JPH07133278A - Production of 1h-pyrazolo(3,2-c)1,2,4-triazole-based compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a coupler for photograph in a high yield by reacting a triazole-based compound substituted by a specific phenyl group substituted with a halogen at an ortho position with an amine compound or a thiol compound. CONSTITUTION:A compound of formula I [R1 and R2 are each a substituent group and either one of R1 and R2 is formula II (Z is a halogen; R3 and R6 are each H or a substituent group and either one of R3 and R5 is nitro; *is bonded to a pyrazolotriazole ring)] is reacted with a compound of the formula R7-NH2 [R7 is an alkyl or a cycloalkyl] in the presence of a base (e.g. potassium carbonate) in a solvent (e.g. DMF) at -10 to 150 deg.C to provide the objective compound of formula III (R8 and R9 are substituent groups and either one of R8 and R9 is formula IV). A compound of formula III substituted by a phenyl substituted with nitrogen or sulfur at an ortho position and useful as a coupler for photograph, especially Magenta coupler or its intermediate is obtained by this method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a 1H-pyrazolo [3,2-c] 1,2,4-triazole compound useful as a photographic coupler, especially a magenta coupler or an intermediate thereof. Specifically, a 1H-pyrazolo [3,2-c] 1,2,4-triazole compound substituted with an ortho-halogenated phenyl group and an amine compound represented by the general formula [III] or a general formula [VIII] By reacting the thiol compound represented by the above, in high yield, a 1H-pyrazolo [3,2-c] 1,2,4-triazole compound substituted with a nitrogen atom or a sulfur atom-substituted phenyl group at the ortho position is produced. It is about how to do it.

[0002]

2. Description of the Related Art 1H-pyrazolo [3,2-c] 1,2,4-triazole compounds are compounds useful as photographic couplers, particularly magenta couplers or intermediates thereof, and various production methods are disclosed. ing.

Compounds of this system are described, for example, in British Patent 1,252,
418, U.S. Pat. No. 3,725,067 or Journal of the Chemical Society Perkin I (1977
Years) 2047-2052 can be manufactured by the method described.

That is, a 5-acylhydrazino-1H-pyrazole-4-carboxylate compound is refluxed with phosphorus oxychloride in benzene for a long time to give 1H-pyrazolo [3,2-c] 1,2,4-triazole-. After the 7-carboxylate compound is obtained, the 1H-pyrazolo [3,2-c] 1,2,4-triazole compound can be produced by heating it under sulfuric acid acidity.

However, in these methods, since there is a condition of heating under strong acidity during the process as described above, the presence of a thioether bond as represented by the general formula [X] in the molecule is satisfied under the condition. In 1H-pyrazolo [3,2-
There are problems such as a decrease in the yield of the C] 1,2,4-triazole compound.

Further, in JP-A-63-231341, a 1,2,4-triazolo [3,4-b] 1,3,4-thiadiazine compound is refluxed in acetic anhydride to obtain a diacetyl compound. After that, it is described that 1H-pyrazolo [3,2-c] 1,2,4-triazole-based compound can be produced by treatment with concentrated hydrochloric acid.

However, in this method, hydrogen sulfide gas is generated by the reaction, which is a problem in terms of environmental pollution.
In industrialization, the treatment of hydrogen sulfide gas imposes a heavy burden, which is not preferable, and the development of a new production method has been desired.

Furthermore, in any of these methods, 1H
-Pyrazolo [3,2-c] 1,2,4-triazole 1H-pyrazolo [3,2-
c] If an amino bond as shown in the general formula [V] is present in the molecule before the formation of the 1,2,4-triazole ring, side reactions such as acylation will occur at that site and the yield Therefore, the development of a new manufacturing method has been desired.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks, and a general formula [IV] useful as a photographic coupler, particularly a magenta coupler or an intermediate thereof.
Or to synthesize a 1H-pyrazolo [3,2-c] 1,2,4-triazole compound substituted by a phenyl group substituted with an ortho nitrogen atom or a sulfur atom represented by [IX] in a high yield It is to provide a manufacturing method capable of

[0010]

The above object of the present invention can be achieved by the following constitution or.

