JPS60215687A - Production of pyrazolo(1,5-b)(1,2,4)triazole derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 and R2 are H, (substituted) alkyl or (substituted)aryl]. EXAMPLE:The compound of formula II. USE:A magenta coupler for photographic use. PREPARATION:The objective compound can be prepared by reacting the aminopyrazole of formula III (e.g. amino-3-methylpyrazole) with the imide ester of formula IV (R3 is alkyl) (e.g. acetoimidic acid ethyl ester hydrochloride), and subjecting the resultant compound of formula V to oxidative condensation preferably at 60-150 deg.C for 0.1-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel pyrazolo[1,5-bl[1,2,4
]) Concerning a method for producing a lyazole derivative.

(Background of the invention) It has a nitrogen atom at the bridgehead position, and this nitrogen atom and another
A general formula with a total of at least 2 and a maximum of 6 nitrogen atoms, in which 10 π electrons can interact, including the lone pair of electrons on each nitrogen atom...; show.

・; Indicates 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., Hetero-cyclic.
Chem, 10, 411 (1973),
H, Koga.

, old robe, T, Okamata, Cher
t, Pharm, Bull-.

22, 482 (1974), J. Balley,
J, C, S, Perkin 12047 (837
? ), Japanese Patent Publication No. 47-27411, Japanese Patent Publication No. 1977-12
11586, etc.).

However, the conventional 7zapentalene compounds have not yet been satisfactory as photographic magenta couplers in terms of hue and light/thermal fastness.

The present inventors have conducted intensive research to develop a new coupler compound that overcomes the drawbacks of the conventional azapentalene compounds, and as a result, when introducing pyrazole),
This group causes an oxidative ring-closing reaction with the pyrazole ring, forming a new azapentalene compound, pyrazolo[1,5-bl
[1,2°4] A triazole compound was prepared and it was found that the compound exhibits extremely excellent properties as a photographic magenta coupler. The present invention has been made based on this knowledge.

(Structure of the Invention) That is, the present invention subjects a compound represented by the general formula (wherein R1 and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group) to an oxidative condensation reaction to obtain a compound represented by the general formula ( In the formula, R1 and R2 have the same meanings as above.) Pyrazolo[
A method for producing a 1,5-bl [1,2,4] triazole derivative is provided.

In this method, the compound represented by the above general formula (II) is preferably an aminopyrazole represented by the general formula (wherein R2 has the same meaning as above) and a general formula (wherein R1 has the same meaning as above). (having the same meaning, R3 represents an alkyl group) is prepared by reacting with 4 imide ester. In this reaction, a compound represented by the general formula (wherein R, R and R3 have the same meanings as above) is produced by a side reaction, but by reacting this compound with ammonium chloride, the above general formula Formula (II
) can be converted to a compound represented by

In addition, if a coupling-off group is introduced into the compound represented by the general formula (m) obtained by the above method, the general formula (wherein R and R2 have the same meanings as above, and ) is obtained.

In the present invention, the general formula (II), (m), (I
In the compounds represented by V), (V), (Vl) and (■), the alkyl groups of R, R and R3 range from lower alkyl groups such as 2 methyl, ethyl, propyl and butyl groups to 22 carbon atoms. It means a higher alkyl group up to, for example, a pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, tridecyl group, octadecyl group, etc., and may be linear or branched.

Aryl groups for R1 and R2 include phenyl and naphthyl groups, and substituted alkyl groups include 2-
Halogen-substituted alkyl groups such as chloroethyl group and trifluoromethyl group, alkoxy-substituted alkyl groups such as 2-ethoxytridecyl group, acylamido-substituted alkyl groups such as 2-acetamidoethyl group, sulfonamide-substituted alkyl groups such as 2-methanesulfonamidoethyl group Group, 3-(
2,4-di-t-amylphenoxy)propyl group, 3-
An alkyl group substituted with a substituted or unsubstituted aryl group such as (4-(2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido)phenyl)propyl group, benzyl group, or phenethyl group is a substituted aryl group. Examples include halogenophenyl group, nitrophenyl group, cyanophenyl group, and alkoxyphenyl group. Moreover, these R and R2 are groups inert to the reaction,
For example, it may have an alkoxyl group, a nitro group, a halogen atom, etc. as a substituent.

In addition, pyrazolo[1,5-b
] [1,2,4] Triazole derivative, R
Compounds in which 1 or R2 has a number and a substituent as described above can be obtained directly according to the reaction scheme described below, or in this scheme, the basic skeleton pyrazolo [
1,5-b][1,2,4]) The lyazole ring may be formed and then guided to a desired substituent by a subsequent reaction.

