JPH06179679A - Production of 7-aryloxy-1h-pyrazolo(1,5-b)-1,2,4-triazoles - Google Patents

Abstract

PURPOSE:To efficiently obtain a 7-aryloxy-1H-pyrazolo[1,5-6]-1,2,4-triazole useful as a coupler of color photography of silver salt form readily obtainable raw materials by reacting a halogeno-1H-pyrazolo-triazole with a phenol in the presence of an organic base. CONSTITUTION:A halogeno-1H-pyrazolo[1,5-6]-1,2,4-triazole is reacted with a phenol (e.g. nitrophenol) in the molar ratio of former to the latter of preferably 1:11-1:10 in the presence of an organic base (preferably tetramethylguanidine or diazabicycloundecene) to give the objective compound of the formula(R1 to R3 are H or substituent group; n is 0-5). The reaction is preferably carried out in an aprotic polar solvent such as N,N-dimethylformamide in an inert gas atmosphere such as nitrogen at 20-150 deg.C.

Description

Detailed Description of the Invention

[0001]

This invention relates to 7-aryloxy-1
The present invention relates to a method for producing H-pyrazolo [1.5- b ] -1,2,4-triazole. For more details, 7-halogeno
7-Aryloxy-1H-pyrazolo [1.5- b , characterized by reacting 1H-pyrazolo [1.5- b ] -1,2,4-triazoles with phenols in the presence of an organic base. ] It is related with the manufacturing method of -1,2,4-triazoles.

[0002]

2. Description of the Related Art 1H-pyrazolo [1.5- b ] -1,
2,4-triazoles are compounds useful as silver salt color photographic couplers or synthetic intermediates thereof. Among them, those having an aryloxy group at the 7-position have a high coupling reactivity with an oxidized product of a developing agent and can provide a more sensitive silver halide color photographic light-sensitive material. No.

By the way, the substituent R ₃ on the aryloxy group is
Nitro group, cyano group, halogen, carboxy group,
A compound containing an electron-withdrawing group such as a sulfamoyl group can be converted from these substituents to another one, so that the leaving ability of the aryloxy group as a leaving group can be adjusted or a photographically useful function for this part can be obtained. It is a compound that is useful in the field of photochemistry.

Regarding the method for synthesizing 7-aryloxy-1H-pyrazolo [1.5- b ] -1,2,4-triazoles, JP-A-61-53644 discloses 7-halogeno-1H-pyrazolo [1. .5- b ] -1,2,4-triazoles and a metal salt of phenols have been described, but when this method is applied to phenols having an electron-withdrawing group such as a nitro group, Targeted 7-aryloxy-1H-pyrazolo [1.5- b ]
It was found that the yield of -1,2,4-triazoles was extremely low.

[0005]

Accordingly, the object of the present invention is, firstly, to be useful as a silver salt color photographic coupler.
-Aryloxy-1H-pyrazolo [1.5- b ]-
The second object is to provide a method for producing 1,2,4-triazoles, and secondly, 7- having an electron-withdrawing group on an aryl group
Aryloxy-1H-pyrazolo [1.5- b ] -1,
It is to establish a method for efficiently synthesizing 2,4-triazoles.

[0006]

The above objects of the present invention are as follows.
-Halogeno-1H-pyrazolo [1.5- b ] -1,2,
7-Aryloxy-1H-pyrazolo [1.5- b ] -represented by the general formula (I), characterized in that 4-triazoles and phenols are reacted in the presence of an organic base containing no metal atom. Achieved by a method for producing 1,2,4-triazoles.

General formula (I)

[Chemical 3] In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent. n represents an integer of 0 to 5, and when n is plural, R ₃ may be the same or different linking groups.

The substituents R ₁ , R ₂ and R ₃ in the general formula (I) will be described in detail.

R ₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a sulfo group, a nitro group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, Alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, aulphonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo A group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphinyl group, an aryloxycarbonyl group, an acyl group, an azolyl group, R ₁
May form a bis form with a divalent group.

