JP2002069071A - 5-sulfonylaminomethyl-1h-pyrrolo-[1,2-b][1,2,4]triazole compound and 5-acylaminomethyl-1h-pyrrolo-[1,2- b][1,2,4]triazole compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily producing an alkyl-eliminating pyrrolotriazole coupler having high versatility in high yield. SOLUTION: 5-Sulfonylaminomethyl-1H-pyrrolo-[1,2-b][1,2,4] triazoles and 5-acylaminomethyl-1H-pyrrolo-[1,2-b][1,2,4]triazoles are produced by using a compound expressed by general formula (I) (R1 is H or a substituent; R2 and R3 are each an electron attractive group having a Hammett's substituent constant σp of >=0.2; R4 and R5 are each a substituent; R6 is an alkyl or an aryl; X is sulfonyl group or carbonyl group; and Y is a non-metallic atom group necessary for forming a ring containing the group). Preferably, the compound of general formula (II) is produced from a compound I-A through compounds of formulas I-B, I-C and I-D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 5-sulfonylaminomethyl-1H-pyrrolo- useful as a photographic coupler.
[1,2-b] [1,2,4] triazole compound and 5-acylaminomethyl-1H-pyrrolo- [1,2-
b] A method for producing a [1,2,4] triazole compound.

[0002]

BACKGROUND OF THE INVENTION In silver halide color photographic materials, US Pat. No. 5,256,526, European Patent No. 545,300, and US Pat.
The pyrrolotriazole-based couplers described in (1) are known, which are excellent in terms of hue, coupling activity, and fastness.

On the other hand, in a reversal film, which is a photographic light-sensitive material, a 4-equivalent coupler is generally used to ensure graininess. However, the pyrrolotriazole type 4-equivalent coupler having a good hue has a problem that a magenta stain is generated in a developing solution due to a reaction between formaldehyde and an addition compound of paraphenylenediamine.

As a coupler which solves this problem, an alkyl-releasing pyrrolotriazole coupler described in JP-A-10-186602 has been proposed. The alkyl-releasing coupler proposed here has a feature that no magenta stain is generated because the coupling position is substituted with an alkyl group. However, the method for synthesizing an alkyl-eliminating coupler described herein has a problem that the number of steps is long, the yield is low, and the versatility is low.

Generally, a method for converting the coupling position of an active methylene compound into a sulfonamidomethyl group or a carbonamidomethyl group is as follows: 1) Formylating the coupling position, converting this formyl group into sulfonimide, and reducing (For example, described in Tetrahendron, 1997, p. 11355) 2)
After converting formyl form to oxime (for example, J. Am. Che
m. Soc., 1954, p. 4391) to obtain an aminomethyl compound by reduction (for example, J. Am. Chem. Soc., 1959, 6).
415), and reacting this with a sulfonyl chloride or an acyl chloride to introduce a sulfonylaminomethyl group or an acylaminomethyl group. 3) Methylolation of the coupling position (for example, Can. J. Chem., 1984).
Year, p. 1945), or halomethylation (eg, Or
g. Syntheses, Coll. Vol. III, 1955, p. 468), and substituting the substituent (hydroxyl group or halogen atom) on the carbon adjacent to the coupling position with a sulfonamide compound or a carbonamide compound. All of these methods are multi-step, and when these methods are applied to a pyrrolotriazole compound, 1) a methylenebis-form of the pyrrolotriazole compound is generated; 2) a chloromethyl form It was not possible to obtain the target compounds sulfonamidomethyl and carbonamidomethyl because the intermediates such as aminomethyl and aminomethyl were not stable enough to be preserved.

A method for introducing a carbon atom to which a nitrogen atom is bonded into a coupling position of an active methylene compound in one step is described in J. Am. Chem. Soc., 1944, page 200. The Mannich reaction is known. However, when this method was applied to a pyrrolotriazole compound, a large amount of a methylenebis-form of the pyrrolotriazole was formed, and the desired sulfonamidomethyl and carbonamidomethyl could not be obtained.

As a method for introducing a sulfonamidomethyl group in one step, J. Chem. Soc., Chem. Commu.
n., 1976, p. 470 and J. Heterocycl. Chem., 1986, 1
There is an intramolecular sulfonylamidomethylation method described on page 701. However, even when this method was applied to a pyrrolotriazole compound, a large amount of a methylenebis-form of the pyrrolotriazole was generated, and the intended sulfonamidomethyl could not be obtained. It has been desired to develop a method for synthesizing an alkyl-elimination-type pyrrolotriazole coupler having high versatility and low generation of by-products by a simple experimental operation that solves these problems.

[0008]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing a highly versatile alkyl-eliminating pyrrolotriazole coupler which is simple, has a high yield, and is highly versatile.

[0009]

The present inventors have conducted intensive studies and as a result, have found that 1H-pyrrolo- [1,1, having a substituted methyl group at the 5-position.
1-H-pyrrolo- [1,2-b] having a sulfonylaminomethyl group or an acylaminomethyl group at the 5-position efficiently from 2-b] [1,2,4] triazole compound
A method for producing a [1,2,4] triazole compound has been found. That is, the present invention provides the following manufacturing method.

(1) 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] represented by the general formula (II) characterized by using the compound represented by the general formula (I)
[1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2
2,4] A method for producing a triazole compound.

