Title of Invention	"N1- ((PYRAZOL-1-YMETHYL)-2-METHYLPHENYL)-PHATALAMIDE DERIVATIVES OF FORMULA (I)
Abstract	Nl-(pyrazol-l-ymethyl)-2-methylphenyl)-phatalamide derivatives of the formula (I) wherein X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-4alkylsulfonyloxy, C1-4alkylsulfinyl,C1-4alkylsulfenyl or C1-4 alkylsulfonyl, R1 represents C1-4alkyl, C1-4alkylthio-C1-4alkyl, C1-4alkylsulfinyl-C1-4alkyl or C1-4alkylsulfonyl-C1-4alkyl, Y represents fluorine, chlorine, bromine or C1-4alkyl, m represents 1, A represents CH2 or CH(CH3), and Q represents 5-membered or 6-membered heterocyclic group containing one to three N-atoms and which heterocyclic group can be optionally substituted by at least one selected from a group consisting of C1-6alkyl, C1-6alkoxy, C1-6alkylthio, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-10haloalkyl, C1-6haloalkoxy, C1--6haloalkylthio, C1-6haloalkylsulfinyl, C1-6haloalkylsulfonyl, C1-6haloalkylcarbonyl, halogen, oxo and hydroxy.

Title of Invention

"N1- ((PYRAZOL-1-YMETHYL)-2-METHYLPHENYL)-PHATALAMIDE DERIVATIVES OF FORMULA (I)

Abstract

Nl-(pyrazol-l-ymethyl)-2-methylphenyl)-phatalamide derivatives of the formula (I) wherein X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-4alkylsulfonyloxy, C1-4alkylsulfinyl,C1-4alkylsulfenyl or C1-4 alkylsulfonyl, R1 represents C1-4alkyl, C1-4alkylthio-C1-4alkyl, C1-4alkylsulfinyl-C1-4alkyl or C1-4alkylsulfonyl-C1-4alkyl, Y represents fluorine, chlorine, bromine or C1-4alkyl, m represents 1, A represents CH2 or CH(CH3), and Q represents 5-membered or 6-membered heterocyclic group containing one to three N-atoms and which heterocyclic group can be optionally substituted by at least one selected from a group consisting of C1-6alkyl, C1-6alkoxy, C1-6alkylthio, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-10haloalkyl, C1-6haloalkoxy, C1--6haloalkylthio, C1-6haloalkylsulfinyl, C1-6haloalkylsulfonyl, C1-6haloalkylcarbonyl, halogen, oxo and hydroxy.

Full Text	• ( (PYRAZOL-l-yMETHYL)-2-METHYIjPHENyL)~ PHATALAMIDE DERIVATIVES AND RELATED COMPOUNDS INSECTICIDES The present invention relates to novel benzenedicarboxamides, processes for the preparation thereof, their intermediates and their use as insecticides. It was akeady known that phthalamide derivatives are useful-as insecticides [see JP-A 11-240857 (1999), JP-A 2001-64258, JP-A 2001-64268, JP-A 2001-131141, JP-A 2003-40864, WO 01/21576 and WO 03/11028], and also that they show medicinal function [see JP-A 59-163353 (1984)]. There have now been found novel benzenedicarboxamides of the formula (T) (Figure Removed) wherein X represents hydrogen, halogen atom, nitro, Ci.6alkylsulfonyloxy, Q-ealkvlsulfinyl, sulfenyl or Ci.6alkylsulfonyl, R1 represents CMalkyl, Ci.6alkylthio-Cwa]]cyl, Ci^alkylsulfinyl-Q-fialkyl or Cw alkylsulfo- Y represents halogen or m represents 0 or 1, A represents O, S, SO, SO2, CH2 or CH(CH3), and Q • represents a 5- or 6-membered heterocyclic group that contains at least one hetero atom selected from the group consisting of N, O and S and can be optionally substituted. The compounds of the formula 0), according to the invention, can be obtained by (a) reacting compounds of the formula (U) wherein R and X have the same definitions as aforementioned, with compounds of the formula (HI) (Figure Removed) wherein Y, A, m and Q have the same definitions as aforementioned, in the presence of inert solvents, and if appropriate in the presence of an acid catalyst, reacting compounds of the formula (IV) (Figure Removed) wherein X, Y, A, m and Q have the same definitions as aforementioned, wilh compounds of the formula (V) H2N-R1 (V) wherein R1 has the same definitions as aforementioned, in the presence of inert solvents, and if appropriate in the presence of an acid catalyst, reacting compounds of the formula (VI) (Figure Removed) wherein X and R1 have the same definitions as aforementioned,, with the compounds of the formula (HT), wherein Y, A, m and Q have the same definitions as aforementioned, in the presence of inert solvents, and if appropriate in the presence of an acid catalyst, reacting compounds of the formula (VTQ (Figure Removed) wherein X, Y, A, m and Q have the same definitions as aforementioned, with the compounds of the formula (V), H2N-R1 (V) wherein R1 has the same definitions as aforementioned, in the presence of inert solvents, and if appropriate in the presence of an acid catalyst, or (e) • compounds of the formula (VET) wherein X, Y, A, m and Q have the same definitions as aforementioned, are reacted with the compounds of the formula (V), H2N-R1 (V) wherein R1 has the same definitions as aforementioned, in the presence of inert solvents, and if appropriate in the presence of an acid catalyst, or (i) in the case that R1 represents C1-6alkylsulfinyl-C1-6allcyl orC1-6alkylsulfonyl-C1-6alkyl in the fonnula (I), reacting compounds of the formula (If) (Figure Removed) wherein RIf represents C1-6alkylthio-C1-6alkyl, and X, Y, A, m and Q have the same definitions as aforementioned, with an oxidizing agent in the presence of inert solvents. According to, the present invention, the benzenedicarboxamides^pf the fonnula (I) show a strong insecticidal action. The compounds of the formula (I) are conceptually embraced in the general formula described in the aforementioned JP-A 11-240857 (1999). But they are not specifically disclosed at all in it and new compounds. Surprisingly, they show particularly remarkable insecticidal -action compared with similar compounds described in the known prior art In the present specification: "Halogen" represents fluorine, chlorine, bromine and iodine., and preferably represents fluorine, chlorine and bromine. "Alky!" represents straight chain or branched chain Chalky!, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. and preferably represents Ci^alkyl. As each alkyl part in "alkylsulfonyloxy", "alkylsulfenyl", "alkylthioalkyl", "alkylsulfinylalkyl", . "alkylsulfonylalkyl", "alkoxy", "alkylthio", "alkylsulfmyr, "alkylsulfonyl", "haloalkyl", "haloalkoxy", "haloalkylthio", "haloalkylsulfinyl", "haloalkylsulfonyl" and "haloalkylcarbonyl", there can be mentioned the same as described in the above-mentioned "alkyl" as examples. As each halogen part in "haloalkyl", "haloalkoxy", "haloalkylthio", "haloalkylsulfinyl"., "haloalkylsulfonyl" and "haloalkylcarbonyl", there can be mentioned the same as described in the above-mentioned "halogen" as examples. "5- or 6-membered heterocyclic group" contains at least one hetero atom selected from the group consisting of N, O and S, and preferably represents a heterocyclic group containing "one to three atoms", or "one O atom", or "one S atom", or "both one S atom and one to two N atoms", or "both one O atom and one to two N atoms", and as specific examples thereof, pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl, furyl, thienyl, oxadiazolyl and pyrimidinyl, and moreover as most preferable examples thereof, pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl, oxadiazolyl and pyrimidinyl are exemplified. In the compounds of the formula (T), according to the invention, the compounds in case that X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, CM alkylsulfonyloxy, C1-6alkylsulfinyl, C1-6alkylsulfenyl or C1-6alkylslfonyl, R1 represents C1-6alky!, C1-6alkylthio-C1-6alkyl, C1-6alkylsulfinyl-C1-6alkyl or C1-6alkylsulfo- Y represents fluorine, chlorine, bromine or CMalkyl, m represents 0 or 1, A represents O, S, SO, S02, CH? or CH(CH3), and Q represents 5-meinbered dr~6-membefed heterocyclic group that contains at least one hetero atom selected from a group consisting of N, 0 and S and can be optionally substituted by at least one selected from a group consisting of C1-6alkyl, C1-6alkoxy, C1-6alkyltbio, C1-6 finyl, C1-6alkylsulfonyl5 C1-60haloalkyl, C1-6haloalkoxy, C1-6haloalkylthio,C1-6haloalkylsulfinyl, C1-6haloalkylsulfonyl, C1-6shaloalkylcarbonyl, halogen, oxo and hydroxy group, • can