The method of the present invention can be expressed by the following reaction scheme.

This reaction scheme is based on the hydrochloride of the imidoester represented by the general formula (V). Although (II) is thought to have the following tautomerism, it is thought that the structure of (II) is more predominant than that of (II) ωc (IIA), so below we will discuss (II) and (IIA). Let us simply represent the mixture by the structure (II).

Furthermore, it is preferable to use a protonate salt of an imidoester which has been at least partially salted than to use the imidoester in a free state. A wide variety of mineral acids and organic acids can be used as protonic acids for salt formation. As the mineral acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, etc. can be used, and as the organic acid, P-)luenesulfonic acid, 2. Examples include 4,6-)limethylphenylsulfonic acid, acetic acid, monochloroacetic acid, etc. Among these, imidoester hydrochloride can be preferably used, and in the following explanation, hydrochloride will be used as a representative example. However, it is not limited to this.The salt production ratio is several percent.
Although a catalytic amount of 100% may be used, an equimolar or stoichiometric amount is preferable from the viewpoint of reaction yield and ease of handling of the imidoester.

The reaction of the aminopyrazole (IV) with the hydrochloride of the imidoester (V) is preferably carried out using a solvent between 0 and 100
°C temperature, preferably 20-80 °C, reaction time 1-80 °C.
This will be done over a period of 10 hours.

If the reaction temperature is below O'C, the reaction is slow. Even if it exceeds lOO'C, there is no major problem, but the yield may decrease.

The reaction solvent is preferably a solvent in which imidoester hydrochloride is soluble, or an alcoholic solvent such as methanol, ethanol, or isopropanol.

The molar ratio of aminopyrazole (IV) to imidoester (V) is preferably in the range of 1:1 to 1:2.

Specific examples of aminopyrazole (IV) include t±, 3-aminopyrazole, 5-ami7-3-methylpyranol,
5-amino-3-phenylvirasol, 5-amino-
Examples include 3-[3'-(p-nitrophenyl)propyl]pyrazole.

Note that aminopyrazole (IV) can be used as a commercially available product, but if necessary, it can be synthesized by reacting an oxopropiononitrile derivative obtained by reacting an acid/\loginide with an enolate of sodium cyanacetate and hydrazine. I can do it. In addition, if R2 is a methyl group, (IV) (
R=-CH3) can be synthesized (J, Heterocy
cl.

0hem, vol. 11, p. 423, 1!374).

Furthermore, aminopyracil (IV) and imidoester (V)
In the reaction with the hydrochloride of the general formula (II), when the reaction is carried out at a low temperature, the proportion of the imide ester compound of the general formula (VD) increases, and when the reaction is carried out at a high temperature for a long time, the proportion of the imide ester compound (II) increases. The imidoester compound of formula (VI) can be easily converted into the desired compound of general formula (II) by adding an excess amount of ammonium chloride and heating under reflux.

Next, pyrazolo[1,5-b] [1°2.4] of general formula (III) is obtained by oxidative condensation of the compound of general formula (rx)
] The synthesis of the triazole compound is carried out at a reaction temperature of 60 to 15
The reaction is carried out at 0°C for a reaction time of 0.1 to 5 hours.

If the reaction temperature is below the lower limit of the above range, for example, only a complex with the oxidizing agent lead tetraacetate is formed, but no cyclized product is produced, and if it exceeds the upper limit, the product decomposes, etc., reducing the yield. There are cases.

As the oxidizing agent, lead tetraacetate, N-halogenosuccinimide, bromine, etc. are used in an amount ranging from 1 to 4 equivalents, preferably 1 equivalent of lead tetraacetate.

As the reaction solvent, acetic acid, chloroform, tricumyloethane, tetrahydrofuran, ethyl acetate, etc. are used.

Although the desired compound obtained in the above reaction step 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 methods include solvent extraction, recrystallization, filtration, and force. Examples include mucochromatography and thin layer chromatography.

In the method of the present invention, the pyrazolo[1,5-bl[1,2,4]) lyazole compound represented by the general formula (m) is further treated to form a coupling known as a photographic coupler at the 7-position. A leaving group may be introduced. This is a method that is appropriately carried out in the production of photographic couplers in order to adjust the coupling reaction rate of the aromatic-class amine oxidized by silver halide with the oxidation product and to reduce the amount of silver used. This is a well-known fact.