[0011]

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(Wherein, R ¹ represents a hydrogen atom or a substituent. R ² and R ³ each independently represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.2 or more. R ⁴ ,
R ⁵ represents a substituent. X represents a sulfonyl group or a carbonyl group. ).

(2) In the general formulas (I) and (II), R¹Is archi
Group, aryl group, heterocyclic group, cyano group, nitro group,
Silamino group, arylamino group, ureido group, sulf
Amoylamino group, alkylthio group, arylthio group,
Heterocyclic thio group, alkoxycarbonylamino group, aryl
Ruoxycarbonylamino group, sulfonamide group, cal
Bamoyl group, sulfamoyl group, sulfonyl group, alcohol
Xycarbonyl group, aryloxycarbonyl group, reed
Ruoxy group, carbamoyloxy group, imide group, sulf
R, a quinyl group, a phosphonyl group, an acyl group,^TwoAnd R^Three
Are each independently an acyl group, an acyloxy group, a carbamo
Yl group, aliphatic oxycarbonyl group, aryloxyca
Rubonyl group, cyano group, nitro group, formyl group, dial
Kilphosphono group, diarylphosphono group, dialkoxy
Phosphoryl group, diarylphosphinyl group, aliphatic sulf
Finyl group, arylsulfinyl group, aliphatic sulfoni
Group, arylsulfonyl group, sulfonyloxy group,
Silthio group, sulfamoyl group, thiocyanate group,
Ocarbonyl group, halogenated alkyl group, halogenated alkyl group
Lucoxy group, halogenated aryloxy group, halogenated
Alkylamino group, halogenated alkylthio group,
Aryl substituted with an electron-withdrawing group having a value of 0.2 or more
Group, heterocyclic group, halogen atom, azo group, or selenosi
Anate group, R ^FourIs a heterocyclic group, hydroxyl group, acyl
An oxy group, an amino group, or an imide group, R^FiveIs alkyl
Group or aryl group, X is a sulfonyl group or carbonyl
5-Sulfur according to the above (1), which is
Honylaminomethyl-1H-pyrrolo- [1,2-b]
[1,2,4] triazole compound or 5-acyl
Aminomethyl-1H-pyrrolo- [1,2-b] [1,
2,4] A method for producing a triazole compound.

(3) The 5-sulfonylaminomethyl-1H-pyrrolo- [1,1] described in the above (1) or (2), wherein R ^{4 in the} general formula (I) is a hydroxyl group.
2-b] [1,2,4] triazole compound or 5
-Acylaminomethyl-1H-pyrrolo- [1,2-b]
[1,2,4] A method for producing a triazole compound.

(4) The 5-sulfonylaminomethyl-1H-pyrrolo- [1,1] described in the above (1) or (2), wherein R ^{4 in the} general formula (I) is an acyloxy group.
2-b] [1,2,4] triazole compound or 5
-Acylaminomethyl-1H-pyrrolo- [1,2-b]
[1,2,4] A method for producing a triazole compound.

(5) The 5-sulfonylaminomethyl-1H-pyrrolo- [1,1] described in the above (1) or (2), wherein R ^{4 in the} general formula (I) is a phthalimide group.
2-b] [1,2,4] triazole compound or 5
-Acylaminomethyl-1H-pyrrolo- [1,2-b]
[1,2,4] A method for producing a triazole compound.

(6) The compound of the above (1) or (2), wherein R ^{4 in the} general formula (I) is an amino group.
Sulfonylaminomethyl-1H-pyrrolo- [1,2-
b] [1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b]
[1,2,4] A method for producing a triazole compound.

(7) Compound (IA) is used as a starting material, and is converted to a compound represented by the general formula (II) via compounds IB, IC, and ID. ) Or 5-sulfonylaminomethyl-1H-pyrrolo- according to (2).
[1,2-b] [1,2,4] triazole compound and 5-acylaminomethyl-1H-pyrrolo- [1,2-
b] A method for producing a [1,2,4] triazole compound.

[0019]

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[0020] (wherein, ^{R 1, R 2, R 3} , R 5 have the same meanings as ^{R 1, R 2, R 3} , R 5 in the general formula (II) in the above (1) .R ⁶ Represents an alkyl group or an aryl group.
Represents a sulfonyl group or a carbonyl group. Y represents a nonmetallic atom group necessary to form a ring containing the same. ).

(8) In the process of using compound IA as a starting material and converting it to compounds represented by general formula (II) via compounds IB, IC and ID, compound IB Is not isolated and purified. 5-Sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] according to the above (7),
Triazole compound or 5-acylaminomethyl-
A method for producing a 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound.

(9) In the process of using compound IA as a starting material and converting it to compounds represented by general formula (II) via compounds IB, IC and ID, compound ID Is characterized by not isolating and purifying 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,
4] A process for producing a triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] triazole compound.

(10) In the process of using compound IA as a starting material and converting it to compounds represented by general formula (II) via compounds IB, IC and ID, compound IB 5- (5), characterized in that both and I-D are not isolated and purified.
Sulfonylaminomethyl-1H-pyrrolo- [1,2-
b] [1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b]
[1,2,4] A method for producing a triazole compound.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the starting compound {general formula (I)} and the target compound {general formula (II)} used in the present invention will be described in detail. R ¹ represents a hydrogen atom or a substituent (including an atom), and the substituent is a halogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylaryl or a heterocyclic group. Thio group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkenyloxy group, formyl group,
Alkyl / aryl or heterocyclic acyl group, alkyl / aryl / heterocyclic sulfonyl group, alkyl / aryl / heterocyclic sulfinyl group, alkyl / aryl / heterocyclic oxycarbonyl group, alkyl / aryl or heterocyclic oxycarbonylamino group, sulfonamide Groups, carbamoyl group, sulfamoyl group, phosphonyl group, imide group, hydroxy group, cyano group, carboxyl group, nitro group, sulfo group, unsubstituted amino group and the like. The alkyl group, aryl group or heterocyclic group contained in these groups may be further substituted with a substituent as exemplified for R ¹ .