be mentioned as preferable. Above all, in the compounds of the formula (I), the compounds in case that X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, methanesulfonyloxy, C1-6alllsulfinyl, C1-6alkylsulfenyl or C1-6alkylslfonyl} R1 represents isopropyl, Ci.2alkylthio-C1-64alkyl, C1-6alkylsulfinyl-C1-6alkyl or C1-6alkylsulfonyl- C1-6alkyl, Y represents fluorine, chlorine or methyl, m represents 0 or 1, A represents O, S, SO, SO2s CH2 or CH(CH3), and Q represents heterocyclic group, selected from a group consisting of pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl, oxadiazolyl andpyrimidinyl, that can be optionally substituted by at least one selected from the group consisting of Chalky!, C1-6alkoxy, C1-6alkylthio, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-68haloalkyl, C1-6haloalkoxy, C1-6haloalkylthio, C1-6haloalkylsulfinyl, C1-6aloalkylsulfonyl,C1-6thaloalkylcarbonyl, fluorine, chlorine, bromine, iodine, oxo andhydroxy group, are particularly preferable. The compounds of the'formula (I), according to the present invention, include stereo isomers (R/S configuration) in case that the group R1 has an asymmetric carbon. The aforementioned process (a) can be illustrated by the following reaction scheme, in case that, for example, 3-(l,l-dimethyl-2-mettiylthioemylimino)^-iodo-3H-isoberizofuran-l-one and l-(4-amino-3- methylbenzyl)-3,5-bis (trifluoromethyl)-lH-pyrazole are used as starting materials. SCH3 He.aforementioned preparation process (b) can be illustrated by the following reaction.scheme_in case that, for example, 2-{4-[335-bis (trifluoromethy3)pyrazo]e-l-yknethyl]-2-methylpheny3}-4-fJuoroisoindole- l,3-clione and (S)-l-me'thyl-2-methylthioe'thylamine are used as starting materials. The aforementioned preparation process (c) can be illustrated by the following reaction scheme in case that, for example, 3-iodo-N-(l,l-dimethyl-2-niethylthioethyl)-phthalamic acid and 2-methyl- [l-(3-trifluoromethylpyrazole-l-yl)-ethyl]-aniline are used as starting materials. The aforementioned preparation process (d) can be illustrated by the following reaction scheme in case that, for example, l-[4-(4-iodo-3-oxo-3H4sobenzofuran-l-yHdenearnino)-3-me1hyl-benzyl]-3,5-bis (trifluoromethyl)-( l,2,4)-triazol and l-methyl-2-methylthioethylamine are used as starting materials. SCH, The aforementioned preparation process (e) can be illustrated by the following reaction scheme in case that, for example, N-{4-[3,5-bis (trifluoromemyl)-lH-pyrazoI-l-ylmethyl]-2-mel:hyl-phenyl}-6-iodophthalamic acid and l-methyl-2-methylthioethylamine are used as starting materials. (Figure Removed) SOH, The aforementioned process (f) can be illustrated by the following reaction scheme in case that, for example, N2-(l-memyl-2-memyl1hioefliyl)-3-iodo-NM2-m^ zol-l-ylmethyl]phenyl}prithalamide and m-chloroperbenzoic acid are used as starting materials. SCH3 + m-chloroperbenzoic acid S02CH3 The compounds of the formula (IT)., used as starting materials in the above-mentioned preparation process (a), are per se known compounds and can be easily prepared according to the process described in, for example, JP-A11-240857 (1999), JP-A 2001-131141. As specific examples of the compounds of the formula (DQ, used as starting materials in the preparation process (a), there can be mentioned the following: 3-isopropylimino-3H-isobenzofuran-l-one, 4-fluoro-3-isopropylirrjino-3H-isobenzofuran-l-one, 4-chloro-3 -isopropylimino-3H-isobenzofuran-l -one, 4-bromo-3-isopropylimino-3H-isobenzoruran-l-one, 4-iodo-3-isopropylimin6-3H-isobenzofuran-1 -one, 3-(l-me(hyl-2-memylsulfanyl-ethylirnino)-3H-isobenzofuran-l-one, 4-fluoro-3-(l-memyl-2-memylsiufanyl-emymnmo)-3H-isobenzofuran-l-one, 4~cnl6ro-3-(l-memyl-2- ;" 4-bromo-3-(l -methyl-2-methylsulfanyi-emylimmo)-3H-is6berizofuran-l -one, 4-iodo-3-(l -methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-l -one, 3-(l,l-dimemyl-2-methylsulfanyl-emylirr±io)-3H-isobenzofuran-l-one, 3-(l, 1 -diniethyl-2-methylsulfanyl-etliylimino)-4-f!uoro-3H-isobenzofiiran-l -one -%hloro-3-(l, 1 -dimemyl-2-memylsulfanyl-emyHmino)-3H-isobenzofuran-l -one, 4-bromo-3-(l, 1 -dimemyl-2-memylsulfanyl-emylimino)-3H-isobenzofuran-l -one, 3-(l,lHiime1hyl-2-me1hy]sulfanyl-emylir^ 3-isopropylirnino-l-oxo-l,3-dmydro-isoberizofuran-4-ylmethanesulfonate 3-(l-memyl-2-memylsiilfanyl-emyliinmo)-l-oxo-^ 3-(l,l-dimemyl-2-memylsulfanyl-ethylirn^ rnethanesulfonate and so on. The compounds of the formula (ID), used as starting materials in the above-mentioned preparation process (a), which are partly novel compounds that are not described in the existing literature yet, can be obtained, for example, by reducing compounds of the formula (IX) wherein Y, A, m and Q have the same definitions as aforementioned, according to the catalytic hydrogen reduction process, a well-known process in the field of organic chemistry, with hydrogen in the presence of a catalytic reduction catalyst, for example, palladium carbon, Raney nickel, platinum oxide, etc. The above-mentioned catalytic hydrogen reduction process can be conducted in an adequate diluent As examples of the diluent used in that case there can be mentioned ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, tetrahydrofuran (THF), etc,; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylerie glycol, etc. and as catalytic reduction catalyst there can be mentioned, palladium carbon, Raney nickel, platinum oxide, etc. The reaction can be conducted at the temperatures generally from about 0 to about 100°C, preferably from room temperature (20°C) to about 80°C. Said reaction can be conducted usually under normal pressure but can be operated optionally also under elevated pressure. For example, a compound of the formula (ID) can be obtained by hydrogenating the compounds of the formula (EX) in a diluent, for example, ethanol, in the presence of 0.1-10% (w/w) palladium carbon. Also by a reduction reaction using metals etc. instead of catalytic hydrogen reduction, the compounds of the formula (ID) can be obtained from the compounds of the formula (IX). As. a reduction process using metals, etc., there can be mentioned, for example, a process of reacting iron pdWder in acetic acid, a process of reacting zinc dust under neutral condition (Organic Syntheses Collective Vol. It, p. 447), a process of reacting stannic chloride under acidic condition (Organic Syntheses Collective Vol. n, p. 254), a process of reacting titanium trichloride under neutral condition, etc. The compounds of the formula (K) are novel compounds and can be obtained by reacting the compounds of the formula (DC) wherein A represents other than oxygen atom, for example, compounds of the formula (X) wherein Y and m have the same definitions as aforementioned, A1 represents S, SO, S02, CH2 or CH(CH3), and M represents chlorine, bromine or methanesulfonyloxy, with compounds of the formula (XT) H-Q (XT) wherein Q has the same definition as aforementioned. The compounds of the formula (X), are are well known in the field of organic chemistry and described in publications, for example, Chem. Abstr., Vol. 58, 3444e (1963); Bull. Soc. Chim. Fr. (1934), p. 539-545; J. Chem. Res. Miniprint, Vol. 8 (1987), p. 2133-2139; J. Chem. Soc. B (1967), p. 1154-1158; J. Chem. Soc. (1961), p. 221-222; J. Amer. Chem. Soc., Vol. Ill (1989), p. 5880-5886; J. Amer. Chem. Soc., Vol. 96 (1974), p. 7770-7781; Can. J. Chem., Vol. 68 (1999), p. 1450-1455, Tetrahedron Letter, vol. 35 (1994), p. 7391-7394. As specific examples of the compounds of the formula (X), there can be mentioned specifically 2-methyl-4-nitrobenzyl chloride, 3-methyl-4-nitroben2yl chloride 4-nitrobenzyl methanesulfonate 2-methyl-4-nitroben2yl methanesulfonate 3-methyl-4-nitrobenzyl methanesulfonate, 4-nitrobenzenesulfenyl chloride, 4-nitrobenzenesulfrnyl chloride, 4-nitrobenzenesulfdnyl chloride, 4-nitro-3 -methylbenzenesulfonyl chloride, 3-fiuoro-4-nitrobensyl bromide, i^hloro-4-nitrobenzyl chloride and so on. The nitro-substituted benzoic acids and their esters, starting materials of the compounds of the formula (X), are known compounds described in, for example, Chem. Ber., Vol. 52 (1919), p. 1083; Bull. Soc. Chim. Fr. (1962), p. 2255-2261; Tetrahedron (1985), p. 115-118; Chem. Pharm. Bull, 41 (1993), p. 894-906; WO 2001/042227. The compounds of the formula (XT) include known compounds and as their specific examples., there can be mentioned: 3,5-bis (trifluoromethyl)-lH-pyrazole, 5-difluoromethoxy-3-trifluoromethyl-lH-pyrazole, 4-pentafluoroethyl-lH-pyrazole, 5-hexafluoro-n-propyl-lH-pyrazole, 3,5-bis (trifluoromethyl)-lH-(l,2,4)-triazole, 5-pentafluoroethyl-3-trifluoromethyl-lH-(l,2,4)-triazole, . 5-difluoromethyl-3-trifluoromethyl-lH-(l,2,4)-triazole, 5-hydroxy-3,5-bis (trifluoromethyl)-lH-4,5-dihydropyrazole, 2,4-bis (trifluoromethyl)-lH-imidazole, 3-(2,2,24rifluoroethyl)-5-trifluoromethyl-l, 2-dihydro-(l,3,4)-triazol-2-one, 2,5-bis(trifluoromethyl)-(l,3,4)-triazole, 5-pentafluoroethyl-lH-pyrazole, 3-pentafluoroethyl-lH-pyrazole, 4-brpmo-3-trifIuoromethyl-lH-pyrazole, 3-trifluoromethyl-lH-pyrazole, 5-(difluorome1hyl)-l,2-dihydro-2-methyl-3H-(l,2,4)-triazol-3-one, 4-(trifluoromethyl)-2H-l,2,3-triazole, 4-iodo-3- pentafluoroethyl-lH-pyrazole, 3-pentafluoroethyl-4-(l,l,2,2-tetrafluoroethyl)-lH-pyrazole, 3,4-bis-pentafluoroethyl-lH-pyrazole, 3,5-diiodo-4-methyl-lH-pyrazole, 3 -Heptafluoropropylsulfanyl-5 -trifluoromethyl-1 H-( 1,2,4)-triazole, 3,5-bis(pentafluoroethyl)-lH-(l,,2,4)-triazole and so on. formula (XT) can be conducted in an adequate diluent. A%xamples of the diluent used in that case there can be mentioned, for example, aliphatic, alicyclic anoaromatic hydrocarbons (maybe optionally chlorinated), for example, pentane, hexane, cyclohexarie, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME)5 tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazoh'dinone, hexamethyl phosphoric triamide (BMPA), etc. The reaction can be conducted in the presence of an acid binder and as said acid binder there can be mentioned, for example, as inorganic base, hydrides, hydroxides, carbonates, bicarbonates, etc. of alkali metals or alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide, etc.; as organic base, alcoholates, tertiary amines, dialkylarninoanilines and pyridines, for example," triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniUne, N,N-diethylaniline, pyridine, 4-dimemylarninopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc. The above-mentioned reaction can also be conducted by a process using a phase transfer catalyst in the presence of a diluent. As examples of the diluent used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc. As examples of the phase transfer catalyst, quaternary ions, for example, tetramethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium bissulfate, tetrabutylammonium iodide, trioctylmethylammonium chloride, benz>'ltriethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, benzyltriethylammonium chloride, etc.; crown ethers, for example, dibenzo-lS-crown-6, dicyclohexyl-18-crown-6, 18-crown-6, etc.; cryptands, for example, [2.2.2]-cryptate, [2.1.1]-cryptate, [2.2.1]-cryptate, [2.2.B]-cryptate, [3.2.2]-cryptate, etc. The above-mentioned reaction can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally from about 0 to about 200°C, preferably from room temperature (20°C) to about 150°C. jjphough said reaction is conducted desirably under normal pressure, it can-be operated also under elevated pressure or under reduced pressure. In conducting the above-mentioned reaction, the aimed compounds of the formula (TX) can be obtained, for example, by reacting 1 mole to a little excess mole amount of the compounds of the formula (XT) to 1 mole of the compounds of the formula (X) in a diluent, for example, DMF, in the presence of potassium carbonate. As the compounds of the formula (IX) obtained according to the above-mentioned process, there can be mentioned, for example, the corresponding 4-nitrobenzyl derivatives to the 4-aminobenzyl derivatives of the formula (HI) mentioned hereinafter. And, as one typical example, l-(3-memyl4-nitroben2yl)-3,5-bis-(trifluorornethyl)-lH-pyrazQle can be mentioned. . Furthermore, in a case where Q represents 2-thiazolyl in 'the formula (K), as a specific example, 2-(3-methyl-4T-nitrobenzyl)-4-pentafluoroethyl-thiazole can be prepared by the following way in which a known compound, 3-methyl-4-nitroben2ylcyanide (see J. Chem. Soc., vol. 97 (1910), p. 2260) is reacted with hydrogen sulfide, and then the product, 3-methyl-4-nitro-benzylthioamide is reacted with a commercial product, l-bromo-3,3,4,4,4-pentafluoro-2-butanone and then cyclized, according to a method described in J. Heterocycl. Chem., vol. 28 (1991) p. 907 to 911. In a case where Q represents l,3,4-oxadiazol-2-yl in the formula (IX), as a specific example, 2-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-l,3,4-oxazole can easily be obtained, according to a method described in Heterocycles, (1994), vol. 38, p. 981 to 990, from the corresponding aldoxime as a starting material which can be prepared by a method described in Justus Liebigs Ann. Chem., (1927) vol. 45, p. 166. And, as another specific example, 2-(3-memyl-4-ni1robenzyl)-5-trifluorornethyl-l,3,4-oxazo}e can easily be obtained, according to a method described in Heterocycles, (1994) vol. 38, p. 981 to 990, from the corresponding 3-memyl-4-ni1xobenzaldehyde oxime. In the above preparation, the oxime can be obtained from a known 3-methyl-4-nitrobenzaldehyde [see J. Chem. Soc. B, (1967) p; 1154 to 1158] as a starting material, according to methods described in J. Chem. Soc. C, (1969) p. 986 to 990 and then Tetrahedron Letter, vol. 35 (1994) p. 9099 to 9100. In a case where Q represents 2H-l,2,3-triazol-2-yl in the formula (IX), as a specific example, 2-(3-memyW-m'trobenzyl)-2H-4-trifluoromethyl-l,2,3-triazole can easily be prepared by a reaction of a known 3-methy3-4-nitrobenzyl chloride with a known 2H-4-trifluoromethyl-l,2,3-triazole described in J. Chem. Soc., Perkin Transaction 2, vol. 10 (1989) p. 1355 to 1375. where Q represents lH-l,2,4-triazol-l-yl in the fomnila (K), as a specific example, 5-mefcyl-4-mirophenyIsulfanyl)-l-memyW can easily be prepared by a reaction of lrfluoro-3-memyl-4-nitrobenzene with a known 5-mercapto-l-methyl-3-trifluoromethyl- lH-l,2,4-triazole described in J. Med. Chem., vol. 35 (1992) p. 2103 to 2112, according to the same preparation as Synthesis Example 47 hereinafter. In a case where Q represents l,2,4-oxazol-3-yl in the formula (K), as a specific example, 3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-l,2,4-oxazole can easily be obtained from 3-methyl- 4-nitrobenzamideoxime, according to a method described in J. Qrg. Chem., vol. 68(2), 2003, p. 605-608. And, 3-methyl-4-mtrobenzamideoxime can be prepared by a reaction of a commercial 3-methyl-4-nitrobenzonitrile with hydroxylamine, according to a method described in Chem. Ber., vol. 22 (1889), p. 2428. And, as another specific example, 3-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-l,2,4-oxazole can easily be obtained from 2-(3-methyl-4-nitrophenyl)-acetamideoxime as well, according to a method described in J. Org. Chem., vol. 68(2), 2003, p. 605-608. And, 2-(3-methyl-4-nitrophenyl)- acetamideoxime can be prepared by a reaction of 3-methyl-4-nitrophenyl-acetonitrile with hydroxylamine, according to a method described in Chem. Ber., vol. 22 (1889), p. 2428. In a case where Q represents lH-l,2,4-triazol-3-yl in the formula (IX), as specific examples, l-methyl-3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-lH-l,2,4-triazole can easily be prepared by a reaction of the above 3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-l,2,4-oxazole with methylhydrazine, according to a method described in J. Org. Chem., vol. 68(2), 2003, p. 605 - 608, and also l-methyl-3-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-lH-l,2,4-triazole can be done by a reaction of the above 3-(3-methyl-4-nitrobenzyI)-5-trifluoromethyl-l,2,4-oxazole with methylhydrazine as well. The compounds of the formula (IX) can be prepared, besides the above-mentioned preparation process, also by the process to be mentioned later in Examples as an alternative. As specific examples of the compounds of the formula (IQ) there can be mentioned, for example, the following: l-(4-amino-3-methylbenzyl)-3,5-bis(trifluorornethyl)-lH-pyrazole, l-(4-ainmp-3-memylbenzyl)-5-difluorometh^ 1 -(4-amino-3 -methylbenzyl)-4-pentafiuoroethyl-lH-pyrazole, 1 -(4-amino-3 -methylbenzyl)-5-hexafluoro-n-propyl- IH-pyrazole, l-(4-amino-3-methylbenzyl)-3,5-bis (trifluoromethyI)-lH-(l,2,4)-triazole, l-(4-arnmo-3-memylben2yl)-5-pentafluoroethyl-3-trifluoromethyl-lH-(l,2,4)-tria2ole5 )-5-difl 4-(4-aroino-3-methylben2yl)-5-difluoromethoxy-l-difluoroiriethyl-3-trifluorome 4-(4-amino-3-mefhylbenzyl)-3-difluo l-(4-anmo-3-methylben2yl)-5-h.ydroxy-3, 5-bis (trifluoromethyl)-lH-4,5-dihydropyrazole, l-(4-anuno-3-methylben2yl)-2.,4-bis(trifluoroniethyl)-lH-imidazole, 4 -3-one, 2 azol-3-one, l-(4-amino-3-methylbenzyl)-2.,5-bis (trifluoromeihyljS-triazole, 2-(4-amino-3-methylberi2yl)^,6-bis(trifluoromethyl)-pyrimidine, 2-(4-ammo-3-melhylphenoxy)^56-bis(trifluorome1hyl)-pyrirnidme, l-(4-airuno-3-mefhylph.enyl)-3,5-bis(trifluoroniethyl)-lH-pyrazole, 1 -(4-amino-3 -methylphenyl)-5-pentafluoroe1:hyl- IH-pyrazole, l-(4-arnino-3-methylphenyl)-3-pentafluoroethyl-lH-pyrazole, l-(4-amino-3-methylphenyl)-4-pentafluoroethyl-lH-pyrazole, l-(4-amiao-3-methylphenyl)-3-methyl-5-trifluoromethyl-lH-pyrazole, !-(4-anrino-3-me1hylphenyl)-5-inethyl-3-trifluoromethyl-lH-pyrazoIe3 l-(4-amino-3-mefliylphenyl)-3-pentafluoroeihyl-5-trifluoromethyl-lH-pyrazole, l-(4-amino-3-methylphenyl)-4-bromo-3-trifIuoromethyl-lH-pyrazole, l-(4-airuno-3-methylphenyl)-3-trifluoromet;hyl-lH-pyrazole, l-(4-an±io-3-methylphenyl)-5-hydroxy-3-(2,2,2-trifluoroe1hyl)-5-trifluoromethyl-lH^,^ , pyrazole, 5-(4-amino-3-mefhylphenyl)-l-(2,2,2-1rifluoroethyl)-3-trifluorome1hyl-pyrazole., 5-(4-anrino-3-methylphenyl)-l-difluoromethyl-3-trifluorome1hyl-pyrazole, S^-amino-S-mefhylplieny^-l-difluoroinethyl-S-difluQromethoxy-pyrazole, l-(4-amino-3-methylbenzyl)-3,4-bis (pentafluoroethyl)-lH-pyrazole, 1 -(4-amino-3-methylbenzyl)-3,5-bis (pentafluoroetliyl)-lH-pyrazole, l-(4-amino-3-methylbenzyl)-3,4-bis (pentafluoropropyl)-lH-pyrazole, 1 -(4-amino-3 -me£hylbenzyl)-3,5-bis (pentafluoropropyl)-1 H-pyrazole, l-(4-amino-3-mefhylbenzyl)-3,5-bis(pentafluoroethyl)-lH-(l,2,4)-triazole, l-(4-amino-3-methylbenzyl)-2J5-bis(pentafluoroethyl)-lH-(l,3,4)-triazole, 2-(4-ari±io-3-me1h3'lphenyl)-5-(trifIuoromethyl)-l,3,4-oxadiazole, 2-(4-amino-3-methy]plieny])-5-(pentafluoroethyl)-l,3J4-oxadiazole3 2-(4-amino-3-methylphenyl)-5-(heptafluoropropyl)-l,3,4-oxadiazole, 2-(4-arQino-3-mefhylbenzyl)-5-(trifluoromethyl)-l3354-oxadiazole,> 2-(4rarQino-3-methylbenzyl)-4-(pentafluoroethyl)-thiazole, x rr-3-me1hylphenyl)sulfaiiyl-l-me1iiyl-3-(trifluorome1hyl)-lH-l,2/-triazole3 3-(4-arnino-3-rnethylphenyl)-5-(trifluorornethyl)-l,2,4-oxadiazole5 3-(4-ainino-3-methylphenyl)-l-methyl-5-(trifluorome1:hyl)-lH-l,234-1iiazole, l-(4-amino-3-chlorobenzyl)-3,5-bis (trifluoromethyl)-lH-pyrazole, l-(4-ainino-3-fluoroben2yl)-3,5-bis(trifluorometh.yl)-lH-pyrazole and so on. The compounds of the formula (IV), used as starting materials in the above-mentioned preparation process (b), are novel compounds and can be easily obtained according to the process described in Japanese Laid-open Patent Publication No. 61-246161 (1986), for example, by reacting compounds of the formula (XD) (Figure Removed) wherein X has the same definition as aforementioned, with the compounds of the formula (HI). Y -OH) wherein Y, A, m and Q have the same definitions as aforementioned, The reaction can be conducted in an adequate diluent As the diluent used in that case there can be mentioned, for example, aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (TJ3F), diethylene glycol dimethyl ether (DGM), etc,; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylforrnamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazoridinone, hexamethyl phosphoric triamide (HMPA), etc.; acids, for example, acetic acid etc. The reaction can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of -generally from room temperature (20°C) to about 200°C, preferably from room temperature to 150°C. aid reaction is conducted desirably under normal pressure, it can -be operated also under elevated pressure or under reduced pressure. In conducting the reaction, the aimed compounds of the formula (IV) can be obtained, for example, by reacting equimolar to a little excess mole amount of the compounds of the formula (EOT) to 1 mole • of the compounds of the formula (XH) in a diluent, for example, acetic acid. Many of the compounds of the above-mentioned formula (XH) are publicly known, and as their specific examples'there can be mentioned, phthalic anhydride, 3-fluorophthalic anhydride, 3-chlorophthalic anhydride, 3-bromophthalic anhydride, 3-iodophthalic anhydride, 3-methanesulfonyloxyphthalic anhydride, etc. Among the above-mentioned compounds, 3-methanesulfonyloxyphthalic anhydride can be easily obtained from 3-hydroxyphthalic anhydride and methanesulfonyl chloride according to the process described in Tetrahedron Letters Vol. 29, p. 5595-8 (1988). As specific examples of the compounds of the formula (IV), used as starting materials in the preparation process.(b), there can be mentioned the following: 4-cHoro-2-{2~me1hyW-[3,5-bis(1riflucn:om 2-{2-memyl-4-[3,5~bis(trifluoromeihyl)-lH^ 4-cWoro-2-[2-me1hyl-(5-difluoromernoxy-3-1riflu indole-l,3-dione, . 4-chloro-2-[2-methyl-4-(4-pentafluoroeihyl-lH-pyrazol-l-yl-memyl)-phenyl]-isomdole-l,3-dione, 4-bromo-2-{2-methyM-[3,5-bis(1iifluOTometh 4-bromo-2-[2-methyl-4-(5-difluoromernoxy-3-ta indole-l,3-dione, 4-bromo-2-[2-methyl4-(4-peoitafluoroethy 4-iodo-2- {2-methyl-4-[3,5-bis(trifluoroniethyl)-lH-pyrazol-l -yl-methyl]-phenyl) -isoindole-1,3-dione, 4-iodo-2-[2-meihyM-(5-difluoromethoxy-34rifluo -indole-l,3-dione, 4-iodo-2-[2-memyl-4-(4-pentafluoroemyl-lH-pyrazol-l-yl-memyl)-phenyl-]isoindole-l,3-dione, 4-iodo-2-[2-methyM-(5-hexafluoro-n-prqpyl-lH- 4-me1hanesulfonyloxy-2-{2-methyl-4-[3,5-bis(Mfluoromemyl)-lH-pyrazol-l-yl-methyl]-phenyl}- isoiridole-l,3-dione,s "' 4-chloro-2-{2-me%l-4-[3,5-bis(tiifluorome%l)4H-(l,2,4)-triazol-l-yl-memylJ-phenyl}-isoindole17 isoindole-1,3-dione, 4-cMoro-2-{2-melhyW-[5-difluoroniethoxy-lisoindole- l,3-dione, 4-iodo-2-{2-methyl-4-[3,5-bis(tifluorome% dione, 4-iodo-2-{2-methyl-4-[5-penMuoroe1hyl-3-trifl isoindole-l,3-dione, 4-iodo-2-{2-me%l[5-Muorome%l-3-trifluoro isoindole-l,3-dione, 4-methanesulfonylo-2-{2-methyl^[3,5-bis(triflucTomeliiyl)-lH-(l,254)-tri -isoindole-l,3-dione, 4-iodo-2-[2-methyM-(5-difluoromethoxy-l^iflu6romethyl-3-trifluoroinethyl-lH-py -phenyl]-isoindole-l,3-dione, 4-iodo-2-[2-methyM-(5-hydroxy-3,5-bis(trifluoromethyl)-lH^5^hydropyrazol-l-yl-met nylj-isoindole-1,3-dione, 4-iodo-2-{2-methyW-[2,4-bis(irifluoromethyl)-lH-imida2ol-l-yl-methyl]-phm 49-3iodo-2-{2-me1hyl4 2,2J2-1rifluoroe%l)-5-1rifluorome%l452-jihydro methyl]-phenyl}-isomdole-l,3-dione5 , 4-iodo-2-{2-methyH-[4-(2,232-trifluoroe%l)-3-trffluoromeihyMJ5-y mefhylj-phenyl} -isoindole-1,3-dione, 4-iodo-2-{2-methyl-4-[2,5-bis(lrifluoromethyl)-(l,3,4)-1riazol-l-yl-me 4-iodo-2-{2-methyl-4-[4,6-bis(trifluoromethyl)pyrirnidin-2-yl-me1iiyl]rphenyl} 4-iodo-2-{2-me1hyl4-[4,6-bis(trifluoromethyl)pyrMdin-2-yloxy]-phenyl}-isoffl 4-cMoro-2-{2-rnethyl-4-[3,5-bis(Mfluoromettiyl)-lH-pyrazpl-l-yl]-phenyl}-isoindoie-l,3-dione, 4^hloro-2-[2-methyl-4-(5-penfafluoroethyl-lH-pyrazol-l-yl)-phenyl]-isoindole-l,3-dione, 4-chloro-2-[2-methyl-4-(3-pentafluoroethyl-lH-pyrazol-l -yl)-phenyl]-isoindole-l,3-dione, 4-cUoro-2-[2-methyM-(4-pentafluoroethyl-lH-pyrazol-l-yl)-p]ienyl3-isoindole-l,3-dione, 