JPS60190779A - Preparation of pyrazolo(1,5-b)(1,2,4)triazole derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for synthesizing an azapentalene compound useful as a magenta coupler for color photography, by subjecting an N-aminotriazolium salt and an acid anhydride to condensation through ring formation. CONSTITUTION:An N-aminotriazolium salt shown by formula I (R1 is H, alkyl, or aryl; R2 is alkyl, or aryl; X is acid radical) is reacted with an acid anhydride shown by the formula II (R3 is H, alkyl, or aryl) in the presence of a base (e.g., amine, or sodium acetate) in a solvent such as dimethylformamide, etc. at 100- 180 deg.C, preferably >= at 120 deg.C for 0.5-20hr, to give the desired substance shown by the formula III. An amount of the compound shown by the furmula II used in the reaction is at least 3 equivalents and an amount of the base is 5 equivalents based on the compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing novel pyrazolo[1,5-bl[1,2°41 triazolyl derivatives].

(Background of the invention) It has a nitrogen atom at the bridgehead position, and
Including a lone pair of electrons on one nitrogen atom, 10 π electrons can interact, a total of at least two...; shows three movable double bonds.

φ; represents a nitrogen or carbon atom.

The 5-5 fused polycyclic compound represented by is commonly called "azapentalene". Until now, this compound has been studied mainly from the viewpoint of structural chemistry, interest as a physiologically active substance, and interest as a magenta coupler in photochemistry (J, Elgureo).

R, Jacquier, S, Migr+onac-
Mondon, J.) Itero-c clic
, CheIll, , 10, 411 (1973
), H, Koga.

Moon, old robe, T, Okamoto, Che+
m, Pharm, Bull, .

22, 482 (1974), J. Balley,
J, C, S, Perkin 12047 (197
? ), Japanese Patent Publication No. 47-27411, Japanese Patent Publication No. 1977-12
(See No. 8586, etc.).

The present inventors have conducted various studies on methods for synthesizing such azapentalene compounds, and as a result, they have succeeded in producing azapentalene compounds with novel skeletons by cyclization condensation of certain N-aminotriazolium salts and acid anhydrides. It has been found that the compound exhibits extremely excellent properties as a magenta coupler for color photography, and based on this knowledge, the present invention has been completed.

(Structure of the Invention) That is, the present invention has the following features: l) General formula (wherein R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R2 represents an alkyl group, a substituted alkyl group, an aryl group) or a substituted aryl group, and X represents an acid radical. 7-acylated pyrazolo [1,5 -bl[
1,2,4]) A method for producing a pyrazolo [1,5-bl[+, 2.4]) lyazole derivative, which is characterized by obtaining a lyazole, and 2) a method for producing a 7-lyazole derivative represented by the general formula (IV). After deacylating the acylated pyrazolo [1,5-bl[1,2,4] triazole, a coupling-off group Y is introduced into -C1 or Zara to form the general formula (wherein R and R3 are as above). pyrazolo [1,5-bl[1,2,4] having the same meaning, Y represents a hydrogen atom or a coupling-off group)
) A method for producing a pyrazolo[1,5-bl[I, , 2.4] triazole derivative, which is characterized by obtaining a lyazole compound.

Above - General formula (II), (m), (■), and (V)
In the compound represented by, the alkyl groups of R and R31 range from lower alkyl groups such as methyl, ethyl, propyl, and butyl groups to higher alkyl groups having up to 22 carbon atoms, such as pentyl group, hexyl group, heptyl group, and octyl group. , decyl group, undecyl group, tridecyl group, octadecyl group, etc., and may be linear or branched. In particular, R1 is preferably a methyl group. Also R,
Examples of the aryl group for R3 include a phenyl group and a naphthyl group, examples of the substituted alkyl group include a benzyl group and a phenethyl group, and examples of the substituted aryl group include a halogenophenyl group, a nitrophenyl group, a cyanophenyl group, and an alkoxyphenyl group. etc. Further, these R and R3 may have a group inert to the reaction, such as an alkoxyl group, a nitro group, a cyano group, a halogen atom, etc., as a substituent.

Next, examples of the alkyl group for R2 in the compounds represented by the above general formulas (II) and (IV) include lower alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, and pentyl group, hexyl group, and dodecyl group. Aryl groups include phenyl groups, naphthyl groups, etc., and substituted alkyl groups include benzyl groups, phenethyl groups, p-methoxyphenylmethyl groups, m-nitrophenylmethyl groups, etc. may have a group inert to the same reaction as R,, R3 as a substituent. In particular, when R2 is an optionally substituted benzyl group, it is easy to reductively remove the substituent in a later step.
This is advantageous when producing an IH unit.

In the above general formula (II), the acid radical of X includes acid radicals such as halogen atoms such as chlorine, bromine, and iodine.

In addition, pyrazolo[1,5-b
][1,2,4]) A lyazole derivative, R,
Compounds having 2 further substituents on the base of R or R3 as described above can be obtained directly according to the reaction scheme described below, but in this step, first, pyrazolo-[1,5- b ] [1, 2, 4
] After forming a 1-riazole ring, it may be induced into a desired substituent through a subsequent reaction. 7 if necessary
It may be induced with a compound having an acyl group at the - position and a protecting group such as a benzyl group at R2. For example, as shown in Example 6 below, the amino group of compound 11 of the present invention can be derived into acid anilide 13 etc. by a known method.

The reaction process of the method of the present invention is as follows when X in the general formula (II) is an iodine ion. An embodiment will be described.

In the present invention, triazole compound (IV) can be easily obtained by reaction of oxadiazole (■) and organic-grade amine (■). The reaction temperature is usually started at a range of 50 to 150°C, and the reaction is completed under conditions where the water produced by the dehydration reaction gently refluxes. The reaction time is usually in the range of 0.1 to 8 hours, but is not limited thereto. Oxadiazole can be synthesized by the method described in Ber, Vol. 32, p. 797 (1899).