More specifically, R ¹ is a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an aliphatic hydrocarbon group (for example, having 1 to 36 carbon atoms, preferably 1 to 36 carbon atoms).
4, a linear or branched alkyl group, alkenyl group,
Alkynyl group) and alicyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group), specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3- Pentadecylphenoxy) propyl, 3- {4-} 2-
[4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3- (2,4-di-t-amylphenoxy) propyl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 22 carbon atoms, for example, phenyl,
Naphthyl, 4-hexadecyloxyphenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl, 3- (2,4-di-t
ert-amylphenoxyacetamide) phenyl),
A heterocyclic group (preferably, an aromatic or non-aromatic 5- or 6-membered ring containing one or two or more nitrogen atoms, oxygen atoms, and sulfur atoms as hetero atoms, and a hydrocarbon ring such as benzene; May be condensed, for example, 3
-Pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), an alkoxy group having 1 to 15 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), having 6 to 20 carbon atoms
Aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 2,4
-Di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy,
3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), an alkyl / aryl or heterocyclic thio group having 1 to 22 carbon atoms (for example, methylthio, ethylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, -Phenoxypropylthio, 3- (4-tert-butylphenoxy) propylthio, phenylthio, 2-butoxy-5-tert
-Octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, 2-benzothiazolylthio, 2,4
-Di-phenoxy-1,3,4-triazole-6-thio, 2-pyridylthio), an acyloxy group having 2 to 22 carbon atoms (eg, acetoxy, hexadecanoyloxy), a carbamoyloxy group having 2 to 22 carbon atoms (Eg, N-ethylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group having 3 to 16 carbon atoms (eg, trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group having 1 to 22 carbon atoms (eg, dodecylsulfonyl) Oxy), having 2 to 2 carbon atoms
2 acylamino groups (e.g., acetamido, benzamido, tetradecaneamido, 2- (2,4-di-ter
t-amylphenoxy) acetamide, 2- [4- (4
-Hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecaneamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t
-Butyl-4-hydroxyphenoxy) butanamide), an alkylamino group having 1 to 22 carbon atoms (eg, methylamino, butylaminododecylamino, dimethylamino, diethylamino, methylbutylamino), an arylamino group having 6 to 30 carbon atoms (For example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, N-acetylanilino, 2-chloro-5- [α-2-tert-butyl-4-hydroxyphenoxy) dodecaneamide] Anilino, 2-chloro-5
-Dodecyloxycarbonylanilino), having 1 to 2 carbon atoms
2 ureido groups (for example, methylureide, phenylureide, N, N-dibutylureide, dimethylureide), and a sulfamoylamino group having 1 to 22 carbon atoms (for example, N, N-dipropylsulfamoylamino, N- Methyl-N-decylsulfamoylamino), having 2 to 2 carbon atoms
22 alkenyloxy groups (eg, 2-propenyloxy), formyl groups, alkyl aryl or heterocyclic acyl groups having 2 to 22 carbon atoms (eg, acetyl, benzoyl, 2,4-di-tert-amylphenylacetyl, 3-phenylpropanoyl, 4-dodecyloxybenzoyl, nicotinoyl, 3-furoyl), having 1 to 1 carbon atoms
22 alkyl aryl or heterocyclic sulfonyl groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl, 8-quinoline sulfonyl), and alkylaryl or heterocyclic sulfinyl groups having 1 to 22 carbon atoms (eg, octanesulfinyl) , Dodecanesulfinyl, phenylsulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl, 1-piperidinesulfinyl), an alkyl / aryl or heterocyclic oxycarbonyl group having 2 to 22 carbon atoms (for example, methoxycarbonyl, butoxycarbonyl, Dodecyloxycarbonyl,
Octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl, 2-pyridineoxycarbonyl), an alkyl / aryl or heterocyclic oxycarbonylamino group having 2 to 22 carbon atoms (for example, methoxycarbonylamino, tetradecyloxycarbonylamino , Phenoxycarbonylamino, 2,4
-Di-tert-butylphenoxycarbonylamino,
2-pyridineoxycarbonylamino), having 1-2 carbon atoms
2 sulfonamide groups (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butylbenzenesulfonamide); Carbamoyl groups (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- [3- (2,4-di-tert-
Amylphenoxy) propyl] carbamoyl), a sulfamoyl group having 1 to 22 carbon atoms (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), a phosphonyl group having 1 to 22 carbon atoms (for example, phenoxyphosphonyl, octyloxyphosphonyl, Phenylphosphonyl), an imide group having 3 to 22 carbon atoms (for example, N-succinimide, hydantoinyl, N-
Phthalimide, 3-octadecenylsuccinimide),
Hydroxy, cyano, carboxyl, nitro,
Examples include a sulfo group and an unsubstituted amino group.