A general method for introducing a coupling-off group will be explained below.

(1) Method for linking oxygen atoms The 4-equivalent mother coupler synthesized by the method of the present invention, a pyrazolo[1,5-bl) riazole coupler, is reacted with the oxidation product of an aromatic-class amine to form a dye. and hydrolyze it in the presence of an acid catalyst to form a ketone body,
This ketone body was subjected to hydrogenation using Pd-carbon as a catalyst, Zn
- 7-hydroxypyrazolo[1,5-bl] by reduction with acetic acid or sodium borohydride
Triazoles can be synthesized. By reacting this with various halides, the desired coupler connecting oxygen atoms can be synthesized. (U.S. Pat. No. 3,928,831,
(Refer to JP-A-57-70817) (2) Method of connecting nitrogen atoms There are roughly three methods for connecting nitrogen atoms. The first method is US Pat. No. 3.41J3! The active coupling site is nitrated with a suitable nitrosating agent as described in No. 111, and then reduced (
For example, hydrogenation using Pd-carbon as a catalyst, chemical reduction using stannous chloride, etc.), 7-amino-pyrazolo[1,5-bl triazole, various halides,
Amide compounds can mainly be synthesized by reacting with

The second method is the method described in Yonezono Patent No. 3,725,087, that is, a suitable halogenating agent, such as fn sulfuryl, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide. After that, the nitrogen heterocycle was halogenated at the 7-position by the method described in Japanese Patent Publication No. 5B-45135 using a suitable base catalyst, triethylamine, sodium hydroxide, zaazabicyclo[2,2,2]
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 1Oπ 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.
Adding π or lOπ electron system aromatic nitrogen heterocycle 50
Aromatic compounds linked by a nitrogen atom at the 7-position by heating at ~150°C without solvent or in an aprotic polar solvent such as dimethylformaldehyde, sulfolane, or hexamethylphosphotriamide at 30~150°C. A nitrogen heterocyclic group can be introduced.

(3) Method of connecting sulfur atoms Couplers substituted with an aromatic mercapto or heterocyclic mercapto group at the 7-position can be prepared by the method described in U.S. Pat. It can be synthesized by dissolving a disulfide in a halogenated hydrocarbon solvent, converting it to sulfenyl chloride with chlorine or sulfuryl chloride, and adding it to a 4-equivalent pyrazo c+[l,5-bl) lyazole coupler dissolved in an aprotic solvent. Done, ゐ. As a method for introducing an alkylmercapto group into the 7-position, US Patent No. 4.28
The method described in No. 4,723, that is, the method of introducing a mercapto group into the coupling active position of the coupler; the method of acting a halide on this mercapto group, and the method of S-(alkylthio)
A one-step synthesis method using isothiourea hydrochloride (or bromine hydrochloride) is effective.

In addition, in the method of the present invention, the substituents R and R2 at the 2-position and 6-position of the pyrazolo[1,5-b][1,2゜4] triazole compound represented by the general formula (m) are themselves It may be converted into a desired photochemically acceptable group by an appropriate treatment according to a known method, for example, the above-mentioned method for introducing a coupling-off group.

Pyrazolo thus derived using the method of the present invention; [
1,5-b] [1,2,4]) The lyazole derivative can be represented by the following general formula.

In the formula, R4 and R5 represent a hydrogen atom or a substituent, and X 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,
ureido group, sulf7moylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group,
Sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
represents an aryloxycarbonyl group or an acyl group, Y is a hydrogen atom, a halogen atom, a carboxy group or an oxygen atom,
Represents a group that couples off with a nitrogen atom, a carbon atom, or a group that bonds to a carbon at a coupling position via a sulfur atom, and R4, R5, or Y may be a divalent group to form a bis form. , In addition, when the vinyl monomer contains a moiety represented by the general formula (Vj[), either R or R5 represents a simple bond or a linking group, and through this, the moiety represented by the general formula (Vl) is The moiety bonded to the vinyl group.