Next, the synthesis of N-aminotriazolium salt (II) by amination of triazole compound (V) is carried out using hydroxylamine-〇-sulfonbutyric, O-(2
,4-C-E-trophenyl)hydroxylamine, 0
-diphenylphosphorylhydroxylamine. Other aminating agents that can be used in the present invention are Y, Tamuraet, al, 5ynth
esis, l577, l~l? and is described in the citation of the same document. This amination reaction is usually carried out at a reaction temperature of 0°C to 100°C for 0.1 to 5 hours. The molar ratio of the triazole compound to the aminating agent is generally 1=1, but the cheaper one of the two may be used in excess.

N-aminotriazolium fl(II) and acid anhydride (m
) is carried out in the presence of a base. As the base, amines, sodium acetate, sodium propionate, etc. can be used. In this reaction, N
- It is desirable to use at least 3 equivalents of the acid anhydride and at least 5 equivalents of the base relative to the aminotriazolium salt. If the amounts of acid anhydride and base are below this lower limit, the yield of one reaction will decrease. This means that if the acid anhydride is below the lower limit,
This is thought to be due to the progress of side reactions that do not yield the target product from reaction intermediates. The reaction temperature is generally 100°C, -180°C.
C. can be used, but 120.degree. C. or higher is preferable.The reaction time varies depending on the type and amount of acid anhydride, and is generally in the range of 0.5 to 20 hours, although there is no particular restriction. The reaction solvent may be any inert solvent, such as dimethylformamide (DMF), dimethylacetamide, N
-Methylpyrrolidone and the like are usually used, but when a lower acid anhydride is used as a reaction component, an excess amount of this can be used as a solvent.

Specific examples of the acid anhydride (m) include phosphoric anhydride, acetic anhydride, propionic anhydride, lauric anhydride, benzoic anhydride,
Examples include methoxycarbonylpropionic anhydride, ethoxycarbonylpropionic anhydride, and 4-(p-nitrophenyl)butyric anhydride. Further, the acid anhydride of the above general formula (m) includes mixed acid anhydrides, and a preferred example in this case is a mixed acid anhydride with trimethyl acetic acid.

The product of this cyclization condensation reaction, 7-acylated pyrazolo[1,5-b][1,2,4]triazole (I
Compound (■) is obtained by deacylating and reducing V).

(X).

Deacylation can be achieved by heating under reflux in an aqueous solution containing a solvent boiling at room temperature to 200°C, such as ethanol, under acidic conditions using a mineral acid, according to a general method. After returning this to neutrality, the target product is isolated by extraction or the like, and purified if necessary.

In addition, when the 7-position is first nitrosated in order to introduce a leaving group having an N atom bonded to the 7-position, the deacylation reaction may be carried out simultaneously with the nitrosation.

Next, by reduction of compound (IX), the substituent R2 bonded to the nitrogen atom at the ■-position is removed, resulting in lH-pyrazolo E
1, 5-b][1,2,4] triazole compound (X) is obtained. It is desirable to select a substituent R2 that can be suitably removed by this reduction treatment. Such protecting groups are described, for example, by Mcomie, Pro.
Tective Groups in Organic
Chemistry (1973, published by Plenum) or Protec by T. W. Green
tive Groups in OrganicSyn
thesis (1981, Wiley-Inte
(published by Rscience). Among these, R2 preferable for use in the present invention is CHCH, CH(Ce H() 2 ).

2 6 5 -C: H2C6H3-3,4-(OCH3) 2゜-C
H2C6H,-o-No,.

CHCHp OCH3゜264-CH(CH-P-OCH3)2゜4-CH-2-pyridyl-N-oxide and the like. Reaction conditions for removing these substituents R2 include catalytic reduction and reduction with an alkali metal. Examples include palladium black/hydrogen, palladium-carbon/hydrogen, palladium-alumina/hydrogen, sodium/liquid ammonia, and lithium/liquid ammonia. Among them, sodium metal/liquid ammonium gives a high yield.

Although the desired compound obtained in each step of the above reaction process may be subjected to the subsequent reaction without being isolated in any way, it is usually isolated and purified by appropriate isolation means. Examples of such means include solvent extraction, recrystallization, filtration, column chromatography, and thin layer chromatography.

In the method of the present invention, tH-
Pirazolo it! The i-bl[1,2,al) lyazole compound is further treated to introduce a well-known coupling-off group at the 7-position to form pyrazolo[1,5-bl[1,2] represented by the general formula (V). , 4] It may also be a triazole compound. Regarding compounds used as couplers in photographic systems, this is done as appropriate to adjust the coupling reaction rate with the oxidation product of aromatic amines oxidized by silver halide and to reduce the amount of silver used. This is a well-known method.

A general method for introducing a carving leaving group will be explained below.

(1) Method for connecting oxygen atoms The 4-equivalent mother coupler of the present invention, pyrazolo [1,5-b
l A triazole coupler and an oxidation product of an aromatic-grade amine are reacted to form a dye, which is hydrolyzed in the presence of an acid catalyst to form a ketone body, and this ketone body is catalyzed by Pd-carbonate. hydrogenation, reduction with Zn-acetic acid or reduction treatment with sodium borohydride,
7-Hydroxypyrazolo[1,5-bl) lyazole can be synthesized. By reacting this with various halides, the desired coupler connecting oxygen atoms can be synthesized. (U.S. Patent No. 3,928,831, Japanese Unexamined Patent Publication No. 57
(Refer to No. 70817) (2) Method for connecting nitrogen atoms There are roughly three methods for connecting nitrogen atoms. The first method is to trosate the coupling active site with a suitable trosation agent as described in U.S. Pat. Amide compounds can mainly be synthesized by reacting with various halides as 7-amino-pyrazolo [1°5-bl) lyazole (hydrogenation method using a catalyst, chemical reduction method using stannous chloride, etc.).

The second method is the method described in U.S. Pat. No. 3,725,087, i.e., using a suitable halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide, etc. After that, the nitrogen heterocycle was halogenated at the 7-position by the method described in Japanese Patent Publication No. 56-45135 using a suitable base catalyst, triethylamine, sodium hydroxide, zaazabicyclo[2,2,23
Substitution in the presence of octane, anhydrous potassium carbonate, etc.,
A coupler linked with a nitrogen atom at the - position can be synthesized.