R ¹ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group. Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyloxy group, imide group, sulfinyl group, phosphonyl group And an acyl group. More preferred are an alkyl group and an aryl group. More preferably, it is an unsubstituted phenyl group or an aryl group having at least one group defined as R ¹ as a substituent. In this case, particularly preferable examples of the substituent at the 3-position of the aryl group include a substituted sulfoamino group, a substituted carbamino group, and a nitro group. Particularly preferable examples of the substituent at the 4-position are a methyl group. Methoxy group, halogen atom, 1-pyrrolidyl group, 1-piperidyl group, morpholino group, nitro group, and the like, but are not limited thereto.

R ² and R ³ are electron-withdrawing groups having a Hammett's substituent constant σp value of 0.2 or more. Preferably, σp
It is an electron-withdrawing group having a value of 0.35 or more, more preferably 0.45 or more. The upper limit is preferably an electron-withdrawing group of 1.0 or less, more preferably 0.75 or less. Hammett's rule was published in 1935 in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. Ha
A rule of thumb proposed by mmett, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σp value and a σm value, and many of these values are described in general books.
A. Dean ed. "Lange's Handbook o
f Chemistry "12th edition, 1979 (Mc
(Graw-Hill) and “Chemical Area Special Edition”, 122
No. 96-103, 1979 (Nankodo).
In the present invention, R ² and R ³ are Hammett's substituent constant σp
Although it is defined by the value, it does not mean that it is limited to only certain substituents with known values in the literature described in these books, and even if the value is unknown in the literature, it may be determined when measured based on Hammett's rule. It goes without saying that it is included as long as it is included in the range.

Specific examples of R ² and R ³ which are electron-withdrawing groups having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group and cyano group. , Nitro group, formyl group, dialkylphosphono group, diarylphosphono group, dialkoxyphosphoryl group, diarylphosphinyl group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfonyloxy group, An acylthio group, a sulfamoyl group, a thiocyanate group, a thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, and a σp value of 0.20 or more. An aryl group substituted with an electron-withdrawing group, Examples include a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group. Among these substituents, the group which can have a substituent may further have a substituent such as those described above for R1. The above-mentioned aliphatic oxycarbonyl group, aliphatic sulfinyl group, and aliphatic sulfonyl group each have a straight-chain, branched-chain, or cyclic aliphatic moiety, and may be saturated. , May be unsaturated. For example, an aliphatic oxycarbonyl group refers to an alkoxycarbonyl group having a linear alkyl chain (for example, methoxycarbonyl), an alkoxycarbonyl group having a branched alkyl chain (for example, iso-propyloxycarbonyl), or a cyclic alkyl chain. A cycloalkoxycarbonyl group (e.g., 2,6-di-t-butyl-4-methylcyclohexylcarbonyl), an alkenyloxycarbonyl group (e.g., allyloxycarbonyl).

If R ² and R ³ are described in more detail,
Examples of the electron-withdrawing group having a value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl) , N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-
(4-n-pentadecanamidophenyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3
-(2,4-di-t-amylphenoxy) propyl] carbamoyl), an aliphatic oxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, Butyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl,
2- (diethylcarbamoyl) ethoxycarbonyl, 2
-(Perfluorohexyl) ethoxycarbonyl, 2-
Decylhexyloxycarbonylmethoxycarbonyl,
2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl, 2,5-diamylphenoxycarbonyl), a cyano group, a nitro group, a formyl group, a dialkylphosphono Groups (eg, dimethylphosphono), diarylphosphono groups (eg, diphenylphosphono),
Dialkoxyphosphoryl group (eg, dimethoxyphosphoryl), diarylphosphinyl group (eg, diphenylphosphinyl), aliphatic sulfinyl group (eg, 3
-Phenoxypropylsulfinyl), arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), aliphatic sulfonyl group (eg, methanesulfonyl, octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (For example, methanesulfonyloxy,
Toluenesulfonyloxy), acylthio group (for example,
Acetylthio, benzoylthio), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N , N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide group (eg, trifluoromethyl, heptafluoropropyl), alkoxy halide (eg, trifluoro Methyloxy), a halogenated aryloxy group (eg, pentafluorophenyloxy), a halogenated alkylamino group (eg, N, N-di- (trifluoromethyl) amino), a halogenated alkylthio group (eg, difluoromethylthio) , 1,1,2,2-tetrafluoroethylthio), an aryl group substituted by another electron-withdrawing group having a σp value of 0.20 or more (for example, 2,4-dinitrophenyl, 2,4,6 -Trichlorophenyl, pentachlorophenyl), a heterocyclic group (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-
Examples thereof include 2-benzimidazolyl, 5-chloro-1-tetrazolyl, and 1-pyrrolyl), a halogen atom (for example, a chlorine atom and a bromine atom), an azo group (for example, phenylazo) and a selenocyanate group. Among these substituents, a group that can have a substituent may further have a substituent.

R ² is preferably a cyano group, an aliphatic oxycarbonyl group having 1 to 36 carbon atoms, preferably 1 to 20 carbon atoms, a C ^{6 to} 36 carbon atom, preferably a 6 to 2 carbon atom.
And an aryloxycarbonyl group of 0, particularly preferably a cyano group.

Preferred examples of R ³ include an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group, a carbamoyl group and a sulfamoyl group, more preferably having 1 to 36 carbon atoms. More preferably, they are an aliphatic oxycarbonyl group having 1 to 20 carbon atoms, and an aryloxycarbonyl group having 6 to 36 carbon atoms, more preferably 6 to 20 carbon atoms. Particularly preferred is a cycloalkyloxycarbonyl group.

