JP2006282535A - Method for producing carboxylic acid amide compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a carboxylic acid amide compound, by which a corresponding carboxylic acid anilide can effectively be produced from an alcoholic hydroxy group-having carboxylic acid and an aromatic or aliphatic amine. <P>SOLUTION: This method for producing the carboxylic acid anilide represented by general formula [IV] is characterized by reacting the alcoholic hydroxy group-having carboxylic acid represented by general formula [I] with the amine represented by general formula [II] in the presence of a carbodiimide condensation agent represented by general formula [III]. In general formulas [I] to [IV], R<SP>1</SP>is an alkyl, an alkenyl, an aryl, or an aromatic heterocyclic group; R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each independently identically or differently H or a substituent; Rc is methylene chain whose hydrogen atoms may be replaced by one or more substituents; (n) is an integer of ≥1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a carboxylic acid amide compound, and specifically relates to a method for efficiently producing a carboxylic acid amide compound from a carboxylic acid having an alcoholic hydroxy group and an aromatic or aliphatic amine.

  1H-pyrrolo- [1,2-b] [1,2,4] triazole compounds are useful as pharmaceuticals, agricultural chemicals, dyes or photographic couplers, or as synthetic intermediates thereof. In particular, as described in Patent Document 1, Patent Document 2, Patent Document 3, and the like, 1H-pyrrolo- [1,2-b] [1,2,4 having electron-withdrawing groups at the 6-position and the 7-position. Triazole compounds are useful as photographic dye-forming couplers with excellent absorption properties.

  As disclosed in Patent Document 4, it has been clarified that the carboxylic acid anilide group on the phenyl group at the 2-position has a great influence on the photographic performance. For this reason, development of a new manufacturing method was needed for the synthesis | combination of the carboxylic acid anilide which has alcoholic hydroxyl group among various carboxylic acids.

  As a known method for producing a carboxylic acid anilide, a 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound having a nitro group on the 2-position phenyl group is produced in advance, A method of converting to a carboxylic acid anilide group through reduction of a group has been disclosed (see Patent Document 5 and Patent Document 6). In this method, anilide is carried out using carboxylic acid chloride and cannot be applied to a carboxylic acid having a hydroxy group.

  Patent Document 4 discloses a method for producing a 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound using benzoic acid having a carboxylic acid anilide group as a starting material. However, in order to produce a carboxylic acid anilide having a hydroxy group by this method, the hydroxy group on the carboxylic acid must be protected in advance, and a long production process is required to produce various analogs. There is a problem that it is necessary and inefficient.

European Patent Publication 491197 A1 US Pat. No. 5,256,526 JP-A-5-204107 JP 2001-342189 A JP 2001-97976 A JP 2001-66742 A

  An object of the present invention is to provide a method for efficiently producing a corresponding carboxylic acid anilide compound from a carboxylic acid having an alcoholic hydroxy group and an aromatic or aliphatic amine.

  As a result of intensive studies to achieve the above object, the present inventors have achieved the above object of the present invention by the following constitution.

(1) A carboxylic acid having an alcoholic hydroxy group represented by the following general formula [I] and an amine represented by the following general formula [II] are converted into a carbodiimide condensing agent represented by the following general formula [III]. A process for producing a carboxylic acid anilide represented by the following general formula [IV], wherein the reaction is carried out in the presence of:

(In the general formulas [I] to [IV], R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aromatic heterocyclic group. R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. Rc represents a methylene chain, a hydrogen atom on the methylene chain may be substituted with a substituent, n represents an integer of 1 or more, and when n is 2 or more, The plurality of Rc may be the same as or different from each other.
(2) represented by the following general formula [VI], wherein a carboxylic acid having an alcoholic hydroxy group represented by the following general formula [I] is reacted with a compound represented by the following general formula [V]. A method for producing a carboxylic acid anilide compound.

(In the general formulas [I], [V] and [VI], Cp represents a dye-forming coupler residue that develops color by reacting with oxidized p-phenylenediamine. R ⁵ represents a substituent. And an integer of 4. When m is 2 to 4, a plurality of R ⁵ may be the same or different from each other, R ² represents a hydrogen atom or a substituent, Rc represents a methylene chain, and the hydrogen atom May be substituted with a substituent, n represents an integer of 1 or more, and when n is 2 or more, a plurality of Rc may be the same or different.
(3) The compound represented by the general formula [V] is a 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound represented by the following general formula [VII]. The manufacturing method according to item (2), which is characterized.

(In the formula, R ² , R ⁵ and m are as defined in the general formula [V]. R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituent, and may be the same or different. X and Y Each independently represents a hydrogen atom or a substituent, and may be the same or different.)
(4) The production method according to (3), wherein the compound represented by the general formula [V] is a compound produced from a compound represented by the following general formula [VIII].

(In the formula, R ⁵ , R ⁶ , R ⁷ , m, X and Y have the same meaning as in the general formula [VII].)

  By the production method of the present invention, a carboxylic acid anilide compound having an alcoholic hydroxy group can be efficiently produced in a short step. Since the reaction proceeds under mild reaction conditions, it is possible to introduce a carboxylic acid having a functional group other than a hydroxy group.

The present invention will be described in detail below.
First, the substituent used in the present invention will be described. Specifically, halogen atom, alkyl group (including cycloalkyl group and bicycloalkyl group), alkenyl group (including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group , Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including alkylamino group and anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio , Heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino Examples include a group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

  More specifically, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). Substituted or unsubstituted bicycloalkyl groups such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and tricyclo structures with many ring structures are also included. To do. A group having an alkyl part in the substituent described below (for example, an alkyl part of an alkylthio group) also represents an alkyl part of such a concept. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a C5-C30 substituted or An unsubstituted bicycloalkenyl group such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl) is there. ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) , For example phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),

Heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or non-substituted having 1 to 30 carbon atoms) Substituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms) For example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetrade Noylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or non-substituted group having 2 to 30 carbon atoms) A substituted heterocyclic oxy group such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably having a carbon number) To 30 substituted or unsubstituted carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn -Octylcarbamoyloxy),

An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (Preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably Is an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N Methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, For example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or non-substituted having 1 to 30 carbon atoms) A substituted aminocarbonylamino, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a group having 2 to 30 carbon atoms). Or an unsubstituted alkoxycarbonylamino group such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably carbon A substituted or unsubstituted aryloxycarbonylamino group of formula 7 to 30, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl or arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino) , Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, Tilthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably carbon number) 2-30 substituted or unsubstituted heterocyclic thio groups such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl groups (preferably substituted or unsubstituted sulfamoyl having 0 to 30 carbon atoms) Groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N ′ -Phenylcarbamoyl) sulfamoyl), sulfo group, alkyl Or an arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- Methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, Phenylsulfonyl, p-methylphenylsulfonyl),

Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms Heterocyclic carbonyl groups bonded to the carbonyl group by an atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryl An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl Group Or a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a 1 to 30 carbon atom substitution). Or an unsubstituted carbamoyl group such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or heterocyclic azo group ( Preferably, it is a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4. -Thiadiazol-2-ylazo), imi A group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted phosphinyloxy groups, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) A phosphinylamino group such as dimethoxyphosphinylamino Dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, benzoylaminosulfonyl and the like.

  The compound represented by the general formula [IV] produced by the production method of the present invention will be described below.

(In the general formula [IV], R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aromatic heterocyclic group. R ² represents a hydrogen atom or a substituent. Rc represents a methylene chain on the methylene chain. The hydrogen atom may be substituted with a substituent, n represents an integer of 1 or more, and when n is 2 or more, a plurality of Rc may be the same or different.

The alkyl group in R ¹ has the same meaning as that of the alkyl group in the substituent explained first (including a cycloalkyl group, a bicycloalkyl group or a polycycloalkyl group), and the preferred range is also the same. The alkyl group may be substituted with the substituent described first.
The alkenyl group in R ¹ has the same meaning as the alkenyl group in the substituent described first (including a cycloalkenyl group, a bicycloalkenyl group, or a polycycloalkenyl group), and the preferred range is also the same. The alkenyl group may be substituted with the substituent described first.
The aryl group in R ¹ is synonymous with the aryl group in the substituent explained first, and the preferred range is also the same. The aryl group may be substituted with the substituent described first.

The aromatic heterocyclic group in R ¹ preferably contains a nitrogen atom, an oxygen atom, or a sulfur atom in the ring constituent atoms, and is preferably a 5- to 6-membered ring group, preferably having 0 to 30 carbon atoms. The aromatic heterocyclic group may be substituted with a substituent, or may be condensed with an aromatic ring, an alicyclic ring, or a heterocyclic ring. Examples of the aromatic heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl.

R ¹ is preferably an aryl group or an aromatic heterocyclic group, more preferably a phenyl group, a naphthyl group or an anthracenyl group, which may have a substituent, and more preferably a substituent. Good phenyl group. Examples of the substituent include those exemplified as the substituent described first.

R ² is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a linear alkyl group having 3 or less carbon atoms, and even more preferably a hydrogen atom.

Rc represents a methylene group, that is, — (CH ₂ ) —. The hydrogen atom on the methylene group may be substituted with a substituent, and examples of the substituent include the substituents described first. The substituents on the methylene group may be bonded to each other to form a ring. n represents an integer of 1 or more. A preferable value is 1-40, More preferably, it is 1-20, More preferably, it is 1-10.

  Of the compounds represented by the general formula [IV], compounds represented by the following general formula [VI] are preferred.

(In the general formula [VI], R ² , Rc and n are as defined in the general formula [IV], and the preferred range is also the same. Cp is the residue of the dye-forming coupler that develops color by reacting with the oxidized p-phenylenediamine. R ⁵ represents a substituent, m represents an integer of 0 to 4. When m is 2 to 4, a plurality of R ⁵ may be the same or different.

Examples of the substituent in R ⁵ include the substituents described first. R ⁵ is an alkyl group, alkenyl group, aryl group, heterocyclic group, halogen atom, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, acylamino group, sulfonamido group, aryloxycarbonyl group , An alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, and a cyano group are preferable.
m is preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.
Cp represents a dye-forming coupler residue that reacts with oxidized p-phenylenediamine, and includes a non-colored coupler residue, preferably a yellow coupler residue, a magenta coupler residue, and a cyan coupler residue. A magenta coupler residue and a cyan coupler residue are more preferred, and a cyan coupler residue is most preferred. The coupler residue is a group obtained by removing a hydrogen atom from a chemical structural formula of a coupler to form a bond.

  Representative coupler residues include, for example, yellow coupler residues such as U.S. Pat. Nos. 3,048,194, 3,447,928, 5,449,598, and JP-A-4-64718. And JP-A-3-228500, JP-A-5-307248, and JP-A-2002-296740. Of these, acylacetanilide type yellow couplers (for example, benzoylacetanilide couplers, pivaloylacetanilide couplers, cyclopropylcarbonylacetanilide couplers), malondianilide type yellow couplers, indonylacetanilide couplers, benzothiadiadiacetanilide couplers are preferred. Couplers, and the like, and more preferred are benzoylacetanilide couplers, pivaloylacetanilide couplers, cyclopropylcarbonylacetanilide couplers, and benzothiadiadiacetanilide couplers.

  The magenta coupler residue is, for example, U.S. Pat. Nos. 2,369,489, 3,725,067, 4,540,654, JP-A-57-17950, and JP-A-59-162548. No. 6, JP-A-6-43611, or each specification. Of these, a pyrazolone magenta coupler and a pyrazolotriazole type magenta coupler (for example, 1H-pyrazolo [1,5-b] -1,2,4-triazole magenta coupler, 1H-pyrazolo [5,1-c] are preferable. -1,2,4-triazole magenta couplers), more preferably 1H-pyrazolo [1,5-b] -1,2,4-triazole magenta couplers.

  Examples of the cyan coupler residue include those described in U.S. Pat. Nos. 2,367,531, 2,423,730, European Patent Nos. 0161626B1, 0250201A1, 0545300, and JP-A-8-110623. It is described in each publication or specification. Among these, a naphthol type cyan coupler, a phenol type cyan coupler, a pyrrolotriazole type cyan coupler, and a pyrazoloazole type cyan coupler are preferable, and a pyrrolotriazole type cyan coupler is more preferable.

  Of the compounds represented by the general formula [VI], compounds represented by the following general formula [IX] are more preferred.

In general formula [IX], R ² , R ⁵ , m, Rc and n have the same meaning as in general formula [VI], and the preferred range is also the same. R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituent, and may be the same or different. X and Y each independently represent a hydrogen atom or a substituent, and may be the same or different.
Examples of the substituent in R ⁶ and R ⁷ include the substituents described first.
R ⁶ is preferably an aryloxycarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a carbamoyl group, a sulfamoyl group, or a cyano group, more preferably an alkoxycarbonyl group, a cyano group, or more preferably an alkoxycarbonyl group.

R ⁷ is preferably an aryloxycarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a carbamoyl group, a sulfamoyl group, or a cyano group, more preferably an alkoxycarbonyl group, a cyano group, or more preferably a cyano group.

  X represents a hydrogen atom or a substituent, and is preferably a group that can be eliminated by reaction with oxidized p-phenylenediamine. More preferably, a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a thioalkyl group, an acyl group, a carbamoyl group, a ureido group, a carbonate group, an alkyl sulfonic acid group or an aryl sulfonic acid group can be mentioned. More preferred is a dialkylaminocarboxyl group. A more preferred example is N, N-di (ethoxycarbonylmethyl) aminocarboxyl group.

  Y represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described above, preferably a group that can be removed by hydrolysis (eg, acyl group, sulfonyl group, phosphoryl group, urethane group, silyl group, etc.), and most preferably a hydrogen atom. It is.

  Specific examples of the compound represented by the general formula [VI], which is a preferred compound among the compounds represented by the general formula [IV], are shown below, but the present invention is not limited thereto.

Next, the manufacturing method of this invention is demonstrated.
The method for producing a carboxylic acid amide compound having an alcoholic hydroxy group represented by the general formula [IV] of the present invention comprises a carboxylic acid having a hydroxy group represented by the following general formula [I] and the following general formula [II]. It is the method of making the amine represented by these react.

In the general formula [I] or [II], R ¹ , R ² , Rc and n have the same meaning as the general formula [IV], and the preferred range is also the same.
In the carboxylic acid having a hydroxy group represented by the general formula [I], the methylene chain in Rc may have a substituent as described above, and a plurality of substituents may be bonded to each other to form a ring. Often, the substituent is preferably an alkyl group. The carboxylic acid having a hydroxy group represented by the general formula [I] is preferably a chain carboxylic acid having a hydroxy group at the terminal carbon, and most preferably 3-hydroxy-2,2-dimethylpropionic acid. .
Specific examples of the compound represented by the general formula [I] are shown below, but the present invention is not limited thereby.

  In order to produce a compound represented by the general formula [VI], which is a preferred compound of the compound represented by the general formula [IV], the compound represented by the general formula [II] In order to produce a compound represented by the general formula [IX], which is a more preferable compound, a compound represented by the following general formula [VII] is used.

In the general formulas [V] and [VII], R ^{5 to} R ⁷ , m, X, and Y are synonymous with the corresponding general formula [VI] or [IX], and preferred ranges are also the same.
The compound represented by the general formula [II] is preferably represented by the general formula [V], and Cp in the general formula [V] is the above-mentioned yellow coupler residue, magenta coupler residue or cyan coupler residue. It is a compound that is a group. More preferably, it is a compound represented by the general formula [VII].
Specific examples of the compound represented by any one of the general formulas [II], [V] and [VII] are shown below, but the present invention is not limited thereby.

  The reaction in the production method of the present invention can be carried out by mixing the above carboxylic acid and the above amine and dehydrating with heating, but using an acid such as p-toluenesulfonic acid or various condensing agents as a catalyst. Can be accelerated. In order to allow the reaction to proceed under a mild condition near room temperature and near neutrality, it is preferable to use a condensing agent. As the condensing agent, a carbodiimide compound represented by the following general formula [III] is preferably used. .

In general formula [III], R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and may be the same or different. Examples of the substituent in R ³ and R ⁴ include the substituents described first.
The substituent in R ³ and R ⁴ is preferably a chain or cyclic alkyl group, more preferably a linear alkyl group. The alkyl group may be further substituted with the substituents described first.
The carbodiimide compound represented by the general formula [III] is not particularly limited, but those other than di-N, N′-cyclohexylcarbodiimide can be preferably used. Preferred are diisopropylcarbodiimide, 1-ethyl-3- (N, N-dimethylamino) propylcarbodiimide (hereinafter referred to as EDC), and more preferred is EDC. When EDC is used, the reaction product N-ethyl-N ′-(N, N-dimethylamino) propylurea can be easily removed at the end of the reaction.

  The reaction in the production method of the present invention may be performed by dissolving or dispersing in an appropriate solvent. Solvents that can be used in the reaction of the present invention include, for example, chlorinated solvents (eg, dichloromethane, chloroform), amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide), nitrile solvents (eg, acetonitrile). , Propionitrile), ureido solvents (eg 1,3-dimethyl-2-imidazolidinone), ether solvents (eg tetrahydrofuran) sulfone solvents (eg sulfolane), sulfoxide solvents (eg dimethyl sulfoxide), phosphoric acid Examples include amide solvents (for example, hexamethylphosphoric triamide).

  These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably 0.1 to 1000 parts by weight, more preferably 0.5 to 100 parts by weight, and still more preferably 1 to 50 parts per 1 part by weight of the compound represented by the general formula [I]. Part by mass.

  In the present invention, the reaction temperature is not particularly limited, but it can be carried out in the range of −50 ° C. to 300 ° C., although it depends on the type of compound used, the presence or absence of an acid, a dehydrating agent, and the like. Is in the range of −10 ° C. to 200 ° C., more preferably in the range of 0 ° C. to 100 ° C.

  In this invention, reaction time can be implemented in the range of 1 minute-50 hours, Preferably it is the range of 1 minute-20 hours, More preferably, it is the range of 1 minute-5 hours.

  The compound represented by the general formula [V] is synthesized from a 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound having a nitro group represented by the following general formula [VIII]. Is preferably used, and can be produced by reducing the compound represented by the general formula [VIII]. The reduction reaction may be a general reduction method, preferably a catalytic reduction method in the presence of a palladium catalyst or a reaction with reduced iron.

  The nitro compound represented by the general formula [VIII] can be produced from the corresponding substituted nitrobenzoic acid by a known method according to JP-A-2001-342189.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

Example 1
<Production of Exemplified Compound (VI-6)>
Exemplified compound (VI-6) was produced as follows.

Amine compound (A) (9.3 g, 11.3 mmol) and 3-hydroxy-2,2-dimethylpropanoic acid (3.9 g, 33.8 mmol) were dissolved in acetonitrile (28 mL). After adding 1-ethyl-3- (N, N-dimethylamino) propylcarbodiimide (EDC) (6.5 g, 33.8 mmol) at 0 ° C., the mixture was stirred for 1 hour while gradually warming to room temperature. 3-hydroxy-2,2-dimethylpropanoic acid (1.3 g, 11.3 mmol) and EDC (2.1 g, 11.3 mmol) were added, and the mixture was further stirred for 1 hour. The reaction was stopped by adding water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated to obtain a crude product. Purification by silica gel column chromatography (ethyl acetate / hexane) gave the target compound 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound (VI-6). (3.9 g, 41% yield).
Melting point: 180-183 ° C
NMR (CDCl ₃ ): δ 8.63 (s, 1H), 8.49 (s, 1H), 7.62 (d, J = 8.7 Hz, 1H), 6.70 (d, J = 8.7 Hz) , 1H), 6.00 (s, 1H), 4.97 (br.s, 1H), 4.37 (s, 2H), 4.32 (q, J = 7.1 Hz, 2H), 4. 29 (s, 2H), 4.26 (q, J = 7.1 Hz, 2H), 4.02 (br.s, 2H), 3.52 (s, 3H), 1.76 to 1.19 ( m, 8H), 1.33 (t, J = 7.1 Hz, 3H), 1.32 (t, J = 7.1 Hz, 3H), 1.31 (s, 6H), 1.09 (d, J = 6.3 Hz, 3H), 0.92 (s, 18H)

Claims (4)

A carboxylic acid having an alcoholic hydroxy group represented by the following general formula [I] and an amine represented by the following general formula [II] in the presence of a carbodiimide condensing agent represented by the following general formula [III] A process for producing a carboxylic acid anilide represented by the following general formula [IV].

(In the general formulas [I] to [IV], R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aromatic heterocyclic group. R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. Rc represents a methylene chain, a hydrogen atom on the methylene chain may be substituted with a substituent, n represents an integer of 1 or more, and when n is 2 or more, The plurality of Rc may be the same as or different from each other. A carboxylic acid represented by the following general formula [VI], wherein a carboxylic acid having an alcoholic hydroxy group represented by the following general formula [I] is reacted with a compound represented by the following general formula [V] A method for producing an anilide compound.

(In the general formulas [I], [V] and [VI], Cp represents a dye-forming coupler residue that develops color by reacting with oxidized p-phenylenediamine. R ⁵ represents a substituent. And an integer of 4. When m is 2 to 4, a plurality of R ⁵ may be the same or different from each other, R ² represents a hydrogen atom or a substituent, Rc represents a methylene chain, and the hydrogen atom May be substituted with a substituent, n represents an integer of 1 or more, and when n is 2 or more, a plurality of Rc may be the same or different. The compound represented by the general formula [V] is a 1H-pyrrolo- [1,2-b] [1,2,4] triazole compound represented by the following general formula [VII]. The manufacturing method according to claim 2.

(Wherein R ² , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a substituent, and may be the same or different. M represents an integer of 0 to 4, where m is 2; In the case of ˜4, the plurality of R ⁵ may be the same or different from each other, X and Y each independently represent a hydrogen atom or a substituent, and may be the same or different. The production method according to claim 3, wherein the compound represented by the general formula [V] is a compound produced from a compound represented by the following general formula [VIII].

(In the formula, R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a substituent, and may be the same or different. M represents an integer of 0 to 4, where m is 2 to 4; And a plurality of R ⁵ may be the same or different from each other. X and Y each independently represent a hydrogen atom or a substituent, and may be the same or different.)