JPH10316654A - 2-aminopyrrole derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound useful as a synthetic intermediate for pyrrolo(1,2-a)pyrimicline, etc., usable as a coupler for a heat-sensitive recording material containing a diazonium salt or as pharmaceuticals, etc. SOLUTION: This compound is expressed by the formula I [A<1> is a 6-20C alkoxycarbonyl, a 7-20C aryloxycarbonyl, etc.; A<2> and A<3> are each H, a (substituted)alkyl, a (substituted)alkenyl, a (substituted)aryl, etc.], e.g. 2-amino-3- cyano-4phenylpyrrole. The compound of the formula I can be produced e.g. by reacting an imidoketone of the formula II (R<1> and R<2> are each H, an alkyl, an alkenyl, an aryl, etc.; Z is a C group necessary for forming an N-containing 5membered ring or 6-membered ring and the 5- or 6-membered ring may be condensed with an aromatic ring) with a nitrile derivative of the formula III (X is cyano, an alkoxycarbonyl, etc.) under basic condition to obtain a 2- aminopyrrole derivative of the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a coupler for a heat-sensitive recording material using a diazonium salt, a coupler for a silver salt photograph or a pyrrolo [1,2-] which can be used as a pharmaceutical.
a) A 2-aminopyrrole derivative which is a synthetic intermediate useful for pyrimidine and the like, 3-cyano-pyrrol-2-yl-oxamate and the like which can be used as a pharmaceutical, and a simple production method thereof.

[0002]

2. Description of the Related Art In recent years, heat-sensitive recording materials have particularly improved color shelf life, image storability, and image fixability, particularly in the purple to cyan region, with the enhancement of performance. There is a strong demand for thermally sensitive recording materials. Regarding the above color development range, Japanese Patent Application Laid-Open No. 2-225082 discloses that 2-hydroxy-3-naphthoic acid anilides and 4-substituted amino-2-alkoxybenzenediazonium salt compounds having particularly excellent performances as color development materials for thermal recording. To produce a bluish dye by performing a coupling reaction with, and this is already known. In heat-sensitive recording, a diazonium salt compound is generally used in the heat-sensitive material, but it is a compound having extremely high chemical activity and easily reacts with a compound called a coupler such as a phenol derivative or a compound having an active methylene group. Azo dyes can be formed. At the same time, it has photosensitivity, decomposes when irradiated with light, and loses its activity. For this reason, diazonium salt compounds have long been used as optical recording materials typified by diazocopy ("Photographic Engineering Fundamentals-Non-Silver Salt Photography-" edited by The Photographic Society of Japan, Corona (1982) 89-117; 182-201).
However, the diazonium salt compound has a longer wavelength λ.
It has the disadvantage of storability of a recording material used having a _max (background coloring being copied before storage) is reduced, and the coupler at the time of light irradiation when using those having a lambda _max to a shorter wavelength side There are disadvantages that the fixability of the formed image is hindered, the storage stability (light fastness) of the color image is not sufficient, and that it is difficult to increase the wave length to cyan in terms of hue. . Therefore, pyrrolo [1,2-
a] A pyrimidine derivative has been found, and the compound is produced by a condensation reaction between a 2-aminopyrrole derivative and a β-ketoester derivative based on, for example, the method described in JP-A-6-130600.

Several methods have been proposed for producing 2-aminopyrrole derivatives which are useful intermediates for the synthesis of the above-mentioned couplers and the like. U.S. Pat. Nos. 3,836,541 and 3,838,166 describe, for example, the synthesis and synthesis of N- (1-methylacetonyl) acetamide by reduction and acetylation of 2,3-butanedione-3-monooxime, followed by malononitrile. 2-amino-3-cyano-
A method for producing 4,5-dimethylpyrrole is described.

[0004] The specification also describes, for example, a method for producing 2-amino-3-cyano-4-phenyl-pyrrole using 2-aminoacetophenone hydrochloride and malononitrile. Such 2-aminoacetophenone hydrochloride is described in J. Am. Heterocyclic. Che
m. , 24 , 297 (1987), a method of reacting phenacyl chloride with hexamethylenetetramine and then hydrolyzing with hydrochloric acid, or Org. Syn. Collect. Vol. V, 909
As described in (1973), it is produced by a method in which phenethylamine is N-chlorinated and then subjected to a rearrangement reaction via aziridine.

[0005] Synthesis, 1 , 51 (197)
6) describes a method for producing 2-amino-3-cyano-4-methyl-pyrrole using acetylaminoacetone and malononitrile. Such acetylaminoacetone is described in Org. Syn. Collect. Vo
l. V, 27 (1973), by reacting glycine with acetic anhydride in pyridine.

[0006] However, US Pat.
The method using a dione monooxime such as 2,3-butanedione-3-monooxime as described in the specification and the specification of Japanese Patent No. 3838166 requires a complicated step in the production of the dione monooxime. There is a disadvantage that. Further, in this method, a 2-aminopyrrole derivative having a hydrogen atom at the 4- or 5-position is not produced.

Further, in the method involving the use of an aminoketone hydrochloride such as 2-aminoacetophenone hydrochloride described in the same specification, the purification of the aminoketone hydrochloride is not easy, so the purification step in the production of the 2-aminopyrrole derivative in the next step Has the disadvantage of adversely affecting Further, the production of such aminoketone hydrochloride has a disadvantage that it requires a complicated process.

[0008] Synthesis, 1 , 51 (197)
The process described in 6) via acylaminoketones such as acetylaminoacetone has the disadvantage that a large excess of base and acid anhydrides or acid chlorides must be used in the preparation of such acylaminoketones. .

On the other hand, protecting an amino group as a cyclic imide group is described in, for example, J. Am. Org. Chem. , 43 , 2
320 (1978), etc., a method for obtaining an amino group from a cyclic imide group, a so-called deprotection method, is generally a method using hydrazine monohydrate or a method using hydrobromic acid, and hydrolysis under basic conditions. However, there was a drawback that good results could not be obtained.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel 2-aminopyrrole derivative useful as a synthetic intermediate and a simple method for producing a 2-aminopyrrole derivative using an easily produced imidoketone derivative. That is.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies on 2-aminopyrrole derivatives which are useful as a synthetic intermediate and on a method for producing the same. As a result, a useful synthetic intermediate is represented by the general formula (I) By further reacting an imidoketone derivative represented by the following general formula (a) with a nitrile derivative represented by the following general formula (b) under basic conditions. The present inventors have found a method for producing a 2-aminopyrrole derivative which can easily produce a 2-aminopyrrole derivative represented by the following general formula (c), and have reached the present invention.

[0012]

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In the general formula (I), A ¹ represents an alkoxycarbonyl group having 6 to 20 carbon atoms, a total of 7 to 20 carbon atoms.
Aryloxycarbonyl group, an alkoxycarbonyl group having 2 to 20 skeleton carbon atoms having a substituent, an aryloxycarbonyl group having 7 to 20 skeleton carbon atoms having a substituent,
Or —CO—N (R ^x ) R ^y , wherein R ^x and R ^y
May be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 total carbon atoms, an alkyl group having 1 to 20 skeleton carbon atoms having a substituent or a substituent. Represents an aryl group having 6 to 20 skeleton carbon atoms. However, R ^x and R ^y do not simultaneously represent a hydrogen atom. A ² and A ³ may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyl group having a substituent, an alkenyl group having a substituent, Represents an aryl group having a substituent, an alkoxycarbonyl group having a substituent, an aryloxycarbonyl group having a substituent, a carbamoyl group, or a heterocyclic group.

[0014]

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In the general formula (a), R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents an alkyl group having a group, an alkenyl group having a substituent, an aryl group having a substituent, an alkoxycarbonyl group having a substituent, an aryloxycarbonyl group having a substituent, a carbamoyl group, or a heterocyclic group. Z represents a group of carbon atoms necessary to form a nitrogen-containing 5- or 6-membered ring, and the nitrogen-containing 5- or 6-membered ring may be further condensed with an aromatic ring. In the general formula (b), X represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, an alkoxycarbonyl group having a substituent, an aryloxycarbonyl group having a substituent, Represents an alkylsulfonyl group having a group, an arylsulfonyl group having a substituent, an aryl group having a substituent, a carbamoyl group, or a sulfamoyl group. In the general formula (c), R ¹ and R ² have the same meaning as in the general formula (a), and X has the same meaning as in the general formula (b).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (I), A ¹ is an alkoxycarbonyl group having a total of 6 to 20 carbon atoms, and a total of 7 carbon atoms.
To 20 aryloxycarbonyl groups, substituted aryloxycarbonyl groups having 7 to 20 skeleton carbon atoms or -CON (R ^x ) R ^y groups are preferred, and 2-ethylhexyloxycarbonyl and 2,6-di-tert are particularly preferred. -Butyl-4-methylcyclohexyloxycarbonyl group,
A 2-tert-butyl-6-methylphenoxycarbonyl group, a (2-ethylhexyl) carbamoyl group, and a dibutylcarbamoyl group are preferred.

In the general formula (I), the alkoxycarbonyl group having 6 to 20 carbon atoms represented by A ¹ includes, for example, hexyloxylcarbonyl, 2-ethylhexyloxycarbonyl, octadecyloxycarbonyl,
Cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 2-tert-butylcyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, 2-isopropyl-5-methylcyclohexyloxycarbonyl group, 2, A 6-dimethylcyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, a norbornyloxycarbonyl group, or an adamantyloxycarbonyl group, and particularly a 2-ethylhexyloxycarbonyl group; 2,6-di-tert-butyl-4
-A methylcyclohexyloxycarbonyl group is preferred.