R ⁴ is a substituent as defined for R ¹ above. Of these, preferred are a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an imide group, a hydroxy group, and an unsubstituted amino group. More preferred as R ⁴ are an acyloxy group, a hydroxy group, an imide group, and an unsubstituted amino group. Further, among the acyloxy groups, preferred are an acetyloxy group, a propionyloxy group, a butyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group and the like, and particularly preferred is an acetyl group. Preferred imide groups include a phthalimide group and a succinimide group, and particularly preferred is a phthalimide group. When these groups are substituted, examples of the substituent include those defined for R ¹ above.

R ⁵ is a substituent as defined for R ¹ above. Of these, preferred are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 36 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 36 carbon atoms. R ⁵ is more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Particularly preferred as R ⁵ is a methyl group, a substituted or unsubstituted aryl group, and particularly preferred as a substituent of the substituted aryl group is an alkyl group,
Examples include an alkoxy group, a nitro group, an alkoxycarbonyl group, and a halogen atom. When these groups are substituted, examples of the substituent include those defined for R ¹ above. The linking group X is a sulfonyl group or a carbonyl group.

In the formula (IB), R ⁶ is a substituent as defined for R ¹ above. Of these, preferred are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 36 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 36 carbon atoms. More preferably, R ⁶ has 1 to 1 carbon atoms.
A substituted or unsubstituted alkyl group of 0; and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Particularly preferred as R ⁶ is a substituted or unsubstituted alkyl group, and a particularly preferred substituent is a methyl group. When these groups are substituted, the substituent may be the above R
Examples include groups as defined in ¹ .

In the formula (IC), the ring formed by Y includes a phthalimide group, a 1,2-cyclohexanedicarboximide group, a succinimide group and the like. is there.
When these groups are substituted, examples of the substituent include those defined for R ¹ above.

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

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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Next, the method for producing the compound represented by the general formula (II) from the compound represented by the general formula (I) will be described in detail.

A method for synthesizing a 4-equivalent pyrrolotriazole coupler is widely known as described in JP-A-2000-44563. Next, compound IA is obtained by methylolating a 4-equivalent pyrrolotriazole coupler. Many methods for converting the coupling position to methylol are known, for example, in Can. J. Chem., 1984.
Year, there is a method described on page 1945. This can also be applied to 4-equivalent pyrrolotriazole couplers,
The synthesis of compound IA is easily achieved.

When compound IB is synthesized from compound IA (step A), compound IA and the acylating agent may be simply mixed, but preferably, they are reacted in the presence of a base. Is good. The method used in step A will be described.

The acylating agents used include acyl halides such as acetyl chloride, acetyl bromide, pivaloyl chloride, benzoyl chloride, acetic anhydride, propionic anhydride,
Acid anhydrides such as trifluoroacetic anhydride are exemplified.
Of these, acetyl chloride and acetic anhydride are preferred,
Particularly preferred is acetic anhydride. The molar ratio of the acylating agent used to the compound represented by the compound IA was 1.
It is 0-100, preferably 1.0-20, and more preferably 1.0-5.0.

As the base to be used, an inorganic base, an organic base, an organic metal base or the like can be used. For example, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydride, potassium t-butoxy, t
-Butoxy sodium, 1,1,3,3-tetramethylguanidine, pyridine, N, N-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5- Diazabicyclo [4,3
0] -5-Nonene (DBN), diisobutylethylamine, triethylamine, sodium acetate, potassium acetate, trimethylsilyloxypotassium, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, water Examples include lithium oxide, sodium amide, n-butyllithium, methyllithium, t-butyllithium, i-propyllithium, lithium diisopropylamide and the like. Among them, pyridine, N, N-dimethylaminopyridine, sodium acetate, potassium acetate and the like are preferable, and among them, N, N-dimethylaminopyridine is more preferable. Compound IA of the base used
The molar ratio to the compound represented by 0.01 to 10
0, preferably 0.1-20, more preferably 0.2
５5.0.

The reaction solvent used in step A includes methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, N,
N-dimethylimidazolidione, ethyl acetate, dioxane, tetrahydrofuran, water, carbon tetrachloride, acetic acid, methanol, ethanol, benzene, toluene, pyridine,
Acetone and the like can be mentioned. These may be used as a mixture, more preferably tetrahydrofuran. The amount of the solvent used is 2 to 2 in mass ratio to the compound used as the raw material.
50 times is appropriate, and 2 to 10 times is preferable.

The reaction temperature in Step A is from -78 ° C to 200
° C, preferably -20 ° C to 150 ° C, more preferably -10 ° C to 120 ° C, and particularly preferably 0 ° C to 50 ° C.
° C. The reaction time is 1 minute to 24 hours, preferably 15 minutes.
Minutes to 12 hours, more preferably 30 minutes to 6 hours.

Next, the method for producing compound IC from compound IB (step B) will be described in detail. Examples of the acid imidizing agent used include sodium salts or potassium salts of acid imides such as phthalimide and succinimide. The preparation of these salts is carried out by treating the acid imide with a base. As the base used at this time, an inorganic base, an organic base, an organic metal base or the like can be used. For example, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride, potassium hydride, lithium hydride, potassium t-butoxy, sodium t-butoxy, 1,1,3,3-tetramethyl Guanidine, pyridine, N, N-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0]
-7-undecene (DBU), 1,5-diazabicyclo [4,3,0] -5-nonene (DBN), diisobutylethylamine, triethylamine, sodium acetate, potassium acetate, trimethylsilyloxypotassium, sodium methoxide, potassium methoxide , Lithium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium amide, n-
Butyllithium, methyllithium, t-butyllithium, i-propyllithium, lithium diisopropylamide and the like. Among them, preferred are sodium methoxide, potassium methoxide, sodium hydride, sodium carbonate, potassium carbonate and the like. In the present invention, it is particularly preferable to use commercially available potassium phthalimide.

