylacetamide, N, N
N-dimethylformamide, N, N-dimethyl-2-imidazolidone, N-methylpyrrolidone, dimethylsulfoxide, sulfolane and the like are preferred, and N, N-dimethylacetamide, N, N-dimethylformamide, N, N- are preferred. Dimethyl-2-imidazolidone, N
-Methylpyrrolidone, most preferably N, N-dimethylacetamide. These solvents may be used alone or as a mixture of two or more.
In the present invention, the amount of the solvent used is not particularly limited, but is preferably 300 to 5000 ml per 1 mol of the compound represented by the general formula (II).

In the present invention, the reaction is usually carried out at 0 to 150 ° C.
Done between. Among them, the temperature is preferably from 15 to 100 ° C, particularly preferably from 20 to 80 ° C. The reaction time is not particularly limited, but is preferably 1 to 8 hours.
The reaction of the present invention may be performed in the air, but is preferably performed in an atmosphere of an inert gas such as nitrogen, helium, or argon. Post-treatment and purification of the reaction can be performed according to a conventional method. For example, the reaction mixture after the reaction is completed, or the solvent is distilled off under reduced pressure, and the residue is added to water. At this time, if necessary, neutralization with an acid may be performed. If crystals of the target substance are precipitated, the crystals are collected by filtration. Otherwise, the crystals are extracted with an organic solvent such as ethyl acetate, chloroform, or dichloromethane and concentrated. The product thus obtained may be purified by recrystallization or column chromatography using silica gel or the like as a carrier.

[0045]

EXAMPLES 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 Exemplified Compound (IV-1)

[0047]

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Compound (III-1) under a nitrogen atmosphere
1 g (0.1 mol) is dissolved in 40 ml of N, N-dimethylacetamide, and 29.1 g of sodium carbonate (0.
After stirring for 10 minutes, the compound (II)
-1) 67.2 g (0.083 mol) of 3% hydrogen peroxide and 5 ml (0.0042 mol) of hydrogen peroxide were added in this order, followed by stirring at 60 ° C. for 2 hours. After cooling, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with aqueous sodium carbonate and aqueous acetic acid, concentrated, and crystallized from acetonitrile / water to remove the bound nitrogen on the azole ring. 74.5 g of compound (IV-1) as a mixture of different isomers (yield 8
8.0%).

Example 2 A reaction was carried out in exactly the same manner as in Example 1 except that the oxidizing agent was changed as shown in Table 1, and the reaction yield of Exemplified Compound (IV-1) was determined by HPLC (high performance liquid chromatography). Was measured. The results are shown in Table 1 below.

[0050]

[Table 1]

As can be seen from Table 1, when the reaction is carried out only with a base without adding an oxidizing agent as in Experiment No. 6, only a low reaction production rate can be obtained. It can be seen that when the reaction of the present invention described below is carried out, the reaction proceeds at a very good reaction generation rate.

Example 3 Synthesis of Exemplified Compound (IV-2)

[0053]

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Compound (III-2) 2.2 under a nitrogen atmosphere
6 g (20.0 mmol) was dissolved in N, N-dimethylacetamide, and 4.2 g (40.0 mm
ol) and stirred for 10 minutes, and then compound (II-2)
7.4 g (15 mmol), 1.7 ml of 3% hydrogen peroxide
(1.5 mmol) in that order and stirred at 70 ° C. for 3 hours. After cooling, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with aqueous sodium carbonate and aqueous acetic acid.
By concentrating and crystallizing from acetonitrile / water,
6.3 g (yield: 80.0%) of compound (IV-2) was obtained as a mixture of isomers having different bonding nitrogens on the azole ring.

Example 4 Synthesis of Exemplified Compound (IV-3)

[0056]

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Compound (III-3) 3.5 under a nitrogen atmosphere
7 g (30.0 mmol) was dissolved in N, N-dimethylacetamide, and 4.2 g of sodium carbonate (40.0 mm
ol) and stirred for 10 minutes, and then the compound (II-3)
7.8 g (20 mmol), 2.3 ml of 3% hydrogen peroxide
(2 mmol) in that order and stirred at 70 ° C. for 5 hours.
After cooling, pour the reaction mixture into water, extract with ethyl acetate,
The organic layer was washed with aqueous sodium carbonate and aqueous acetic acid, concentrated, and crystallized from acetonitrile / water to give 6.4 g of compound (IV-3) as a mixture of isomers having different bonded nitrogens on the azole ring ( Yield 75.0%).

Example 5 Synthesis of Exemplified Compound (IV-4)

[0059]

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In a nitrogen atmosphere, compound (III-4) 2.7
9 g (30.0 mmol) was dissolved in N, N-dimethylacetamide, and 4.2 g of sodium carbonate (40.0 mm
ol) and stirred for 10 minutes, and then the compound (II-4)
10.2 g (20 mmol), 3% hydrogen peroxide 2.3 m
1 (2 mmol) in that order and stirred at 60 ° C. for 2 hours. After cooling, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with aqueous sodium carbonate and aqueous acetic acid.
By concentrating and crystallizing from acetonitrile / water,
8.2 g (yield: 78.0%) of compound (IV-4) was obtained as a mixture of isomers having different bonding nitrogens on the azole ring.

[0061]

According to the production method of the present invention, by-products are suppressed and the desired 7-azolyl-1H-
Pyrazolo-triazoles can be obtained, and an excellent effect of significantly reducing the load on the purification step can be obtained.

Claims (2)

[Claims] 1. A compound represented by the following general formula (II) and an azole which are reacted in the presence of an oxidizing agent and a base, wherein 7-azolyl-represented by the following general formula (I): A method for producing 1H-pyrazolo-triazoles. General formula (I) Wherein X ₁ and X ₂ are each ＝ C (R ₂ ) — or ま た は N
And R ₁ and R ₂ represent a hydrogen atom or a substituent. A represents a nonmetallic atomic group necessary for forming an azole ring together with a nitrogen atom. ) General formula (II) Wherein X ₁ and X ₂ are each ＝ C (R ₂ ) — or ま た は N
And R ₁ and R ₂ represent a hydrogen atom or a substituent. ) 2. The 7-azolyl-1H-pyrazolo- according to claim 1, wherein the oxidizing agent is hydrogen peroxide.
Method for producing triazoles.