A compound represented by the following general formula [IV] characterized by reacting a compound represented by the following general formula [I] with a compound represented by the following general formula [III] under basic conditions.
Process for producing 1H-pyrazolo [3,2-c] 1,2,4-triazole compound.

[0012]

[Chemical 11]

[In the formula, R ₁ or R ₂ represents a substituent,
Any _{one of 1} and R ₂ is represented by the following general formula [II]

[0014]

[Chemical 12]

[In the formula, Z represents a halogen atom, and R ₃ ,
R ₄ , R ₅ and R ₆ represent a hydrogen atom or a substituent, but R ₃ and R
Any one of ₅ represents a nitro group. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ]

[0016]

[Chemical 13]

[In the formula, R ₇ represents an alkyl group or a cycloalkyl group. ]

[0018]

[Chemical 14]

[In the formula, R ₈ or R ₉ represents a substituent,
_{One of 8} and R ₉ is the following general formula [V]

[0020]

[Chemical 15]

[0021] _{wherein, R 3, R 4, R} 5, R 6 has the same meaning as _{R 3, R 4, R 5} , R 6 in the general formula (II), R ₇ is the formula [III] Synonymous with R ₇ of. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ] The compound represented by the following general formula [I] and the following general formula [VII
1H-pyrazolo represented by the following general formula [IX], characterized by reacting the compound represented by I] under basic conditions
A method for producing a [3,2-c] 1,2,4-triazole compound.

[0022]

[Chemical 16]

[In the formula, R ₁ or R ₂ represents a substituent,
Any _{one of 1} and R ₂ is represented by the following general formula [II]

[0024]

[Chemical 17]

[In the formula, Z represents a halogen atom, and R ₃ ,
R ₄ , R ₅ and R ₆ represent a hydrogen atom or a substituent, but R ₃ and R
Any one of ₅ represents a nitro group. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ]

[0026]

[Chemical 18]

[In the formula, R ₂₇ represents an alkyl group, a cycloalkyl group or an aryl group. ]

[0028]

[Chemical 19]

[In the formula, R ₂₈ or R ₂₉ represents a substituent,
One of R ₂₈ and R ₂₉ is represented by the following general formula [X]

[0030]

[Chemical 20]

[0031] _{wherein, R 3, R 4, R} 5, R 6 has the same meaning as _{R 3, R 4, R 5} , R 6 in the general formula [II], R ₂₇ is the formula [VIII] It is synonymous with R ₂₇ of. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. The present invention will be described in detail below.

The substituent represented by R ₁ or R ₂ in the general formula [I] represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. As the alkyl group represented by R ₁ or R ₂ , Examples thereof include methyl group, ethyl group, isopropyl group, t-butyl group, decyl group and dodecyl group.

Examples of the cycloalkyl group represented by R ₁ or R ₂ include a cyclopropyl group, a cyclopentyl group,
Examples thereof include cyclohexyl group, 1-methylcyclopropyl group, 1-methylcyclohexyl group and the like.

Examples of the aryl group represented by R ₁ or R ₂ include a phenyl group and a naphthyl group.

Examples of the heterocyclic group represented by R ₁ or R ₂ include pyridyl group, thienyl group and furyl group.

The alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ₁ or R ₂ may have a substituent, and the substituent may be a nitro group, a cyano group, an alkyl group, an aryl group. Group, alkylsulfonyl group, arylsulfonyl group and the like.

The substituent represented by R ₁ or R ₂ is preferably an alkyl group or an aryl group.

In the general formula [II], R ₃ , R ₄ , R ₅ and R ₆
The substituent represented by is synonymous with the substituent represented by R ₁ or R _{2 in} the general formula [I].

As R ₃ , R ₄ , R ₅ and R ₆ , a hydrogen atom or an alkyl group is preferable.