The molar ratio of the acid imidizing agent used to the compound represented by the compound IB is from 1.0 to 100, preferably from 1.0 to 20, more preferably from 1.0 to 5.
0. The reaction solvent used in Step B includes methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethylsulfoxide, N, N
-Dimethylimidazolidione, ethyl acetate, dioxane, tetrahydrofuran, water, carbon tetrachloride, acetic acid, methanol, ethanol, benzene, toluene, pyridine,
Acetone and the like can be mentioned. These may be used as a mixture, and more preferably N, N-dimethylformamide. The amount of the solvent to be used is appropriately 2 to 50 times, preferably 2 to 10 times, by mass relative to the compound used as a raw material.

The reaction temperature in Step B is from -78 ° C to 200
° C, preferably −20 ° C. to 150 ° C., more preferably −10 ° C. to 120 ° C., and particularly preferably 20 ° C. to 1 ° C.
00 ° C. The reaction time is 1 minute to 24 hours, preferably 15 minutes to 12 hours, more preferably 30 minutes to 6 hours.

Next, the method for producing compound ID from compound IC (step C) will be described in detail. When an acid imide such as compound IC is led to ID by hydrolysis, the reagents used are hydrochloric acid, hydrobromic acid, hydrohalic acid such as hydroiodic acid, or sodium carbonate, potassium carbonate, Carbonates such as lithium carbonate. Further, it is possible to lead to ID by decomposition using amines represented by ammonia or hydrazine, and the reagent used in this case includes hydrazine monohydrate, phenylhydrazine and the like. Of these, a decomposition reaction using hydrazine monohydrate is more preferable. The molar ratio of the hydrazine to the compound represented by the compound IC is 1.0 to 100, preferably 1.0 to 20, and more preferably 1.0 to 5.0.

The reaction solvent used in Step C includes methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, N,
N-dimethylimidazolidione, ethyl acetate, dioxane, tetrahydrofuran, water, carbon tetrachloride, acetic acid, methanol, ethanol, benzene, toluene, pyridine,
Acetone and the like may be mentioned, and these may be used as a mixture. More preferred are methanol and ethanol, and particularly preferred is ethanol. The amount of the solvent to be used is appropriately 2 to 50 times, preferably 3 to 30 times, the mass ratio of the compound used as a raw material. The reaction temperature in step C is
-78 ° C to 200 ° C, preferably -20 ° C to 150 ° C,
The temperature is more preferably -10C to 120C, and particularly preferably 20C to 100C. Reaction time is 1 minute to 24
Time, preferably 15 minutes to 12 hours, more preferably 30 minutes to 6 hours.

Next, a method for producing the compound represented by the general formula (II) from the compound ID (step D) will be described in detail. In the step D, the compound ID and the sulfonylating agent or the acylating agent may be simply mixed, but preferably the two are reacted in the presence of a base. The method used in step D will be described.

Examples of the sulfonylating agent used include alkylsulfonyl chloride, arylsulfonyl chloride, alkylsulfonic anhydride, and arylsulfonic anhydride. These substituents may further have a substituent. . Of these, methanesulfonyl chloride and substituted or unsubstituted arylsulfonyl chloride are more preferable, and examples of the substituent include a methyl group, an alkoxy group, a nitro group, and a halogen atom.

Examples of the acylating agent to be used include acyl halides such as acetyl chloride, acetyl bromide, pivaloyl chloride and benzoyl chloride, and acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride. . These substituents may further have a substituent. Of these, acetyl chloride and substituted or unsubstituted aromatic carboxylic acid chlorides are more preferable, and examples of the substituent include a methyl group, an alkoxy group, a nitro group, and a halogen atom.

The molar ratio of the sulfonylating agent or acylating agent used to the compound represented by the compound ID is 1.0 to 100, preferably 1.0 to 20, more preferably 1.0 to 5 0.0.

As the base to be used, an inorganic base, an organic base, an organic metal base or the like can be used. For example, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydride, potassium t-butoxy, t
-Butoxy sodium, 1,1,3,3-tetramethylguanidine, pyridine, 2,6-lutidine, 2-picoline, N, N-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7 -Undecene (DBU),
1,5-diazabicyclo [4,3,0] -5-nonene (DBN), diisobutylethylamine, triethylamine, sodium acetate, potassium acetate, trimethylsilyloxypotassium, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide , Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium amide, n-butyllithium, methyllithium, t-butyllithium, i-propyllithium,
Lithium diisopropylamide and the like. Among them, preferred are potassium carbonate, pyridine, triethylamine, etc., of which pyridine,
Triethylamine.

The reaction solvent used in Step D includes methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, N,
N-dimethylimidazolidione, ethyl acetate, dioxane, tetrahydrofuran, water, carbon tetrachloride, acetic acid, methanol, ethanol, benzene, toluene, pyridine,
Acetone and the like may be mentioned, and these may be used as a mixture. Preferred is methylene chloride. The amount of the solvent to be used is suitably 2 to 50 times, preferably 3 to 20 times by mass, the compound represented by the formula (ID) used as a raw material.