More specifically, R ₁ is 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, an aralkyl group, an alkenyl). Group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-). Amylphenyl, 4-
Tetradecanamidophenyl), a heterocyclic 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 -Dodecyloxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl) Phenoxy), an acylamino group (eg, acetamide, benzamide, tetradecanamide, 2- (2,4-di-t)
-Amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2-
{4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (eg, phenylamino, 2-chloroanilino, 2 -Chloro-5
Tetradecaneaminoaniline, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino,
2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), a ureido group (eg, phenylureido, methylureido,
N, N-dibutylureido), a sulfamoylamino group (for example, N, N-dipropylsulfamoylamino,
N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy))
Propylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 3
-Pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfone) Amide, benzenesulfonamide, p-
Toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), 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-ethylflufamoyl, N, N
-Dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl),
Sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyl Tetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (For example,
Acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide A group (for example, N-succinimide, N-
Phthalimide, 3-octadecenylsuccinimide),
A heterocyclic thio group (eg, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio), sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl,
Octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), 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, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁ is an alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, urethane group,
An acylamino group can be mentioned.

R ₂ is a group similar to the substituents exemplified for R ₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group. A group and a cyano group. R ₃ is the same group as the substituent exemplified for R ₁ , but when n is 1 or more, at least one R ₃ is a nitro group, a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, or a sulfinyl group. And the like are preferably electron-withdrawing groups having a σ p value of 0.0 or more. Here, the σp value is the parameter of the Hammet equation.
Position substituent constants, AJ Gordon, RAFord, The
Chemist's Companion, John Wiley & Sons, New York
(1972) and so on. The preferred σ p value is 0.
1 to 0.8.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

The reaction of the present invention is represented in the following scheme. Scheme 1

[Chemical 8] 7-halogeno-1H-pyrazolo [1.5- b ] represented by the general formula (III), which is a raw material of the present invention in the above scheme
The -1,2,4-triazoles will be described.

General formula (III)

[Chemical 9] In the formula, R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formula (I). X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.

7-halogeno-represented by the general formula (III)
1H-pyrazolo [1.5- b ] -1,2,4-triazoles are disclosed in JP-A-60-190779 and 60-19.
7688, 60-215687 and 61-1
No. 7-substituted 1H-pyrazolo [1.5- b ]-, which can be synthesized by the method described in No. 45163 or the like.
1,2,4-triazoles are disclosed in JP-A-60-17298.
2, suitable halogenating agents (sulfuryl chloride, chlorine gas, N-chlorosuccinimide,
It can be easily synthesized by treating with N-bromosuccinimide, bromine, etc.).

The phenols used as another starting material in the present invention are those represented by the general formula (II).

General formula (II)

[Chemical 10] Wherein, R ₃ and n have the same meanings as R _3, n in the general formula (I). In the reaction of the present invention, the general formula (III)
The pKa of the phenols represented by is 3.0 to 10.0
Is preferable, and the case of 4.0 to 9.0 is more effective.

This pKa measurement can be carried out in water at 25 ° C. For the pKa value, see “The Ch” by S. Patai.
emistry of the hydroxy group '' 1971 (Intersience P
Published by ublishers, Inc.) Table 374, page 374, etc. Incidentally, water-insoluble phenol can be similarly measured in a THF-containing aqueous solution.

Specific examples of the compounds represented by the general formula (II) are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 11]

[0026]

[Chemical 12]

The organic base used in the present invention is preferably one that reversibly retains hydrogen ionic to an appropriate degree. Specifically, amines (eg diisopropylethylamine, triethylamine), guanidines (eg tetramethylguanidine), pyridines (eg pyridine, 4-N,
N-dimethylaminopyridine lutidine), heterocycles (diazabicycloundecene (abbreviated as DBU), diazabicyclononenene (hereinafter abbreviated as DBN), and the like, among which tetramethylguanidine DBU, DB
N is particularly preferred.

The amount of these bases is 7-halogeno-1H-pyrazolo [1.5- b ] -represented by the general formula (III).
It is preferable to use 0.5 to 2 times the total molar amount of 1,2,4-triazoles and phenols represented by the general formula (II), and to use 0.8 to 1.2 times the same. Is most preferred.

In the present invention, 7-halogeno-1H-pyrazolo [1.5- b ] -1, represented by the general formula (III),
The molar ratio of the 2,4-triazoles to the phenols represented by the general formula (II) is in the range of 1: 1 to 1: 100, preferably 1/11 to 1:10.

The solvent used in the reaction of the present invention is preferably a so-called aprotic polar solvent. Specific examples of the solvent that can be used in the reaction of the present invention include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane,
Hexamethylphosphoric triamide, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidone and the like can be mentioned. Further, even a protic solvent having low nucleophilicity such as t-butyl alcohol can be used as a solvent for the reaction of the present invention.