In the general formula [II], Z represents a halogen atom, of which a chlorine atom or a bromine atom is preferable.

The alkyl groups represented by R ₇ and R ₂₇ in the general formulas [III] and [VIII] are, for example, methyl group,
Ethyl group, isopropyl group, butyl group, sec-butyl group,
Examples of the cycloalkyl group represented by R ₇ and R _27, which represents a decyl group, a dodecyl group or the like, include, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-methylcyclopropyl group, 1-methylcyclohexyl group, etc. Can be mentioned.

In the general formula [VIII], examples of the aryl group represented by R ₂₇ include a phenyl group and a naphthyl group.

In the general formulas [III] and [VIII], R ₇ , R
_The alkyl group, cycloalkyl group or aryl group represented by ₂₇ may have a substituent, and examples of the substituent include a nitro group, a cyano group, a hydroxyl group, an alkyl group, an aryl group, a sulfonyl group, an arylsulfonyl group and an alkyloxy group. Group, aryloxy group and the like.

In the general formula [IV], the substituent represented by R ₈ or R ₉ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₁ or R _{2 in} the general formula [I] represents It has the same meaning as the alkyl group, cycloalkyl group, aryl group or heterocyclic group of the substituent.

In the general formula [IX], the substituent represented by R ₂₈ or R ₂₉ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₁ or R _{2 in the} general formula [I] is
It has the same meaning as the alkyl group, cycloalkyl group, aryl group or heterocyclic group of the substituent represented by.

In the general formula [V], R ₃ , R ₄ , R ₅ , R
₆ is R _3, R _4, synonymous with R _5, R ₆ of Formula II,
R ₇ has the same meaning as R _{7 in} formula [III].

In the general formula [X], R ₃ , R ₄ , R ₅ , R
₆ is R _3, R _4, synonymous with R _5, R ₆ of Formula II,
R ₂₇ has the same meaning as R _{27 in} formula [VIII].

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

[0052]

[Chemical formula 24]

[0053]

[Chemical 25]

The above-mentioned compounds represented by the general formula [I] are described in, for example, British Patent 1,252,418 and US Patent 3,725,067.
No. or Journal of the Chemical Society Perkin I (1977), pages 2047-2052.

Specific examples of the compound represented by the general formula [III] used in the present invention are shown below, but the present invention is not limited thereto.

[0056]

[Chemical formula 26]

Specific examples of the compound represented by the general formula [VIII] used in the present invention are shown below, but the present invention is not limited thereto.

[0058]

[Chemical 27]

In this reaction, in the general formula [III] or [VII]
The compound of I] is 1.0 to 1 mol per mol of the compound of general formula [I].
It is used in the range of 3.0 mol, preferably in the range of 1.0 to 1.5 mol.

In the present invention, the solvent used in the reaction includes methanol, ethanol, isopropanol,
Tetrahydrofuran, 1,4-dioxane, acetonitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO) and the like are preferable, but among them, DMF and DMA
C and DMSO are particularly preferable.

The amount of the solvent to be used is not particularly specified because it is not an important requirement of the present invention, but the amount by volume with respect to the raw material is used.
It can be used in a range of up to 100 times, and is preferably used in a range of 1 to 10 times.

The base used in the present invention may be an inorganic base or an organic base, but an inorganic base is preferred.

As the inorganic base, potassium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium t-butoxide, potassium carbonate, sodium carbonate and sodium hydride are preferable.

As the organic base, triethylamine, N,
Examples thereof include N-dimethylbenzylamine.

The base used in this reaction has the general formula [I]
The compound is used in an amount of 1.0 to 10.0 mol, preferably 1.0 to 3.0 mol, per mol of the compound.

The reaction temperature is preferably -10 to 150 ° C, more preferably 0 to 100 ° C.

Next, the general formula [I
Representative compounds of V] are shown below,
The present invention is not limited to this.

[0068]

[Chemical 28]

[0069]

[Chemical 29]

[0070]

[Chemical 30]

[0071]

[Chemical 31]

Next, the general formula [IX] obtained by the present invention
Typical compounds represented by are shown below, but the present invention is not limited thereto.