Among compounds linked by oxygen atoms, compounds having a phenoxy group at the 7-position can also be synthesized by this method.

The third method is an effective method when introducing a 6π or 10π electron system aromatic nitrogen heterocycle at the 7-position, and is
As described in No. 7-38577, more than twice the molar amount of 6 to the 7-halogen compound synthesized by the second method.
50 by adding a π or 10π electron system aromatic nitrogen heterocycle
Aromas linked by a nitrogen atom at the 7-position by heating at ~150°C without solvent or at 30-150°C in an aprotic polar solvent such as dimethyformaldehyde, sulfolane or hexamethylphosphotriamide. A group nitrogen heterocyclic group can be introduced.

(3) Method for linking sulfur atoms Couplers in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position are prepared using the method described in U.S. Pat. It can be synthesized by dissolving the disulfide in a halogenated hydrocarbon solvent, converting it to sulfenyl chloride with chlorine or sulfuryl chloride, and adding it to a 4-equivalent pyrazolo [1,5-bl) lyazole coupler dissolved in an aprotic solvent. I can do it. A method for introducing an alkylmercapto group into the 7-position is described in US Patent No. 4.
284,723, that is, a method in which a mercapto group is introduced into the coupling active position of the coupler and a halide is applied to this mercapto group, and S-(alkylthio)thiourea hydrochloride (or bromate hydrochloride) is used in one step. A method of synthesis is effective.

In addition, in the method of the present invention, general formulas (X) and (V)
Pyrazolo [1,5-b) [1,2,41
) Substituents R and R at the 2-position and 8-position of the riazole compound
3 may be converted into a desired photochemically acceptable group by an appropriate treatment according to a method known per se, for example, the above-mentioned method for introducing a coupling-off group.

Thus pyrazolo [
1,5-blll, 2.4]) The lyazole derivative can be represented by the following general formula.

However, in the formula, R4 and R5 represent a hydrogen atom or a substituent, and Y represents a hydrogen atom or a coupling-off group.

Preferably, R4 and R5 are a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, or an alkylthio group. group, arylthio group, alkoxycarboxylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamide group, imide group, heterocyclic thio group, sulfinyl group, Represents a phosphonyl group, aryloxycarbonyl group, or acyl group, and Y
represents a group that couples off at a hydrogen atom, a halogen atom, a carboxy group, an oxygen atom, a nitrogen atom, a carbon atom, or a group bonded to a carbon at a coupling position via a sulfur atom, and R4, 1 to 5 or Y may be a divalent group to form a bis body, and when the moiety represented by the general formula (X[) is included in the vinyl monomer, either R4 or R5 may be a simple bond or a connecting group. The moiety represented by the general formula (X[) is bonded to the vinyl group through this.

More specifically, R4 and R5 are each a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (
Straight chain or branched alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups having 1 to 32 carbon atoms,
A cycloalkenyl group, which is substituted with an oxygen atom, a nitrogen atom, a substituent linked with a carbonyl group, a hydroxy group, an amino group, a nitro group, a carboxy group, a cyano group, or a halogen atom. For example, methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 2-methanesulfonylethyl group, 3-(3-hentadecylphenoxy)propyl group, 3- (4- (2-[4-(4-hydroxyphenylsulfonyl)phenoxy] dodecamino)phenyl)propyl group, 2-ethoxytridecyl group, trifluoromethyl group, cyclopentyl group, 3-(2,4-di-monoamylphenoxy) ) propyl group, etc.) aryl group (
For example, phenyl group, 4-t-butylphenyl group, 2
, 4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic groups (e.g., 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, 2
-benzothiazolyl group, etc.), cyanogen group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyl ethoxy group, 2-methanesulfonyl ethoxy group, etc.), aryloxy group (e.g.
Phenoxy group, 2-methylphenoxy group, 4-t-
butyl phenoxy group, etc.), acylamino group (e.g.
Acetamide group, benzamide group, tetradecanamide group, α-(2,4-di-amylphenoxy)butyramide group, γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(4-(4- -hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanaminoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group) , N-acetylanilinono, (,2-chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group, such as phenylureido group, methylureido group Base, N
, N dibutylureido group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulf7moylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group) , octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(
4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phekylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group) ,
4-tetradecanamidophenylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzene sulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfona, mido group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N, N -dibutylcaroctamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(3-(2,4-di-tert-amylphenoxy)propyl)carbamoyl group, etc. ), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,
N-dipropylsulfamoyl group, N'-(2-dodecyloxyethyl)sulfamoyl L N-ethyl-N-
dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfokol group, benzenesulfonyl group, toluenesulfokol group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), heterocyclic oxy group (e.g., l-phenyltetrasol-5-oxy group, 2-
tetrahydropyranyloxy group, etc.), carbamoyloxy group (e.g., N-methylcarbamoyloxy group, N
-phenylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, dibutylmethylsilyloxy group, etc.), aryloxycarboxylamino group (e.g., phenoxycarbonylamino group, etc.),
Imide group (e.g., N-succinimide group, N-7 talimide group, 3-octadecylsulcinimide group, etc.)
, heterocyclic thio group (e.g., 2-benzothiazolylthio group, 2,4-di-phenoxy-1,3,5-triazole-6-thio group, 2-pyridylthio group, etc.), sulfinyl group (e.g., dodecanesulfinyl group, 3-
pentadecylphenylsulfinyl group, 3-phenoxypropylsulficol group, etc.), phosphonyl group (e.g., phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group, etc.), aryloxycarbokol group ( For example, phenoxycarbonyl group, etc.),
Acyl group (e.g., acetyl 3-7-nyl)
Y represents a hydrogen atom, a halogen atom (e.g. 1 chlorine atom, bromine atom, iodine atom, etc.), or a carboxy group. , and groups linked by elementary atoms (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyl group) Oxy group, phenoxy group, 4-cyanophenokyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2 -cyanoethoxy group, benzyloxy group, 2
-phenethyloxy group, 2-phenoxyethoxy group, 5
-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked via a nitrogen atom (e.g.
Benzenesulfonamide group, N-ethyltoluenesulfonamide group, he'butafluorobutanamide group, 2.
3. 4゜5.6-pentafluorobenzamide group,
Octane sulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamono, ylamino group,
1-piperidyl group, 5,5-dimethyl-2,4-dioxy-3-oxazolidinyl group, l-benzyl-ethoxy-3-hythantoynyl group, 2N-1,1-dioxo-3(2H)-oxo-1, 2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-l.