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 may be substituted with an oxygen atom, nitrogen atom, sulfur atom, a substituent linked with a carbonyl group, a hydroxy group, an amine group, a nitro group, a carboxy group, a cyano group, or a halogen atom. , for example, methyl group, propyl group, t-butyl group, tridecyl group, 2
-methanesulfonylethyl group, 3-(3-pentadecylphenoxy)propyl group, 3-(4-(2-[4-(
4-hydroxyphenylsulfonyl)phenoxy] dodecamino)phenyl)propyl group, 2-ethoxytridecyl group, trifluoromethyl group, cyclopentyl group, 3-(2,4-di-t-amylphenoxy)propyl group, etc.) Aryl group (e.g., phenyl group, 4-t-butylphenyl group, 2,4-di-monoamyl phenyl group,
4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, ?-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyan group, alkoxy group (e.g., methoxy group, ethoxy group, 2-
methoxyethoxy group, 2-dodecylethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (
For example, phenoxy group, 2-methylphenoxy group, 4-
t-butylphenoxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α-(2,4-di-t-amylphenoxy)butylamide group, γ-(3-t,-butyl) -4-hydroxyphenoxy)butyramide group, α-(4-(4-hydroxyphenylsulfonyl)phenoxy·)decaneamide group, etc.), achorino group (e.g. phenylamino group, 2
-Chloroanilino group, ? -chloro-5-tetradecanaminoanilino group, 2-chloro-5-dodecyloxycarbonylanilino & N-acetylanilino group, 2-chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy) ) dodecanamide) anilino group, etc.), ureido group (e.g. phenylureido group, methylureido group,
N,N-dibutylureido group, etc.), sulfamoylamide 7 group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group ( For example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4
-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-
5-t-cutylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), alkoxycarbonylamine group (e.g., methoxycarbonylamino group, tetradecyl oxycarbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, P-)luenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t -butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group) , N
-(3-(2,4-di-t-7-milphenoxy)proyl)carbamoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl, 1.N,N~dipropylsulfamoyl group, N-( 2-dodecyloxyethyl)
sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.),
Sulfonyl groups (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.) ), peterocyclic oxy groups (e.g. l-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group, etc.), acyloxy groups (e.g. acetoxy group, etc.), carbamoyloxy groups (e.g. N-methyl carbamoyloxy group, N-phenylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, dibutylmethylsilyloxy group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, etc.), imide group (e.g., N-succinimide group, N-phthalimide FM, 3-octadecenylsulcinimide 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-phenoxypropylsulfinyl group, etc.),
Phosphonyl group (e.g., phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group, etc.)
, aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), acyl group (e.g., acetyl group, 3
- phenylpropanoyl group, benzoyl group, 4-dodecyloxybenzoyl group, etc.), where X is a hydrogen atom,
A halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxy group, or a group linked with an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, ?, 4-dichlorobenzoyloxy group, Ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenokyl group, 4-methanesulfonamidophenoxy group, 4
-thanesulfonylphenoxy 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 through nitrogen atoms (e.g., benzenesulfonamide group) , N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4゜5.6-bentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamono ylami 7 group, l-piperidyl group, 5,5-dimethyl-2,
4-dioxo-3-oxazolidinyl group, l-benzyl-ethoxy-3-hytantoynyl group, 2N-1,1-dioxo-3(2)1)-oxo-1,2-benzointhiazolyl group, 2-oxo -1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3.5-diethyl-1゜2.4-triazol-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.), groups linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, -Octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, l-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolyl group, thiocyano group, N , N-diethylthiocarbonylthio group, dodecyloxythiocarbonylthio group, etc.), groups linked by carbon atoms (e.g., triphenylmethyl group, hydroxymethyl group, N-morpholinomethyl group, hydrogen atom, alkyl group, aryl group,
represents a heterocyclic group, R4 and R5 have the same meanings as defined above, etc.).

To describe in more detail the divalent group in which R, R5 or .10-decylene group, -CH2CH2-O-C
H2CH2-1, etc.), substituted or unsubstituted phenylene groups (
For example, 1,4-phenylene group, l,3-phenylene group, -NHCO-R8-CONH- group (R8 is substituted or unsubstituted fullkylene group or phenylene group -NHCO-R8-CONH- group)
), representing H2CH2CONH-1 H3.

Next, pyrazolo[1,
5-b] [Specific examples of the 1,2,41 triazole derivatives are illustrated below, but it goes without saying that the present invention is not limited thereto.

JP-A-215687 (11) Melting points are summarized in the following table as representative physical data of the above-mentioned exemplified compounds.

