JPH03184980A - Production of 1h-pyrazolo(1,5-b)-1,2,4-triazole-based compound - Google Patents

Abstract

PURPOSE:To readily obtain the subject compound useful as a coupler for a silver halide color photograph in high yield by affecting phosphonium salts, etc., formed from tertiary phosphines and a halogenating agent to amide oximes, etc., and condensing with dehydration. CONSTITUTION:Tertiary phosphines expressed by the formula (Y)3P (Y is alkyl, aryl, alkoxy, alkyloxy or amino) are reacted with a halogenating agent expressed by the formula Hal-Q (Hal is halogen; Q is substituting group) to form phosphonium salts or phosphoranes expressed by formula I or formula II and affected to amidoximes expressed by formula III (R1 is H or substituting group; R2 is H, alkyl, aryl or heterocycle; X is H or substituting group) or 1-amino-5-acylaminopyrazoles expressed by formula IV, then condensed with dehydration to afford the aimed compound expressed by formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to 1H pyrazolo [1°b] (1) useful as a silver halide color photographic coupler.

The present invention relates to a method for producing a 2°4-triazole compound.

(Prior Art) 1H-pyrazolo(1,5-b)-1,2,4-triazole compounds are useful compounds as couplers for silver halide color photography. 1H-pyrazolo(1,5-
b:] -1,2,4 triazole compounds are synthesized by JP-A-60-197688 and JP-A-61-2094.
The synthesis method described in No. 57 and the like is known. That is, as shown in the reaction scheme below, it is a method for producing a 1H-pyrazolo(1,5-b)-1,24-triazole compound by subjecting the amidoxime compound (III) to dehydration and cyclocondensation. .

As the dehydration condensation agent used in the above synthesis method, methanesulfonyl chloride, p-toluenesulfonyl chloride, thionyl chloride, phosphorus oxychloride, etc. are known. However, especially the amidoxime compound (DI
), when the substituent R1 is an alkoxy group or an aryloxy group, there is a problem that the yield is low when the above-mentioned dehydration cyclocondensation agent is used. Similar problems also occur when the substituent R2 is an aryl group or a heterocyclic group.

(Problems to be Solved by the Invention) As mentioned above, a method for dehydrating 1H-pyrazolo(1,5-b)-1,2°4-triazole compounds by applying a dehydrating agent to amidoximes. Regarding odor, it has been known that p-)luenesulfonic acid chloride and the like are excellent dehydrating agents.

In this synthesis method, for some amidoximes, the reaction solvent used in the tosylation step and the reaction solvent used in the next ring-closing step must be different in terms of yield. , its operability was complicated.

In particular, the substituent R of the compound represented by the general formula (1))
In the case of compounds in which 2 is an aryl group or a heterocyclic group, yields were low in conventional synthesis methods. Further, even when the substituent R1 is an alkoxy group or an aryloxy group, the yield is low and further improvement is desired.

Our objective is to produce 1H-pyrazolo(1,5-b) 1.2.4- by a simpler method and with good yield using the amidoximes represented by the general formula (I[I) as raw materials. An object of the present invention is to provide a method for producing a triazole compound.

(Means for Solving the Problems) The object of the present invention is a 1H phosphine represented by the following general formula (II), which includes a step using a tertiary phosphine represented by the following general formula (1). -Pyrazolo CI,
5-b) Distantly related to the method for producing -1,,2,4-triazole compounds.

General formula (+) (y), lp General formula (II) The present invention will be described in detail below. As a specific manufacturing method of the present invention, a tertiary phosphine represented by the above general formula (1), a tertiary phosphine represented by the following general formula (rV), a tertiary phosphine represented by the following general formula (rV), and the following general formula (V) or the general formula ( The phosphonium salts or phosphoranes represented by VI) can be expressed by the following general formula (
adoximes represented by III) or general formula (I
1H-pyrazolo[15-b] represented by the general formula (II), including a step of dehydration condensation by acting on l-amino-5-acylaminopyrazoles represented by II-1)
)-1,2,4-triazole compounds.