2.4-1 riazol-1-yl, 5 or 6-promobenzotriazol=1-yl, 5-methyl-1,2,
3,4-) lyazol-1-yl group, benzimidazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, 1-engineered toxycarbonyltridecylthio group, 2,3,4.5-tetrazolylthio group, 2-benzothiazolyl group, thiocyano group, N,N-diethylthiocarbonylthio group, dodecyloxythiocarbonylthio group, etc.), groups connected by carbon atoms (e.g., triphenylmethyl group, hydroxymethyl group, N-morpholinomethyl group, L4, where R6.R7 is a hydrogen atom, an alkyl group, an aryl group,
represents a heterocyclic group, R4 and R5 have the same meanings as defined above, etc.).

R4. To describe in more detail the divalent group in which R5 or Y becomes a divalent group to form a bis body, R,, R5 is a substituted or unsubstituted fullkylene group, for example, a methylene group, an ethylene group, 1.10 -Decylene group, -CH CH -0
-CH2CH,, -, 2, etc.), substituted or unsubstituted phenylene groups (e.g., 1, 4
-phenylene group, 1,3-phenylene group, -NHCO-R8-CONH- group (R8 represents a substituted or unsubstituted alkylene group or phenylene group, for example, -NHCOCH2CH2CONH).

H a shows. ).

Next, pyrazolo[1.
5-b][1, 2, 4] Specific examples of the triazole derivative are illustrated below, but it goes without saying that the present invention is not limited thereto.

/ / (Physical data) Ha H3 15°C 7/''/' (Effects of the invention) According to the present invention, it is useful as a magenta coupler for color photography and as an intermediate for the production of photographic sensitizing dyes. , a new azapentalene compound, pyrazolo [1,5-
bl[1,2,4] triazole derivatives can be produced. Furthermore, the compound of the present invention has the possibility of being used as a physiologically active substance, and can also be used as an intermediate for pharmaceutical production.

This compound is coupled with an oxidation product of an aromatic-grade amine to produce a magenta dye with extremely good hue and superior light and heat fastness than conventional pyrazolone dyes.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 (Synthesis of Exemplary Compounds 1 and 2.3) (A) 1-
Synthesis of amino-4-benzyl-3,5-dimethyltriazolium iodide (II) In the following examples, (I
I), unless otherwise specified, this 1-amino-
4-Benzyl-3°5-dimethyltriazolium iodide was used.

(i) 2,5-dimethyl-1,3,4-oxadiazole obtained by thermal decomposition of tetraacetylhydrazine (
■) 19g (0.19mol) and benzylamine 3
1g (0.29mol) was reacted at 110°C for 4 hours to form 4-benzyl-3,5-dimethyl-1,2,4-
28 g of triazole (VI) was obtained. Yield 73%, melting point 125-127°C.

Hydroxylamine-〇-sulfonic acid s6g (0,58
mal) and 40 g potassium hydroxide (85%, 0.81
An aqueous solution of potassium hydroxylamine-〇-sulfonate prepared from @ol) and the above triazole (Vl)
After reacting with 75 g (0.4 mol) at 80 to 80°C for 6 hours and returning to room temperature, the pH was adjusted to 8 to 8 with a 50% aqueous potassium carbonate solution. The generated potassium sulfate was filtered off, and the filtrate was extracted three times with chloroform. The starting material triazole was extracted from this chloroform extract.
4g (59%) recovered. The aqueous layer was adjusted to pH 3 with a 57% aqueous hydriodic acid solution under water cooling, and crystals were precipitated. The crystals were filtered and recrystallized from ethanol at -20°C to obtain 39 g (31%) of (II) as pale yellow crystals.

(ii) 0-(2,4-dinitrophenyl)hydroxylamine (J, Org, Che
rs, No. 1239 (1973)), (II) was synthesized as follows.

4-Benzyl-1,2,4-) Riasor (VI) 3
5 g, c 0.19 mol) in dichloroethane 3
0-'(2,4-dinitrophenyl)hydroxylamine (0,131101) was added little by little (approx.
(over 5 minutes) and stirred for a further 2 hours at this temperature. After dichloroethane was distilled off under reduced pressure, the residue was dissolved in 100 mL of water, and the pH was adjusted to 3 with a 57% aqueous solution of hydroiodic acid. 2,4-dinitrophenol precipitated, but was removed by extraction with ethyl acetate (three times).

The aqueous layer was concentrated and the residue was I++ crystallized from ethanol to give (II) in 70% yield.

In addition, O-diphenylphosphinylhydroxylamine (Synthesis) is used as an aminating agent.

592 (1882)-, Tetrahedron L
ett, 23, 3835 (1982)), the procedure is almost the same, but in this case, after treatment with hydroiodic acid, diphenylphosphinic acid is recovered by filtration (90% or more) without extraction. was completed.

(B) 7-acetyl-1-benzyl-2,6-dimethylpyrazolo[1,5-b] [1,2,4], triacy-N-aminotriazolium iodide (II) 8 g (
Dissolve 0.025 mol) in 50 ml of DMF (dimethylformamide), add 40 ml of acetic anhydride, and dissolve 1
Heated to 20°C. Then 12.5g of sodium acetate
was added and stirred at 120-130°C for 4 hours.