)) ノ/ (Effects of the Invention) According to the present invention, it can be used as a magenta coupler in color photography, as a dye developer in color diffusion transfer photography, as a compound during the synthesis of a dye release agent, and as an intermediate in the production of sensitizing dyes for photography. Pyrazolo [
1,5-b][1,2,41 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 (Transformation) (■) 1 -Amino-3-methyl obtained by reaction of 3-aminocrotononitrile and hydrazine hydrate Pyrazole (I
V) 10 g (0,103 mol) and 12.7 g (0,103 mol) of ethyl 7cetimidate hydrochloride were dissolved in 200 mM ethanol, stirred at room temperature for about 30 minutes, and then heated under reflux for about 3 hours. (In this case, there was almost no by-product of 1). ) After neutralizing the solution with a 2N aqueous sodium hydroxide solution, the phlegm was distilled off under reduced pressure, a 1=1 mixed solvent of ethanol and chloroform was added to the residue, and insoluble salts were removed by filtration. The filtrate was concentrated, and (II) obtained as an oil (partially crystallized) was dissolved in 50 mJL of acetic acid, and 49.8 g (0,103 mol) of lead tetraacetate was added little by little at room temperature under a nitrogen stream. . After the addition was completed, the mixture was heated under reflux for 2 hours.

Distill the acetic acid under reduced pressure and add 5:1 of chloroform and methanol.
By adding a mixed solvent, removing insoluble materials, and then purifying with silica gel column chromatography, 1 was converted to 1.4
I got g.

Melting point 274-275℃ (decomposition) Mass spectrometry 136 (M”, 100%) Elemental analysis value C (%) H (%) N (%) Theoretical value 5
2.93 5.112 41.15 Measured value 52.88
B, 03 41.0? Nuclear magnetic resonance spectrum (CDC observation: viridine-d5=1:1) δ(p p
m): 2.35 (3H, s) 2.42 (3) 1.
s) 5.50 (IH, s) <Example 2> (IQ 1 Methyl physocaproimidate hydrochloride could be quantitatively synthesized from commercially available isocabminitril by a conventional method.

20 g of 5-amino-3-methylpyrazole (0,206
+*ol) and methyl incaproimidate hydrochloride 51g
(0,309 o1) was dissolved in 200 mJL of methanol and stirred at room temperature for about 1 hour. Spots of the main product (II) and by-product (Vl) were observed on silica gel TLC (chloroform:methanol = 6 = 1). Ta. When 5 g of ammonium chloride was added to this solution and heated under reflux for about 2 hours, (Vl) disappeared and became mostly (II). The filtered methanol was distilled off under reduced pressure, a 5=1 mixed solvent of chloroform and methanol was added to the residue, and insoluble matter was removed by filtration. The crude product thus obtained was oxidized by the method described in Example 1 to yield 3.2 g of 17.

Melting point 140-142°C Mass spectrometry 192 (M”) 136 (b, p) Nuclear magnetic resonance spectrum (observed by CDC) δ (p p m): Q, 90 (OH, d, J=7
) 1.55 to 1.110 (3N) 2.45 (3H, s
) 2.90 (2H, brt.

J=7) 5.80 (IH, s) 13.3 (IH) (
Example 3) 2-Ethylhexanenitrile from 8-2-ethyl acetic acid chloride was prepared by Org, Syn, Ca11. Vol.
It was synthesized by the method described in Vol. 3, p. 490 (1955), dissolved in 1 equivalent of methanol, and added to the solution at 0°C.
1 equivalent of dry hydrogen chloride gas was absorbed. When the mixture was left in a refrigerator (~5°C) for about 20 days, crystals of methylimide ester hydrochloride precipitated, so ether was added thereto and filtered. Yield 48% of this imidoester hydrochloride Log(5
1,6m+wol) and (IV) (R2=-CH3)5
g (51,5m+5ol) and methanol 150mJ
The mixture was stirred at 40° C. in L. Approximately 7 hours later TLC (S I
When looking at O2, chloroform:ethanol=4:l), two spots were observed. Low polarity Subo/ )
has the structure (Vl). When an excess amount of ammonium chloride is added to this solution and heated under reflux for about 2 hours, (Vl) disappears and only II) is left. Methanol was distilled off under reduced pressure, and the residue was mixed with 50 ml of chloroform and 10 ml of methanol.
M was added and insoluble matter was removed by filtration. After concentrating the filtrate, it was purified using a small amount of silica gel column to obtain 8 g (70%) of (II) as an oil.

Nuclear magnetic resonance spectrum (CI) C1:CD30D=3:2) δ (P P m): 0.7-1.2 (8H) 1
．． 2-L, 5 (4H) 1.8-2.1 (4H) 2.
32(3)1. s) 2.80 (18, quintet
.