These solvents may be used alone,
You may use it in mixture of 2 or more types. The solvent has the general formula (I
0.5 to 1000 per part by weight of the compound represented by II)
It is used in a proportion of 1 part by weight, preferably 1 to 50 parts by weight.

The reaction of the present invention may be accelerated by adding a quaternary ammonium salt. Examples of the quaternary ammonium salt that can be used include tetrabutylammonium bromide, butylammonium chloride, and benzyltrimethylammonium hydroxide. The addition amount of these quaternary ammonium salts is represented by the general formula 7
-Halogeno-1H-pyrazolo [1.5- b ] -1,2,
The amount is 1 to 200 mol%, preferably 10 to 50 mol% with respect to 4-triazoles.

The reaction temperature is preferably 0 to 200 ° C, more preferably 20 to 150 ° C. The reaction time is usually several hours when the reaction temperature is 100 ° C. or higher, but it may take several days when the reaction is performed at a lower temperature.

The reaction of the present invention may be carried out in the air, but is preferably carried out in an atmosphere of an inert gas such as nitrogen, helium or argon.

The post-treatment of the reaction can be carried out by the following method. That is, the reaction mixture after completion of the reaction is added as it is, or the residue obtained by distilling off the solvent under reduced pressure is added to water, and when crystals of the target substance are precipitated, they are collected by filtration; Extract with an organic solvent such as ethyl, chloroform, dichloromethane, and concentrate. The crude product thus obtained can be purified by a recrystallization method or column chromatography using silica gel as a carrier.

The compound represented by the general formula (I) which can be synthesized by the production method of the present invention is a crystalline, non-crystalline or oily substance and is generally colorless, but when it is colored in light yellow, light brown or the like. There is also.

[0037]

The method of the present invention and the above-mentioned JP-A-61-5
Table 1 shows a comparison with the method described in No. 3644, that is, the method using a metal salt of phenols.

[0038]

[Table 1]

By using the method of the present invention, 7-allyloxy-1H-pyrazolo [1.
5- b ] -1,2,4-triazoles are efficiently and readily available in 7-halogeno-1H-pyrazolo [1.
It can be synthesized from 5- b ] -1,2,4-triazoles.

[0040]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 (Synthesis of Exemplified Compound E-1)

[Chemical 13]

Compound (A)

[Chemical 14]

Nitrophenol (II-1) 11.1 g was added to 1,3-dimethyl-2-imidazolidone (hereinafter referred to as DMI).
Abbreviated) and dissolve in 100 ml and stir at room temperature. In addition to this, tetramethylguanidine (hereinafter abbreviated as TMG) 1
Add 5.0 ml dropwise. After the addition, the mixture was stirred as it was at room temperature for 5 minutes. 25.5 g of the compound (A) was added thereto, and the mixture was stirred at 80 ° C. for 2 hours under a nitrogen atmosphere. After cooling, the reaction mixture was added to 450 cc of water and extracted with 250 cc of ethyl acetate. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. The residue obtained by concentration is purified by silica gel column chromatography (eluent is a mixed solvent of ethyl acetate and n-hexane) and the solvent is concentrated to dryness to obtain 7.01 g of glassy exemplary compound E-1. It was

Proton NMR spectrum (CDCl ₃ ) δ (ppm) (multiplicity, integrated value) 8.15 (d, 2)
H), 7.8 (d, 1H), 7.56 (dd, 1H),
7.04 (d, 2H), 6.97 (d, 1H), 4.0
9 (t, 2H), 3.05 to 3.30 (m, 3H),
2.18 (s, 3H), 1.60 to 1.90 (m, 4
H), 1.15 to 1.50 (m, 19H), 0.79 to
1.04 (m, 3H), 0.72 (s, 9H)

Example 2 (Synthesis of Exemplified Compound E-2)

[Chemical 15]

4-hydroxy-3-nitrobenzaldehyde (II-2) 13.4 g, TMG 15.0 ml,
The same operation as in Example 1 was carried out using 25.5 g of the compound (A) to obtain 5.44 g of Exemplified compound E-2.