After removing DMF, acetic anhydride, etc. under reduced pressure, the mixture was made basic with a saturated aqueous sodium carbonate solution, and then extracted with chloroform.
After drying the extract over anhydrous magnesium sulfate, the solvent was distilled off to obtain a brown oil. This was purified using a silica gel column in a solvent system of n-hexane-ethyl acetate to obtain 7-acetyl-1-benzyl-2,8-dimethylpyrazolo[1].

5-b] [1.2.4]) Riazole (↓)
3.2 g' (47%) was obtained. Melting point 105-10
7°C nuclear magnetic resonance spectrum (CDC13) δ (pP m): 2.3fi (3H, s)
2.43 (3H, s) 2, 60 (3) 1, s) 5
．． 80(2)1,s) 7.0~7.2(2H)'
7.2-7.38(38) (C) 1-benzyl-2,6-dimethylpyrazolo[1
,5-b] [1,2,4]) Synthesis of lyazole (2) 1. 2 g (7.5 mmol) was dissolved in 20 m4 of ethanol, and this was mixed with 20 m9 of concentrated hydrochloric acid. Add and heat to reflux. The ethanol was removed under reduced pressure for about 6 hours, the ethanol was basified with a saturated aqueous solution of sodium bicarbonate, and the deacetylated 1-benzyl-2 was almost pure when extracted with ethyl acetate.
,6-dimethylpyrazolo[1,5-bl[1,2,4
] 1.6 g (95%) of triazole (2) was obtained. Melting point 87-88°C Nuclear magnetic resonance spectrum (CDC13) δ (pp m): 2.32 (3) 1. s)
2.44(3)1. s) 5.02 (2H, s) 5
．． 22 (IH, s) 7.10-7.40 (511) (
D) LH-2,8-dimethylpyrazolo[1,5-bl
[1,2,4]) Synthesis of lyazole (3) l-benzyl-2,6-dimethylpyrazolo [1,5-bl[1,
2, 4] Triatool (2) 1. Ei g (7.1m
mol) with liquid ammonia (approximately 0.8 g of sodium metal) to obtain the desired IH-2,6-dimethylpyrazolo [1,5-bl [1,:! , 4] Triazole (3) - 0.87 g (70%) was obtained as colorless crystals. Melting point 2
74-275°C (decomposition) Mass spectrometry 13B (M", 100%) Elemental analysis value C (%) H (%L N (%) theoretical value 5
2.93 5.92 41', 15 measurement value 52.85
B, 02 41.01 Nuclear magnetic resonance spectrum (CDC
13:pyridine-d5=1:1) δ (P p m): 2.35 (3H, s) 2.
43(3H,s) 5.50(IH,s) <Example 2> (Synthesis of Exemplary Compound 5) N-aminotriazolium iodide shown in Example 1 (
II) 5g (18mmol) and 5 equivalents of lauric anhydride 3Qg (71ammol) and tripropylamine 11g (77mmol) in 100ml of DMF!
140-150°C for about 10 hours. DMF
was removed using a biheporator, ethyl acetate was added, and precipitated unreacted lauric anhydride was removed by filtration. The filtrate was transferred to a separating funnel, and a 2N aqueous sodium hydroxide solution was added thereto and thoroughly shaken to separate the layers. The aqueous layer was further extracted twice with ethyl vinegar,
After washing the ethyl acetate layer with saturated brine, it was dried over magnesium sulfate [7. To the resulting residue, 30 ml of concentrated hydrochloric acid and 50 ml of ethanol were added, and after heating under reflux for about 4 hours, the ethanol was removed, and the mixture was diluted with ethyl acetate. Extracted. After the usual post-treatment, the 1-benzyl compound was purified using a silica gel column.
．． 8g (14%) obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (P p m): 0.88 (3H, brt, J
= ~? ) 1.30 (20H, brs) 2.40 (3
H,s) 2. C0 (2H, t, J=7.5) 5.0
3 (2H, s) 5.25 (IH, s) 7.10-7.
45(5H) This 1-benzyl compound was reduced with sodium in liquid ammonia to obtain Exemplified Compound 5, which is sparingly soluble in organic solvents other than alcohol, with a yield of about 80%. Melting point 154-1
55°C <Example 3> (Synthesis of Exemplified Compound 6) 7.2 g (55 mmol) of n-hebutanoic acid was dissolved in 15 m of dimethylformamide (DMF), and 7.9 g (55+ smol) of tri-n-propylamine was dissolved therein.
was added, and then 8.1 g (51+*mol) of trimethyl 4-cetyl chloride dissolved in DMFlomM was added dropwise. After stirring for 10 minutes at room temperature, 5 g (15.8 gmol) of N-aminodriazolium iodide (II)
and tri-n-propylamine 11.3 g (79 mmo
1) was added and gradually heated to 150°C, followed by IW stirring at that temperature for about 5 hours.

After distilling off DMF and the amine under reduced pressure, add 100 ml of a 2N aqueous solution of I.lium hydroxide, and add 31-1 with ethyl acetate.
1, and the extract was washed with water and saturated brine, and dried over magnesium sulfate. It was filtered and concentrated under reduced pressure, and the residue was purified by silica gel chromatography to obtain (IV) (R1=
-CH3,R2=-C)(2-◎,R3=''''C6Hl
3) 2.9g (45%) was obtained.

When this was deacylated and debenzylated by the methods shown in (C) and (D) of Example 1, 1.0g of 6 (E18
%) could be obtained. Melting point 10.5-110 °C Nuclear magnetic resonance spectrum (DMSO-d6') δ (P p
m): 0.85 (3H, brt, J= ~?)
1.32 (8H, brs) 2.45 (3H, s)
2.58(2H,t, J=7.5)5,[1O(IH
,,s) <Example 4> (Synthesis of Exemplary Compound 7) (II) 1.0 g (3.18 mmol) was added to anhydrous D
Dissolve 8 m of MF and add 3.0 m of benzoic anhydride to the solution.
6g (15.8mmol) and tri-n-propylamine
2.3 g (15.8 mmol) was added, and the mixture was heated and stirred at 130° C. for 24 hours. After DMF and tri-n-propylamine were distilled off under reduced pressure, 30 ml of ethanol and 10 ml of concentrated hydrochloric acid were heated under reflux for a processing time of 5E1. After distilling off ethanol and concentrated hydrochloric acid under reduced pressure, extraction with ethyl acetate, drying, concentration, and purification with silica gel chromatography yielded 1-benzyl compound 0.
．． 2g (22%) was obtained.

Nuclear magnetic resonance spectrum (CDCl2) δ (p p m): 2.35 (3H, s) 4.9
5 (2H, s) 5.85 (IH, s) 7.05~7
．． 50 (8H) 7.80 (2H, dd, J=9.0
゜1.5) 0.2 g (0,'89m5+ol) of 1-benzyl compound was reduced with 0.05 g of sodium in liquid ammonia, and 1
0.12g (87%) of the target 7 was obtained. Melting point ~1
90°C (decomposition) <Example 5> (Synthesis of exemplified compounds 8 and 9) 1.00 g
(32 mmol) of (II) was added to 15 mJL of N-methylpyrrolidone and stirred at room temperature. To this was added 2.93 g of methoxycarbonylpropionic anhydride and 4.8 mJl of tripropylamine in order, and heated in an oil bath at 130 °C. Heated on top for 3 hours. After cooling, it was diluted with ethyl acetate and washed with water (100ml x 2). The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and 30 mL of methanol and 20 mL of concentrated hydrochloric acid were added thereto, followed by heating under reflux for 7 hours. After cooling, depressurize the ethanol! The residue was poured into 100 m of ice water, neutralized to pH 7, and extracted with ethyl acetate (50 m JLX3). The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and purified with a silica gel column (20 g) to give 80.16 g (
17%) was obtained as an oil.

Nuclear magnetic resonance spectrum (CDC13) δ (P p m): 2.42 (3) 1. s)2.
6Q ~3.15 (4H.

m) 3.83 (3H, s) 5.02 (2H, s) 5.2
8 (IH, s) 7.12-7.50 (5H,, m) Elemental analysis value C (%) H (%) N (%) Theoretical value 8
4.41 θ, 08 18. ? θ experimental value 84.22
B, 30 18.55 This N-benzyl compound was reduced with sodium in the same manner as above to obtain Exemplary Compound 8 in a yield of about 80%. Melting point: 120-122°C <Example 6> (Example Compound 11.12.13.14 combination! 11.5 g (30 mn+ol) of (II) and 65 g (150 mmol) of anhydrous 4-(p-nitrophenyl) ) Butyric acid and 57 mmol (300+ imol) of tripropylamine were dissolved in 150 mJ of DMF. The mixture was stirred for 4 h on a 130 °C oil bath, followed by 2 h on a 1'40 °C oil bath. The mixture was further heated on an oil bath at 180°C for 6 hours.

After DMF was distilled off under reduced pressure, it was dissolved in ethyl acetate, and this ethyl acetate solution was washed (twice) with 2N NaOH aqueous solution. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (600 g of silica gel).

Eluent: hexane:ethyl acetate = 2:1 to 1:1), and 7.8 g (45%) of (IV) (R, = -C
H3゜n2 = -CH2 heat n3 = -CCH2) 3C6H, -NO,,) was obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (p p m): 2.40 (3H, s) 1.8
-3.3 (12H.

n+) 5.80 (2H, s) 7.0~7.4 (9H
, m) 8-1 (4H.

m) 7.6 g (13 mmol) of (IV) as E t O
It was dissolved in a mixed solvent of 150 mJ1 of HCl and 50 m of concentrated hydrochloric acid, and heated under reflux for 10 hours. After adding 100mM of water, ethanol was removed by concentration under reduced pressure. After neutralization with aqueous ammonia, extraction was performed with ethyl acetate, and the ethyl acetate layer was dried over anhydrous magnesium sulfate. After concentration, it was subjected to silica gel column chromatography (140 g of silica gel, eluent: hexane: ethyl acetate = 1:1) (IX) (R, =
-CH3,n2= -CH2-<EE>, n3=-
(CH2) 3C6H4No2) 3.8g (78%)
I got it.

Nuclear magnetic resonance spectrum (CDCl2) δ (P pm) + 2.03 (2H, m) 2.4
4 (3H, s) 2.58-2.85 (4) 1. m)
5.02 (2H, S) 5.20 (IH, s) 7.
04-7.40 (7H, m) 8.04 (2H, d, J
=8.0) 1 reduced iron in 80mM isopropyl alcohol
8g (0.32mol), ammonium chloride 1.
3g (25mmol) and 8mM of water were added, and the mixture was heated with vigorous stirring until it reached a reflux state. To this was added 0.2 ml of concentrated hydrochloric acid, and the mixture was heated under reflux for 30 minutes. To this, 18.0 g (47.9 mmol) of the nitro compound described above was added little by little over 20 minutes, and the mixture was further heated under reflux for 1 hour.

It was filtered through Celite, and the Celite was thoroughly washed with ethanol.

The filtrate was concentrated, dissolved in ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. Concentrate to obtain the crude aniline compound ((■) n3=-(,CH2)3
15.8 g (85%) of C6H4NH2 was obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (p p m) + 1.95 (2H, m) 2.
38 (3H, s) 2.40-2.78 (4H, m) 3
．． 38(2H,br)j,9? (2H,s)5.20(
IH, s) 8.53 (2H, m) 6.91 (2H,
m)? ', 00 to 7.38 (5H, m) 15.8 g (45.7 mmol) of this aniline compound was added to 200 mM of liquid ammonia under reflux and stirred. 2.8 g (0.11 mol) of metallic sodium was added little by little to this. Ammonium chloride was added little by little to this, and the mixture was left to stand overnight to remove ammonia. 2 residues
Dissolved in aqueous N HCI and washed with ethyl acetate. The aqueous layer was neutralized with aqueous ammonia, and the precipitate was collected by filtration. The precipitate was washed with water and then with acetonitrile and dried to obtain almost pure 117. sg (as%) was obtained.

Melting point 198-203℃ Nuclear magnetic resonance spectrum (CDCl +, DMSO-d6) δ (p p m): 1.88 (:!H, br, q
uintet, J=-7)2.41 (3H,s)
2.3-2.8 (4H) 5.42 (IH, s) 0.
56 (2H, d, J=8.5) [f, 90 (2H,
d, J = 8.5) Mass spectrometry spectrum 255 (M', 20% > 136 (100)
, +19 (90) 10B (50) Infrared absorption spectrum (KBr) 3340, 1805.150? , 1380.1270
cm'11 3.0Hg (11.7 mmol) was added to 50 mJ1 of acetonitrile, 25 ml of N,N-dimethylacetamide was added thereto, and the mixture was heated with a stirrer until it reached a reflux state. Add acid chloride r@-c H20+5O to this
2-@=OCH(n-C1oH2,)COCl)7.1
A solution of 9 g (12,'9 mmol) in acetonitrile (
20 mfL) was added dropwise over 20 minutes, and the mixture was refluxed for an additional 20 minutes. Furthermore, 0.72 g (0,1
3 mmol) acetonitrile solution (10 mjJ)
After dropping for 0 minutes, refluxing was continued for 30 minutes. After cooling, the mixture was poured into 500mM water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (300 g of silica gel).
', eluent chloroform:methanol = 60:1)
7.25 g (80%) (7)+2 (solid) was obtained.

Elemental analysis value C (%) H (%) N (%) S (%) Theoretical value 8
9. Ei5 6.88 9.02' L13 measurement value 8
8.99 8.90 8.110 4.0? Mass spectrometry (
FD) 77B (M”, b, p) Nuclear magnetic resonance spectrum (CDCl2) δ (P p m): 0.8B (3H, brt,
J=7) 1.0-2.2 (208, m) 2.38 (
3H, s) 2.5-2.8 (48, m) 4.88 (I
H, brt, J=8) 5.05 (2H, p) 5.4
5 (IH, s) 6.9-7.4 (13H, m) 7.
7-7.9 (4H, m)'8.17 (IH, 5) 11.
8 (IH, br) 3.3 g (4.3 mn+ol) of benzyl compound 12 was dissolved in 80 m of THF, and 10% Pd/CO 0.68 g was added.

This was stirred for 3 hours at eo'c under a hydrogen atmosphere of 60 atm. After cooling, the catalyst was removed by filtration and the filtrate was concentrated. Silica gel column chromatography (silica gel 80g
, Eluent chloroform:methanol-1:0-30:
1) to obtain 2.7 g (f32%) of 13 as a solid.

Mass spectrometry (FD) 887 (M” + 2.50%)
68El (M” + 1.100)885 (M+
, 30) 4.25 g (8,2On+mol) of daughter and THF5
0rnQ was added to 100 mJlj of dichloromethane and dissolved by stirring at room temperature. This includes 795 mg (5,
95 mmol) of N-chlorosuccinimide was added, and 1
Stirred for 5 minutes at room temperature. Clean with water (150m x 2)
It was then dried over anhydrous magnesium sulfate. After concentration, silica gel column chromatography (silica gel 100
g, eluent chloroform:methanol-5 (1:1-3
0:1) 4.04 g (90%) of Dish 14 was obtained as a solid.

Mass spectrometry (FD) 722.721.720 (9 near: 9) 220 (b, P) <Example 7> (Synthesis of exemplified compound 15.18) 11 -
1 → Costopoda, 1.79 g (7,00 mmol) and 15 mM of N,N-dimethylene) Lt7mid in 30 m 5 L of acetonitrile
The mixture was heated and stirred until it reached reflux. To this, acid chloride C(t-C3H,,)2C6H30CR(n-C
4H9)'COCl )2.83g (?,?Omn+
An acetonitrile solution (10 mL) of ol) was added dropwise over 15 minutes, and reflux was continued for an additional 30 minutes. After cooling, it was poured into 300 m of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (silica gel 100
The product was fractionated using an eluent of chloroform:methanol (70:1) to obtain 3.12 g (78%) of 15 as a solid.

Elemental analysis value C (%) H (%) N (%) Theoretical value?
3.81 8.7? 11.95 measurement value? 3.84.
8.95 11.93 Nuclear magnetic resonance spectrum (CDC1
3) δ (p p m): 0.50 to 1.00 (7H',
m) 1.00-2.16 (28H, m) 2.44 (
3H, s) 2.46 ~ 2.80 (4H, m) 4, E1
8(1)1. t, J = 6.0) 5.44 (IH, s
) 8.90 -7.34 (6H, m) 7.84 (IH
, d, J=9.0) 7.87 (III, br.

S) 3.10 g (5.29 mmol) of 15 and T HF
50ml was added to 100mJL of dichloromethane, and the mixture was stirred and dissolved at room temperature. To this was added 7011 t+mg (5.29 mmol) of N-chlorosuccinimide, and the mixture was further stirred for 10 minutes. After washing with water (150 mJlj x 2), it was dried over anhydrous magnesium sulfate. After concentration, acetonitrile was added to crystallize, and the mixture was heated to reflux once. After cooling, it was collected by filtration, washed with acetonitrile, and dried.
Obtained 2.4 g (73%) of 6 as a solid.

Elemental analysis value C (%) H (%) N (%) C1 (%) Theoretical value 69.71 8.12 11.29 5.72 Measured value [
(9,368,2111,255,78 nuclear magnetic resonance spectrum (CDC13) δ (P p m): 0.48-1.OO(?H,
m) 1.06-2.1.8 (28H, m) 2.45
(3H, s) 2.48 - 2.82 (4H, m) 4.
67 (IH, t, J=6.0) 8.85 (IH, d,
J=8.5) 8.81~7.34(BH,ll)'
7.87 (IH, s) <Example 8) (Example Compound 21
．． 22.17 synthesis) 2.93 g (5,0Hmmo
15 of 1) was added to 25ml of acetic acid and stirred at room temperature.