General formula (I[I) General formula (III-1)
N.H.

(wherein, R R2 and X are general formula ([)) general formula (IV) an general formula (V) [(Y)3P-Ha I! , ]" (Some of these production methods are thought to proceed according to the reaction scheme (A) shown below.

/ 10 General formula (Iff
) R1 in the amidoxy group represents a hydrogen atom or a substituent. Substituents include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups,
heterocyclic oxy group, alkylthio group, arylthio group,
Heterocyclic thio group, amino group, anilino group, acylamino group, ureido group, urethane group, alkoxycarbonyl group, sulfonamide group, sulfamoyl group, sulfonyl group, cyano group, nitro group, hydroxyl group, etc.

To explain the substituents in more detail, an alkyl group refers to a straight chain or branched chain substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and the substituents of the substituted alkyl group include:
Halogen atoms (e.g. fluorine, chlorine, bromine), cyano groups, nitro groups, aryl groups (e.g. phenyl, naphthyl)
, heterocyclic groups (e.g., furyl, ■-pyrazolyl), alkoxy groups (e.g., methoxy, ethoxy, isopropyloxy, butoxy, dodecyloxy), aryloxy groups (e.g., phenoxy, 2-4-di-tert-phenoxy, 3-methanesulfonamidophenoxy), alkylthio groups (e.g. methylthio, ethylthio, octylthio, hexadecylthio), arylthio groups (e.g. phenylthio, 2-butoxy-5-t-octylphenylthio, 4-dodecyloxyphenylthio, 2-pivalo ylaminophenylthio), amino groups (e.g. dimethylamino, diethylamino, dibutylamino, diphenylamino), acylamino groups (e.g. N-methylacetylamino, N-butyltetradecanoylamino)), ureido groups (e.g. N , NN′-triethylureido), urethane groups (e.g. N-butyl-phenylurethane, N-
octylethyl urethane), alkoxycarbonyl group (
(e.g. methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl), sulfonate groups (e.g. methylsulfonyl, ethanesulfonamide, hexadecanesulfonamide, p-toluenesulfonamide),
Sulfamoyl Ig (e.g., N-methylsulfamoyl, N-butylsulfamoyl, N,N-dioctylsulfamoyl), sulfonyl group (e.g., methylsulfonyl, ethylsulfonyl, hexadecylsulfonyl,
phenylsulfonyl), etc., and may have two or more substituents. Furthermore, when two or more substituents are present, they may be the same or different.

The aryl group may have a substituent as described for the substituted alkyl group (for example, phenyl, dichlorophenyl, 2-methoxyphenyl, 2,4 dimethoxyphenyl,
(4-t-butylphenyl), heterocyclic groups (e.g. 3-pyridyl, 4-pyridyl), alkyl groups of alkoxy groups may have substituents of the above-mentioned substituted alkyl groups (e.g. methoxy, ethoxy, propyl). oxy, butyloxy, isopropyloxy, t-butoxy, 2-phenoxyethoxy, l-(2,4-di-t-amylphenoxyethoxy), 2-methylsulfonylethoxy), aryloxy groups (e.g. phenoxy, 2-methoxy) phenoxy, 2,4-dimethoxyphenoxy, 2,6-dimethoxyphenoxy, =13 2,4-di-t-amylphenoxy, 2-ethoxycarbonylphenoxy), heterocyclic oxy group, alkylthio group (e.g. methylthio, ethylthio, hexadecylthio ), arythio groups (e.g. phenylthio, 2-ethoxycarbonylphenylthio, 2-butoxy-5-t-octylphenylthio, 2-pivaloylamidophenylthio), heterocyclic thio groups, amino groups (e.g. dimethyl amino, diethylamino, diisopropyla ξ), dibutylamino), anilino group (e.g. 2,5-dichloroanilino, 2-ethoxycarbonylanilino), acylamino group (e.g. N-methylacetyla ξ), N-phenylacetyl amino, N-butylpivaloylamino, N-methyltetradecanoylamino), ureido groups (e.g.
N,N,N'triethylureido), urethane groups (e.g. N-methylphenylurethane), alkoxycarbonyls (e.g. methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl), sulfonamide groups (e.g. methanesulfonamide, ethane sulfonamide, hexadecane sulfonamide, N-methyloctanesulfonamide, 1)-) luenesulfonamide), sulfamoyl group (e.g., N-butylsulfamoyl, methylsulfamoyl, ethylsulfamoyl, phenylsulfamoyl), Represents a cyano group, nitro group, hydroxyl group, etc. When R1 is an alkoxy group or an aryloxy group, the effects of the present invention are great.