The substituent of the alkoxycarbonyl group having a skeleton having 2 to 20 carbon atoms and having a substituent represented by A ¹ includes:
Halogen atom, alkenyl group having 2-20 carbon atoms, aryl group having 6-20 carbon atoms, alkoxy group having 1-20 carbon atoms, alkenyloxy group having 2-20 carbon atoms, 6-20 carbon atoms An aryloxy group, a C2-20 alkoxycarbonyl group or a C1-30 carbamoyl group is preferable, and in particular, a C1-20 alkoxy group or a C2-20 alkenyloxy group is particularly preferable. preferable.

In the general formula (I), examples of the aryloxycarbonyl group having 7 to 20 carbon atoms represented by A ¹ include a phenoxycarbonyl group, a naphthyloxycarbonyl group and an anthranyloxycarbonyl group.

The substituent of the aryloxycarbonyl group having a skeleton having 7 to 20 carbon atoms and having a substituent represented by A ¹ includes a halogen atom, a cyano group, a nitro group and a total carbon number of 1 to 1.
20 alkyl groups, alkenyl groups having 2 to 20 carbon atoms in total,
An aryl group having a total number of carbon atoms of 6 to 20, an alkoxy group having a total number of carbon atoms of 1 to 20, an alkenyloxy group having a total number of carbon atoms of 2 to 20,
Aryloxy group having 6 to 20 total carbon atoms, 2 to 2 total carbon atoms
An alkoxycarbonyl group having 0, a carbamoyl group having 1 to 30 total carbon atoms, an acyloxy group having 2 to 20 total carbon atoms, or an acylamino group having 2 to 20 total carbon atoms is preferable, and an alkyl group having 1 to 20 total carbon atoms is particularly preferable. .

In the general formula (I), represented by A ¹
The total number of carbon atoms of R ^x and R ^y of the CON (R ^x ) R ^y group is 1 to
Examples of the alkyl group of 20 include a methyl group, an ethyl group, a butyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group and an octadecyl group, and particularly a butyl group, a 2-ethylhexyl group or a decyl group. Groups are preferred.

[0022] -CON (R ^x) of the R ^y group R ^x, and R
Examples of the substituent of the alkyl group having 1 to 20 skeleton carbon atoms having a substituent of ^y include a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a total number of 1 to 20 carbon atoms. Are preferably an alkoxy group, an alkenyloxy group having a total of 2 to 20 carbon atoms, an aryloxy group having a total of 6 to 20 carbon atoms, or an alkoxycarbonyl group having a total carbon number of 2 to 20, particularly preferably a halogen atom and a total carbon number of 6 to 20. And an alkoxy group having a total of 1 to 20 carbon atoms is preferred.

In the general formula (I), A¹-C represented by
ON (R^x) R^yGroup R^xAnd R ^yTotal carbon number of 6-2
The aryl group of 0 includes, for example, a phenyl group, a naphthyl group,
And an anthranyl group.

R ^x and R ^{y of the} —CON (R ^x ) R ^y group
Examples of the substituent of the aryl group having a skeleton having 6 to 20 carbon atoms include a halogen atom, a cyano group, a nitro group, an alkyl group having a total carbon number of 1 to 20, an alkenyl group having a total carbon number of 2 to 20, C6-20 aryl group, total carbon number 1
To 20 alkoxy groups, 2 to 20 carbon atoms, alkenyloxy group, 6 to 20 carbon atoms, aryloxy group, 2 to 20 carbon atoms, alkoxycarbonyl group, 2 to 20 carbon atoms
An acyloxy group having 20 or an acylamino group having 2 to 20 carbon atoms is preferable, and a halogen atom and a total carbon number of 1 to 20 are particularly preferable.
An alkyl group having 20 and an alkoxy group having 1 to 20 carbon atoms in total are preferable.

As described above, R in the --CON (R ^x ) R ^y group
Among ^x and R ^y , a hydrogen atom, an alkyl group having a total carbon number of 1 to 20 or an aryl group having a total carbon number of 6 to 20 is preferable, and a hydrogen atom or an alkyl group having a total carbon number of 1 to 20 is particularly preferable. R ^x and R ^y do not simultaneously represent a hydrogen atom.

In the general formula (I), represented by A ¹
Examples of CON (R ^x ) R ^y groups include methylcarbamoyl, (2-ethylhexyl) carbamoyl, decylcarbamoyl, phenylcarbamoyl, dibutylcarbamoyl, di (2-ethylhexyl) carbamoyl, and butyl-dodecylcarbamoyl. , A diphenylcarbamoyl group and the like, particularly (2-ethylhexyl)
A carbamoyl group, a decylcarbamoyl group or a dibutylcarbamoyl group is preferred.

In the general formula (I), A ² is preferably an alkyl group, an alkenyl group, an aryl group, an alkoxycarbonyl group, an alkyl group having a substituent, an aryl group having a substituent, a carbamoyl group, or a heterocyclic group. Particularly, an aryl group, an aryl group having a substituent, an alkoxycarbonyl group, and a carbamoyl group are preferable.

In the general formula (I), A ³ is a hydrogen atom,
An alkyl group and an aryl group are preferred, and a hydrogen atom is particularly preferred.

In the general formula (I), A ² or A ³
The alkyl groups represented by may be the same or different, and are preferably alkyl groups having a total of 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, octyl, 2-ethylhexyl Group, decyl group,
Examples include a dodecyl group, an octadecyl group, an eicosyl group, and the like.

Examples of the substituent of the alkyl group having a substituent represented by A ² or A ³ include a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a 2 to 20 carbon atoms. Alkenyloxy group, an aryloxy group having a total of 6 to 20 carbon atoms, an alkoxycarbonyl group having a total of 2 to 20 carbon atoms, or a carbamoyl group having a total of 1 to 30 carbon atoms, and particularly an alkoxycarbonyl group having a total carbon number of 2 to 20 Alternatively, a carbamoyl group having 1 to 30 carbon atoms is preferable.

In the general formula (I), A ² or A ³
The alkenyl groups represented by may be the same or different, and are preferably alkenyl groups having 2 to 20 carbon atoms in total.
For example, a vinyl group, a 1-propenyl group, a 2-butenyl group, an oleyl group and the like can be mentioned.

The substituent of the alkenyl group having a substituent in A ² or A ³ is preferably an aryl group having 6 to 20 carbon atoms in total.

In the general formula (I), A ² or A ³
The aryl groups represented by may be the same or different, and are preferably aryl groups having a total carbon number of 6 to 20, and examples include a phenyl group, a naphthyl group and an anthranyl group.

Examples of the substituent of the aryl group having a substituent represented by A ² or A ³ include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, Aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
20, alkenyloxy group, aryloxy group having 6 to 20 total carbon atoms, alkoxycarbonyl group having 2 to 20 total carbon atoms, carbamoyl group having 1 to 30 total carbon atoms, 2 to 2 total carbon atoms
20 acyloxy groups, alkylsulfonyloxy group having 1 to 30 total carbon atoms, arylsulfonyloxy group having 6 to 30 total carbon atoms, acylamino group having 2 to 20 total carbon atoms, alkylsulfonamide group having 1 to 30 total carbon atoms Or an arylsulfonamide group having a total of 6 to 30 carbon atoms, particularly a halogen atom, a cyano group, an alkyl group having a total of 1 to 20 carbon atoms or an alkoxy group having a total of 1 to 20 carbon atoms.

In the general formula (I), A ² or A ³
The alkoxycarbonyl group represented by may be the same or different, and is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a 1,1-dimethylethoxycarbonyl group, An ethylhexyloxycarbonyl group, an octadecyloxycarbonyl group, or 2,6-di-te
Examples thereof include an rt-butyl-4-methylcyclohexyloxycarbonyl group and the like, and a 2-ethylhexyloxycarbonyl group and a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group are particularly preferable.

The substituent of the alkoxycarbonyl group having a substituent represented by A ² or A ³ includes a halogen atom, an alkenyl group having 2 to 20 carbon atoms, and a total of 6 to 2 carbon atoms.
0 aryl groups, alkoxy groups having 1 to 20 total carbon atoms, alkenyloxy groups having 2 to 20 total carbon atoms, 6 to 2 total carbon atoms
An aryloxy group having 0 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms or a carbamoyl group having 1 to 30 carbon atoms is preferable, and an alkoxy group having 1 to 20 carbon atoms or an alkenyloxy group having 2 to 20 carbon atoms is particularly preferable. Is preferred.

In the general formula (I), A ² or A ³
The aryloxycarbonyl groups represented by may be the same or different, and are preferably aryloxycarbonyl groups having a total of 7 to 20 carbon atoms, such as a phenoxycarbonyl group, a naphthyloxycarbonyl group or an anthranyloxycarbonyl group.

Examples of the substituent of the aryloxycarbonyl group having a substituent represented by A ² or A ³ include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms. Group, total carbon number 6
To 20 aryl groups, 1 to 20 carbon atoms, alkoxy group, 2 to 20 carbon atoms, alkenyloxy group, 6 to 20 carbon atoms, aryloxy group, 2 to 20 carbon atoms, alkoxycarbonyl group, A carbamoyl group having 1 to 30 carbon atoms, an acyloxy group having 2 to 20 total carbon atoms, or an acylamino group having 2 to 20 total carbon atoms are preferable, and an alkyl group having 1 to 20 total carbon atoms is particularly preferable.

In the general formula (I), A^TwoOr A^Three
The carbamoyl groups represented by are the same or different
-CONH_Two, -CONH-R^a, -CON
R^bR^cWhere R^aIs a group having 1 to 20 carbon atoms
Represents an alkyl group or an aryl group having 6 to 20 carbon atoms.
Then R^b, R^cMay be the same or different,
Alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms
R represents an aryl group ^a, R^b, And R^cThe alkyl of
The group and the aryl group may have a substituent.

The substituent of the alkyl group having the substituents of R ^a , R ^b and R ^c includes a halogen atom, a total carbon number of 2
-20 alkenyl group, 6-20 carbon atoms aryl group, 1-20 carbon atoms alkoxy group, 2-2 total carbon atoms
An alkenyloxy group of 0, an aryloxy group having a total carbon number of 6 to 20 or an alkoxycarbonyl group having a total carbon number of 2 to 20 is preferable, and particularly a halogen atom and a total carbon number of 6 to 20 are preferable.
And an alkoxy group having a total of 1 to 20 carbon atoms is preferred.

Examples of the substituent of the aryl group having a substituent of R ^a , R ^b , and R ^c include a halogen atom, a cyano group,
Nitro group, alkyl group having 1 to 20 total carbon atoms, 2 total carbon atoms
-20 alkenyl group, 6-20 carbon atoms aryl group, 1-20 carbon atoms alkoxy group, 2-2 total carbon atoms
An alkenyloxy group of 0, an aryloxy group having a total carbon number of 6 to 20, an alkoxycarbonyl group having a total carbon number of 2 to 20, an acyloxy group having a total carbon number of 2 to 20 or an acylamino group having a total carbon number of 2 to 20, Particularly, a halogen atom, an alkyl group having a total carbon number of 1 to 20, a total carbon number of 1 to 20
Are preferred.

Among the above R ^a , R ^b and R ^c , an alkyl group having 1 to 20 carbon atoms or a total of 6 to 6 carbon atoms.
An aryl group having 20 is preferable, and an alkyl group having 1 to 20 carbon atoms is particularly preferable.

Examples of such a carbamoyl group include a methylcarbamoyl group, a (2-ethyl-hexyl) carbamoyl group, a phenylcarbamoyl group, a diethylcarbamoyl group, a butyl-dodecylcarbamoyl group, and a diphenylcarbamoyl group. 2-ethyl-
A hexyl) carbamoyl group or a dibutylcarbamoyl group is preferred.

In the general formula (I), A ² or A ³
The heterocyclic group represented by may be the same or different, and includes a saturated heterocyclic monocyclic group, an unsaturated heterocyclic monocyclic group, a saturated heterocyclic condensed group or an unsaturated heterocyclic condensed group. May have a substituent. Among these, an unsaturated heterocyclic monocyclic group or an unsaturated heterocyclic condensed ring group is preferable.
A membered or 6-membered unsaturated heterocyclic monocyclic group, or a 5- or 6-membered unsaturated heterocondensed ring group is preferred.

Examples of such a heterocyclic group include a pyrrol-2-yl group, an N-methylpyrrol-2-yl group,
5-dimethylpyrrol-3-yl group, flu-2-yl group, thien-2-yl group, thiazolyl-2-yl group, virid-2-yl group, pyridi-3-yl group, pyridi-4-yl group
An yl group, a pyrazinyl group, an indol-3-yl group or a benzofuran-2-yl group.

Among the compounds represented by the general formula (I), the compounds represented by the following general formulas (I-1) to (I-6) are preferable. Particularly, in view of the performance when a coupler is formed, (I) −
1) and (I-2) are preferred.

[0047]

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Formulas (I-1), (I-2) and (I-
A ^{4 in} 4) represents an alkyl group, an alkenyl group, an aryl group, an alkyl group having a substituent, an alkenyl group having a substituent, or an aryl group having a substituent. A ⁵ in the general formula (I-2) represents an aryl group having 6 to 19 carbon atoms in total or an aryl group having 6 to 19 skeleton carbon atoms having a substituent. A ⁶ in the general formula (I-3) has a total carbon number of 5-1.
9 represents an alkyl group, an aryl group having 6 to 19 carbon atoms in total, an alkyl group having 1 to 19 skeleton carbon atoms having a substituent, and an aryl group having 6 to 19 skeleton carbon atoms having a substituent. R ^x and R in the general formulas (I-4), (I-5) and (I-6)
^y has the same meaning as in formula (I). Formula (I-
5) A ⁷ is alkyl group having a total carbon number of 1 to 19 in, aryl group having a total carbon number of 6 to 19, skeletal carbon atoms 1 having a substituent
6 to 19 skeleton carbon atoms having an alkyl group or a substituent
To 19 represents an aryl group.

In the general formula (I-2), examples of the aryl group having 6 to 19 carbon atoms represented by A ⁵ include a phenyl group, a naphthyl group and an anthranyl group.

[0050] Examples of the substituent of the aryl group of the backbone carbon atoms 6 to 19 having a substituent represented by A ^5, a halogen atom, a cyano group, a nitro group, alkyl group having a total carbon number of 1 to 20 carbon atoms in total 2-20 alkenyl groups, total carbon number 6-2
0 aryl groups, alkoxy groups having 1 to 20 total carbon atoms, alkenyloxy groups having 2 to 20 total carbon atoms, 6 to 2 total carbon atoms
0 aryloxy group, 2 to 20 carbon atoms alkoxycarbonyl group, 1 to 30 carbon atoms carbamoyl group, 2 to 20 total acyloxy group or 2 to 2 carbon atoms
An acylamino group of 0 is preferable, and particularly a total carbon number of 1 to 20.
Are preferred.

Of such A ⁵ , the total carbon number is 1 to 20.
A phenyl group substituted with an alkyl group is preferable, and a 2-tert-butyl-6-methylphenyl group is particularly preferable.

In formula (I-3), examples of the alkyl group having 5 to 19 carbon atoms represented by A ⁶ include a hexyl group, 2-ethylhexyl group, octadecyl group, cyclopentyl group, cyclohexyl group, Methylcyclohexyl group, 2-tert-butylcyclohexyl group, 4-methylcyclohexyl group, 2-isopropyl-5-methylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,6-di-tert-butyl-4-methylcyclohexyl Group, norbornyl group or adamantyl group.

Examples of the substituent of the alkyl group having 1 to 19 skeleton carbon atoms having a substituent represented by A ⁶ include a halogen atom, an alkenyl group having 2 to 20 carbon atoms, and a total of 6 to 2 carbon atoms.
0 aryl groups, alkoxy groups having 1 to 20 total carbon atoms, alkenyloxy groups having 2 to 20 total carbon atoms, 6 to 2 total carbon atoms
An aryloxy group having 0, an alkoxycarbonyl group having 2 to 20 total carbon atoms, or a carbamoyl group having 1 to 30 total carbon atoms is preferable, and an alkoxy group having 1 to 20 total carbon atoms or an alkenyloxy group having 2 to 20 total carbon atoms is particularly preferable. Is preferred.

In the general formula (I-3), examples of the aryl group having ⁶ to 19 carbon atoms represented by A ⁶ include a phenyl group, a naphthyl group and an anthranyl group.

Examples of the substituent of the aryl group having ⁶ to 19 skeleton carbon atoms having a substituent represented by A ⁶ include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 total carbon atoms, and a total carbon number. 2-20 alkenyl groups, total carbon number 6-2
0 aryl groups, alkoxy groups having 1 to 20 total carbon atoms, alkenyloxy groups having 2 to 20 total carbon atoms, 6 to 2 total carbon atoms
0 aryloxy group, 2 to 20 carbon atoms alkoxycarbonyl group, 1 to 30 carbon atoms carbamoyl group, 2 to 20 total acyloxy group or 2 to 2 carbon atoms
An acylamino group of 0 is preferable, and in particular, a total carbon number of 1 to 2
An alkyl group of 0 is preferred.

Of such A ⁶ , the total number of carbon atoms is 5 to 19
Is preferred, and a 2-ethylhexyl group is particularly preferred.

In the general formula (I-5), the alkyl group having 1 to 19 carbon atoms represented by A ⁷ includes, for example, a methyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, an octadecyl group, Or 2,6-di-te
rt-butyl-4-methylcyclohexyl group.

A ⁷ having a substituted skeleton carbon atom in A ⁷
Examples of the substituent of the alkyl group of to 19 include a halogen atom,
C2-C20 alkenyl group, C6-C20 aryl group, C1-C20 alkoxy group, C2-C20 alkenyloxy group, C6-C20 aryloxy A group, an alkoxycarbonyl group having 2 to 20 total carbon atoms or a carbamoyl group having 1 to 30 total carbon atoms is preferable, and an alkoxy group having 1 to 20 total carbon atoms or an alkenyloxy group having 2 to 20 total carbon atoms is particularly preferable.

In the general formula (I-5), examples of the aryl group having 6 to 19 carbon atoms represented by A ⁷ include a phenyl group, a naphthyl group and an anthranyl group.

[0060] Examples of the substituent of the aryl group of the backbone carbon atoms 6 to 19 having a substituent represented by A ^7, halogen atom, a cyano group, a nitro group, alkyl group having a total carbon number of 1 to 20 carbon atoms in total 2-20 alkenyl groups, total carbon number 6-2
0 aryl groups, alkoxy groups having 1 to 20 total carbon atoms, alkenyloxy groups having 2 to 20 total carbon atoms, 6 to 2 total carbon atoms
0 aryloxy group, 2 to 20 carbon atoms alkoxycarbonyl group, 1 to 30 carbon atoms carbamoyl group, 2 to 20 total acyloxy group or 2 to 2 carbon atoms
An acylamino group of 0 is preferable, and particularly a total carbon number of 1 to 20.
Are preferred.

Of such A ⁷ , the total number of carbon atoms is 1 to 19
Is preferred, and an isopropyl group is particularly preferred.

Formulas (I-1), (I-2) and (I-
In 4), the alkyl group represented by A ⁴ is preferably an alkyl group having a total of 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, Examples include a decyl group, a dodecyl group, an octadecyl group, an eicosyl group, and the like.

[0063] As the substituent of the alkyl group having a substituent in A ^4, a halogen atom, aryl group having a total carbon number of 6 to 20, the total alkoxy group having 1 to 20 carbon atoms, the total carbon number of 2-20 alkenyloxy Group, an aryloxy group having a total carbon number of 6 to 20, an alkoxycarbonyl group having a total carbon number of 2 to 20 or a carbamoyl group having a total carbon number of 1 to 30, particularly preferably an alkoxycarbonyl group having a total carbon number of 2 to 20 or a total carbon atom A carbamoyl group of the number 1 to 30 is preferred.

Formulas (I-1), (I-2) and (I-
In 4), the alkenyl groups represented by A ⁴ may be the same or different, and are preferably alkenyl groups having 2 to 20 carbon atoms, for example, vinyl group, 1-propenyl group, 2-butenyl group or oleyl group. And the like.

The substituent of the alkenyl group having a substituent represented by A ⁴ is preferably an aryl group having 6 to 20 carbon atoms in total.

Formulas (I-1), (I-2) and (I-
In 4), the aryl groups represented by A ⁴ may be the same or different, and are preferably aryl groups having a total of 6 to 20 carbon atoms, such as phenyl, naphthyl and anthranyl groups.

The substituent of the aryl group having a substituent in A ⁴ includes a halogen atom, a cyano group, a nitro group,
C1-C20 alkyl group, C2-C20 alkenyl group, C6-C20 aryl group, C1-C20 alkoxy group, C2-C20 alkenyloxy group An aryloxy group having a total carbon number of 6 to 20, an alkoxycarbonyl group having a total carbon number of 2 to 20, a total carbon number of 1
Carbamoyl group, acyloxy group having 2 to 20 total carbon atoms or acylamino group having 2 to 20 total carbon atoms, particularly halogen atom, cyano group, and 1 to 20 total carbon atoms.
And an alkoxy group having 1 to 20 carbon atoms in total.

Of such A ⁴ , the total carbon number is 6 to 20.
6 to 20 skeleton carbon atoms having an aryl group or a substituent
Is particularly preferable, and a phenyl group or a phenyl group substituted with a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms is particularly preferable.

The general formula (I) and the general formula (I) of the present invention
The novel 2-aminopyrrole derivatives represented by -1) to (I-6) include an imidoketone derivative represented by the general formula (a) and a nitrile derivative represented by the general formula (b) described in the present specification. Can be obtained by a reaction under basic conditions. Sci Vol.
43 103 (1988); Am. Chem. So
c. , 112 , 2465 (1990); Am. Ch
em. Soc. , 80 , 5332 (1958); H
eterocyclic. Chem. , 24 , 297
(1987) and the like.

Specific examples of the novel 2-aminopyrrole derivative of the present invention are shown below, but the present invention is not limited thereto.

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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Next, a method for producing the 2-aminopyrrole derivative of the present invention will be described. The present invention provides a method for reacting an imidoketone derivative represented by the general formula (a) with a nitrile derivative represented by the general formula (b) under basic conditions to obtain a 2-imide represented by the general formula (c). This is a production method capable of producing an aminopyrrole derivative.

[0089]

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In the general formula (a), R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents an alkyl group having a group, an alkenyl group having a substituent, an aryl group having a substituent, an alkoxycarbonyl group having a substituent, an aryloxycarbonyl group having a substituent, a carbamoyl group, or a heterocyclic group. Z represents a group of carbon atoms necessary to form a nitrogen-containing 5- or 6-membered ring, and the nitrogen-containing 5- or 6-membered ring may be further condensed with an aromatic ring.

In the general formula (b), X represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylsulfonyl group, arylsulfonyl group, aryl group, substituted alkoxycarbonyl group, substituted aryloxycarbonyl group, substituted alkylsulfonyl group, substituted arylsulfonyl group, substituted aryl group , A carbamoyl group,
Or a sulfamoyl group.

In the general formula (c), R ¹ and R ² have the same meaning as in the general formula (a), and X has the same meaning as in the general formula (b).

In the general formulas (a) and (c), R
¹ is preferably an alkyl group, an alkenyl group, an aryl group, an alkyl group having a substituent, an alkenyl group having a substituent, an aryl group having a substituent, a carbamoyl group, or a heterocyclic group, particularly an alkyl group, an aryl group, An alkyl group having a substituent, an aryl group having a substituent, or a heterocyclic group is preferable.

In the general formulas (a) and (c), R ²
Is preferably a hydrogen atom, an alkyl group, an aryl group, an alkyl group having a substituent or an aryl group having a substituent, particularly preferably a hydrogen atom, an alkyl group or an alkyl group having a substituent.

In the general formulas (a) and (c), R ¹
Alternatively, the alkyl group represented by R ² may be the same or different, and is preferably an alkyl group having a total of 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, Examples thereof include a 2-ethylhexyl group, a decyl group, a dodecyl group, an octadecyl group and an eicosyl group.

Examples of the substituent of the alkyl group having a substituent in R ¹ or R ² include a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a total number of 2 to 20 carbon atoms. Alkenyloxy group, an aryloxy group having a total of 6 to 20 carbon atoms, an alkoxycarbonyl group having a total of 2 to 20 carbon atoms, or a carbamoyl group having a total of 1 to 30 carbon atoms, and particularly an alkoxycarbonyl group having a total carbon number of 2 to 20 Alternatively, a carbamoyl group having 1 to 30 carbon atoms is preferable.

In the general formulas (a) and (c), R ¹
Alternatively, the alkenyl groups represented by R ² may be the same or different, and are preferably alkenyl groups having a total of 2 to 20 carbon atoms, for example, a vinyl group, a 1-propenyl group, a 2-
Butenyl group or oleyl group.

The substituent of the alkenyl group having a substituent in R ¹ or R ² is preferably an aryl group having 6 to 20 carbon atoms in total.

In the general formulas (a) and (c), R ¹
Alternatively, the aryl groups represented by R ² may be the same or different, and are preferably aryl groups having 6 to 20 carbon atoms in total, such as phenyl, naphthyl, and anthranyl groups.

Examples of the substituent of the substituted aryl group represented by R ¹ or R ² include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, Aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
20, an alkenyloxy group, an aryloxy group having a total of 6-20 carbon atoms, an alkoxycarbonyl group having a total carbon number of 2-20, a carbamoyl group having a total carbon number of 1-30, a total carbon number of 2-20
20 acyloxy groups, alkylsulfonyloxy group having 1 to 30 total carbon atoms, arylsulfonyloxy group having 6 to 30 total carbon atoms, acylamino group having 2 to 20 total carbon atoms, alkylsulfonamide group having 1 to 30 total carbon atoms Or an arylsulfonamide group having a total carbon number of 6 to 30, particularly a halogen atom, a cyano group, an alkyl group having a total carbon number of 1 to 20, an alkenyl group having a total number of 2 to 20 and a total number of 6 to 20 Aryl group, alkoxy group having 1 to 20 total carbon atoms, alkenyloxy group having 2 to 20 total carbon atoms, carbamoyl group having 1 to 30 total carbon atoms, or 1 to 30 total carbon atoms
Alkylsulfonyloxy group, arylsulfonyloxy group having a total of 6 to 30 carbon atoms, acylamino group having a total of 2 to 20 carbon atoms, alkylsulfonamide group having a total of 1 to 30 carbon atoms, or arylsulfonamide group having a total of 6 to 30 carbon atoms Groups are preferred.

In the general formulas (a) and (c), R ¹
Alternatively the alkoxycarbonyl group represented by R ² may be the same as or different from each other, an alkoxycarbonyl group having a total carbon number of 2 to 20 are preferred, for example, a methoxycarbonyl group, an ethoxycarbonyl group, 1,1-dimethylethoxy group , A 2-ethylhexyloxycarbonyl group, or an octadecyloxycarbonyl group.

Examples of the substituent of the alkoxycarbonyl group having a substituent in R ¹ or R ² include a halogen atom, an alkenyl group having 2 to 20 carbon atoms, and a total number of 6 to 2 carbon atoms.
0 aryl groups, alkoxy groups having 1 to 20 total carbon atoms, alkenyloxy groups having 2 to 20 total carbon atoms, 6 to 2 total carbon atoms
An aryloxy group having 0, an alkoxycarbonyl group having 2 to 20 total carbon atoms, or a carbamoyl group having 1 to 30 total carbon atoms is preferable, and an alkoxy group having 1 to 20 total carbon atoms or an alkenyloxy group having 2 to 20 total carbon atoms is particularly preferable. Is preferred.

In the general formulas (a) and (c), R ¹
Alternatively, the aryloxycarbonyl groups represented by R ² may be the same or different, and have 6 to ² carbon atoms in total.
An aryloxycarbonyl group of 0 is preferable, and examples thereof include a phenoxycarbonyl group, a naphthyloxycarbonyl group and an anthranyloxycarbonyl group.

The substituent of the substituted aryloxycarbonyl group represented by R ¹ or R ² includes a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms. Group, total carbon number 6
To 20 aryl groups, 1 to 20 carbon atoms, alkoxy group, 2 to 20 carbon atoms, alkenyloxy group, 6 to 20 carbon atoms, aryloxy group, 2 to 20 carbon atoms, alkoxycarbonyl group, A carbamoyl group having 1 to 30 carbon atoms, an acyloxy group having 2 to 20 total carbon atoms or an acylamino group having 2 to 20 total carbon atoms are preferable, and a halogen atom, a cyano group, an alkyl group having 1 to 20 total carbon atoms, An alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 total carbon atoms, an alkoxy group having 1 to 20 total carbon atoms, and a 2 to 2 total carbon atoms
An alkenyloxy group of 20, a carbamoyl group having a total of 1 to 30 carbon atoms, or an acylamino group having a total of 2 to 20 carbon atoms is preferable.

In the general formulas (a) and (c), R ¹
Alternatively, the carbamoyl groups represented by R ² may be the same or different, and may be -CONH ₂ , -CONH-R
^l, include -CONR ^m R ^n, wherein R ^l represents an alkyl group or an aryl group having a total carbon number of 6 to 20 carbon atoms in total 1 to 20, R ^m, R ⁿ are each different and the same And represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ¹ , R ^m , and R
The alkyl group and the aryl group of ⁿ may have a substituent.

Examples of the substituent of the alkyl group having a substituent of R ¹ , R ^m , and R ⁿ include a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a total carbon atom. An alkoxy group having 1 to 20 carbon atoms and a total carbon number of 2 to 2
An alkenyloxy group of 0, an aryloxy group having a total carbon number of 6 to 20 or an alkoxycarbonyl group having a total carbon number of 2 to 20 is preferable, and particularly a halogen atom and a total carbon number of 6 to 20 are preferable.
And an alkoxy group having a total of 1 to 20 carbon atoms is preferred.

Examples of the substituent of the aryl group having a substituent of R ¹ , R ^m and R ⁿ include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms and a total number of 2 to 20 carbon atoms. An alkenyl group, an aryl group having a total of 6 to 20 carbon atoms, an alkoxy group having a total of 1 to 20 carbon atoms, a total number of 2 to 2 carbon atoms
20, an alkenyloxy group, an aryloxy group having a total carbon number of 6 to 20, an alkoxycarbonyl group having a total carbon number of 2 to 20, an acyloxy group having a total carbon number of 2 to 20 or an acylamino group having a total carbon number of 2 to 20, Particularly, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a total carbon number Two
An alkenyloxy group of 20 or an acylamino group having 2 to 20 carbon atoms is preferred.

Examples of such a carbamoyl group include a methylcarbamoyl group, a (2-ethyl-hexyl) carbamoyl group, a phenylcarbamoyl group, a diethylcarbamoyl group, a butyl-dodecylcarbamoyl group and a diphenylcarbamoyl group.

In the general formulas (a) and (c), R ¹
Alternatively, the heterocyclic groups represented by R ² may be the same or different, and may be a saturated heteromonocyclic group, an unsaturated heteromonocyclic group,
A condensed heterocyclic group or a condensed heterocyclic group may be mentioned, and these heterocyclic groups may have a substituent. Among these, an unsaturated heterocyclic monocyclic group or an unsaturated condensed heterocyclic group is preferable, and in particular, a 5- or 6-membered unsaturated heteromonocyclic group,
Alternatively, an unsaturated heterocyclic group composed of a 5- or 6-membered ring is preferable.

Examples of such a heterocyclic group include a pyrrol-2-yl group, an N-methylpyrrol-2-yl group,
5-dimethylpyrrol-3-yl group, flu-2-yl group, thien-2-yl group, thiazolyl-2-yl group, pyridi-2-yl group, pyridi-3-yl group, pyridi-4-yl group
An yl group, a pyrazinyl group, an indol-3-yl group or a benzofuran-2-yl group.

Among the compounds represented by the general formula (a), the compounds represented by the following general formulas (d) to (h) are preferable.

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In the general formulas (d) to (h), R ¹ and R ² have the same meaning as in the general formula (a). In the general formula (d), R ³ , R ⁴ , R ⁵ and R
⁶ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (e), R ⁷ and R ⁸ may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (f), R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are
They may be the same or different and represent a hydrogen atom, a halogen atom or an alkyl group. In the general formula (g),
R ¹³ and R ¹⁴ may be the same or different,
Represents a hydrogen atom, an alkyl group or an aryl group.

Of these compounds, the compounds represented by the general formula (f)
The compound represented by is preferred.

The compounds represented by the above general formulas (d) to (h) include the following.

[0116]

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[0117]

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[0118]

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[0119]

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In the general formulas (b) and (c), X represents a cyano group, an alkoxycarbonyl group, an arylsulfonyl group, an aryl group, an arylsulfonyl group having a substituent, an aryl group having a substituent, a carbamoyl group, or a sulfamoyl group. Groups are preferred, and particularly preferred are a cyano group, an alkoxycarbonyl group, a carbamoyl group, or a sulfamoyl group.

In formulas (b) and (c), the alkoxycarbonyl group represented by X is preferably an alkoxycarbonyl group having a total of 2 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, 1,1-dimethyl Ethoxycarbonyl group, 2-ethylhexyloxycarbonyl group, octadecyloxycarbonyl group, isopropoxycarbonyl group, cyclobutoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 2-tert-butylcyclohexyl Oxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, 2-isopropyl-5-methylcyclohexyloxycarbonyl group, 2,6-dimethylcyclohexyloxycarbonyl , 2,6-di -tert- butyl -
Examples thereof include a 4-methylcyclohexyloxycarbonyl group, a norbornyloxycarbonyl group, and an adamantyloxycarbonyl group.

The substituent of the alkoxycarbonyl group having a substituent represented by X includes a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a total number of 1 to 20 carbon atoms. An alkoxy group having a total carbon number of 2 to 2
An alkenyloxy group of 0, an aryloxy group having a total of 6 to 20 carbon atoms, an alkoxycarbonyl group having a total of 2 to 20 carbon atoms or a carbamoyl group having a total of 1 to 30 carbon atoms is preferable,
In particular, an alkoxy group having a total of 1 to 20 carbon atoms or a total of 2 carbon atoms
Preferred are -20 alkenyloxy groups.

In the general formulas (b) and (c), the aryloxycarbonyl group represented by X has a total carbon number of 6 to
20 aryloxycarbonyl groups are preferred, for example, a phenoxycarbonyl group, a naphthyloxycarbonyl group or an anthranyloxycarbonyl group.

Examples of the substituent of the aryloxycarbonyl group having a substituent represented by X include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. An aryl group having a total of 6 to 20 carbon atoms, an alkoxy group having a total of 1 to 20 carbon atoms, and a total carbon number of 2
-20 alkenyloxy group, 6-20 carbon atoms aryloxy group, 2-20 carbon atoms alkoxycarbonyl group, 1-30 carbon atoms carbamoyl group, 2 carbon atoms
Preferred are acyloxy groups having from 20 to 20 or acylamino groups having from 2 to 20 carbon atoms, particularly halogen atoms, cyano groups,
C1-C20 alkyl group, C2-C20 alkenyl group, C6-C20 aryl group, C1-C20 alkoxy group, C2-C20 alkenyloxy group And a carbamoyl group having 1 to 30 carbon atoms or an acylamino group having 2 to 20 carbon atoms.

In the general formulas (b) and (c), the alkylsulfonyl group represented by X is preferably an alkylsulfonyl group having a total of 1 to 20 carbon atoms, for example, a methylsulfonyl group, a butylsulfonyl group, a 2-ethyl- A hexylsulfonyl group or a hexadecylsulfonyl group is exemplified.

The substituent of the alkylsulfonyl group having a substituent represented by X includes a halogen atom, a total carbon number of 2
-20 alkenyl group, 6-20 carbon atoms aryl group, 1-20 carbon atoms alkoxy group, 2-2 total carbon atoms
An alkenyloxy group of 0, an aryloxy group having a total of 6 to 20 carbon atoms, an alkoxycarbonyl group having a total of 2 to 20 carbon atoms or a carbamoyl group having a total of 1 to 30 carbon atoms is preferable,
In particular, an alkoxy group having a total of 1 to 20 carbon atoms or a total of 2 carbon atoms
Preferred are -20 alkenyloxy groups.

In the general formulas (b) and (c), the arylsulfonyl group represented by X is preferably an arylsulfonyl group having 6 to 20 carbon atoms, for example, a phenylsulfonyl group, a naphthylsulfonyl group or an anthranylsulfonyl group. No.

The substituent of the arylsulfonyl group having a substituent represented by X includes a halogen atom, a cyano group,
Nitro group, alkyl group having 1 to 20 total carbon atoms, 2 total carbon atoms
-20 alkenyl group, 6-20 carbon atoms aryl group, 1-20 carbon atoms alkoxy group, 2-2 total carbon atoms
0 alkenyloxy group, aryloxy group having 6 to 20 total carbon atoms, alkoxycarbonyl group having 2 to 20 total carbon atoms, carbamoyl group having 1 to 30 total carbon atoms, 2 to 2 total carbon atoms
Preferred are acyloxy groups having 20 or acylamino groups having 2 to 20 total carbon atoms, particularly halogen atoms, cyano groups, alkyl groups having 1 to 20 total carbon atoms, alkenyl groups having 2 to 20 total carbon atoms, and 6 to 20 total carbon atoms. Aryl group, total carbon number 1
Preferred are an alkoxy group having 20 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, and an acylamino group having 2 to 20 carbon atoms.

In formulas (b) and (c), the aryl group represented by X is preferably an aryl group having a total of 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group or an anthranyl group.