Add to this 580 mg of isoamyl nitrite (5,00 mmoi
) was added dropwise and further stirred for 1 hour.

This was slowly added to 300 mM water, and the precipitate precipitated was collected by filtration and washed with water. It was dried under reduced pressure to obtain 2.95 g (88%) of 7-nitrone compound 21 as a solid.

Melting point: Approximately 85°C 2.85g (4.83mmol) of 7-nitrone 2
1 was dissolved in 50 mM ethanol and heated to reflux under a nitrogen atmosphere. To this, 4.38 g of stannous chloride (
23,1+aa+ol) in concentrated hydrochloric acid solution (10ml)
It was added dropwise over 0 minutes. After continuing to reflux for an additional 30 minutes, the mixture was cooled. This was poured into 150 ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated to dryness. Thus, 7-amine compound 2
A complex of 2 and tin was obtained.

Free 22 can be obtained by treatment with base, but is susceptible to air oxidation. Here, the complex was used in the next reaction as is.

This 7-amino compound 22 was dissolved in 25 mJL of pyridine and stirred under a nitrogen stream while cooling with water. To this was added 2.15 g of acid chloride [H(CF2) 8COCl (4,
f (3 mmol) was added dropwise, and the mixture was further stirred for 1 hour.

This was poured into 250ml of water and extracted with ethyl acetate.

The ethyl acetate layer was washed with 2N hydrochloric acid and then with water. After drying the ethyl acetate layer over anhydrous magnesium sulfate,
Concentrated. Silica gel column chromatography (150 g of silica gel, eluent chloroform: methanol = t
oo:1), the eluate was concentrated to dryness, and 173
．． 43g (72%) was obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (p p m): 0.52 to 1.01 (7■,
m) 1.02-2.15 (2flH, m) 2.42
(3H, s) 2.46-2.78 (4) 1. m)4
．． 60 (IH, t, J=8.0) 6.30 (1) 1
．． tt, J=51.0°5.0) 7.45(IH
, d, J=8.5) 8.85-7.3B (811,
■) 8.90 (1) 1. brs) 10.0 (1B,
brs) 10.3 (ill, brs) procedural amendment (voluntary) io month 1982? Mr. Manabu Shiga, Commissioner of the Japan Patent Office, 1, Indication of the case, Patent Application No. 45601, filed in 1982, 2, Name of the invention, Process for producing pyrazolo [1,5-b] [1,2,4] triazole derivatives 3 , Relationship with the case of the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520)
Representative of Fuji Photo Film Co., Ltd. Nagisa Dai Nishi 4, Agent address: 2nd floor 6, Nagakubo Building, 2-14-6 Shinbashi, Minato-ku, Tokyo Number of inventions increased by amendment - 107, Subject of amendment: ""Claimscolumn" and "Detailed description of the invention column" 8. Contents of amendment (1) The statement in the "Claims" section of the specification will be amended as shown in the attached sheet.

(2) The statement in the "Detailed Description of the Invention" column of the specification is amended as stated in F.

1) 1812 Hesi 14 line tEl Norc) (SOeJ
4 2) Correct “triazole” in the first line of page 13 to “triazole”.

Claims (1) General formula (wherein R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R2 represents an alkyl group, a 11\-substituted alkyl group, represents an aryl group or a 1δ-substituted aryl group, and X represents an acid radical. ) is subjected to chemical condensation with an acid anhydride represented by the following to form a 7-acylated pyrazolo [4,5-b ]
[1,2,4] 1- characterized by obtaining triazole
A method for producing a pyrazolo [1,5'-bl [1,2,4] triazole derivative.

(2) General formula: 1 (wherein, R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R2 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. ) A triazole compound represented by the above general formula (wherein R and R2 have the same meanings as above) is obtained by N-aminating the triazole compound represented by the above formula.

X represents an acid radical. ) Pyrazolo [1,5-bl[1,2
, 4]) Method for producing a lyazole derivative.

(3) General formula (wherein R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, R2 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and X represents N-aminotriazolium salts represented by the general formula (wherein R3 is a hydrogen atom, an alkyl group, a substituted alkyl group,
An aryl group or a substituted aryl group is cyclized and condensed with an acid anhydride represented by (indicates), and is represented by the general formula (wherein R, R and R3 have the same meanings as above). 7-acylated pyrazolo [1,5-bl[
1,2,4] A triazole is obtained, which is deacylated and then reduced to introduce a leaving group Y to obtain the general formula (wherein R and R3 have the same meanings as above, and Y is a hydrogen atom or represents a coupling-off group) pyrazolo [1; 5-bl[1,2,
A method for producing a pyrasolo[1,5-b][1,2,4] triazole derivative, the method comprising obtaining a 41 triazole compound.

Claims (3)

[Claims] (1) General formula (wherein R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, R2 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and X represents (representing an acid radical) and an acid anhydride represented by the following formula: By condensation, 7-acylated pyrazolo [1,5=b][
1,2,4]) A method for producing a pyrazolo [1,5-bl [1,2,4]) lyazole derivative, which comprises obtaining lyazole. (2) General formula (wherein, R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R2 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.) A patent for obtaining an N-aminotriazolium salt represented by the general formula (wherein R and R2 have the same meanings as above, and X represents an acid group) by N-aminating a triazole compound represented by Pyrazolo[1,5-bl[1,2,
4] Method for producing h-lyazole derivative. (3) General formula (wherein R1 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, R2 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and X represents represents an acid radical) and the general formula (wherein R3 is a hydrogen atom, an alkyl group, a substituted alkyl group,
Indicates an aryl group or a substituted aryl group. ) to form a 7-acylated pyrazolo [1,5-bl [
1,2,4] A triazole is obtained, which is deacylated and then reduced to introduce a leaving group Y to obtain the general formula (wherein R and R3 have the same meanings as above, and Y is a hydrogen atom or represents a coupling-off group) pyrazolo El, 5-bl[L 2.
4]) A method for producing a pyrazolo[1,5-b][1,2,4]) lyazole derivative, which comprises obtaining a lyazole compound.