In addition, 1-amino 5- represented by general formula (III-1)
R, , R, and X of the azilaginopyrals are the same as explained in the general formula (Ill) above.

The substituent represented by X represents a hydrogen atom or a substituent,
As the substituent, halogen atom, or C, N, ○
A monovalent group having at least two atoms selected from the group consisting of , S, P and H.

Preferably, X is a hydrogen atom, a halogen atom, a cyano group,
3 containing ○, N or S as a nitro group, heteroatom
to 10-membered heterocyclic group, alkoxycarbonyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, etc. More specifically, , alkoxy groups (e.g. methoxy, ethoxy)
, aryloxy groups (e.g. phenoxy, 4-methylphenoxy, 4-ethoxycarbonylphenoxy, 2-ethoxycarbonylphenoxy, 4-cyanophenoxy,
4-methylsulfonylphenoxy), heterocyclic oxy groups, alkylthio groups (e.g. methylthio, dodecylthio,
1-ethoxycarbonyldodecylthio), an arylthio group (eg, phenylthio, 2-ethoxycarbonylphenylthio, 2-butoxy-5-toctylphenylthio), and the like.

R2 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. To explain in more detail, the alkyl group of R2 represents a linear or branched substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and the substituents of the substituted alkyl group include those explained in the substituent R1 above. It has the same meaning as the substituent for the substituted alkyl group, and may have two or more substituents, and in that case, those substituents may be the same or different. The aryl group for R2 represents a substituted or unsubstituted aryl group, and the substituents for the unsubstituted aryl group (e.g., phenyl, naphthyl) and substituted aryl group include the substituted alkyl group for R1 above. synonymous with the group (e.g. 34-dichlorophenyl, 3.5
-)1 lorophenyl, 2-nitrophenyl, 3-nitrophenyl, 2-methoxyphenyl, 2,4-dimethoxyphenyl).

The heterocyclic group represented by R2 represents, for example, 3-pyridyl or 4-pyridyl. In the present invention, the effect of the present invention is great when R2 is an aryl group or a heterocyclic group. The effect is particularly great for aryl groups.

Typical specific examples of the compound represented by the general formula (III) are shown below, but the present invention is not limited thereto.

7 8 ■ 9 ■ 3 ■ 4 ■ 1) ゝC8゜/N 0 ■0 1 ■ 6 ■ 7 CI2) 125 ■ 8 2 ■ 19 ■ 0 ■ 2 ■ 3 NO□ 5 1 0 2 6 ■ 39 9- ■ 2 ■ 3 0 ■ 46 ■ 7 ■ 8 The raw material used in the present invention, that is, the general formula (I[[)
Amidoximes represented by JP-A-61-1451
63, that is, the reaction scheme described below.

3 Y in the tertiary phosphine represented by the general formula (1) represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group. Represents a chain or branched substituted or unsubstituted alkyl group, and the substituent of the substituted alkyl group has the same meaning as the substituent of the substituted alkyl group shown by R1 of the amodooxime compound represented by the general formula (III) above. and may have two or more of these substituents. When two or more substituents are present, they may be the same or different. The aryl group represents a substituted or unsubstituted aryl group, and the substituents of the substituted aryl group have the same meaning as the substituents of the substituted alkyl group. Alkoxy groups (e.g. methoxy, ethoxy, propyloxy, butyloxy, isopropyloxy), oryloxy groups (e.g. phenoxy, naphthyloxy), amino groups (e.g. dimethylamino, diethylamino, dipropylamino,
dibutylamino, diisopropylamino). Preferably Y is an aryl group or a dialkylamino group, particularly preferably a phenyl group.