(Amorphous solid) Proton NMR spectrum (CDCl ₃ ) δ (ppm) (multiplicity, integrated value) 9.93 (bs, 1)
H), 8.48 (d, 1H), 8.02 (dd, 1)
H), 7.84 (d, 1H), 7.52 (dd, 1)
H), 7.18 (d, 1H), 6.94 (dm, 1),
5.37 (t, 1H), 4.10 (dt, 2H), 3.
10 to 3.38 (m, 3H), 2.21 (s, 3H),
1.20 to 1.80 (m, 27H), 0.82 to 0.9
2 (m, 3H), 0.73 (brs. 9H)

Example 3 (Synthesis of Exemplified Compound E-3)

[Chemical 16]

Compound (B)

[Chemical 17]

6.95 g of nitrophenol (II-1) is dissolved in 80 ml of DMI and stirred at room temperature. D to this
BU (11.2 ml) was added dropwise and the mixture was stirred as it was at room temperature for 5 minutes. To this, 5.43 g of the compound (B) was added, and the mixture was stirred at 110 ° C. for 2 hours under a nitrogen atmosphere. After cooling, the reaction mixture was added to 200 ml of water and extracted with 250 ml of ethyl acetate. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. The residue obtained by concentration is subjected to silica gel chromatography (eluents are ethyl acetate and n-
Purification with a mixed solvent of hexane), and 1.50 g of Exemplified Compound E-3 was obtained. (Amorphous solid)

Proton NMR spectrum (CDCl ₃ ) δ (ppm) (multiplicity, integrated value) 8.63 (d, 2)
H), 7.68 (d, 2H), 3.00 (q, 2H),
1.49 (t, 3H)

Example 4 (Synthesis of Exemplified Compound E-4)

[Chemical 18]

Compound (C)

[Chemical 19]

Ethyl m-hydroxybenzoate (II-3)
3.32 g is dissolved in 30 ml of DMI and stirred at room temperature. To this was added 3.76 ml of TMG, and the mixture was stirred as it was at room temperature for 5 minutes. Compound (C) (10.9 g) was added thereto, and the mixture was stirred under a nitrogen atmosphere at 120 ° C. for 3 hours. After cooling, the reaction mixture was added to 100 ml of water and extracted with 200 ml of ethyl acetate. After washing the organic layer with saturated saline,
It was dried over anhydrous magnesium sulfate. The residue obtained by concentration is purified by silica gel chromatography (eluent is a mixed solvent of ethyl acetate and n-hexane), and 3.
60 g of exemplary compound E-4 was obtained. (Amorphous solid) The compound was identified by analysis of NMR spectrum and MS spectrum.

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[Procedure amendment]

[Submission date] November 12, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

[Title of Invention] 7-aryloxy -1H- pyrazolo [1, 5- b] method for producing 1,2,4-triazoles

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent. N represents an integer of 0 to 5, and when n is plural, R ₃ may be the same or different substituents. .)

[Procedure 3]

[Document name to be amended] Statement

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[Correction method] Change

[Correction content]

[0001]

This invention relates to 7-aryloxy-1
H- pyrazolo [1, 5- b] -1,2,4- process for the preparation of triazoles. More particularly 7-Harogeno 1H- pyrazolo [1, 5- b] -1,2,4- triazoles and phenols which comprises reacting in the presence of an organic base 7 aryloxy -1H- pyrazolo [1, 5- b] process for the preparation of 1,2,4-triazoles.

[Procedure amendment 4]

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[0002]

2. Description of the Related Art 1H-pyrazolo [1 , 5, -b ] -1,
2,4-triazoles are compounds useful as silver salt color photographic couplers or synthetic intermediates thereof. Among them, those having an aryloxy group at the 7-position have a high coupling reactivity with an oxidized product of a developing agent and can provide a more sensitive silver halide color photographic light-sensitive material. No.

[Procedure Amendment 5]

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[Correction method] Change

[Correction content]

[0004] 7-aryloxy -1H- pyrazolo [1, 5-b]-1,2,4-For triazoles synthetic methods, in JP-A-61-53644 7-halogeno -1H- pyrazolo [1 , 5- b ] -1,2,4-triazoles are reacted with metal salts of phenols, but this method is described as a method of using a phenol-containing electron-withdrawing group such as a nitro group. 7-aryloxy-1H-pyrazolo [1,5, b ] , which is the target when applied to
It was found that the yield of -1,2,4-triazoles was extremely low.