4-iodo-2-[2-methyl4-[3-me%l-5-trifluoromethyl-lH-pyrazol-l-yl3-pheiiyl]-isoindole-l,3-dioiie, 4-iodo-2-[2-methyM-(5-methyl-3-trifluoromethyl-lH-pyrazol-l-yl)-phenyl]-isoindole-l,3-dione, 4-iodo-2-[2-methyW-(3-pentafluoroethyl-5-trifluorpmethyl-lH-pyrazoI-l-yl)-pheaiyl]-isoindole-l,3- dione, 4-iodo-2-[2-methyW-(4-bromo-3-1rifluorome1:hyl-lH-pyrazoll-yl)phenyyi 4-iodo-2-[2-methy]-4-(3 -trifluoromethyl- lH-pyrazol-1 -yl)-phenyl] -isoindole-1,3 -dione, 4-iodo-2-{2-me%l-4-[5-hydroxy-3-(2,2,2-tffluoroe%^^ yl]-plienyl}-isoindole-l,3-dione, dione., l-3-difl 4-iodor2-{2-methyM-[3,5-bis(trifluoromethyl)-lH-pyra2ol-l-yl]-phenyl}-isoindole-l,3-di 4-iodo-2-[2-me1hyl^-(5-pentafluoroethyl-lH-pyrazol-l-yl)-phenylJ-isoindole-l,3-diane, 4-iodo-2-[2-methyW-(3-pentafluoroethyl-lH-pyrazol-l-yl)-plienyl]-isoindole-l33-dione, 4-iodo-2-[2-meftyM-(4-pentafluoroethyl-lH-pyrazol-l-yI)-phenyl]-isoindole-l53-dione3 4-bromo-2-{2-methyW-[3,5-bis(trifluoromethyl)-lH-pyrazol-l-yl]-phenyl}-isoindole-lJ3-dioneJ 4-bromo-2-[2-methyW-(5-pentafluoroetfayl-lH-pyrazol-l-yl)-phenyl-isoindole-l,3-dione, 4-bromo-2-[2-methyl^3-pentafluoroe%l-lH-pyrazol-l-yl)-phenyl]-isoindole-l33-dione, 4-bromor2-[2-methyM-(4-pentafluoroethyl-lH-pyrazol-l-yl)-plienyl]-isoindole-l,3-dione, 4hloro-2-{2-mefhyl^[3,4-bis(pentafluoroethyl)-lH-pyrazol-l-y]methyl]-phenyl}-i^^ dione, , 4^Horo-2-{2-methyM-[3J5-bis(heptafluoropropyl)-lH-pyrazol-l-ylmethyl]-phenyl}- dione, 4-cHoro-2-[2-methyl-(5-trifluorome1 4-chloro-2-[2-methyl-4-(5-pentafluoroethyl-l ,3,4-oxadiazol-2-yl)-phenyl]-isoindole-l ,3-dione, 4-cUoro-2-[2-methyl-4-(5-heptafluoropropyl-l,3,4-oxadiazol2-yl)-phenyl]-isoindole-l33-dione," 4-cUoro-2-[2-mefeyW-(5-1rifluorometh^ 4-ch]oro-2-[2-methyW-(4-lrifluorome1hyl-2H-l,23-triazol-2-yl-methyl) 4-cWoro-2-[2-me&yM-(4-(pentafluoroethyl)-thiazol-2-yl-methyl)-pheny]]-isoindole-l, 4-ch]oro-2-{2-methyM-[l-methyl-3-(trifluoromefliyl)-lH-l^,4-triazol-5-yl-sufanyl]-ph indole-l,3-dione, 4;Woro-2-[2-meihyl-4-(5-tri£luorornefhyl-l,234-oxadiazol-3-yl)-phenylJ-isoindole-l,3-dione, 4-cWpro-2-[2-methyW^l-methyl-5-trifluoromethyl-lH-l3234-triazol-3-yI)-pheaiyl]-isoindol^ 4-iodo-2-[2-methyl-4-(5-trifluoromethyl-l3334-oxadiazol-2-yl)-phenyl]-isoindole-l,3-dione and so on. The compounds of the formula (V), used as starting materials in the preparation process (b), are either compounds well known in the field of organic chemistry or can be synthesized according to the process described in DE-A 20 45 90531WO 01/23350. As their specific examples there can be mentioned euiylamine, diethylamine, n-propylamine, isopropylamine, n-butylainine, sec-butylamine, isobutylamine, t-butylamine, t-amylamine, 2-(methyl19 thio)-ethylamine., 2-(emylmio)-emylamine, l-methyl-2-(methylfhio)-ethylamine3 thfK-(methylthio)-ethylarnine and so on. ' • ' The compounds of the formula (VI)., used as starting materials in the preparation process (c), include publicly known compounds and can be easily prepared according to the process described in JP-A 11-240857 (1999), JP-A 2001-131141, etc. As their specific examples there can be mentioned the following: N-isopropyl-phthalamic acid, 3-fluoro-N-isopropyl-phthalamicacid, 3-chloro-N-isopropyl-phthalamicacid, 3-bromo-N-isopropyl-phthalamicacid, 3-iodo-N-isopropyl-phthalamic acid, N-(l -methyl-2-methylsulfanyl-ethyl)-phthalamic acid, 3-fluoro-N-(l -methyl-2-methylsulfanyl-ethyl)-phthalarnic acid, 3-cMoro-N-(l-memyl-2-methylsiilfanyl-ethyl)-phmalamic acid, 3-bromo-N-(l -methyl-2-methylsulfanyl-ethyl)-phthalamic acid, 3-iodo-N-(l-methyl-2-methylsulfanyl-ethyl)-phthalamicacid, N-(l,lrd4methyl-2-memylsulfanyl-emyl)-phmalarnic acid, N-(l,l-dimethyl-2-methylsulfanyl-ethyl)-3-fluoro-phthalarnic acid, 3-cWoro-N-(l,l-dimemyl-2-methylsiilfanyl-ethyl)-phthalamicacid, 3-bromo-N-(l , 1 -dimemyl-2-memylsulfanyl-ethyl)-phthalatnic acid, N-(l,l-dimethyl-2-memylsulfanyl-emyl)-3-iodo-phthalamicacid, N-isopropyl-3-methanesulfonyloxy-phthalamic acid, N-(l-methyl-2-memylsulfanyl-ethyl)-3-methanesulfonyloxy-phthalamicacid, N-(l-meihyl-2-me1hylsulfanyl-ethyl)-3-iiitro-phthalamic acid, 3 -chloro-N-(2-ethylsulfanyl- 1 -methyl-ethyl)-phthalamic acid, 3-bromo-N-(2-ethylsulfanyl-l-methyl-ethyl)-phthalamicacid, N-(2-ethylsulfanyl-l -methyl-ethyl)-3-iodo-phthalarnic acid, N-(2-ethylsulfanyl-l-methyl-ethyl)-3-nitro-phthalamic acid, N-(2-etiiylsulfanyl-r-methyl-ethyl)-3-methanesulfonyloxy-phthalamicacid, N-(l,l-dimethyl-2-memylsulfanyl-ejhyl)-3-methanesulfonyloxy-phthalarnic acid and so on. The above-mentioned compounds of the formula (VT) can be easily obtained generally by reacting phthalic anhydrides of the aforementioned formula (XH) wherein X has the same definition as aforementioned, with amines of the formula H2N-R1 pan) wherein R1 has the same definitions as aforementioned, The compounds of the above-mentioned formula (XIE) are weU known in the field of organic chemistry and there can be specifically mentioned, for example, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, t-amylamine, 2-(methylthio)etiiylamine, 2-(ethylthio)ethylamine, l-methyl-2-(methylthio)ethylamine, 1, l-dmefeyl-2-(methyl1m"o)ethylamine, etc. These' amines can be easily obtained also by the process described in DE-A 20 45 905, WO 01/23350, etc. The above-mentioned reaction of the compounds of the formula (Xn) with the amines of the formula (X33I) can be conducted according to the process described in, for example, J. Org. Chem., Vol. 46, p. 175 (1981) etc. Said reaction can be conducted in an adequate diluent, and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichlordethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetoniirile, propiomtrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc. The above-mentioned reaction can be conducted in the presence of a base, and as said base there can be mentioned, for example, tertiary amines, dialkylammbanilines arid pyridines,' for example, triethylamine, 1,1.,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylanihne, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP)_, l,4-diazabicyclo[2,2,2]octane (DABCO), l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc. Tb£ibove-mentioned reaction can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally from about -70 to about 1.00°-C, preferably from about -50 to about 80°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure. In conducting the above-mentioned reaction, the aimed compounds of the formula (VI) can be obtained, for example, by reacting 1-4 moles of the compounds of the formula (XIH) to 1 mole of the compounds of the formula (XT!) in a diluent, for example, acetonitrile. The compounds of the formula (VH), used as starting materials in the preparation process (d), are novel compounds and can be easily obtained, for example, by reacting the compounds of the formula (VIE), starting materials in the below-mentioned preparation process (e), according to the process described in J. Med. Chem., Vol. 10, p. 982 (1967) etc. in the presence of a condensing agent. As specific examples of the compounds of the formula (VH), there can be mentioned the following: l-[4-(4-iodo-3-oxo-3H-isobenzoiuran-l-yMdeneamino)-3-methyl-benzyl]-3,5- bis(trifluoromethyl)-lH-pyrazole,: l-[4-(4-cMoro-3-oxo-3H-isoberizofuran-l-ylideneamino)-3-methyl-benzyl]-3,5- bis(trifluoromethyl)-lH-pyrazole, : l-[4-(4-iodo-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-memyl-benzyl]-3,5- bis(trifluoromethyl)-l,2,4-triazole, 1 -[4-(4-iodo-3-oxo-3H-isobenzofuran-l -ylideneamino)-3-methylpbenyl]-3,5- bis(trifluoromethyl)-lH-pyrazole, l-[4-(4-cHoro-3-oxo-3H-isobenzofuran-l-ylideneammo)-3-me1hyl-benzyl]-354 bisfcentafluoroernyty-lH-pyrazole, l-[4-(4-cUoro-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methyl-ben2yl]-3,5- bis(pentafluoroethyl)-lH-pyrazole, l-[4-(4-cMoro-3-oxo-3H-isobenzof\Kan-l-ylideneamino)-3-methyl-benzyl]-3,4- bis(heptafluoropropyl)-lH-pyrazole, l-[4-(4-cMoro-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methyl-benzyl]-3,5- bis(heptafluoropropyl)-lH-pyrazole, , 