Specific examples of tertiary phosphines represented by general formula (1) are shown below, but the present invention is not limited thereto.

■ (CH,IhP ■ (CJ5+rP ■ (CH30-) DingP ■ (C,05#rP (C4H10+rP I 9 (CtHq+-rP general formula (IV)
Hal in the halogenating agent represented by represents a halogen atom (e.g., chlorine, bromine), and Q represents a substituent.The substituent includes a halogen atom (e.g., chlorine, bromine),
imide groups (e.g. succinimide, phthalimide),
Represents a halogenated alkyl group (eg trichloromethyl, tribromomethyl, pentachloroethyl, pentabromoethyl).

Preferred specific examples of the halogenating agent represented by the general formula (TV) are shown below, but the present invention is not limited thereto.

IV-1cz.

IV2 Brz ■ C14 ■ CB r a The phosphonium salts represented by the general formula (V) and the phosphoranes represented by the general formula (VI) are the tertiary phosphines represented by the general formula (2〇) and the tertiary phosphines represented by the general formula (IV), respectively. derived from the halogenating agent shown. Those Y, H
al and Q have the same meanings as described in the general formula (1) and general formula (IV), respectively.

By the method of the present invention, a 1H-pyrazolo(1,5-b)-1,2°4-triazole compound represented by the following general formula (II) is obtained.

2 (R,, X, and R2 have the same meanings as described above for general formula (III).) Representative specific examples of the compound represented by general formula (n) are shown below, but the present invention is not limited by these. It is not something that will be done.

8 7 1 2 12 3 5 5 6 9 0 0 50 Next, embodiments of the present invention will be described.

In the dehydration condensation reaction of amidoximes represented by the general formula (I[[) using a tertiary phosphine represented by the general formula (I) and a halogenating agent represented by the general formula (IV), It may be carried out without a solvent or by dissolving or dispersing it in an appropriate solvent. Typical solvents that can be used in the present invention include acetonitrile, dimethylsulfoxide, sulfolane, dimethylacetamide, dimethylimidazolitone, tetrahydrofuran, ethyl acetate, 1,2-dimethoxyethane, Hensen, and toluene. It will be done. These three solvents may be used alone or in combination of two or more.

The amount of solvent used is 1 to 100 per part by weight of the amidoxime represented by the general formula (Ill) or (I[+-1).
It is used in a proportion of 0 parts by weight, preferably 1 to 30 parts by weight.

Amidoximes represented by general formula (Ill) or (I[1-1) and compounds represented by general formula (1) are 1:
Used in a molar ratio of 0.5 to 1:20, preferably 1:
A molar ratio of 1 to 1:10 is used.

The compound represented by general formula (1) and the halogenating agent represented by general formula (IV) are used in a molar ratio of 1:1 to 1:100, preferably in a molar ratio of 1:1 to 1:10. used.

The reaction temperature can be carried out at -20°C to 150°C, but from 20°C to
80°C is preferred, and -20°C to 50°C is particularly preferred.

The reaction time is 30 minutes to 48 hours when the reaction temperature is 120°C to 150°C.

4 (Examples) Some specific examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 (Exemplary Compound M-21) Amidoxime (I[Ia) 92.3g (0,25
mol), carbon tetrachloride 501n1 to acetonitrile 500
- was added thereto, and the mixture was cooled to 5°C to 10°C and stirred.

Add to this 34.0g of triphenylphosphine (0°13
After stirring for 3 hours at 5-10° C., a further 34.0 g (0.13 mol) of triphenylphosphine were added. After the addition was complete, stirring was continued for 5 hours at 5-10°C. After the reaction is complete, add 50 ml of water to the reaction solution while stirring.
0- was added dropwise. The precipitated crystals were collected in a furnace and mixed with methanol.
After washing with a mixed solvent of water (1:1), it was dried. 6
1.7 g (70.3%) of exemplary compound M-21 was obtained.