[Procedure correction 6]

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[0005]

Accordingly, the object of the present invention is, firstly, to be useful as a silver salt color photographic coupler.
- aryloxy -1H- pyrazolo [1, 5- b] -
The second object is to provide a method for producing 1,2,4-triazoles, and secondly, 7- having an electron-withdrawing group on an aryl group
Aryloxy -1H- pyrazolo [1, 5- b] -1,
It is to establish a method for efficiently synthesizing 2,4-triazoles.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006]

The above objects of the present invention are as follows.
-Halogeno 1H-pyrazolo [1 , 5, -b ] -1,2,
4- triazoles and phenols represented by the general formula (I) which comprises reacting in the presence of an organic base containing no metal atom 7- aryloxy -1H- pyrazolo [1, 5- b] - Achieved by a method for producing 1,2,4-triazoles.

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[0016]

[Chemical 6]

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[0017]

[Chemical 7]

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The reaction of the present invention is represented in the following scheme. Scheme 1

[Chemical 8] In the above scheme, the general formula (III) which is a raw material of the present invention
In represented by 7-halogeno -1H- pyrazolo [1, 5-
b ] -1,2,4-triazoles are described.

[Procedure Amendment 11]

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[0020] 7-halogeno -1H- pyrazolo [1, 5-b] represented by the general formula (III)-1,2,4-triazoles, JP 60-190779, the 60-
197688, 60-215687 and 61.
7-position of the unsubstituted 1H- pyrazolo can be synthesized by the method described in -145163 Patent etc. [1, 5-
b ] -1,2,4-triazoles are disclosed in JP-A-60-17.
As described in 2982, it can be easily synthesized by treating with a suitable halogenating agent (sulfuryl chloride, chlorine gas, N-chlorosuccinimide, N-bromosuccinimide, bromine, etc.).

[Procedure Amendment 12]

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The organic base to be used in the present invention is water Motoi on an appropriate extent, reversibly good to hold. In particular,
Amines (eg diisopropylethylamine, triethylamine), guanidines (eg tetramethylguanidine), pyridines (eg pyridine, 4-N, N-)
Dimethylaminopyridine lutidine), heterocycles (diazabicycloundecene (abbreviated as DBU), diazabicyclononenene (hereinafter abbreviated as DBN), and the like, among which tetramethylguanidine DBU and DBN are particularly preferable. .

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The amount of these bases is represented by the general formula (III) 7- halogeno -1H- pyrazolo [1, 5- b]
It is preferable to use 0.5 to 2 times the total molar amount of the 1,2,4-triazoles and the phenols represented by the general formula (II), and to use 0.8 to 1.2 times the same. Is most preferred.

[Procedure Amendment 14]

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[Correction method] Change

[Correction content]

In the present invention, 7-halogeno 1H-pyrazolo [1 , -b ] -1, represented by the general formula (III),
The molar ratio of the 2,4-triazoles to the phenol represented by the general formula (II) is in the range of 1: 1 to 1: 100, preferably 1: 1.1 to 1:10. is there.

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The reaction of the present invention may be accelerated by adding a quaternary ammonium salt. Examples of the quaternary ammonium salt that can be used include tetrabutylammonium bromide, butylammonium chloride, and benzyltrimethylammonium hydroxide. The addition amount of these quaternary ammonium salts is represented by the general formula 7
-Halogeno 1H-pyrazolo [1 , -b ] -1,2,4
-It is 1 to 200 mol%, preferably 10 to 50 mol% with respect to the triazoles.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

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By using the method of the present invention, 7-allyloxy-1H-pyrazolo [1 ,
- b]-1,2,4-triazoles efficiently, readily available, 7- Harogeno 1H- pyrazolo [1, -
b ] -1,2,4-triazoles.

Claims (3)

[Claims] 1. A 7-halogeno-1H-pyrazolo [1.5
- b]-1,2,4-triazoles and phenols represented by the general formula (I) which comprises reacting in the presence of an organic base 7 aryloxy -1H- pyrazolo [1.5- b ] A method for producing 1,2,4-triazoles. General formula (I) (In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent. N represents an integer of 0 to 5, and when n is plural, R ₃ may be the same or different substituents. .) 2. The method according to claim 1, wherein the phenol is represented by the following general formula (II). General formula (II) (In the formula, R ₃ and n have the same meanings as R ₃ and n represented by the general formula (I), and when R ₃ is 1 or more, at least one R ₃ is a nitro group, a sulfamoyl group or a carbamoyl group. , A halogen atom, a cyano group, a sulfinyl group and the like are electron withdrawing groups having a σp value of 0.0 or more.) 3. The organic base is a metal atom-free organic base selected from primary to tertiary alkylamines, primary to tertiary anilines, guanidines and heterocycles. Manufacturing method.