The substituent of the aryl group having a substituent represented by X includes a halogen atom, a cyano group, a nitro group,
C1-C20 alkyl group, C2-C20 alkenyl group, C6-C20 aryl group, C1-C20 alkoxy group, C2-C20 alkenyloxy group An aryloxy group having a total carbon number of 6 to 20, an alkoxycarbonyl group having a total carbon number of 2 to 20, a total carbon number of 1
A carbamoyl group of up to 30; an acyloxy group having a total number of carbon atoms of 2 to 20; or an acylamino group having a total number of carbon atoms of 2 to 20, particularly preferably a halogen atom, a cyano group or a nitro group.

In the general formulas (b) and (c),
The carbamoyl group represented is -CONH_Two , -CONH
-R^o, -CONR^pR^qWhere R^oIs total
An alkyl group having 1 to 20 carbon atoms or a total of 6 to 20 carbon atoms;
Represents an aryl group;^p, R ^qAre the same or different
An alkyl group having 1 to 20 carbon atoms or a total
Represents an aryl group having 6 to 20 carbon atoms;^o, R^p, And
And R^qThe alkyl group and the aryl group have a substituent
Is also good.

Examples of the substituent of the alkyl group having a substituent of R ^o , R ^p and R ^q include a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a total carbon atom. Alkoxy groups of 1 to 20, total carbon number of 2 to 2
An alkenyloxy group of 0, an aryloxy group having a total carbon number of 6 to 20 or an alkoxycarbonyl group having a total carbon number of 2 to 20 is preferable, and particularly a halogen atom and a total carbon number of 6 to 20 are preferable.
And an alkoxy group having a total of 1 to 20 carbon atoms is preferred.

Examples of the substituent of the aryl group having the substituents of R ^o , R ^p and R ^q include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, and a total number of 2 to 20 carbon atoms. An alkenyl group, an aryl group having a total of 6 to 20 carbon atoms, an alkoxy group having a total of 1 to 20 carbon atoms, a total number of 2 to 2 carbon atoms
20, an alkenyloxy group, an aryloxy group having a total carbon number of 6 to 20, an alkoxycarbonyl group having a total carbon number of 2 to 20, an acyloxy group having a total carbon number of 2 to 20 or an acylamino group having a total carbon number of 2 to 20, Particularly, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a total carbon number Two
An alkenyloxy group of 20 or an acylamino group having 2 to 20 carbon atoms is preferred.

Examples of such a carbamoyl group include a methylcarbamoyl group, a (2-ethyl-hexyl) carbamoyl group, a phenylcarbamoyl group, a diethylcarbamoyl group, a butyl-dodecylcarbamoyl group and a diphenylcarbamoyl group.

In the general formulas (b) and (c), the sulfamoyl group represented by X is -SO ₂ NH ₂ , -SO
₂ NH—R ^r , —SO ₂ NR ^s R ^t , wherein R ^r is an alkyl group having 1 to 20 carbon atoms or a total of 6 carbon atoms.
It represents 20 aryl group, R ^s, R ^t each may be the same or different, represent an alkyl group or an aryl group having a total carbon number of 6 to 20 carbon atoms in total 1 to 20, R ^r, R
The alkyl group and the aryl group represented by ^s and R ^t may have a substituent.

Examples of the substituent of the alkyl group having a substituent of R ^r , R ^s and R ^t include a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a total carbon atom. An alkoxy group having 1 to 20 carbon atoms and a total carbon number of 2 to 2
An alkenyloxy group of 0, an aryloxy group having a total carbon number of 6 to 20 or an alkoxycarbonyl group having a total carbon number of 2 to 20 is preferable, and particularly a halogen atom and a total carbon number of 6 to 20 are preferable.
And an alkoxy group having a total of 1 to 20 carbon atoms is preferred.

Examples of the substituent of the aryl group having substituents of R ^r , R ^s and R ^t include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms and a total number of 2 to 2 carbon atoms. 20 alkenyl groups, aryl groups having 6 to 20 total carbon atoms, alkoxy groups having 1 to 20 total carbon atoms, 2 total carbon atoms
~ 20 alkenyloxy groups, aryloxy groups having 6-20 carbon atoms in total, alkoxycarbonyl groups having 2-20 total carbon atoms, acyloxy groups having 2-20 total carbon atoms, and acylamino groups having 2-20 total carbon atoms are preferred. Particularly, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a total carbon atom Number 2
An alkenyloxy group having from 20 to 20 or an acylamino group having from 2 to 20 carbon atoms is preferred.

As an example of such a sulfamoyl group,
Examples include a methylsulfamoyl group, a (2-ethyl-hexyl) sulfamoyl group, a phenylsulfamoyl group, a diethylsulfamoyl group, a butyl-dodecylsulfamoyl group, and a diphenylsulfamoyl group.

The method for producing the 2-aminopyrrole derivative of the present invention is represented by the following formula 1.

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The method for producing the 2-aminopyrrole derivative of the present invention is carried out by a method in which an imidoketone derivative, a nitrile derivative and a base are mixed and stirred in a solvent, and the nitrile derivative and the imidoketone derivative are added sequentially to a mixture of the base and the solvent. Preferably, the nitrile derivative or imido ketone derivative may be added after dissolving in a reaction solvent.

The imidoketone derivative used in the production method of the present invention is described in J. Am. Am. Chem. Soc. , 1950,
72 , 2786, the method of the following formula 2, or the method of the following formula 3 can be easily produced.

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The reaction solvent used in the production method of the present invention is preferably water or a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N N-dimethylacetamide and the like. These solvents may be used as a mixture. Among these solvents, especially water, methanol, ethanol, isopropanol, a mixed solvent of water and methanol,
A mixed solvent of water and ethanol or a mixed solvent of water and isopropanol is preferred.

The amount of the reaction solvent to be used is preferably 0.5 l to 5.0 l, more preferably 0.5 l to 3.0 l, per 1.0 mol of the imido ketone derivative.

As the base used in the production method of the present invention, either an inorganic base or an organic base can be used. Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and sodium methoxide. Organic bases include, for example, triethylamine, pyridine, dimethylaminopyridine, imidazole or triphenylguanidine. Of these bases, inorganic bases are preferred, and sodium hydroxide, potassium hydroxide or sodium methoxide is particularly preferred.

The amount of the base used is 1.0
It is preferably from 1.0 mol to 3.0 mol, and particularly preferably from 1.1 mol to 2.1 mol, per mol.

The novel 2-aminopyrrole derivatives represented by general formula (I) and general formulas (I-1) to (I-6) of the present invention (for example, No. 1-1 to No. 11-) 3)
Can also be obtained by the production method of the present invention. Further, specific examples of the 2-aminopyrrole derivative obtained by the production method of the present invention are shown below. However, the present invention is not limited by this.

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[0150]

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[0151]

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Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0160]

【Example】

Example 1 Production of 2-amino-3-cyano-4-phenylpyrrole (Compound 12-25)
In addition to a mixed solution of 0 ml and 50 ml of water, 20.6 g of malononitrile and 63.8 g of 2-phthalimidoacetophenone were added. After stirring at an internal temperature of 20 ° C. to 40 ° C. for 1 hour, the mixture was added to 3 l of water, and the precipitated crystals were collected by filtration to obtain 35.6 g of 2-amino-3-cyano-4-phenylpyrrole (yield 81%, 171 ° C).

Example 2 Production of 2-amino-3-cyano-4-phenylpyrrole (Compound 12-25) 93 g of a 28% sodium methoxide methanol solution was added to 300 ml of methanol, and 20.6 g of malononitrile was added.
And 63.8 g of 2-phthalimidoacetophenone. After stirring at an internal temperature of 20 ° C. to 40 ° C. for 1 hour, the mixture was added to 3 l of water, and the precipitated crystals were collected by filtration to obtain 35.2 g of 2-amino-3-cyano-4-phenylpyrrole (yield: 80).
%, Melting point 171 ° C).

Example 3 Preparation of 2-amino-3-cyano-4- (3,4-dichlorophenyl) pyrrole (Compound 12-29) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-3 ′. , 4'-dichloroacetophenone
Except having changed to 2 g, 2-
Amino-3-cyano-4- (3,4-dichlorophenyl) pyrrole was obtained (yield 90%, melting point 183 ° C).

Example 4 Production of 2-amino-3-cyano-4- (2,4-dichlorophenyl) pyrrole (Compound 12-30) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-2 ′. , 4'-dichloroacetophenone
Except having changed to 2 g, 2-
Amino-3-cyano-4- (2,4-dichlorophenyl) pyrrole was obtained (87% yield, mp 185 ° C).

Example 5 2-amino-3-cyano-4- (4-cyanophenyl)
Preparation of pyrrole (compound 12-31) 2-amino-imidone was prepared in the same manner as in Example 1 except that 2-phthalimidoacetophenone in Example 1 was changed to 69.6 g of 2-phthalimido-4′-cyanoacetophenone.
3-Cyano-4- (4-cyanophenyl) pyrrole was obtained (yield 85%, melting point 200 ° C).

Example 6 Preparation of 2-amino-3-cyano-4- (4-trifluoromethylphenyl) pyrrole (Compound 12-33) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-4 '-Trifluoromethylacetophenone 7
Except having changed to 9.9 g, 2-amino-3-cyano-4- (4-trifluoromethylphenyl) pyrrole was obtained in the same manner as in Example 1 (yield 75%, melting point 175).
° C).

Example 7 2-amino-3-cyano-4- (4-chlorophenyl)
Preparation of pyrrole (compounds 12-28) 2-amino-imidoacetophenone was prepared in the same manner as in Example 1 except that 2-phthalimido-4'-chloroacetophenone was changed to 71.9 g of 2-phthalimidoacetophenone.
3-Cyano-4- (4-chlorophenyl) pyrrole was obtained (yield 70%, melting point 203 ° C).