The melting point was 216-218°C. The NMR of this compound matched that of the exemplified compound described in Example 3 of JP-A No. 63-307453, and it was confirmed that it was the same compound.

7 Amidoxime compound (I[[b) 44.8 g (0.1 mol) and 30% of acetonitrile were added to 30% of carbon tetrachloride and stirred at room temperature. In this, triphenylphosphine 3
After adding 1.0 g (0.12 mol) and continuing stirring at room temperature for 5 hours, 20 g (0.076 mol) of triphenylphosphine was added and stirring was continued for 3 hours. After the reaction was completed, 300 g of water was added dropwise under stirring. The precipitated crystals were collected in a furnace, washed with a mixed solvent of methanol and water (1:1), and dried. 31.2 g (72.6%) of exemplary compound M-44 was obtained. The melting point was 201-205°C.

Example 3 (Exemplary Compound M-44) Amidoxime compound (Il[b) 44.8 g (0.1 mol), triphenylphosphine 31.0 g (0°12
Add 250-mol of tetrahydrofuran to O℃~5
The mixture was cooled to ℃ and stirred. Add 16% of N-chlorosuccinimide to this. Og (0.12 mol) was added slowly in several portions. After the addition was complete, the mixture was stirred at 0°C to 5°C for 3 hours, and then continued stirring at room temperature for an additional 4 hours. After the reaction was completed, the reaction solution was poured into 1,000 ml of water with stirring. The precipitated gummy material was washed with water and then purified by column chromatography (chloroform/methanol).

Crystallization from acetonitrile gave 28.6 g (66.6%) of Exemplified Compound M-44.

The melting point was the same as that obtained in Example 2.

Examples 4 to 13 and Example 15 were carried out in the same manner as in Example 1 except that the amidoxime compound was changed.

Example 14 was conducted according to the same method as Example 3.

The yields and melting points of the compounds obtained in Examples 1 to 15 are shown below.

59- (Comparative Example-1) The conventional synthesis method of the compound shown in Example-1 (Exemplified Compound M-21) is described in JP-A-63-307453, and the yield of Exemplified Compound M-21 is 35. %Met.

(Effects of the Invention) The synthesis method of the present invention makes it possible to synthesize 1H-pyrazolo(1,5,-b)-1,2,4-triazole compounds more easily and in good yields. Ta. Furthermore, as shown in the comparative examples, in the case of compounds in which R1 is an aryloxy group or an alkoxy group and R2 is an aryl group, there is a distant improvement in yield, which shows that the present invention is superior. I understand.

Furthermore, as shown in the comparative example, the present invention was found to be simpler and superior in operability of the tosylation and ring-closing steps described in JP-A-63-307453 and the like.

Claims (2)

[Claims] (1) The following general formula (I) is characterized by including a step of using a tertiary phosphine represented by the following general formula (I).
II), 1H-pyrazolo[1,5-b]-1
, 2,4-triazole compound manufacturing method. General formula (I) (Y)_3P [wherein, Y is an alkyl group, an aryl group, an alkoxy group,
Represents an aryloxy group or an amino group. ] General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a hydrogen atom or a substituent, and R_
2 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. X represents a hydrogen atom or a substituent. ] (2) The following general formula (V) or the general formula (
Phosphonium salts or phosphoranes represented by VI) are dehydrated by acting on amidoximes represented by the following general formula (III) or 1-amino-5-acylaminopyrazoles represented by the general formula (III-I). General formula (I) according to claim (1), characterized in that it includes a step of condensing
1H-pyrazolo[1,5-b]-1, represented by I)
A method for producing a 2,4-triazole compound. General formula (III) General formula (III-I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2 and X are synonymous with general formula (II). ) General formula (IV) Hal-Q [In the formula, Hal represents a halogen atom and Q represents a substituent. ] General formula (V) [(Y)_3P-Hal]^+Q^- [wherein Y, Hal, and Q each represent the general formula (I)
and has the same meaning as general formula (IV). ] General formula (VI) (Y)_3P(Hal)_2 [wherein Y and Hal have the same meanings as in general formula (I) and general formula (IV), respectively. ]