JPH0372232B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application] The present invention relates to a method for producing N-substituted amides.
Specifically, an N-substituted amide in which a specific N-halomethylamide and a specific heteroaryl are reacted in the presence of at least one catalyst selected from the group consisting of iron halide, iron oxide, zinc halide, and zinc oxide. The present invention provides a method for manufacturing. [Prior art and problems to be solved by the invention] Conventionally, as a method for producing an amide compound, as shown in the following formula (1), an aromatic compound is treated with an N-halomethylamide compound in the presence of aluminum chloride. A reaction for obtaining an amidomethylated aromatic ring compound is known. However, R in () and () is a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, or a nitro group, and Ary in () and () is a substituted or unsubstituted aryl group. ) However, there is still no known method for producing an amide compound having a heterocycle by reacting a heterocycle with an N-halomethylamide compound. The present inventors have attempted to produce an amide compound having a heterocycle by reacting the above-mentioned heterocyclic compound with an N-halomethylamide compound. However, when a similar reaction was attempted using furan instead of the aromatic ring compound in () above, most of the compound was converted into a resin, and the desired product was not obtained at all. That is, even if the above reaction formula is known, the same reaction cannot proceed simply by using a heterocyclic compound instead of an aromatic ring compound. Therefore, there has been a need to develop an effective catalyst for producing an amide compound having a heterocycle by reacting a heterocycle with an N-halomethylamide compound. [Means for Solving the Problems] The present inventors have been conducting research on the production of amide compounds having a heterocycle for many years. As a result, when producing the aforementioned compound by reacting N-halomethylamide with a heterocyclic compound, the specific metal halide and/or metal oxide becomes a catalyst that can provide the target product in good yield. They discovered this and completed the present invention. That is, the present invention is based on the general formula () (However, R ¹ is an alkyl group, an alkoxy group, a phenyl group which may be substituted with a halogen atom, or a saturated or unsaturated aliphatic hydrocarbon group which may be substituted with a halogen atom, and R ² and R ³ are Same or different hydrogen atoms or alkyl groups, R ⁴
is a haloalkyl group, and X is a halogen atom. ) and N-halomethylamide represented by (b)

【formula】

[Formula] or

[Formula] (A is an oxygen atom, a sulfur atom, or a N-R
(R is a hydrogen atom or an alkyl group having 5 or less carbon atoms). ) A 5-membered ring or fused 5-membered ring heterocyclic compound represented by the substituent; -R ⁵ , -OR ⁵ , -SR ⁵ ,

【formula】

[Formula]-B-COOR ⁶ ,

[Formula] -B-CN, -X, -NH ₂ , -NHCOR ⁵ or -NO ₂ (Among the above substituents, R ⁵ is an alkyl group or a haloalkyl group, and R ⁶ is a hydrogen atom, an alkyl group, a monovalent is a metal ion, divalent metal ion or ammonium salt, and B is

[expression] or

[Formula] (where R ⁸ is a hydrogen atom or an alkyl group, l is 0 or a positive integer of 10 or less), R ⁷ is a hydrogen atom or an alkyl group, and X is a It is a halogen atom. ) with an optionally substituted heterocyclic compound in the presence of at least one catalyst selected from the group consisting of iron halide, iron oxide, zinc halide and zinc oxide. formula() (However, R ¹ , R ² , R ³ , R ⁴ and Ar are the same as above.) This is a method for producing an N-substituted amide. In the following description of the present invention, the general formula (), Ar-H...() may be used to represent the heterocyclic compound shown as the above-mentioned raw material (b). The most important feature of the present invention lies in the catalyst used in the reaction between the N-halomethylamide represented by the general formula () and the heteroaryl represented by the general formula (). That is, the catalyst used in the present invention is at least one compound selected from the group consisting of iron halide, iron oxide, zinc halide, and zinc oxide. The reason why only these limited compounds work effectively as catalysts for the above reaction and their effects are still unclear, but as a result of the inventors' systematic study of a large number of various metal halides and metal oxides. As a result, the effects of the present invention in this field are immeasurable. Among the above catalysts, halides of metal halides such as iron halide and zinc halide include fluoride,
Any of chloride, bromide or iodide can be used without particular limitation. In the present invention, the molar amount of at least one compound selected from the group consisting of iron halide, iron oxide, zinc halide, and zinc oxide used as a catalyst (in the case of two or more types, the sum of the moles of each compound) is: Since the optimum amount varies depending on the reaction conditions, it cannot be absolutely limited. Therefore, it may be determined in advance according to the set reaction conditions. Generally, the amount of the catalyst suitably used may be selected in the molar ratio (hereinafter simply referred to as molar ratio) to the compound represented by the general formula () in the range of 0.001 to 1000, preferably 0.01 to 100. In particular, when using only the above metal halide, the amount used is preferably in the range of 0.01 to 3 in terms of molar ratio,
When only the above metal oxide is used, the amount used is preferably 0.1 to 100 in molar ratio. Most of the target products of the present invention, ie, the N-substituted amides represented by the above general formula (), are new compounds. For example, among the compounds represented by the above general formula (), general formula (A) (However, _R ^x is a hydrogen atom or an _alkyl group; The N-substituted-halomethylamides shown are known. Therefore, compounds represented by the above general formula () other than the above general formula (A) are new compounds. These new compounds have particularly excellent herbicidal activity and are generally used as herbicides. Whether the compound is represented by the general formula () is confirmed by instrumental analysis such as infrared absorption spectrum, ¹ H-nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum, mass spectrometry, elemental analysis, etc. I can do it. These compounds also have specific physical constants such as melting point, boiling point, and refractive index. Furthermore, the compound represented by the above general formula () is usually a colorless, pale yellow, or pale brown solid or viscous substance, although it varies somewhat depending on its purity. As mentioned above, among the N-substituted amides represented by the general formula (), the combination of the N-halomethylamide of the general formula () and the heteroaryl of the general formula (), which is a raw material corresponding to a new compound, is It is new. However, as is clear from the structures of the general formulas (), (), and (), the reaction in the present invention is based on the structure of the N-halomethylamide represented by the general formula (). X represented by and Ar-H represented by general formula ()
and H react to cause a dehydrohalogenation reaction.If necessary, these raw material compounds can be used as long as they can be dehydrohalogenated and have the function of retaining the above-mentioned skeletons. can be selected and used. Examples of raw materials that can generally be suitably used are as follows. N-halomethylamide, which is a raw material used in the present invention, has the general formula (), that is, (However, R ¹ is a substituted or unsubstituted hydrocarbon group,
R ² and R ³ are the same or different hydrogen atoms or alkyl groups, R ⁴ is substituted or unsubstituted alkyl, X
is a halogen atom. ). In the above general formula (), R ¹ is a phenyl group or a saturated or unsaturated aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited and can be selected as required, but from the viewpoint of easy availability of raw materials, carbon atoms such as methyl group, ethyl group, isopropyl group, allyl group, butyl group, and the like have a carbon atom number of 1. ~10 is preferred. Further, the above phenyl group may be substituted with an alkyl group, an alkoxy group, or a halogen atom. Typical examples of these substituents include lower alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl, and butyl groups, and methoxy and ethoxy groups as alkoxy groups. As the halogen atom, chlorine, bromine, iodine or fluorine are preferably used, respectively. Further, the aliphatic hydrocarbon group may be substituted with a halogen atom such as chlorine, bromine, iodine or fluorine. In addition, in the general formula (), the alkyl groups represented by R ² and R ³ are not limited in any way, but from the viewpoint of easy availability of raw materials, carbon atoms such as methyl, ethyl, isopropyl, and butyl groups have 1 to 1 carbon atoms. The lower alkyl group of 5 is preferred. R ⁴ is a haloalkyl group, and the halogen atom is preferably the halogen atom listed above, and the alkyl group is preferably the alkyl group listed above. Furthermore, the halogen atom represented by X is chlorine, bromine,
Iodine and fluorine atoms can be used without any restriction, but chlorine atoms and bromine atoms are preferably used because of their ease of raw material availability. Other raw material compounds used in the present invention are heterocyclic compounds represented by the general formula (), () or (). (However, A in (), (), and () is an oxygen atom, a sulfur atom, or a five-membered heterocyclic ring represented by N-R ^y (R ^y is a hydrogen atom or an alkyl group having 5 or less carbon atoms). When using this compound, the desired compound represented by the general formula () can be obtained in high yield.Heterocyclic compounds represented by the general formula (), (), and () may be substituted with a substituent. Good. Substituents represented by the following formulas () to (XI) are preferably used. -R ⁵ ... () -OR ⁵ ... (XI) -SR ⁵ ... (XII) -B-COOR ⁶ ...() -B-CN ... () -X ... () -NH ₂ ... () -NHCOR ⁵ ... () -NO ₂ ... (XI) In the above formula, R ⁵ is an alkyl group, and R ⁶ is a hydrogen atom, an alkyl group, a monovalent metal ion, a divalent metal ion, or an ammonium salt, and B is

[expression] or

〔effect〕

By using the specific catalyst proposed in the present invention, the reaction between the N-halomethylamide and the heteroaryl compound proceeds extremely stably, and the N-substituted amide can be obtained in high yield. Therefore, N
This is an industrially excellent method in that it not only allows the production of -substituted-amides at low cost, but also allows for extremely easy reaction operations. Further, the target product obtained by the present invention has excellent herbicidal activity, and exhibits the effect of weeding a wide range of weeds even with a small amount of active ingredient. [Examples] Examples are given below to explain the present invention more specifically, but the present invention is not limited to these Examples. Example 1 1.40 g of β-(2'-furyl)propionic acid was dissolved in 20 ml of methylene chloride and 1.50 g of zinc chloride was added with stirring. Next, a solution of 2.74 g of N-chloromethyl-chloroaceto-2,6-diethylanilide dissolved in 15 ml of methylene chloride was added dropwise with stirring, and the mixture was heated under reflux for 7 hours while stirring.
The mixture was then cooled to room temperature and poured into 50 ml of ice water with stirring. After stirring for 10 minutes, 5% aqueous sodium hydrogen carbonate solution was added dropwise to make it basic. The aqueous layer obtained by separating the solution was acidified with 1N hydrochloric acid and extracted with ether. After drying the ether layer with Glauber's salt, the ether was distilled off and the residue was purified by column chromatography [the carrier was silica gel, the developing solvent was benzene-acetone (volume ratio 5:1)] to obtain pale yellow crystals. 1.53g of the target product was obtained.
The isolated product was found to be β-[5-(N-chloroacetyl-2',
It was confirmed that it was 6'-diethylanilino)methyl-2-furan]propionic acid. The IR chart was as shown in Figure 1 of the attached drawings. Absorption based on aromatic ring carbon-hydrogen bonds between 315 cm ^-1 and 3000 cm ^-1 , absorption based on aliphatic carbon-hydrogen bonds between 3000 cm ^-1 and 2850 cm ^-1 , and 3200 cm ^-1
Broad absorption based on hydroxyl groups at ~2900 cm ^-1 , 1725 cm
An absorption based on the carbon-oxygen double bond of the carboxylic acid group was observed at ^-1 , and an absorption based on the carbon-oxygen double bond of the amide group was observed at 1620 cm ^-1 . Figure 2 of the attached drawings shows the ¹ H-NMR chart (tetramethylsilane reference: δppm 60MHz). At 10.2 ppm, the proton of the hydroxyl group appears as a single proton, and at 7.6 to 7.0 ppm, the proton of the benzene ring appears as a multibullet, equivalent to 3 protons. At 6.10 ppm and 5.91 ppm, the proton of the furan ring appears as a doublet (spin bond, respectively). One proton appears at a constant rate of 3 Hz),
Two singlet methylene protons connecting the nitrogen atom and the furan ring appear at 4.76 ppm.
At 3.70 ppm, the proton of the chloroacetyl group appears as a singlet, equivalent to two protons, and from 3.2 to
At 2.0 ppm, the methylene proton of propionic acid and the methylene proton of the ethyl group appeared as a multiplet, equivalent to 8 protons, and at 1.16 ppm, the methyl proton of the ethyl group appeared as a triplet (spin coupling constant 7 Hz), equivalent to 6 protons. ¹³ C−
As a result of NMR (tetramethylsilane standard; δppm) measurement, the chemical shift of the compound was assigned as follows. The chemical shift (ppm) of each carbon in the above structure is shown below. 177.4 23.1 32.4 One is 147.8 and the other is 153.8 106.6 111.3 41.6 45.4 166.9 136.7 141.7 126.6 129.2 23.1 14.1 Results of mass spectrum measurement (m/e, 20eV),
The following peaks were observed. m/e379,378
and 377 (molecular ion peak, corresponding to M), m/
e342 (equivalent to M -Cl) Elemental analysis values are carbon 63.45wt%, hydrogen 6.51wt%,
Nitrogen 3.68wt%, chlorine 9.95wt%,
The theoretical value of C ₂₀ H ₂₄ NO ₄ Cl, carbon 63.57wt%,
Hydrogen was 6.40wt%, nitrogen was 3.71wt%, and chlorine was 9.38wt%, which all agreed within the analytical error range. The structures of the products in the following examples were also determined in the same manner as above. Example 2 The reaction and post-treatment were carried out in the same manner as in Example 1, except that chloroform was used instead of methylene chloride as the solvent in Example 1, and the reaction system was heated under reflux for 5 hours. 1.38 g of the same product was obtained. Example 3 The reaction and post-treatment were carried out in the same manner as in Example 1, except that the amount of zinc chloride used in Example 1 was changed to 0.6 g, and the same product as obtained in Example 1 was obtained.
0.75g was obtained. Example 4 Ferric chloride instead of zinc chloride in Example 1
All the reactions and post-treatments were carried out in the same manner as in Example 1, except that 1.62 g was used, and 0.73 g of the same product as obtained in Example 1 was obtained. Example 5 Zinc chloride instead of zinc chloride in Example 1
All the reactions and post-treatments were carried out in the same manner as in Example 1, except that 8.14 g was used, and 1.32 g of the same product as obtained in Example 1 was obtained. Example 6 In place of zinc chloride in Example 1, dichloride was used.
All reactions and post-treatments were carried out in the same manner as in Example 1, except that 16.0 g of iron was used, and 0.95 g of the same product as in Example 1 was obtained. Example 7 Zinc bromide was used instead of zinc chloride in Example 1.
The reaction and post-treatment were carried out in the same manner as in Example except that 2.48 g was used, and 1.51 g of the same product as obtained in Example 1 was obtained. Example 8 In place of zinc chloride in Example 1, ferric bromide
The reaction and post-treatment were carried out in the same manner as in Example 1, except that 2.96 g of iron was used, and 0.71 g of the same product as in Example 1 was obtained. Example 9 The reaction was carried out in the same manner as in Example 1, except that 3.16 g of N-bromomethyl-chloroaceto-2,6-diethylanilide was used instead of N-chloromethyl-chloroaceto-2,6-diethylanilide in Example 1. and after-treatment, 1.45 g of the same product as obtained in Example 1 was obtained. Example 10 The reaction was carried out in the same manner as in Example 1 except that N-bromomethyl-chloroaceto-2,6-diethylanilide was used instead of N-chloromethyl-chloroaceto-2,6-diethylanilide in Example 1. As a result, 1.35 g of a pale yellow solid was obtained as a product. Elemental analysis values are 61.71wt% carbon and 5.65wt% hydrogen.
%, nitrogen 3.92wt%, chlorine 10.28wt%,
This coincided with the theoretical values of C ₁₈ H ₂₀ NO ₄ Cl of 61.80 wt% carbon, 5.76 wt% hydrogen, 4.00 wt% nitrogen, and 10.13 wt% chlorine within the analytical error range. Based on this result, Example 1
Taking into account the results of instrumental analysis conducted in the same manner as above, the structure of the product was determined to be β-[5-N chloroacetyl-2',
It was confirmed that it was 6'-dimethylanilino)methyl-2-furan]propionic acid. Example 11 3.78g of methyl furoate was added to methylene chloride.
20 ml and added 1.50 g of zinc chloride with stirring. Next, a solution of 2.74 g of N-chloromethyl-chloroaceto-2,6-diethylanilide dissolved in 15 ml of methylene chloride was added dropwise with stirring, and the mixture was heated under reflux for 7 hours while stirring. It was cooled to room temperature and poured into 50 ml of ice water with stirring. Ten
After stirring for a minute, the mixture was separated into an organic layer and an aqueous layer. The organic layer was washed with water and then dried with sodium sulfate. The residue obtained by distilling off methylene chloride was purified by column chromatography to obtain 0.56 g of a colorless sticky liquid. Elemental analysis values are carbon 62.51wt%, hydrogen 6.13wt%, nitrogen 3.69wt%,
Chlorine is 9.87wt%, and the theoretical value of C ₁₉ H ₂₂ NO ₄ Cl is 62.72wt% carbon, 6.09wt% hydrogen, and 3.85wt nitrogen.
%, chlorine 9.74wt%, within the analytical error range.
Taking these results into consideration and the results of instrumental analysis conducted in the same manner as in Example 1, the structure of the product is methyl 5-(N-chloroacetyl-2',6'-diethylanilino)methylfurancarboxylate. I confirmed that there is. Example 12 Thiophene-3-acetic acid was used instead of 2-methyl-3-(2'-furyl)propionic acid in Example 1.
When the reaction and post-treatment were carried out in the same manner as in Example 1 using 1.42 g, 5-
(N-chloroacetyl-2',6'-diethylanilino)methyl-3-thiopheneacetic acid and the following formula (
) 2-(N-chloroacetyl-2',
6'-diethylanilino)methyl-3-thiopheneacetic acid was isolated. The elemental analysis value of compound (XII) is carbon 60.15wt%,
Hydrogen 5.78wt%, nitrogen 3.53wt%, chlorine 9.21wt%, and the elemental analysis value of the compound () is carbon
59.95wt%, hydrogen 5.71wt%, nitrogen 3.45wt%, chlorine
It was 9.50wt%. Both contain 60.07wt% carbon, 5.84wt% hydrogen, and nitrogen, which are the theoretical values of C ₁₉ H ₂₂ NO ₈ ClS.
3.69wt% and chlorine 9.33wt%, both within the analytical error range. In the mass spectra, the molecular ion peak for both was 379, which matched the theoretical molecular weight of C ₁₉ H ₂₂ NO ₈ ClS. In the proton-NMR spectrum of compound (XII), the aromatic ring proton appears as a multiplet of 5 protons at 7.5 to 6.6 ppm, and the methylene proton connecting the nitrogen atom and the thiophene ring appears as a singlet of 2 protons at 4.85 ppm. Appear,
At 3.67 ppm, the methylene proton of the chloroacetyl group appears as a singlet, equivalent to two protons,
At 3.52 ppm, the methylene proton of the acetate group appears as a singlet, equivalent to 2 protons, and at 2.31 ppm, the methylene proton of the ethyl group appears as a quartet (spin coupling constant 7 Hz), equivalent to 4 protons.
At 1.06 ppm, 6 protons of methyl protons in the ethyl group appeared as a triplet (spin coupling constant 8 Hz). one proton of compound ()
In the NMR spectrum, the aromatic ring protons at 7.5 to 6.6 ppm appear as a multiplet, equivalent to 5 protons, the methylene proton connecting nitrogen and the thiophene ring appears as a single proton at 4.95 ppm, equivalent to 2 protons, and the chloroacetyl proton appears at 3.67 ppm. The methylene proton of the group appears as a singlet, equivalent to 2 protons, and the methylene proton of the acetate group appears as a singlet, equivalent to 2 protons, at 3.29 ppm.
At 2.31 ppm, the methylene proton of the ethyl group appeared as a quartet (spin coupling constant 7 Hz), equivalent to 4 protons, and at 1.06 ppm, the methyl proton of the ethyl group appeared as a triplet (spin coupling constant 8 Hz), equivalent to 6 protons. Compound (XII) and (
) The chemical shift, splitting pattern, spin coupling constant, and relative intensity ratio of each peak in each ¹ H-NMR spectrum support the above structural formula. Example 13 1.48 g of 3-methylbenzothiophene was dissolved in 2.0 ml of methylene chloride, and 1.50 g of zinc chloride was added with stirring. Next, a solution of 2.74 g of N-chloromethyl-chloroaceto-2,6-diethylanilide dissolved in 15 ml of methylene chloride was added dropwise with stirring, and the mixture was heated under reflux for 7 hours while stirring. The mixture was then cooled to room temperature and poured into 50 ml of ice water with stirring. After stirring for 10 minutes, 5% aqueous sodium hydrogen carbonate solution was added dropwise to make it basic. The aqueous layer obtained by separating the solution was acidified with 1N hydrochloric acid and extracted with ether. After drying the ether layer with Glauber's salt, the ether was distilled off and the residue was purified by column chromatography [the carrier was silica gel, the developing solvent was benzene-acetone (volume ratio 50:1)] to obtain white crystals. 2.70 g of the target product was obtained. The isolated product was confirmed to be 2-(N-chloroacetyl-2',6'-diethylanilino)methyl-3-methylbenzothiophene shown in the following formula by the various measurement results listed below. . The IR chart was as shown in Figure 3 of the attached drawings. 3100cm ^-1 ~3000cm ^-1 Carbon of aromatic ring −
Absorption based on hydrogen bonds, absorption based on aliphatic carbon-hydrogen bonds at 3000 to 2800 cm ^-1 , and absorption based on carbon-oxygen double bonds of amide groups at 1665 cm ^-1 were observed. FIG. 4 of the attached drawings shows a chart of H-NMR (tetramethylsilane standard; δppm, 60MHz). At 7.8 to 7.0 ppm, seven benzene ring protons appear as a multiplet, at 4.98 ppm, two methylene protons connecting the nitrogen atom and the thiophene ring appear as a singlet, and at 3.68 ppm, a chloroacetyl group proton appears as a singlet. At 2.60-2.05ppm, 4 methylene protons of the ethyl group appear as a multiple, at 1.89ppm, 3 protons of the methyl group attached to the 3-position of benzothiophene appear as a singlet, and at 0.96ppm, ethyl protons appear as a singlet. Six protons of methyl protons appeared in a triplet with a spin coupling constant of 8 Hz. The results of mass spectrum measurement (m/e, 20eV),
The following peaks were observed. m/e385, 386,
387, 388 [molecular ion peak (hereinafter abbreviated as M ⁺ )],
m/e350 (M ⁺ −Cl), m/e307 (M ⁺ −ClCH ₂ CO),
m/e292 (M ⁺ _-ClCH2O - _CH3 ). Elemental analysis values are carbon 68.65wt%, hydrogen 6.34wt%,
Nitrogen 3.49wt%, chlorine 9.01wt%, sulfur 8.43wt%, which is the theoretical value of C ₂₂ H ₂₄ NOCl, carbon 68.46wt
%, hydrogen 6.27wt%, nitrogen 3.63wt%, chlorine 9.19wt
%, sulfur content was 8.31wt%, within the analytical error range. Example 14 The reaction was carried out in the same manner as in Example 1 except that the raw materials were selected to correspond to the products in Table 1, and an N-substituted amide represented by the following general formula () was synthesized. . Regarding the structure of the product in Table 1, R ¹ , R ² and Ar in the above general formula () are shown by the following structural formula.

[Formula] [However, when R ¹ is a phenyl group (No. 1 to 189 in Table 1)]

[Formula] [However, Ar is a five-membered heterocyclic ring Case (No. 1 to 95 in Table 1)]

[Formula] [However, when Ar is a fused five-membered heterocyclic ring (Nos. 96 to 206 in Table 1)] (However, in Nos. 1 to 76 of Table 1, R ⁹ is -B
−COOR ⁶ , and the classification in column B is ().

[Formula] Classification is ()

[Formula] respectively) In addition, in Table 1, the numerical value of the bonding position of Ar is the following functional group, i.e. indicates the position of carbon substituted with Ar. Furthermore, the abbreviations used in Table 1 have the following meanings. Et: ethyl group, Me: methyl group, i-Pr: isopropyl group, n-Bu: normal-butyl group,
Ac: methyl carbonyl group, i-Bu: isobutyl group, n-Pr: normal propyl group,

【table】

【table】

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【table】

【table】 [Brief explanation of drawings]

The accompanying drawing, Figure 1, shows the product obtained in Example 1.
This is an IR chart, and Figure 2 is also ^{a 1} H-NMR chart.
This is the chart. Figure 3 of the attached drawings is an IR chart of the product obtained in Example 10, and Figure 4 is ^{a 1} H-NMR chart.

Claims (1)

[Claims] 1 (a) General formula (However, R ¹ is an alkyl group, an alkoxy group, a phenyl group which may be substituted with a halogen atom, or a saturated or unsaturated aliphatic hydrocarbon group which may be substituted with a halogen atom, and R ² and
R ³ is the same or different hydrogen atom or alkyl group, R ⁴ is a haloalkyl group, and X is a halogen atom. ) and (b) [Formula] [Formula] or [Formula] (where A is an oxygen atom, a sulfur atom, or an N-R
(R is a hydrogen atom or an alkyl group having 5 or less carbon atoms). ) A 5-membered ring or fused 5-membered ring heterocyclic compound represented by: -R ⁵ , -OR ⁵ , -SR ⁵ , [Formula] [Formula] -B-COOR ⁶ , [Formula] -B -CN, -X, _-NH2 , ^-NHCOR5 or _-NO2 (Among the above substituents, ^R5 is an alkyl group or a haloalkyl group, and ^R6 is a hydrogen atom, an alkyl group, a monovalent metal ion, a divalent metal ion, A valent metal ion or ammonium salt, B is a group represented by [Formula] or [Formula] (wherein R ⁸ is a hydrogen atom or an alkyl group, and l is 0 or a positive integer of 10 or less) , R ⁷ is a hydrogen atom or an alkyl group, and X is a halogen atom.) A heterocyclic compound optionally substituted with General formula, characterized in that the reaction is carried out in the presence of at least one selected catalyst. (However, R ¹ , R ² , R ³ , R ⁴ and Ar are the same as above.) A method for producing an N-substituted amide.