Example 8 2-amino-3-cyano-4- (4-biphenylyl)
Preparation of pyrrole (compounds 12-37) A method similar to that of Example 1 except that 2-phthalimidoacetophenone in Example 1 was changed to 81.8 g of 2-phthalimido-4′-phenylacetophenone, and the reaction temperature was changed to 65 ° C. To give 2-amino-3-cyano-4- (4-biphenylyl) pyrrole (89% yield, mp 258).
° C).

Example 9 2-amino-3-cyano-4- [3- (2,4-di-t
Preparation of tert-pentylphenoxy) ethoxyphenyl] pyrrole (Compound 12-39) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-3 ′-(2,4-di-tert-pentylphenoxy) ethoxyacetophenone 129.6 g. Was changed to 2-amino-3-cyano-4- [3- (2,4) in the same manner as in Example 1 except that the reaction temperature was changed to 65 ° C.
-Di-tert-pentylphenoxy) ethoxyphenyl] pyrrole was obtained (95% yield, melting point: 188 ° C).

Example 10 2-amino-3-cyano-4- [4- (2-ethyl) hexyloxyphenyl] pyrrole (compound 12-38)
The reaction was carried out in the same manner as in Example 1 except that 2-phthalimidoacetophenone in Example 1 was changed to 94.3 g of 2-phthalimido-4 ′-(2-ethyl) hexyloxyacetophenone, and the reaction solution was treated with acetic acid. It was extracted with ethyl and concentrated under reduced pressure to give 2-amino-3-cyano-4- [4- (2-ethyl) hexyloxyphenyl] pyrrole (yield 7).
0%, pale yellow oil).

Example 11 Production of 2-amino-3-cyano-4-methylpyrrole (Compound 12-2) Example 2 was repeated except that 2-phthalimidoacetophenone in Example 1 was changed to 48.7 g of phthalimidoacetone. 2-amino-3-cyano-4-methylpyrrole was obtained in the same manner as in Example 1 (yield 79%, melting point 120 ° C).

Example 12 Preparation of 2-amino-3-cyano-4-propylpyrrole (Compound 12-4) The 2-phthalimidoacetophenone of Example 1 was changed to 15.4 g of 1-phthalimido-2-pentanone. Other than that, 2-amino-3-cyano- was obtained in the same manner as in Example 1.
4-propylpyrrole was obtained (yield 73%, melting point 75).
° C).

Example 13 Production of 2-amino-3-cyano-4,5-dimethylpyrrole (Compound 13-1) The 2-phthalimidoacetophenone of Example 1 was replaced with 1-phthalimido-1-methyl-2- Except having changed to 52.1 g of propanone, 2-amino- was prepared in the same manner as in Example 1.
3-cyano-4,5-dimethylpyrrole was obtained (yield 7).
6%, mp 165 ° C).

Example 14 2-amino-3-cyano-4- (2-methylphenyl)
Preparation of pyrrole (compounds 12-46). 2-Amino-3-cyano-4- (2-methylphenyl) was prepared in the same manner as in Example 1 except that 2-phthalimidoacetophenone in Example 1 was changed to 67.0 g of 2-phthalimido-2'-methylacetophenone. ) Pyrrole was obtained (83% yield, mp 148 ° C).

Example 15 Preparation of 2-amino-3-cyano-4- (3,4-dimethoxyphenyl) pyrrole (Compound 12-48) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-3 ′. , 4'-Dimethoxyacetophenone 7
Except having changed to 8.0 g, 2-amino-3-cyano-4- (3,4-dimethoxyphenyl) pyrrole was obtained in the same manner as in Example 1 (yield 82%, melting point 186).
° C).

Example 16 2-amino-3-cyano-4- [4- (2- (2,4-
Di-tert-pentylphenoxy) butyrylamino)
Preparation of phenyl] pyrrole (compound 12-50) 2-phthalimidoacetophenone of Example 1 was converted to 2-phthalimido-4 ′-(2- (2,4-di-tert-pentylphenoxy) butyrylamino) acetophenone 13
Except having changed to 9.7 g, 2-amino-3-cyano-4- [4- (2- (2,4
-Di-tert-pentylphenoxy) butyrylamino) phenyl] pyrrole was obtained (yield 75%, melting point 19).
0 ° C).

Example 17 2-amino-3-cyano-4- [2- (2- (2,4-
Di-tert-pentylphenoxy) butyrylamino)
Preparation of phenyl] pyrrole (compound 12-51) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-2 ′-(2- (2,4-di-tert-pentylphenoxy) butyrylamino) acetophenone 13
Except having changed to 9.7 g, 2-amino-3-cyano-4- [2- (2- (2,4
-Di-tert-pentylphenoxy) butyrylamino) phenyl] pyrrole was obtained (77% yield, melting point 1).
14 ° C).

Example 18 Preparation of 2-amino-3-cyano-4- (2-fluorophenyl) pyrrole (Compound 12-61) The 2-phthalimidoacetophenone of Example 1 was converted to 2-phthalimido-2′-fluoro 2-amino-3-cyano-4- (2-fluorophenyl) pyrrole was obtained in the same manner as in Example 1 except that acetophenone was changed to 67.9 g (yield 86%, melting point 166 ° C).

Example 19 Production of 2-amino-3-cyano-4- (flu-2-yl) pyrrole (Compound 12-59) The 2-phthalimidoacetophenone of Example 1 was replaced with 2- (2
-Phthalimidoacetyl) furan was changed to 61.2 g by the same method as in Example 1 except for changing to 2-amino-3-.
Cyano-4- (fur-2-yl) pyrrole was obtained (70% yield, mp 147 ° C).

Example 20 2-Amino-3-cyano-4- (2-phenylsulfonate
Preparation of (loxyphenyl) pyrrole (compounds 12-55)
The 2-phthalimidoacetophenone of Example 1 was
Luimide-2'-phenylsulfonyloxyacetophene
Non-same as Example 3 except that it was changed to 101.0 g
2-amino-3-cyano-4- (2-phen)
Nylsulfonyloxyphenyl) pyrrole was obtained (yield)
70%, oily,¹HNMR (CDCl _Three): Δ8.4
7 (1H, brs), 7.95-7.20 (9H,
m), 6.39 (1H, s), 4.21 (2H, br)
s)).

Example 21 2-amino-3-cyano-4- (3,5-dichloro-2
Preparation of-(3,5,5-trimethylhexyloxy) phenyl) pyrrole (Compound 12-62) The 2-phthalimidoacetophenone of Example 1 was replaced with 2-phthalimido-3 ′, 5′-dichloro-2 ′-(3, 5,5
-Trimethylhexyloxy) acetophenone 114.
Except that the amount was changed to 2 g, 2 g was prepared in the same manner as in Example 3.
-Amino-3-cyano-4- (3,5-dichloro-2-
(3,5,5-trimethylhexyloxy) phenyl)
Pyrrole was obtained (97% yield, oil, ¹ H NMR)
(CDCl ₃ ): δ 8.71 (1H, brs), 7.4
0 (1H, s), 7.25 (1H, s), 6.60 (1
H, s), 3.72 (2H, m), 1.80-1.60
(2H, m), 1.50-1.40 (1H, m), 1.
20-1.00 (2H, m), 0.84 (12H,
m)).

Example 22 2-Amino-3- (2,6-di-tert-butyl-4)
Preparation of -Methylcyclohexyloxycarbonyl) -4-phenylpyrrole (Compound 1-1) 106.0 g of 2-phthalimidoacetophenone and 117.2 g of cyanoacetate (2,6-di-tert-butyl-4-methylcyclohexyl) ester To ethanol 4
48 ml of an aqueous solution of sodium hydroxide 67 g
Was added dropwise. After refluxing for 6 hours, 1.5 l of water was added, and the precipitated crystals were collected by filtration and 2-amino-3- (2,6-di-te).
124 g of rt-butyl-4-methylcyclohexyloxycarbonyl) -4-phenylpyrrole was obtained (yield 7).
6%, mp 193-195 ° C).

Example 23 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4- (4
Preparation of -Cyanophenyl) pyrrole (Compound 1-7) 116.0 g of 2-phthalimido-4'-cyanoacetophenone of 2-phthalimidoacetophenone of Example 22
Except having been changed to 2,
-Amino-3- (2,6-di-tert-butyl-4-
Methylcyclohexyloxycarbonyl) -4- (4-
Cyanophenyl) pyrrole was obtained (yield 79%, melting point 1).
45-148 ° C).

Example 24 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4-
(3,5-dibutoxyphenyl) pyrrole (compound 1-
8) Preparation of 2-phthalimidoacetophenone of Example 22 was replaced with 2-phthalimido-3 ′, 5′-dibutoxyacetophenone 1
Except having changed to 63.6 g, 2-amino-3- (2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl) -4 was obtained in the same manner as in Example 22.
-(3,5-Dibutoxyphenyl) pyrrole was obtained (yield 80%, melting point 70-73 ° C).

Example 25 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4- (4
Production of -chlorophenyl) pyrrole (Compound 1-4) 119.8 g of 2-phthalimido-4'-chloroacetophenone of 2-phthalimidoacetophenone of Example 22
Except having been changed to 2-
Amino-3- (2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl) -4- (4-chlorophenyl) pyrrole was obtained (yield 82%, melting point 21).
3-215 ° C).