The reaction temperature in Step D is from -78 ° C to 200
° C, preferably -20 ° C to 150 ° C, more preferably -10 ° C to 120 ° C, and particularly preferably 0 ° C to 10 ° C.
0 ° C. The reaction time is 1 minute to 24 hours, preferably 1 minute.
5 minutes to 12 hours, more preferably 30 minutes to 6 hours.

The compound represented by the formula (IB) obtained in the step A does not need to be particularly isolated and purified, and can be used as it is in the next step B. No decrease in yield is observed as compared with the case of isolation and purification, and the experimental procedure can be simplified. Further, the compound represented by the formula (ID) obtained in Step C does not need to be particularly isolated and purified, and can be used as it is in the next Step D. No decrease in yield is observed as compared with the case of isolation and purification, and the experimental procedure can be simplified.

[0067]

Next, the present invention will be described in more detail by way of examples. Embodiments of the present invention are not so limited. <Example 1> (Synthesis of Exemplified Compound II-1) In a tetrahydrofuran solution (100 mL) of Exemplified Compound I-1 (23.8 g, 21.4 mmol), acetic anhydride (3.03 mL, 32.1 mmol) and dimethyl Aminopyridine (2.61 g, 21.4 mmol) was added,
Stirred at room temperature for 1 hour. After confirming the disappearance of the raw materials (Exemplified Compound I-5 was generated at this time), the reaction solution was concentrated to obtain a solution of dimethylformamide (100 mL). Here, potassium phthalimide (8.50 g, 45.
9 mmol) and stirred at 80 ° C. for 1 hour. The reaction was stopped with water, and the organic layer was extracted with ethyl acetate.
It was washed once with saturated saline. After drying over anhydrous magnesium sulfate and concentration, the precipitated solid was washed with a mixed solvent of acetonitrile and ethyl acetate to give 15.8 g of Exemplified Compound I-8.
(72% yield).

Subsequently, the exemplified compound I-8 (4.88 g,
Hydrazine monohydrate (1.0 mL, 20.1 mmol) in an ethanol solution (5.0 mL) of 5.02 mmol).
l) was added and the mixture was stirred at room temperature for 2 hours (at this point, Exemplified Compound I-13 had been formed). The precipitated insoluble solid was removed while washing with ethanol, and the filtrate was concentrated under reduced pressure. This was made into a methylene chloride (50 mL) solution, and then pyridine (0.89 mL, 11.0 mmol) and p
-Nitrosulfonyl chloride (1.11 g, 5.02 m
mol) were added sequentially. After stirring at room temperature for 1 hour, the reaction was stopped with water, and the organic layer was extracted with methylene chloride.
The extract was washed once with water and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 4) to obtain 2.10 g of Exemplified Compound II-1 (yield: 39).
%).

<Example 2> (Synthesis of Exemplified Compound II-2) According to the method described in Example 1, in Step D, instead of p-nitrosulfonyl chloride, toluenesulfonyl chloride was used instead of Exemplified Compound II-2. Was synthesized.
The yield is shown in Table 1.

Example 3 (Synthesis of Exemplified Compound II-3) According to the method described in Example 1, methanesulfonyl chloride was used instead of p-nitrosulfonyl chloride.
Example Compound II-3 was synthesized. The yield is shown in Table 1.

Example 4 (Synthesis of Exemplified Compound II-4) According to the method described in Example 1, the synthesis of Exemplified Compound II-4 was carried out using p-toluoyl chloride instead of p-nitrosulfonyl chloride. went. The yield is shown in Table 1.

[0072]

[Table 1]

From the results, it is understood that the present production method is applicable to various compounds represented by the general formula (II). It is considered that the compound represented by the general formula (II) can be easily synthesized by converting the hydroxyl group of the compound IA in the present invention into an appropriate leaving group and introducing a nitrogen functional group into the hydroxyl group. However, this object was not achieved in the following comparative examples.

Comparative Example 1 4-equivalent cyan coupler (II
The following experiment was conducted for the purpose of introducing a chloromethyl group having a chlorine atom capable of leaving at the active position of I).
A 4-equivalent cyan coupler (III) (1.
00g, 1.15 mmol) was dissolved in acetic acid (5.0 mL) and chloroform (5.0 mL), and the mixture was stirred at room temperature.
Here, zinc chloride (0.16 g, 1.15 mmol) and chloromethyl methyl ether (0.09 g, 1.15 mm
ol) were sequentially added, and the mixture was stirred at room temperature for 1 hour. The reaction was stopped with water, the organic layer was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated. When this was developed by thin layer chromatography, the raw material (III) disappeared, and a new product was confirmed. This was isolated and purified by silica gel column chromatography, and proton NMR and MS spectra were measured. This compound was not the intended chloromethyl form (I-15), but the methylenebis form (IV) of pyrrolotriazole. It was confirmed.

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Comparative Example 2 The following experiment was conducted for the purpose of converting the hydroxyl group of the compound represented by IA into a methanesulfonyloxy group as a leaving group. Methanesulfonyl chloride (0.13 mL, 1.67 mmol) was added to a pyridine solution (7.0 mL) of Exemplified Compound I-1 (1.00 g, 1.11 mmol), and the mixture was stirred at room temperature for 1 hour. The reaction was stopped with water, the organic layer was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated. When this was developed by thin-layer chromatography, many products were confirmed, and it was difficult to determine the structure. Also, the target product (I-16) could not be confirmed.