[0073]

[Chemical 32]

[0074]

[Chemical 33]

[0075]

[Chemical 34]

[0076]

[Chemical 35]

[0077]

[Chemical 36]

[0078]

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

Comparative Example 1 Synthesis of 1H-pyrazolo [3,2-c] 1,2,4-triazole compound not according to the present invention.

The compound IV-2 was tried to be synthesized by the following method, but the yield of the compound (C) was low, and in the reaction for obtaining the compound (D), the target compound ( D) was not observed.

[0081]

[Chemical 37]

Example 1 (Synthesis of Exemplified Compound IV-2) Exemplified Compound IV-2 was synthesized by the following method.

[0083]

[Chemical 38]

(1) Synthesis of compound (F) 50.0 g of compound (E) was heated under reflux for 2 hours in 90 ml of thionyl chloride. After completion of the reaction, thionyl chloride was distilled off under reduced pressure to obtain acid chloride.

On the other hand, 45.7 g of compound (B) was mixed with 40% of ethyl acetate.
The mixture was dispersed in 0 ml, and an aqueous solution of potassium acetate (potassium acetate 48.7 g / water 98 ml) was further added, and the mixture was vigorously stirred, to which 250 ml of the above acid chloride dissolved in ethyl acetate was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at room temperature for 2 hours, and the precipitated solid was collected by filtration. This solid was washed thoroughly with water and then with a small amount of cold ethyl acetate to give compound (F) 77.9
g (yield 85.4%) was obtained.

(2) Synthesis of compound (G) After 75.0 g of compound (F) was refluxed under heating in 400 ml of phosphorus oxychloride for 4 hours, phosphorus oxychloride was distilled off under reduced pressure. The residue was poured into 1 liter of ice water, neutralized with sodium carbonate, and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and dried over anhydrous magnesium sulfate,
Further, the solvent was distilled off to obtain a residue. The residue was crystallized in methanol to obtain 61.3 g of compound (G) (yield 85.9%).

(3) Synthesis of Exemplified Compound I-1 30.0 g of compound (G) was added to 30 ml of concentrated sulfuric acid and 30 ml in 60 ml of acetic acid.
Water (ml) was added, and the mixture was heated under reflux for 7 hours. After cooling, the mixture was poured into 1 liter of ice water and neutralized with potassium carbonate. The precipitated solid was collected by filtration, washed with water, and recrystallized from methanol to obtain 22.3 g (yield 93.6%) of Exemplified Compound I-1.

(4) Synthesis of Exemplified Compound IV-2 I-1 10.0 g was added to N, N-dimethylformamide (DMF) 10
Dissolve in 0 ml, add 3.9 g of n-butylamine and stir at room temperature for 30 minutes, then add 5.8 g of sodium methoxide at 80-90 ° C.
And stirred for 3 hours. After the reaction was completed, the contents were cooled to room temperature, the contents were put into 2 liters of ice water, and the precipitated solid was collected by filtration. The obtained solid was recrystallized from ethyl acetate to obtain 9.2 g of Exemplified compound IV-2 (yield 81.3%).

FAB-MASS m / e = 315 (M ⁺ ), I
R, NMR supported the structure of IV-2.

As described above in Comparative Example 1 (Comparative) and Example 1 (Invention), in comparison with the conventionally known production method, in the present invention, 1H substituted with ortho-position nitrogen atom-substituted phenyl group was used. It can be seen that the -pyrazolo [3,2-c] 1,2,4-triazole compound can be produced in good yield.

Comparative Example 2 Synthesis of 1H-pyrazolo [3,2-c] 1,2,4-triazole compound not according to the present invention.

The Exemplified Compound IX-12 was attempted to be synthesized by the following method, but the desired compound (B ′) was not found by high performance liquid chromatography in the reaction for obtaining the compound (B ′).