J=7) 5.70 (38, broad) 8.20 (
IH, 5) (II) 2, 6 g (12 mmol)
Dissolve in 50m of acetic acid and add 5.8g of lead tetraacetate at room temperature.
(12 mmol) was added little by little under a nitrogen stream. After the addition was completed, the mixture was heated under reflux for 3 hours. Acetic acid was distilled off under reduced pressure, extracted three times with a 30=1 mixed solvent of chloroform and ethanol, washed with a saturated aqueous sodium bicarbonate solution and brine, and dried over magnesium sulfate. After filtration and concentration, the product was purified by silica gel chromatography to obtain 0.15 g (5.7%) of 18. Melting point 110~115°C Mass spectrometry 220 (M”), 15'5,130 Nuclear magnetic resonance spectrum (CDCl2) δ (pp m): 0.7~1.2 (OH) 1.
2-1.55 (4H) 1.55-2.20 (4H) 2
．． 45 (3H, s) 2.95 (IH, qujntet
.

J-7) 5.62(1)1. s) 12.8 (IH
) <Example 4> Methyl 4-(p-nitrophenyl)butyroimidate hydrochloride was prepared by first synthesizing nitrile from 4-(p-nitrophenyl)acetic acid, and then adding it to methanol (1 equivalent) with dry hydrogen chloride gas, It was synthesized with a yield of 97% by treating with 1 equivalent or more.

5-amino-3-methylpyrazole log (0,103
mo1) and 26.6g (0,103mol) (7)4
From methyl (P-nitrophenyl)butyroimidate hydrochloride, <Example 1> In almost the same manner as <Example 2), 1
I was able to obtain 3.5g of 9. Melting point 203-212°C Mass spectrometry 285 (M"") 149 (b, p) Nuclear magnetic resonance spectrum (DMSO-'d8) δ (p p m
): 2.05 (2H, m) 2.45 (3H, s)
2.58-2.88 (4H, m) 5.80 (IH, s
) 7.25 (2H, d.

J=8.0) 8.05(2)1. d, J=8.0)
(Example 5) (II) Sauce p-nitrophenylacetonitrile is not very soluble in methanol, but when suspended in 1 equivalent of methanol, 1
Methyl imidate hydrochloride could be quantitatively synthesized by absorbing more than an equivalent amount of hydrogen chloride gas and leaving it in the refrigerator overnight.

23 g (0.1 ol) of this methyl imide hydrochloride and 5
-amino-3-methylpyrazole 9.7 g (0,1 mo
l ) and (Example 1) 2.8 g of 32 can be obtained by almost the same operation as in Example 2. Nuclear magnetic resonance spectrum (DMSO-d6) δ (P P m): 2.0
5(2H,i) 2.45(3)1. s) 2.56~
2.88(4)1. 5.60 (IH, s) 7
．． 25 (2H, d.

J = 8.0) 8.05 (2H, d, yJ = 8.0)
Example 5> (Additional 32 p-Nitrophenylacetonitrile is not very soluble in methanol, but when suspended in 1 equivalent of methanol, 1
Methyl imidate hydrochloride could be quantitatively synthesized by absorbing more than an equivalent amount of hydrogen chloride gas and leaving it in the refrigerator overnight.

23 g (0.1 ol) of this methyl imide hydrochloride and 5
-Amino-3-methylpyrazole 9.7g (0,1■o
1), 2.8 g of 32 could be obtained in substantially the same manner as in Example 1 and Example 2. Melting point ~251"
0 (decomposition)

Claims (4)

[Claims] (1) A compound represented by the general formula (in the formula, R and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group) is subjected to an oxidative condensation reaction, and the compound represented by the general formula (in the formula, R and R2 has the same meaning as above.) Pyrazolo[
5-b], [t, 2.4] Method for producing a triazole derivative. (2) A compound represented by the general formula (wherein R1 and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group) is a compound represented by the general formula (wherein R2 has the same meaning as above). ) and an imide ester represented by the general formula (wherein R has the same meaning as above and R3 represents an alkyl group). A method for producing a pyrazolo[1,5-bco[1,2,4])lyazole derivative according to Scope 1. (3) A compound represented by the general formula (wherein R and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group) is a compound represented by the general formula (wherein R1 and R2 are as defined above) have the same meaning, and R3 is an alkyl group.) Pyrazolo[1,5,-bl[1,2,4 ] Method for producing a triazol derivative. (4) Introducing a coupling-off group into a compound represented by the general formula (wherein R and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group),
General formula (wherein, X represents a coupling-off group, R1 and R2
has the same meaning as above. ) A method for producing a pyrazolo[1,5-bl[1,2,4]triazolyl derivative according to claim 1, which obtains a compound represented by: