MXPA00002257A - Process for the preparation of 2-aryl-5-(perfluoroalkyl) pyrrole compounds from n-[1-chloro-1-(perfluoroalkyl) methyl]arylimidoyl chloride compounds - Google Patents

Abstract

There is provided a process for the preparation of 2-aryl-5-(perfluoroalkyl)pyrrole compounds of formula I from N-Ä1-chloro-1-(perfluoroalkyl)methylÜarylimidoyl chloride compounds. The 2-aryl-5-(perfluoroalkyl) pyrrole compounds are useful for the control of insect and acarid pests, and may also be used to prepare other pesticidal arylpyrrole compounds. In addition, the present invention provides compounds which are useful as intermediates in the preparation of arylpyrrole compounds.

Description

PROCESS FOR THE PREPARATION OF 2-ARIL- 5- (PERFLÜORO-ALQÜIL) COMPOUNDS PIRROL OF N- [1-CHLORO-1- (PERFLUOROALKAL) - METHYL] ARILIMIDOILO CHLORIDE COMPOUNDS Field of the Invention Compounds 2- aryl-5- (perfluoroalkyl) pyrrole are useful as insecticidal and acaricidal agents. In addition, these compounds are also useful for the preparation of other insecticidal and acaricidal agents. In particular, the 2-aryl-5- (perfluoroalkyl) pyrrole compounds are key intermediates for the preparation of arylpyrrole compounds such as, for example, chlorfenapyr. Accordingly, there is research to discover new methods for the preparation of 2-aryl-5- (perfluoroalkyl) pyrrole compounds.

BACKGROUND OF THE INVENTION The prior art discloses that the compounds of 2-aryl-5- (trifluoromethyl) pyrrole can be prepared by reacting a N- (benzyl-substituted-2,2-, 2, 2-trifluoro-acetimidoyl chloride compound. with a nitrile, ester or nitro compound REF .: 32800 a-halo-a, ß-unsaturated in the presence of a base. However, the prior art process is not completely satisfactory because the nitrile, ester or nitro α-halo-α, β-unsaturated compound is prepared in a two step halogenation / dehydrohalogenation process. The prior art also discloses that the 2-aryl-5- (trifluoromethyl) pyrrole compounds can be obtained in several steps from the suitable aldehyde. These processes require the use of an aminonitrile intermediate which is obtained by means of the Strec er synthesis of the appropriate aldehyde. However, the use of the Strecker synthesis is not completely satisfactory due to the waste streams containing cyanide. Therefore, it is an object of the present invention to provide a novel process for the preparation of 2-aryl-5- (perfluoroalkyl) pyrrole compounds which avoids the use of nitrile, ester or nitro a-halo-a, β-no saturated and the synthesis of Strecker. It is also an object of this invention to provide a novel process for the preparation of arylpyrrole compounds such as, for example, chlorfenapyr. Another objective of the present invention is to provide intermediate compounds that are useful for the processes described hereinafter. These and other objects of the present invention will be obvious by taking the detailed description below.

Description of the Invention The present invention provides a novel process for the preparation of 2-aryl-5- (perfluoroalkyl) pyrrole compounds having the following structural formula I: (I) where e s h i drógeno or CmF2 m +?; Y e s CN, N02 or C02R; R is C? -C alkyl; m and n are each independently an integer of 1, 2, 3, 4, 5, 6, 7, or 8; L is hydrogen or halogen; M and Q are independently hydrogen, halogen, CN, N02, C? -C4 alkyl, C? -C haloalkyl, Ci-C4 alkoxy, Cx-C4 haloalkoxy, C? -C4 alkylthio, C? -C4 haloalkylthio, alkylsulfinyl C ? -C4, haloalkylsulfinyl C? ~ C4, alkylsulfonyl C? ~ C, haloalkylsulfonyl C1-C4, or when M and Q are in the adjacent positions can be taken together with the carbon atoms to which they are attached to form a ring where MQ represents the structure -OCH20-, -0CF20- or -CH = CH-CH = CH; Ri, R2 and R3 are each independently hydrogen, halogen, N02, CHO or R2 and R3 can be taken together with the atoms to which they are attached to form a ring where R2R3 is represented by the structure: -c = c-c = c- R4, R5, Re and R7 are each independently hydrogen, halogen, CN or N02; and X is O or S; which process comprises reacting a N- [1-chloro-l- (perfluoroalkyl) met il] arylimidoyl chloride compound having the structural formula II (II) where A and n are as described above with a dienophile compound having the structural formula III (III) where W and Y are as described above and a base in the presence of a solvent.

The present invention also provides novel compounds having the structural formulas II, IV and V (II) (IV) (V) where n and A are as we describe here above.

Detailed Description of the Invention The process of the "present invention" • - + - ***** preferably comprises reacting a N- [1-chloro-1- (perfluoroalkyl) -methyl] arylimidoyl chloride compound of the formula II with at least about one. molar equivalent, preferably between about one and four molar equivalents, of a dienophile compound of formula III and at least about one molar equivalent, preferably between about one and four molar equivalents, of a base in the presence of a solvent preferably , at a temperature within a range between about 5 ° C and 100 ° C to form the 2-aryl-5- (perfluoro-alkyl) pyrrole compounds of the formula I. Alternatively, the compounds of the formula I are they can be prepared by forming the dienophile compounds of formula III in situ. This process comprises reacting a N- [1-chloro-1- (perfluoroalkyl) met yl] arylimidoyl compound of the formula II with preferably between about one to four molar equivalents of a substituted haloethane compound having the structural formula VI Z Y I I HC-CH-IIWH (VI) where Y and Y are as described above and Z is Cl, Br or I, and at least about two molar equivalents, preferably between about two to five molar equivalents, of a base in the presence of a solvent preferably within a temperature range between 5 ° C to 100 ° C to form the 2-aryl-5- (perfluoro-alkyl) pyrrole compounds of the formula I. Advantageously, the present invention provides novel processes for the preparation of 2-aryl-5- (perfluoro-alkyl) pyrrole compounds which avoid the use of the nitrile, ester or nitro α-halo-α, β-unsaturated compounds and the Strecker synthesis. The compounds of the formula I of this invention can be isolated by means of conventional procedures such as, for example, dilution of the reaction mixture with water and filtration or, alternatively, extraction with a suitable solvent. Suitable extraction solvents include water immiscible solvents such as ether, ethyl acetate, toluene, methylene chloride and the like.

Suitable bases for use in this invention include tri- (alkyl Ci-C) amines such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine and the like; alkali metal carbonates such as, for example, potassium carbonate and sodium carbonate; alkali metal hydroxide such as, for example, potassium hydroxide and sodium hydroxide; alkali metal acetates such as, for example, potassium acetate and sodium acetate; and heterocyclic tertiary amines including, but not limited to 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU); 1/5-diaza-bicyclo [4.3.0] non-5-ene (DBN); 1,4-diazabicyclo [2.2.2] -octane; pyridine; substituted pyridines such as, for example, 2,6-dimethylpyridine, 2-methylpyridine, 3-met ilpyridine, 4-met ilpyridine and the like; quinoline; and substituted quinolines. Preferred bases include tri- (C 1 -C 6 alkyl) -amines, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1/5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo t 2.2.2] -octane, potassium carbonate and sodium carbonate. Solvents suitable for use in the present invention include, but are not limited to, carboxylic acid amides, such as, for example, N, N-dimethylformamide, N, N-dimethylacetamide, and the like; N-substituted pyrrolidinones such as, for example, N-methyl-pyrrolidinone and the like; nitriles such as, for example, acetonitrile, propionitrile and the like; halogenated hydrocarbons such as, for example, methylene chloride, chloroform, carbon tetrachloride and the like; ethers such as, for example, tetrahydrofuran, dioxane and the like; sulfoxides such as, for example, dimethyl sulfoxide and the like; and its mixtures. Preferred solvents include the carboxylic acid amides and nitriles and mixtures thereof. Preferred solvents include the carboxylic acid amides and nitriles and mixtures thereof. N is especially preferred, N-dimethylformamide and acetonitrile and mixtures thereof, for use in the present invention. The halogen examples mentioned hereinabove are fluorine, chlorine, bromine and iodine. The terms "haloalkyl C? -C4", "haloalkoxy C? -C4", "haloalkylthio C? -C4", "haloalkylsul finyl Cx-C4" and "haloalkylsulfonyl C? -C4" are defined as a C? Alkyl group? C4, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, or C 1 -C 4 alkylsulfonyl, substituted with one or more halogen atoms, respectively. The present invention is especially useful for the preparation of the compounds of formula I where hydrogen is; And it's CN; n is 1 or 2; L is hydrogen or halogen; and M and Q are each independently hydrogen, halogen, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy. In particular, the present invention is useful for the preparation of: 2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-Searbonitrile; 2- (p-bromophenyl) -5-trifluoromethyl) pyrrole-Searbonitrile; 2- (3,5-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 2- (3,4,5-trichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; and 2- [4- (trifluoromethyl) phenyl] -5- (trifluoromethyl) pyrrole-3-carbonitrile, among others. The present invention also relates to the N- [1-chloro-1- (perfluoroalkyl) met yl] -arylimidoyl compounds having the structural formula II (II) where n is an integer of 1, 2, 3, 4, 5, 6, 7 or 8; L is hydrogen or halogen; M and Q are independently hydrogen, halogen, CN, N02, C? -C4 alkyl, C? -C4 haloalkyl, CX-C4 alkoxy, C? -C4 haloalkoxy, C1-C4 alkylthio, C? -C4 haloalkylthio, alkylsulfinyl C? ~ C4, haloalkylsulfinyl C? ~ C4, alkylsulfonyl C1-C4, haloalkylsulfonyl C? -C4, or when M and Q are in the adjacent positions can be taken together with the carbon atoms to which they are attached to form a ring where MQ represents the structure -OCH20-, -OCF20- or -CH = CH-CH = CH; Ri, R2 and R3 are each independently hydrogen, halogen, N02, CHO or R2 and R3 can be taken together with the atoms to which they are attached to form a ring where R2R3 is represented by the structure: R4, R5, R6 and R are each independently hydrogen, halogen, CN or N02; and X is 0 or S. Preferred compounds of formula II of this invention are those where: n is 1 or 2; L is hydrogen or halogen; and M and Q are each independently halogen, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy. Compounds of formula II which are particularly useful in the processes of this invention include N- [1-chloro- (2,2,2-trifluoroethyl)] -4-chlorobenzimidoyl chloride; N- [1-Chloro- (2, 2, 2-trifluoroethyl)] -4-bromobenzimidoyl chloride; N- [1-Chloro- (2, 2, 2-trifluoroethyl)] -3,5-dichlorobenzimidoyl chloride; N- [1-chloro- (2, 2, 2-trifluoroethyl)] -3,5,5-t-ricloro-benzimidoyl chloride; and N- [1-chloro- (2, 2, 2-trifluoroethyl)] -4- (trifluoromethyl) -benzimidoyl chloride, among others. The starting compounds of N- [l-chloro-1- (perfluoroalkyl) met yl] -arylimidoyl chloride of the formula II can be prepared as illustrated in Flow Diagram I by reacting an arylamide compound having the structural formula VII with a C 1 -C 7 hemiacetal alkyl (perfluoroalkyl) aldehyde compound having the structural formula VIII to form a N- [1-hydroxy-1- (perfluoroalkyl) et il] arylamide compound having the structural formula IV; and reacting the compound of formula IV with a phosphorus pentachloride.

FLOW DIAGRAM I (alkyl C? -C6) (VIII) (IV) PCI, Cl Cl X NX nF2n + l (ID Alternatively, the N- [1-chloro-l- (perfluoroalkyl) -methyl] aryl idolo chloride compounds of the formula II can be prepared, as illustrated in Flow Diagram II, by reacting an N- [1-] hydroxy-1- (perfluoroalkyl) methyl] -arylamide of the formula IV with phosphorus trichloride to form a compound N- [1-chloro-1- (perfluoroalkyl) met il] -arylamide having the structural formula V, and reacting to the compound of formula V with phosphorus pentachloride.

FLOW DIAGRAM II (IV) PCI, (V) PCI, (II) The present invention also relates to the compounds of the formula IV and V which are used to prepare the compounds of the formula II. In particular, the present invention provides N- [1-hydroxy-1- (perfluoroalkyl) methyl compounds} arylamide having the structural formula IV and the N- [1-chloro-l- (perfluoroalkyl) met il] -aryl amide compounds having the structural formula V (IV) (V) where n is an integer of 1, 2, 3, 4, 5, 6, 7 or 8 L is hydrogen or halogen; M and Q are independently hydrogen, halogen, CN, N02, C? -C4 alkyl, C? -C4 haloalkyl, Ci-C4 alkoxy, C? -C4 haloalkoxy, C? -C4 alkylthio, C? -C haloalkyl, alkylsulfinyl C? ~ C4, haloalkylsulfinyl Ci-C, alkylsulfonyl C? ~ C, haloalkylsulfonyl C1-C4, or when M and Q are in adjacent positions can be taken together with the carbon atoms to which they are attached to form a ring where MQ represents the structure -OCH20-, -OCF20- or -CH = CH-CH = CH; Ri, R2 and R3 are each independently hydrogen, halogen, N02, CHO or R2 and R3 can be taken together with the atoms to which they are attached to form a ring where R2R3 is represented by the structure: R4, R5, R6 and R7 are each independently hydrogen, halogen, CN or N02; and X is 0 or S. The preferred compounds of formula IV and V of this invention are those wherein n is 1 or 2; L is hydrogen or halogen; and M and Q are each independently halogen, haloalkyl of C? -C4 or haloalkoxy C? -C4. Compounds of the formula IV which are particularly useful for the preparation of the arylpyrrole compounds include: N- (1-hydroxy-2,2,2-t-trifluoroethyl) -4-chlorobenzamide; N- (1-hydroxy-2,2,2-t-trifluoroethyl) -4-bromobenzamide; N- (1-hydroxy-2,2,2,2-trifluoroethyl) -3,5-dichlorobenzamide; N- (1-hydroxy-2,2,2-t-rifluoroethyl) -3,4,5-trichloro-benzamy; and N- (1-hydroxy-2, 2, 2-t ri f1uoroet i 1) -4- (trifluoromethyl) -benzamide, among others. The compounds of the formula V which are particularly useful for the preparation of the arylpyrrole compounds include: N- (1-chloro-2,2,2-trifluoroethyl) -4-chlorobenzamide; N- (1-chloro-2,2,2-trifluoroethyl) -4-bromobenzamide; N- (1-chloro-2,2,2-t-trifluoroethyl) -3,5-di chlorobenzamide; N- (1-chloro-2,2,2-trifluoroethyl) -3,4,5-trichloro-benzamide; and N- (1-chloro-2,2,2-trifluoroethyl) -4- (trifluoromethyl) -benzamide, among others. The compounds of formula I are useful for the control of insect pests and acarids. In addition, the compounds of the formula I can be used to prepare other insecticidal and acaricidal agents of arylpyrrole having the formula structure IX: J (IX) where Y is CN, N02 or C02R; R is C 1 -C 4 alkyl; n is an integer of 1, 2, 3, 4, 5, 6, 7, or 8; L is hydrogen or halogen; M and Q are independently hydrogen, halogen, CN, N02, d-C4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, haloalkylsulfinyl Ci-C4, alkylsulfonyl C1-C4, haloalkylsulfonyl C1-C4, or when M and Q are in the adjacent positions can be taken together with the carbon atoms to which they are attached to form a ring where MQ represents the structure -0CH20- , -0CF20- or -CH = CH-CH = CH; Ri, R2 and R3 are each independently hydrogen, halogen, N02, CHO or R2 and R3 can be taken together with the atoms to which they are attached to form a ring where R2R3 is represented by the structure: ? 4? S? ? 7 -c = c-c = c- R4, R5, R6 and R are each independently hydrogen, halogen, CN or N02; and X is 0 or S. Hal is a halogen atom; and J is hydrogen or Ci-Cβ alkoxymethyl. The present invention is especially useful for the preparation of arylpyrrole compounds of the formula IX wherein Y is CN; n is 1 or 2; L is hydrogen or halogen; M and Q are each independently hydrogen, halogen, haloalkyl of C? -C4 or haloalkoxy of C? -C4; Hal is Br or Cl; and J is hydrogen or ethoxymethyl. In particular, the present invention is useful for the preparation of arylpyrrole compounds of the formula IX such as, for example, -bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3- carbonitrile, (chlorfenapyr); 4-bromo- 2- (3,5-dichlorophenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 4-bromo-2- (3,5-dichlorophenyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile; and 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, among others. Advantageously, the arylpyrrole compounds of the formula IX can be prepared by means of a process comprising: (a) reacting a N- [l-chloro-1- (perfluoroalkyl) -methylaminimidoyl chloride compound of the formula II with a dienophile compound having the structural formula X: (X) where Y is as described above and a base in the presence of a solvent to form a 2-aryl-5- (perfluoro-alkyl) pyrrole compound having the structural formula XI (b) halogenating the compound of the formula XI to form the arylpyrrole compound of the formula IX wherein J is hydrogen; and (c) optionally alkoxymethylating the compound of the formula IX wherein J is hydrogen to form the arylpyrrole compound of the formula IX wherein J is Ci-Cβ alkoxymethyl.

Alternatively, the arylpyrrole compounds of the formula IX can be prepared by means of a process comprising: (a) reacting a N- [1-chloro-l- (perfluoroalkyl) -methyl] arylimidoyl chloride compound of the formula II with a substituted haloethane compound having the structural formula XII Z Y I I HC-CH I I H H (XII) where Y is as described above and Z is Cl, Br, or I, and at least about two molar equivalents of a base in the presence of a solvent to form a 2-aryl-5- (perfluoroalkyl) pyrrole compound having the structural formula XI H (XI) (b) halogenating the compound of the formula XI to form the arylpyrrole compound of the formula IX wherein J is hydrogen; (c) optionally alkoxymethylating the compound of the formula IX wherein J is hydrogen to form the arylpyrrole compound of the formula IX wherein J is Ci-Cβ alkoxymethyl. Halogenation methods may be any of the known methods such as, for example, those described in U.S. Patent No. 5,010,098 and U.S. Patent No. 5,449,789. Suitable alkoxymethylation procedures for use in this invention. they include conventional procedures known in the art (see for example, U.S. Patent No. 5,010,098 and U.S. Patent No. 5,359,090). In a preferred embodiment of this invention, the alkoxymethyllation process comprises reacting a compound of the formula IX wherein J is hydrogen with a compound of di- (C 1 -C 6 alkoxy) methane, N, N-dimethylformamide and phosphorus oxychloride in the presence of an aprotic solvent to form the reaction mixture and treat the reaction mixture with a tertiary amine.

To facilitate the best understanding of this invention, the following examples are presented primarily for the purpose of illustrating their more specific details. The scope of the invention should not be limited by the examples, but includes the entire subject defined in the claims.

EXAMPLE 1 Preparation of N- (l-hydroxy-2.2.2-trifluoroethyl) -4-chlorobenzamide A solution of 4-chlorobenzamide (22.0 g, 0.141 mol) and trifluoroacetaldehyde ethyl hemiacetal (25.0 g as such, 22.5 g real, 0.156 mol) in dioxane (100 ml) was treated with anhydrous sodium sulfate (10 g, to dry 10% water in the hemiacetal) and refluxed for 60 hours. The solids were filtered and the filtrate was evaporated to a solid. The solids were dissolved in about 100 ml of 15% ethyl acetate in heptane. The unreacted starting material (5.6 g) was crystallized and filtered. The title product was obtained from the mother liquors as a white crystalline solid (22.1 g, 82.9% based on the recovery of the starting material): m.p. 139.5-140.5 ° C; characterized by XH and 19F NMR and Mass Spectrum. XH NMR (DMS0-d6) d 9.45 (d, J = 8.7 Hz, NH), 7.93, 7.54 (AB with fine division, J = 8.4 Hz, ArH), 7.54 (broad s, OH), 5.90 (m, J = 8.7, 2.9, 5.8 Hz, CH); 19F NMR d -80.3 (d, J = 5 Hz). Following essentially the same procedure, but using the suitably substituted benzamide, the following compounds were obtained: M p.f. ° C Cl H Cl 152.5 - 153 H Br H 148-148, 5 H CF3 H 124-124.5 EXAMPLE 2 Preparation of N-ri-chlorobenzoimidoyl chloride (2.2 r 2- trifluoroethyl)] -4-chlorobenzimidoyl METHOD A A mixture of N- (1-hydroxy-2,2,2-trifluoroethyl) -4-chlorobenzamide (22.1 g, 0.087 mol) in phosphorus oxychloride (8 ml) was treated with phosphorus pentachloride (40.0 g) 0.192 mol), heated and maintained at 100 ° C for 15-20 minutes, cooled and concentrated in vacuo to obtain a residue. The residue was distilled to give the title product as a clear liquid (22.2 g, 87.8% yield): bp 77-78 ° C (0.1 mm); characterized by IR; XH and 19F NMR, and Mass Spectrum. XH NMR (CDC16) d 8.06, 7.44 (d with fine division, J = 8.9 Hz, ArH), .92 (q, J = 4.9 Hz, CH); 19F NMR d - 77.9 (d, J = 5 Hz METHOD B A mixture of N- (1-hydroxy-2,2,2-trifluoroethyl) -4-chlorobenzamide (16.3 g, 0.064 mol) in phosphorus oxychloride (10 ml) was treated with phosphorus trichloride (9.3 g, 0.675 mol) and heated and maintained at 80 ° C for 15-20 minutes. 19 F NMR shows a clear and complete conversion in N- (1-chloro-2,2,2-trifluoroethyl) -4-chlorobenzamide. The reaction mixture was then cooled to room temperature, treated with phosphorus pentachloride (28.0 g, 0.135 mol) and heated and maintained at 100 ° C for 1 hour. The phosphorus oxychloride was then removed in vacuo and the resulting residue was distilled in vacuo to give the title product as a clear liquid (18.5 g, 100% yield): bp 94-96 ° C (0.5 mm) ). Following essentially the same procedure as described in Method A, but using the N- (1-hydroxy-2, 2, 2-trifluoroethyl) -4-benzamide suitably substituted, the following compounds were obtained: M Q b £ Cl H Cl 114 ° C (0.3 mm) H Br H 95-96 ° C (0.07 mm) H CF3 H Waxy solid EXAMPLE 3 Preparation of 2- (p-chloro-nyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile A solution of N- [1-chloro- (2,2,2-trifluoroethyl)] -4-chlorobenzimidoyl chloride (5.80 g, 0.02 mol) and acrylonitrile (1.33 g, 0.025 mol) in N , N-dimethylformamide (15 ml) was treated with 1,8-diazabicyclo- [5.4.0] ndec-7-ene (DBU, 8.53 g, 0.056 mol) for 1 hour while maintaining the temperature at 45-50 ° C. The reaction mixture was then stirred at 50 ° C for 4 hours, warmed with dilute HCl, and extracted with ethyl acetate. The organic extract was concentrated in vacuo to obtain a residue. The flash chromatography of the residue on the silica gel was packed and eluted with 20% ethyl acetate in heptane, and the crystallization of heptane and small amount of ethyl acetate gives the title product as a white crystalline solid. (2.1 g, 38.9% yield): P.F. 239-240 ° C (dec). Following essentially the same procedure, but using N- [1-chloro- (2, 2, 2-trifluoroethyl)] benzimidoyl chloride, the following compounds were obtained: M Q .. E ^ Cl H Cl 236.5 - 237 H Br H 248 - 249 H CF3 H 216.5 - 218.5 EXAMPLE 4 Preparation of methyl 2- (4-chlorophenyl) -5- (trifluoromethyl) pyrrolo-3-carboxylate A solution of N- [1-chloro- (2,2,2-trifluoroethyl)] -4-chlorobenzimidoyl chloride (3.40 g, 0.012 mol) and methyl acrylate (1.26 g, 0.015 mol) in N , N-dimethylformamide (10 ml) was treated with 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, 5.0 g, 0.033 mol) for 1 hour. The reaction mixture was then kept at 60 ° C for 15 minutes, warmed with dilute HCl, and extracted with ethyl acetate. The organic extract was concentrated in vacuo to obtain a residue. Flash chromatography of the residue on silica gel, packed and eluted with 20% ethyl acetate in heptane, and crystallization from heptane gave the title product as a yellow solid (0.95 g, 25% yield) which was identified by spectral analysis 1H and 19F NMR. EXAMPLE 5 Preparation of 4-bromo-2- (4-chlorophenyl) -5- (tri-fluoroornethyl) pyrrole-3-carbonitrile Br, A solution of N- [1-chloro- (2, 2, 2-trifluoroethyl)] -4-chlorobenzimidoyl chloride (5.80 g, 0.02 mol) and acetonitrile (1.33 g, 0.025 mol) in N, N-dimethylformamide (15 ml) under a nitrogen atmosphere was treated with N, N-diisopropylethylamine (DIPEA, 7.8 g, 0.06 mol) for 30 minutes, heated and maintained at a temperature of 45 g. -47 ° C for 18 hours, cooled to room temperature, treated with bromine (3.2 g, 0.02 mol), stirred at room temperature for 1 hour, warmed with water, and extracted with ethyl acetate . The organic extract was concentrated in vacuo to obtain a residue. Flash column chromatography of the residue on silica gel, packed and eluted with 20% ethyl acetate in heptaho, gave the title product as a white solid (1.6 g, 22.9% yield) which was identified by means of the XH and 19F NMR spectral analyzes. EXAMPLE 6 Preparation of N- (1-chloro-2,2,2-trifluoro-ethyl) -4-chlorobenzamide A mixture of N- (1-hydroxy-2,2,2-trifluoroethyl) -4-chlorobenzamide (2.53 g, 0.01 mol) in phosphorus oxychloride (2 ml) was treated with phosphorus trichloride (1, 57 g, 0.012 mol), heated and maintained at 80 ° C for 30 minutes, and concentrated in vacuo to obtain a residue. The residue was dissolved in hot heptane, decanted from the waxy phosphorus products, and crystallized to give the title product as a white crystalline solid (2.43 g, 89.3% yield): P.F. 119.0-121.0 ° C; IR (Nujol) 3266, 1668 cm-1; XH NMR (CDC13) d 7.76 and 7.46 (AB with fine division, ArH), 6.86 (d, J = 8.5 Hz, NH, moves to 10.24 in DMSO-d6), 6 55 (m, CH); 19F NMR d-77.7 (d, J = 5 Hz). Following essentially the same procedure, but using the suitably substituted N- (1-hydroxy-2, 2, 2-trifluoroethyl) benzamide, the following compounds were obtained: L M Q P. F: ° C Cl H Cl 163.5-164 H Br, H 135-136.5 H CF3 H 122.5-123.5 It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the description as above, property is claimed as contained in the following:

Claims (11)

1. A compound that has the formula II, IV or (II) (IV) O (V) where n is an integer between 1 and 8 inclusive; L is hydrogen or halogen; M and Q are independently hydrogen, halogen, CN, N02, C1-C4 alkyl, C1-C4 haloalkyl, CX-C4 alkoxy, C1-C4 haloalkoxy, CX-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, haloalkylsulfinyl C ? C4, C? -C alkylsulfonyl, C? -C4 haloalkylsulfonyl, or when M and Q are in the adjacent positions can be taken together with the carbon atoms to which they are attached to form a ring where MQ represents the structure -OCH20 -, -OCF20- or -CH = CH-CH = CH; Ri, R2 and R3 are each independently hydrogen, halogen, N02, CHO or R2 and R3 can be taken together with the atoms to which they are attached to form a ring where R2R3 is represented by the structure: R4, R5, Re and R7 are each independently hydrogen, halogen, CN or N02; and X is 0 or S.

2. The compound according to claim 1 selected from the group consisting of: N- [1-Chloro- (2, 2 > 2-trifluoroethyl)] -4-chlorobenzimidoyl chloride; N- [1-chloro- (2, 2, 2-trifluoroethyl)] -4-bromobenzimidoyl chloride; N- [1-chloro-] chloride. { 2, 2, 2-trifluoroethyl)] -3,5-dichloro-benzimidoyl; N- [1-chloro- (2, 2, 2-trifluoroethyl)] -3,4,5-trichloro-benzimidoyl chloride; N- [1-Chloro- (2, 2, 2-trifluoroethyl) chloride} -4- (trifluoromethyl) -benzimidoyl; N- (1-hydroxy-2,2,2,2-trifluoroethyl) -4-chlorobenzamide; N- (1-hydroxy-2,2,2-t-trifluoroethyl) -4-bromobenzamide; N- (1-hydroxy-2,2,2,2-trifluoroethyl) -3,5-dichlorobenzamide; N- (1-hydroxy-2,2,2-t-trifluoroethyl) -3,4,5-trichlorobenzamide; N- (1-hydroxy-2,2,2-trifluoroethyl) -4- (trifluoromethyl) -benzamide; N- (1-chloro-2,2,2,2-trifluoroethyl) -4-chlorobenzamide; N- (1-chloro-2,2,2,2-trifluoroethyl) -4-bromobenzamide; N- (1-chloro-2,2, 2-1 ri fluoroet i 1) -3,5-dichlorobenzamide; N- (1-chloro-2,2,2,2-trifluoroethyl) -3,4,5-trichloro-benzamide; and N- (1-chloro-2,2,2-trifluoroethyl) -4- (trifluoromethyl) -benzamide.

3. A process for the preparation of an N- [1-chloro-l- (perfluoroalkyl) methyl] arylimidoyl chloride compound of claim 1 having the formula II (II) whose process is characterized in that it comprises reacting: a N- [1-hydroxy-l- (perfluoroalkyl) met il] arylamide compound having the formula IV (IV) Or an N- [l-chloro-l- (perfluoroalkyl) methyl] arylamide having the formula V (V) with phosphorus pentachloride, where n and A are as described above.

4. A process for the preparation of a 2-aryl-5- (perfluoroalkyl) pyrrole compound having the formula I and w? N CnF2n + l I H (I) where W is hydrogen or CmF2m + ?; And it is CN, N02 or C02R; R is C 1 -C 4 alkyl; m and n are each independently an integer between 1 and 8 inclusive; Y A is as described above, whose process is characterized in that it comprises reacting a N- [l-chloro-1- (perfluoroalkyl) ethyl] arylimidoyl chloride compound of claim 1 having the formula II (II) wherein A and n are as described above, with a dienophilic compound or a compound of substituted haloethane, and a base, in the presence of a solvent, the dienophile compound has the formula III and the substituted haloethane has the formula VI (III) (VI) where W and Y are as described above, and Z is Cl, Br or I. The process according to claim 4, characterized in that the base is selected from the group consisting of a tri- (alkyl C? Cß) amine, an alkali metal carbonate and a heterocyclic tertiary amine. 6. The process according to claim 4, characterized in that the solvent is selected from the group consisting of a carboxylic acid amide and a nitrile, and mixtures thereof. 7. The process according to claim 4, characterized in that the dienophile is between one and four molar equivalents and the base is between about one to four molar equivalents. The process according to claim 4, characterized in that the substituted haloethane compound is between about one to four molar equivalents and the base is present in an amount between about two to five molar equivalents. 9. The compound of claim 1 or the process according to claim 3, characterized in that n is 1 or 2; L is hydrogen or halogen; and M and Q are each independently hydrogen, halogen, C? -C4 haloalkyl or C? -C4 haloalkoxy; or the process according to claim 4 wherein it is hydrogen; And it's CN; N is 1 or 2; L is hydrogen or halogen; and M and Q are each independently hydrogen, halogen, C1-C4 haloalkyl or C? -C4 haloalkoxy. 10. A process for the preparation of an arylpyrrole compound having the formula IX J (IX) where Y is CN, N02 or C02R; R is C? -C4 alkyl; n and A are as described above; Hal is a halogen atom; and J is hydrogen or Ci-Ce alkoxymethyl, which process characterized in that it comprises: (a) reacting an N- [1-chloro-l- (perfluoroalkyl) -methyl] arylimidoyl chloride compound of claim 1 having the formula II (II) where A and n are as described above, with a dienophile compound or a substituted haloethane compound, and a base, in the presence of a solvent, the dienophile compound having the formula X and the substituted haloethane compound having the formula XII Z Y I I HC-CH or I I H H (X) (XII) where Y is as described above, and Z is Cl, Br or I, to form a 2-aryl-5- (perfluoroalkyl) pyrrole compound having the formula XI H (XI) (b) halogenating the compound of the formula XI to form an arylpyrrole compound of the formula IX wherein J is hydrogen; and (c) optionally alkoxymethylating to the compound of formula IX. The process according to claim 10 wherein step (c) is characterized in that it comprises reacting said compound of formula IX with a compound of di- (C 1 -C 6 alkoxy) methane, N, N-dimethylformamide and phosphorus oxychloride in the presence of an aprotic solvent to form a reaction mixture, and treat the reaction mixture with a tertiary amine.