[0093]

[Chemical Formula 39]

Example 2 (Synthesis of Exemplified Compound IX-12) Exemplified Compound IX-12 was synthesized by the following method.

[0095]

[Chemical 40]

(1) Synthesis of Exemplified Compound IX-12 10.0 g of Exemplified Compound I-1 synthesized in the same manner as in Example 1.
Was dissolved in 100 ml of N, N-dimethylformamide (DMF), 4.0 g of benzenethiol was added, and after cooling with an ice bath, 4.3 g of sodium methoxide was added at an internal temperature of 5 ° C or lower and stirred at 5 ° C or lower for 10 minutes. After that, the ice bath was removed and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the content was put into 1 liter of ice water, and the precipitated solid was collected by filtration. The obtained solid was recrystallized from acetone to give 11.1 g (yield 87.7) of Exemplified Compound IX-12.
%)Obtained.

FAB-MASS m / e = 352 (M ⁺ ), I
R, NMR supported the structure of IX-12.

As described above in Comparative Example 2 (Comparative) and Example 2 (Invention), in comparison with the conventionally known production method, in the present invention, 1H substituted with the ortho-position sulfur atom-substituted phenyl group was used. It can be seen that the -pyrazolo [3,2-c] 1,2,4-triazole compound can be produced in good yield.

[0099]

INDUSTRIAL APPLICABILITY According to the present invention, 1H-pyrazolo [3,2-c] 1,2, substituted with a phenyl group substituted with an ortho nitrogen atom or a sulfur atom, which is useful as a photographic coupler, particularly a magenta coupler or an intermediate thereof, It is possible to provide a production method capable of synthesizing a 4-triazole compound in a simple and high yield.

Claims (2)

[Claims] 1. A compound represented by the following general formula [IV] characterized by reacting a compound represented by the following general formula [I] with a compound represented by the following general formula [III] under basic conditions.
Process for producing 1H-pyrazolo [3,2-c] 1,2,4-triazole compound. [Chemical 1] [In the formula, R ₁ or R ₂ represents a substituent, and any _one of R ₁ and R ₂ is represented by the following general formula [II] [In the formula, Z represents a halogen atom, and R ₃ , R ₄ , R ₅ , R ₆
Represents a hydrogen atom or a substituent, and any one of R ₃ and R ₅
One represents a nitro group. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ] [Chemical 3] [In the formula, R ₇ represents an alkyl group or a cycloalkyl group. ] [Chemical 4] [In the formula, R ₈ or R ₉ represents a substituent, and any one of R ₈ and R ₉ is represented by the following general formula [V] _{Wherein, R 3, R 4, R} 5, R 6 has the same meaning as _{R 3, R 4, R 5} , R 6 in the general formula (II), R ₇ is the formula [III]
Synonymous with R ₇ of. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ] 2. A compound represented by the following general formula [IX] characterized by reacting a compound represented by the following general formula [I] with a compound represented by the following general formula [VIII] under basic conditions.
Process for producing 1H-pyrazolo [3,2-c] 1,2,4-triazole compound. [Chemical 6] [In the formula, R ₁ or R ₂ represents a substituent, and any _one of R ₁ and R ₂ is represented by the following general formula [II]: [In the formula, Z represents a halogen atom, and R ₃ , R ₄ , R ₅ , R ₆
Represents a hydrogen atom or a substituent, and any one of R ₃ and R ₅
One represents a nitro group. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ] [Chemical 8] [In the formula, R ₂₇ represents an alkyl group, a cycloalkyl group or an aryl group. ] [Chemical 9] [In the formula, R ₂₈ or R ₂₉ represents a substituent, and one of R ₂₈ and R ₂₉ is represented by the following general formula [X] [In the formula, R ₃ , R ₄ , R ₅ and R ₆ have the same meanings as R ₃ , R ₄ , R ₅ and R _{6 in the} general formula [II], and R ₂₇ represents the general formula [VII].
It is synonymous with R _{27 of [} I]. * Means attached to the pyrazolotriazole ring at that position. ] Represents the group represented by. ]