Example 26 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4-
(3,4-dichlorophenyl) pyrrole (compound 1-
Preparation of 2) 2-phthalimidoacetophenone of Example 22 was replaced with 2-phthalimido-3 ′, 4′-dichloroacetophenone 13
Except having changed to 3.6 g, 2-amino-3- (2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl) -4- was obtained in the same manner as in Example 22.
(3,4-dichlorophenyl) pyrrole was obtained (yield 7).
4%, ¹ H NMR (CDCl ₃ ) δ: 7.82 (1
H, s), 7.45-7.15 (3H, m), 6.02
(1H, s), 5.89 (1H, s), 1.30-0.
80 (23H, m)).

Example 27 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4- (2
Preparation of -Chlorophenyl) pyrrole (Compound 1-6) Except that 2-phthalimidoacetophenone in Example 22 was changed to 119.8 g of 2-phthalimido-2′chloroacetophenone, 2-amino-pyrrole was prepared in the same manner as in Example 22. 3- (2,6-Di-tert-butyl-4-methylcyclohexyloxycarbonyl) -4- (2-chlorophenyl) pyrrole was obtained (83% yield, ¹ HNM).
R (CDCl ₃ ) δ: 7.79 (1H, s), 7.45
-7.20 (5H, m), 6.07 (1H, s), 5.
86 (1H, s), 1.30-0.80 (23H,
m)).

Example 28 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4- (4
-Trifluoromethylphenyl) pyrrole (compound 1-
Preparation of 5) 2-phthalimidoacetophenone of Example 22 was converted to 2-phthalimido-4'trifluoromethylpyrrole.
Except having changed to 2 g, 2-amino-3- (2,6-di-tert-butyl-4) was obtained in the same manner as in Example 22.
-Methylcyclohexyloxycarbonyl) -4- (4
-Trifluoromethylphenyl) pyrrole was obtained (81% yield, mp 198-200 ° C).

Example 29 2-Amino-3- (2,6-di-tert-butyl-4)
-Methylcyclohexyloxycarbonyl) -4- (2
Production of -fluoromethyl) pyrrole (Compound 1-3) 113.2 g of 2-phthalimido-2'fluoroacetophenone of 2-phthalimidoacetophenone of Example 22
Except having been changed to 2-
Amino-3- (2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl) -4- (2-fluoromethyl) pyrrole was obtained (yield 80%, melting point 20).
9-211 ° C).

Example 30 Preparation of 2-amino-3- (2-tert-butyl-6-methylphenyl) -4-phenylpyrrole (Compound 2-5) The cyanoacetic acid (2,6- Except that di-tert-butyl-4-methylcyclohexyl) ester was changed to 92.4 g of cyanoacetate (2-tert-butyl-6-methylphenyl) ester, 2-amino- 3- (2-tert-butyl-
6-Methylphenyl) -4-phenylpyrrole was obtained.
(Yield 53%, melting point 255-256 ° C).

Example 31 Production of 2-amino-3-decylcarbamoyl-4-phenylpyrrole (compound 4-1) Cyanoacetic acid (2,6-di-tert-butyl-4-methylcyclohexyl) of Example 22 )) 2-Amino-3-decylcarbamoyl-4-phenylpyrrole was obtained in the same manner as in Example 22 except that the ester was changed to 89.6 g of N-decylcyanoacetamide (yield 51%,
111 ° C).

Example 32 Production of 2-amino-3,4-di (2-ethylhexyloxycarbonyl) pyrrole (compound 3-3) 22.5 g of iron powder and 2.15 g of ammonium chloride were mixed with 90 ml of isopropanol and 30 ml of water. And heated at 85 ° C. To this, 33.9 g of 2-nitro-3,4-di (2-ethylhexyloxycarbonyl) pyrrole was added for 40 minutes.
Added in portions over minutes. After stirring the reaction mixture for 1 hour, iron powder was removed by filtration through celite, and the obtained filtrate was washed with 500 ml of water.
ml. The precipitated solid was collected by filtration, and 2-amino-
3,4-Di (2-ethylhexyloxycarbonyl) pyrrole was obtained (yield 95%, melting point 111 ° C.).

Example 33 2-Amino-3- (2-ethylhexyl) carbamoyl-4-propyloxycarbonylpyrrole (compound 5-
2) Production. The 2-nitro-3,4-di (2-ethylhexyloxycarbonyl) pyrrole of Example 32 was replaced with 2-nitro-3-
(2-Ethylhexyl) carbamoyl-4-propyloxycarbonylpyrrole was changed to 28.2 g,
According to a method similar to that in Example 32, 2-amino-3- (2
-Ethylhexyl) carbamoyl-4-propyloxycarbonylpyrrole was obtained (96% yield, melting point 103).
° C).

Example 34 Production of 2-amino-3,4-di (2-ethylhexyl) carbamoylpyrrole (compound 6-1). The 2-nitro-3,4-di (2-ethylhexyloxycarbonyl) pyrrole of Example 32 was replaced with 2-nitro-3,4
-Di (2-ethylhexyl) carbamoylpyrrole 3
Except having changed to 3.8 g, 2-amino-3,4-di (2-ethylhexyl) carbamoylpyrrole was obtained in the same manner as in Example 32 (95% yield, melting point 109).
° C).

Example 35 Production of 2-amino-3,4-di (dibutylcarbamoyl) pyrrole (compound 6-6). The 2-nitro-3,4-di (2-ethylhexyloxycarbonyl) pyrrole of Example 32 was replaced with 2-nitro-3,4
2-amino-3,4-di (dibutylcarbamoyl) pyrrole was obtained in the same manner as in Example 32, except that 33.8 g of -di (dibutylcarbamoyl) pyrrole was used (yield 97%, melting point 97 to 98%). 99 ° C).

[0195]

According to the present invention, as intermediates useful for synthesizing pyrrolo [1,2-a] pyrimidine derivatives and the like, compounds represented by general formula (I) and general formulas (I-1) to (I-6) are used. New 2-aminopyrrole derivative can be provided. Further, according to the production method of the present invention, a 2-aminopyrrole derivative including the 2-aminopyrrole derivative can be produced very simply and in a high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masanobu Takashima 200 Fujinaka-shi, Fujinomiya-shi, Shizuoka Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] 1. A 2-aminopyrrole derivative represented by the following general formula (I). Embedded image In the general formula (I), A ¹ represents an alkoxycarbonyl group having a total of 6 to 20 carbon atoms, an aryloxycarbonyl group having a total of 7 to 20 carbon atoms, and a skeleton having 2 to 20 carbon atoms having a substituent.
An aryloxycarbonyl group having a skeleton of 7 to 20 carbon atoms having a substituent, or -CO
—N (R ^x ) R ^y , wherein R ^x and R ^y may be the same or different,
Hydrogen atom, alkyl group having 1 to 20 total carbon atoms, 6 total carbon atoms
To 20 aryl groups and 1 to 2 skeleton carbon atoms having a substituent
6 to 2 skeleton carbon atoms having 0 alkyl groups or substituents
Represents an aryl group of 0. However, R ^x and R ^y do not simultaneously represent a hydrogen atom. A ² and A ³ may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyl group having a substituent, an alkenyl group having a substituent, Represents an aryl group having a substituent, an alkoxycarbonyl group having a substituent, an aryloxycarbonyl group having a substituent, a carbamoyl group, or a heterocyclic group. 2. The 2-aminopyrrole derivative according to claim 1, represented by the following general formulas (I-1) to (I-6). Embedded image A in the general formulas (I-1), (I-2) and (I-4)
⁴ represents an alkyl group, an alkenyl group, an aryl group, an alkyl group having a substituent, an alkenyl group having a substituent, or an aryl group having a substituent. General formula (I-2)
A ⁵ in represents an aryl group skeleton carbon number 6 to 19 having a total aryl group or a substituent having a carbon number of 6 to 19. A ⁶ in the general formula (I-3) represents an alkyl group having 5 to 19 total carbon atoms, an aryl group having 6 to 19 total carbon atoms, an alkyl group having 1 to 19 skeleton carbon atoms having a substituent, and a substituent. Represents an aryl group having 6 to 19 skeleton carbon atoms. General formula (I-4),
^Rx and ^Ry in (I-5) and (I-6) have the same meaning as in the case of formula (I). A ⁷ in the general formula (I-5)
Represents an alkyl group having 1 to 19 carbon atoms, an aryl group having 6 to 19 carbon atoms, an alkyl group having 1 to 19 skeleton carbon atoms having a substituent, or an aryl group having 6 to 19 skeleton carbon atoms having a substituent. . 3. A compound represented by the following general formula (c) by reacting an imidoketone derivative represented by the following general formula (a) with a nitrile derivative represented by the following general formula (b) under basic conditions. A method for producing a 2-aminopyrrole derivative, characterized by producing a 2-aminopyrrole derivative to be used. Embedded image In the general formula (a), R ¹ and R ² may be the same or different and each have a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a substituent. Alkyl group, alkenyl group having a substituent, aryl group having a substituent, alkoxycarbonyl group having a substituent,
Represents a substituted aryloxycarbonyl group, a carbamoyl group, or a heterocyclic group. Z represents a group of carbon atoms necessary to form a nitrogen-containing 5- or 6-membered ring, and the nitrogen-containing 5- or 6-membered ring may be further condensed with an aromatic ring. In the general formula (b), X represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, an alkoxycarbonyl group having a substituent, an aryloxycarbonyl group having a substituent, Represents an alkylsulfonyl group having a group, an arylsulfonyl group having a substituent, an aryl group having a substituent, a carbamoyl group, or a sulfamoyl group. In the general formula (c),
R ¹ and R ² have the same meanings as in formula (a),
Has the same meaning as in formula (b).