[0077]

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As described above, in synthesizing the compound represented by the general formula (II), R ^{4 in the} general formula (I) is a certain amount such as a halogen atom (chlorine atom), a methanesulfonyloxy group or a toluenesulfonyloxy group. When trying to convert to a compound having an elimination ability, a large amount of a methylenebis-form of pyrrolotriazole was generated or the reaction became complicated. This has been a major problem in synthesizing the compound represented by the general formula (II).

In comparison with this, in the present invention, the formation of the methylenebis-form of pyrrolotriazole, which was a problem, could be completely suppressed. In addition, compounds IB and ID could be used for the next reaction without isolation and purification, and simplification of the experimental operation was also achieved. No decrease in yield is observed as compared with the case where compounds IB and ID are isolated and purified.

Using the exemplified compound ID obtained by the subsequent reaction, various 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] represented by the general formula (II) can be used.
[1,2,4] triazole compound and 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,
4] It is possible to synthesize a triazole compound,
The method of the present invention is very versatile.

[0081]

According to the present invention, 1H-pyrrolo- [1,2-b] [1,2,4] triazoles having various sulfonylaminomethyl groups and acylamino groups at the 5-position can be obtained by a simple operation. It has become possible to manufacture efficiently.

 ──────────────────────────────────────────────────続 き Continued on the front page (54) [Title of the Invention] 5-Sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] triazole compound and 5-acylaminomethyl-1H For producing pyrrolo- [1,2-b] [1,2,4] triazole compound

Claims (10)

[Claims] 1. A compound represented by the general formula (I), wherein 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1] represented by the general formula (II) is used. , 2,
4] A process for producing a triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] triazole compound. Embedded image (In the formula, R ¹ represents a hydrogen atom or a substituent. R ² and R ³ each independently represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.2 or more. R ⁴ , R ⁵ Represents a substituent, and X represents a sulfonyl group or a carbonyl group.) 2. In the general formulas (I) and (II), R ¹ is an alkyl group,
Aryl group, heterocyclic group, cyano group, nitro group, acylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group , A sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group, a phosphonyl group, an acyl group, and R ² and R ³ are Acyl group, acyloxy group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, formyl group, dialkylphosphono group, diarylphosphono group, dialkoxyphosphoryl group, diary Ruphosphinyl group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated An aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with an electron-withdrawing group having a value of σp of 0.2 or more,
A heterocyclic group, a halogen atom, an azo group, or a selenocyanate group, R ⁴ is a heterocyclic group, a hydroxyl group, an acyloxy group, an amino group, or an imide group; R ⁵ is an alkyl group or an aryl group; X is a sulfonyl group or a carbonyl group 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1,
2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4]
A method for producing a triazole compound. 3. The 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] according to claim 1 or 2, wherein R ^{4 in the} general formula (I) is a hydroxyl group.
[1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2
2,4] A method for producing a triazole compound. 4. The 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] according to claim 1, wherein R ^{4 in the} formula (I) is an acyloxy group.
[1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2
2,4] A method for producing a triazole compound. 5. The 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] according to claim 1, wherein R ^{4 in the} general formula (I) is a phthalimide group.
[1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2
2,4] A method for producing a triazole compound. 6. The 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1] according to claim 1 or 2, wherein R ^{4 in the} formula (I) is an amino group. , 2,
4] A process for producing a triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] triazole compound. 7. A method according to claim 1, wherein the compound IA is used as a starting material.
Via B, IC, and ID, the compound is converted into the compound represented by the general formula (II).
3. The method according to claim 1, wherein
Sulfonylaminomethyl-1H-pyrrolo- [1,2-
b] [1,2,4] triazole compound and 5-acyl
Aminomethyl-1H-pyrrolo- [1,2-b] [1,
2,4] A method for producing a triazole compound. Embedded image(Where R¹, R^Two, R^Three, R^FiveIs the general term in claim 1
R in the formula (II)¹, R^Two, R ^Three, R^FiveIs synonymous with R⁶Is
Represents an alkyl group or an aryl group. X is a sulfonyl group or
Represents a carbonyl group. Y forms a ring containing it
Represents a group of nonmetallic atoms necessary for ) 8. Compound IB, starting from compound IA,
8. The 5-sulfonyl compound according to claim 7, wherein the compound IB is not isolated and purified during the process of converting the compound represented by the general formula (II) via IC and ID. Aminomethyl-
Method for producing 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] triazole compound . 9. Compound IB, starting from compound IA
The compound according to claim 7, wherein the compound ID is not isolated and purified in the process of converting the compound represented by the general formula (II) via IC and ID. Sulfonylaminomethyl-1H-pyrrolo- [1,2-b] [1,2,4] triazole compound or 5-acylaminomethyl-1H-
A method for producing a pyrrolo- [1,2-b] [1,2,4] triazole compound. 10. Compound I-A starting from compound IA
B, IC, in the process of converting to the compound represented by the general formula (II) through ID, characterized in that both compounds IB and ID are not isolated and purified, The 5-sulfonylaminomethyl-1H-pyrrolo- [1,2-b] according to claim 7.
[1,2,4] triazole compound or 5-acylaminomethyl-1H-pyrrolo- [1,2-b] [1,2
2,4] A method for producing a triazole compound.