2-[4-(4-cHoro-3-oxo-3H-isober^ofOTan-l-ylidenea oxadiazole, 2-[4-(4-cMoro-3-oxo-3H-isobenzofuran-l-ylide -oxadiazole, 4-(4-cHoro-3-oxo-3H-isobemzofuran-l-yM 4-oxadiazole, 2-[4-(4-cUoro-3-oxo-3H-isobeffizofuran-l-ylidenearnmo)-3 oxadiazole, 2-[4-(4-chloro-3 -oxo-3H-isobenzofuran-l -ylideneamino)-3-methylben2yl] -4-(trifluoromethyl)-2H- 1,2,3-triazole, 2-[4-(4-cUoro-3H3xo-3H-isobenzofuran-r-y thiazole, 5-[4-(4-cWoro-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methylphenyl]siilfanyl-l-methyl-3- fluoromethyl)-lH-l,2,4-triazole, 3-[4-(4-chloro-3-oxo-3H-isobenzofoan-l-ylideneamino)-3-meth)dphenyl]- 5-(trifluoromethyI)-1,2,4-oxadiazole, 3-[4-(4-cUoro-3-oxo-3H-isobenzofi methyl)-lH-l,2,4-triazole, 2-[4-(4-iodo-3-oxo-3H-isobenzofiffan-l-ylideneainmo)-3-mefo oxadiazole and so on. The compounds of the formula (V), similarly used as starting materials in the preparation process (d), are the same as explained in the aforementioned preparation process (b). The compounds of the formula (VET), used as starting materials in the preparation process (e), are novel compounds and can be easily obtained, for example, by reacting phthalic anhydrides of the aforementioned formula (XS) with the compounds of the aforementioned formula (HI).. The above-mentioned reaction can be conducted in an adequate diluent, and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol •dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile/acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc. The above-mentioned reaction can be conducted in the presence of a base, and as said base there can be mentioned tertiary amines, dialkylarninoanilines and pyridines. for example, triethylamine, 1,1,4,4-teframethyleihylenediaimne (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-aefliylamJnopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc. The above-mentioned reaction can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally from about -70 to about 100°C, preferably from about -50 to about 80°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure. As specific examples of the compounds of the formula (VEQ), there can be mentioned the following: N-{4-[3is(trifluorotnethyl)-l N- {4-[335-bis(trifluoromethyl)-lH-pyrazol-l -yl-mefhyl]-2-methyl-phenyl} -6-chloro-phthalamic acid, N- {4-[3,5-bis(trifluoromethyl)-(l ,2,4)-triazol-l-yl-methyl]-2-meuiyl-phenyl}-6-iodo-phthalamicacid, N-{4-[3,5-bis(trifluoromethyl)-lH-pyrazol-l-yl]-2-memyl-phenyl}-6-iodo-phthaIamicacidJ N-{4-[3,4-bis(pentafluoroethyI)-lH-pyrazol-l-yl-methyl]-phenyl}-6-cWoro-phmalamicacid, N-{4-[3,5-bis(pe»tafluoroethyl)-lH-pyrazol-l-yl-methyl]-phenyl}-6-chloro-phthalamic acid, N-{4-[3,4-bis(heptafluoropropyl)-lH-pyrazol-l-yl-methyl]-phenyl}-6-cMoro-phthalamic acid, N-{4-[3,5-bis(b.eptafluoropropyl)-lH-pyrazol-l-yl-memyl]-phenyl}-6-cMoro-ph1ha]arnic acid, Nr[2-memyl^5-1rifluorome1hyl-l,3,4-oxadiazol-2-yl)-phenyl]-6-cWoro-phmalannc N-[2-memyl-4-(5-pentafluoroethyl-l,3,4-oxadiazol-2-yl)-phenyl]-6-chloro-phthalarnic acid, N-[2-methyl-4-(5-heptafluoropropyl-l,3,4-oxadiazol-2-yl)-phenyl]-6-cHoro-phflialamicacid, N-p-memyW-(5-1rifluoromemyl-l,3,4-oxadiazol-2-yl-memyl)-phenyl]-6-chloro-ph1i^^ acid, N-[2-memyM-(4-trifluoromemyl-2H-l,2,3-triazol-2-yl-methyl)-phenylj-6-cMoro-ph^ N-[2-memyM-(4-pentafluoroemyl-thiazol-2-yl-methyl)-phenyl]-6-cMoro-phmalaniicacid, N-{2-methyl-4-[l-methyl-3-(trifluoro phthalamic acid, _ N-[2-memyM-(5-trifluoromemyl-l,2,4-oxadiazol-3-yl)-phenyl]-6-cMoro-phmalarm N-[2-memyl-4-(l-memyl-5-1riiluoromemyl-lH-l,2,4-triazol-3-yl)-phenyl]-6-chloro-phmalan^ N-[2-methyW-(5-1rifluorome%l-l,3,4-oxadiazol-2-yl)-phenyl]-64odo-phmalarnic acid and so on. The compounds of the formula (V), similarly used as starting materials in the preparation process (e), can be the same as ones used in the aforementioned preparation processes, (b) and (d)f The compounds of the formula (If), used as starting materials in the preparation process (f), are compounds included in the formula (T) of the present invention. yoxidizing the group R^ in the compounds of the formula (If), namely, C1-6alkylthio-C1.6alkyl, the compounds of the formula (I), in which the group Rff corresponds to C1-6alkylsulfrnyl-C1-6alkyl or l, can be obtained. The compounds of the formula (If) can be prepared by the processes of the aforementioned preparation processes (a), (b), (c), (d) and/or (e). As specific examples of the compounds of the formula (If), there can be mentioned the following: 3-iodo-N2l-methyl-2-methylsulfanyl-ethyl)-N1-{2-memyW-[3,5-bis(trifluorom 1-yknelhyl]-phenyl}phthalamide, N2-(l,l-dime%l~2-me1hylsulfmyl-e^ pyrazol-l-ylmethyl]-phenyl}phthalamide, 3 -iodo-N2-(l -me&yl-2-methylsulfanyl-ethyl)-N'- {2-methyl-4-[3,5-bis(trifluoromethyl)- (l,2,4)-triazol-l-yhnethyl]-phenyl}phthalamide, 3-cttoro-N2-(l-me%l-2-methylsulf^^ -l-yhnethyl]-phenyl}phthalamide, 3-chloro-N2-( 1 -mernyl-2-methylsuifanyl-ernyl)-N!r {2-methyl-4-[3,4-bis(pentafluoro-ethyl)-lH-pyrazoH- ylmemyl]-phenyl}phthalamide, 3-cWoro-N2-(l-memyl-2-methylsulfanyzol-l-ylmethyl]-phenyl}phthalamide, 3-chloro-N2Kl-me^l-2Hmeftylsulfanyl razol-l-yhnethyl]-phenyl}phthalamide, 3-cMoro-N2-(l-memyl-2-memylsulfanyl^myl)-N1-{2-methyl^[3,5-bis(heptafIuoro-propyl)-lH^^ razol-l-ylmethyl]-phenyl}phthalamide and so on The reaction of the aforementioned preparation process (a) can be conducted in an adequate diluent singly or mixed. As examples of the diluent used in that case there can be mentioned water; aliphatic, . alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichIoroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl .ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc. r, The preparation process (a) can be conducted in the presence of an acid catalyst, and as examples of said acid catalyst there can be mentioned mineral acids, for example, hydrochloric acid and sulfuric act; organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. The preparation process (a) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally from about -20 to about 100°C, preferably from about 0 to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure. In conducting the preparation process (a), the aimed compounds of the formula (I) can be obtained, for example, by reacting 1 to a little excess mole amount of the compounds of the formula (ID) to 1 mole of the compounds of the formula (IT) in a diluent, for example, 1,2-dichloroethane in the presence of 0.01-0.1 mole amount of p-toluenesulfonic acid. The reaction of the aforementionedpreparation process (b) can be conducted in an adequate diluent. As examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and.aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon .tetrachloride, 1,2-dichloroethane., chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3 -dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (BMPA), etc. The preparation process (b) can be conducted in the presence of an acid catalyst and as examples of said acid catalyst there can be mentioned mineral acids, for example, hydrochloric acid and sulfuric acid; organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. The preparation process (b) can be conducted in a substantially.wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally from about -20 to about 150°C, preferably from room temperature (20°C) to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure. IrFconducting the preparation process (b), the aimed compounds of the formula (I) can be obtained., for example, by reacting 1-25 moles of the compounds of the formula (V) to 1 mole of the compounds of the formula (TV) in a diluent, for example, dioxane in the presence of 0.01-0.5 mole amount of acetic acid. The aforementioned preparation processes (c), (d) and (e) can be conducted under the similar condition as the above-mentioned preparation process (a). The reaction of the aforementioned preparation process (f) can be conducted in an adequate diluent. As examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; alcohols, for example, methanol, ethanol, isopropanol andbutanol; acids; formic acid, acetic acid, etc. As the oxidizing agents usable in the aforementioned preparation process (f) there can be mentioned, for example, m-chloroperbenzoic acid, peracetic acid, potassium metaperiodate, potassium hydrogen persulfate (oxon), hydrogen peroxide, etc. The preparation process (f) can be conducted in a substantially .wide range of temperature. It is . adequate to conduct it at the temperatures in a range of generally firom about —50 to about 150°C, preferably from about--10 to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure. In conducting the preparation process (f), the aimed compounds of the corresponding formula (I) can be obtained, for example, by reacting 1-5 moles of an oxidizing agent to 1 mole of the compounds of the formula (If) in a diluent, for example, dichloromethane. The reaction of the aforementioned preparation process (f) can be conducted, for example, according to the process described in JIKKENKAGAKU KOZA (Lecture on experimental chemistry) edited by the- Chemical Society of Japan, 4th ed., Vol. 24, p. 350 (1992) published by MARUZEN or ibid. p. 365. The compounds of the formula.(!) of the present invention show strong insecticidal action. The compounds of the formula (I), according to the present invention can, therefore, be used as insecticidal agents. And the active compounds of the formula (T) of the present invention exhibit exact controlling effect against harmful insects without giving phytotoxiciiy on cultured plants. And tbf vompounds of the present invention can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain.pests, hygienic pests, etc. and applied for their extermination. As examples of such pests there can be mentioned the following pests: As insects, there can be mentioned: Coleqptera pests, for example, Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptnts oryzophilus, Lyctus bruneiis; Lepidoptera pests, for example, Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella; Hemiptera pests, for example, Nephqtettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki,; Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Khopalosiphum pseudqbrassicas, Stephanitis nashi, Nazara spp., Trialeurodes vaporariorum, Psylla spp.; Tfiysanopterapests, for example, Thrips palmi, Frankliniella occidental; Orthoptera pests, for example, . Blatella gennanica, Periplaneia americana, Gryllotalpa africana, Locusta migratoria migratoriodes; Homoptera pests, for example, Reticulitermes speratus, Coptotermes formosanus; Diptera pests, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, Liriomyzae trifolii etc. Moreover, as mites there can be mentioned, for example, Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemns spp., etc. Furthermore, as nematodes there can be mentioned, for example, Meloidogyne incognita, Biirsaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines, Pratylenchus spp., etc. Upldition, in the field of veterinary medicine, the novel compounds of the present invention can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helrninthes. As examples of such animal-parasitic pests there can be mentioned the following pests: As insects there can be mentioned, for example, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, Cimex lectularius etc. As mites there can be mentioned, for example, Ornithodoros spp., Jxodes spp., Boophilus spp., etc. In the present invention, substances having insecticidal action against pests, which include all of them, are in some cases called as insecticides. All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds. Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats. The active compounds; according to the present invention, can :be converted into the customary formulation forms, when they are used as insecticides. As formulation forms there can be mentioned, for example, solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compound, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc. These formulations can be produced according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents or carriers; liquefied gas diluents or carriers; solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents. In case that water is used as extender, for example, organic solvents can also be used as auxiliary solvents. As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydroparbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols and their ethers, esters, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example,-dimethylformamide, dimethyl sulfoxide, etc.), and water. Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons. . As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.). As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic or organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.), etc. As-emulsifiers "and/or Tfoam-forming agents, there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers), alkylsulfonates, alkylsulfates, arylsulfonates, etc.], albumin hydrolysis products, etc. 30 Jjl^persants include, for example., lignin sulfite waste liquor and methyl cellulose. Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tacldflers, there can be mentioned, for example, carboxymethyl cellulose, natural or synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.). Colorants can also be.used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such, as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Said formulations can contain the aforementioned active component of the amount in the range of generally 0.1-95% by weight, preferably 0.5-90% by weight. The active compounds of the formula (I) of the present invention can exist also as a mixed agent with other' active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators or herbicides in the form of their commercially useful formulations and in the application forms prepared from such formulations. Here, as the above-mentioned insecticides, there can be mentioned, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microorganisms, etc. . Further, the active compounds of the formula (I) of the present invention can exist also as a mixed agent with a synergist, and such formulations and application forms can be mentioned as commercially useful. Said synergist itself must not be active, but is a compound that enhances the action of the active compound. Particularly favourable mixing components are, for example, the following compounds: Fungicides: 2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benalaxyl- M; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S; boscalid; bromuconazole; bupirimate; buthiobate; butylamine; calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone; chinomethionat; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon; cyazofarnid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram: Dagger G; debacarb; dichlofluanid; dichlone; dicMorophen; diclocymst; diclorneziiie; dicloran; diethofencarb: difeno31 cbnazple; diflumetorirn; dimethiiimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithiione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenarimol; feribuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; fefbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluororhide; fluoxastrobin; fluquinconazole; flurprimidol; 'flusilazole; flusulfairdde; flutolanil; flutriafol; folpet; fosetyl-Al; fosetyl-sodium; fiiberidazole; furalaxyl; furametpyr; furcarbanil; funnecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazol; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocafb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoxim-methyl; mancozeb; maneb; rneferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxarn; metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin; mcobifen; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; peneonazole; pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazopnos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine; quinconazole; qurnoxyfen; quintozene; simeconazole; spiroxamine; sulfur, tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)-N-[2-[4- [[3-(4-cUprophenyl)-2-propynyl]oxy]-3-methoxyphenyl]emyl]-3-me1hyl-2-[(memylsulfo^ butanamide; l-(l-naphthalenyl)-lH-pyrrol-2,5-dione; 2,335,6-tetrachloro-4-(me1iiylsulfonyl)-pyiidine; 2-arnino-4-me1hyl-N-phenyl-5-traazolecarboxarnide; 2-chloro-N-(2^-dihydro-lJ,3j-trirnethyl-lH-inden- 4-yl)-3-pyridinecarboxamide; SAS-trichloro^^-pyridinedicarbonitrile; actinovate; cis-l-(4-chloroprienyl)- 2-(lH-l,2,4-triazol-l-yl)-cycloheptanol; methyl., l-(2,3-dihydro-232-dimethyl-lH-inden-l-yl)- lH-imidazole-5-carboxylate; mono potassium carbonate; N-(6-methoxy-3-pyridinyl)-cyclopropane: cafboxamide; N-butyl-8-(l J-dimethylethyl)-l-oxaspiro[4.5]decan-3-amine; sodium tetrathiocarbonate; and copper salts and preparations, such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulphate; cufraneb; copper oxide; mancopper; oxine-copper. Bactericides: bronopol, dichlorophen, nitrapyrin,..nickel dimethyldithio^arbamate, .kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper, sulphate and other copper preparations. Insecticides / aeari cities / nematicides: ffAcetylcholinesterase (ACliE) inhibitors 1.1 Cafbamates (e.g. alanycafb, aldicarb, aldoxycarb, allyxycarb, aminocarb, azamethiphos, bendiocarbj benfuracarb, bufencarb, butacafb, butocarboxim, butoxycafboxim, carbaiyl, carbofuran, carbosulfan, chloethocarb, coumaphos, cyanofenphos, cyanophos, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocafb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, xylylcafb) 1.2 Qrganophosphates (e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butalbiofos, cadusafos, carbophenotbion, chlorethoxyfos, chlorfenviaphos, cblormephos, chloipyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demeton-s-methyl., demeton-s-meth.ylsulpb.on, dialifos, diazinon, dichlofenthion, dichlorvos/ddvp, dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, epn, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl o-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, meyinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion (-methyl/-ethyl), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, tbiometon, triazophos, triclorfon, vamidothion) 2. Sodium channel modulators/voltage dependant sodium channel blockers 2.1 Pyrethroids (e.g. acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-s-cyclopentjd-isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmetbrin, cis-permethrin, clocythrin, cycloproflmn, cyfluthrin, cyhalotixtin, cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, DDT, deltamethrin, empenthrin (IR-isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythririate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprolhrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (IR-trans isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, lau-fluvalinate, tefluthrin, terallethrin, tetramethrin (IR-isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum)) 2.2 Oxadiazine (e.g. indoxacarb) 3. Acetylclioline receptor agonists/-antagonists 3.1 Qilo'rbnicotinyls/nebnicotinbids (e:g. acetamiprid, clothianidin, dinotefuran, ;imidacloprid, :nitenpyram, rnithiazine, thiacloprid, thiamethoxam) 3.2 nicotine, bensultap, cartap 4. Acetylcholine receptor modulators 4.1 Spinosyns (e.g. spinosad) 5. SABA gated chloride channel antagonists 5.1 Cyclodiene organochlorines (e.g. camphechlor, chlordane, endosulfan/gamma-HCH, HCH, heptachlor, lindane, methoxycblor 5.2Fiproles (e.g. acetoprole, ethiprole, fipronil, vaniliprole) 6. Chloride channel activators 6.1 Mectins (e.g. abamectin, avermectin, emamectin, emamectin-benzoate, ivermectin, milbemectin, milbemycin) 7. Juvenile hormone mimics (e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene) 8. Ecdysone agonists/disrupters 8.1 Diacylhydrazines (e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenoadde) 9. Inhibitors ofchitin biosynthesis 9.1 Benzoylureas (e.g. bistrifluron, cblofluazuron., diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflurnuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron) 9.2 buprofezin 9.3 cyromazine 10. Inhibitors ofoxidativephosphorylation, ATP-disruptors 10.1 diafenfhiuron 10.2 Organotins (e.g. azocyclotin, cyhexatin, fenbutatiB-oxide) 11. Decoupler ofoxidativephoshorylation by diruption of Hproton gradient 11.1 Pyrroles (e.g. cblorfenapyr) ' 11.2 Dinitrophenoles (e.g. binapacyrl, dinobuton, dinocap, DNOC) 12. Site I electron transport inhibitors 12.1 MEITs (e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad,J:olfenpyrad) 12.2 hydramethylnone 12.3 dicofol 13. Site H electron ti-ansport inhibitors 13.1 rotenone 14. Site ID. electron transport inhibitors 14.1 acequinocyl, fluacrypyrim 15. Microbial disrupters of insect midgut membranes Bacillus thuringiensis strains 16. Inhibitors of lipid synthesis 16.1 Tetronic acid insecticides (e.g. spirodiclofen, spiromesifen) 16.2 Tetramic acid insecticides [e.g. 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3- en-4-yl ethyl carbonate (alias: carbonic acid, 3-(2,5-dimefhylplienyl)-8-mefhoxy-2-oxo-l-azaspiro[4.5]- %i-3-en-4-yl ethyl ester, CAS-Reg.-No.: 382608-10-8) and carbonic acid, cis-3-(235-dimethylphenyl)- 8-methoxy-2-oxo-l -azaspiro[4.5]dec-3-en-4-yl ethyl ester (CAS-Reg.-No.: 203313-25-1)] ' 17. Carboxamides (e.g. flonicamid) 18. Octopaminergic agonists (e.g. amitraz) 19. Inhibitors of magnesium stimulated ATPase (e.g. propargite) 20. Phthalamides (e.g. NMU-dimethyl-2-(memylsulf methyl)ethyl]phenyl]-l,2-benzenedicafboxamide (CAS-Reg.-No.: 272451-65-7, flubendiamide)) 21. Nereistoxin analogues (e.g. thiocyclam hydrogen oxalate, thiosultap-sodium) 22. Biologica, hormones orpheromones (e.g. azadirachtin, Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec., Paecilomyces spec.,- thuringiensin, Verticillium spec.) 23. Compounds of unknown or non-specific mode of action 23.1 Fumigants (e.g.' aluminium phosphide, methyl bromide, sulfuryl fluoride) 23.2 Selective feeding blockers (e.g. cryolite, flonicamid, pymetrozine) . . 23.3 Mite growth inhibitors (e.g. clofentezine, etoxazole, hexythiazox) 23.4 amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, chinomethionat, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone, japonilure, metoxadiazone, petroleum, piperonyl butoxide, potassium oleate, pyrafluprole, pyridalyl, pyriprole, sulfluramid, tetradifon, tetrasul, triarathene, vefbutin further the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3-(5-chloro-3- pyridinyl)-8-(232J2-trifluoroemyl)-8-azabicyclo[3.2.1]octan-3-carbonitrile(CAS-Reg.-Nr. 185982-80-3) and the corresponding 3-endo isomer (CAS-Reg.-Nr. 185984-60-5) (cf. WO 96/37494, WO 98/25923), and preparations comprising insecticidal active plant extracts, nematodes, fungi or viruses. A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners and/or semiochemicals is also possible. When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds, which increase %•. action of the active compounds, without it being necessary for the synergistic agent added to be active itself. When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with inhibitors which reduce degradation of the active compound after use in the vicinity of the plant, on the surface of parts of plants or in plant tissues. The content of the active compounds of the formula (T) of the present invention in a commercially useful application form can be varied in a wide range. The concentration of the active compounds of the formula (!) of the present invention at the time of actual usage can be, for example, in the range of 0.0000001-100% by weight, preferably 0.00001-1% byweight. . The pompounds of the formula (I) of the present invention can be applied by usual methods suitable to the application forms. In case of application against hygiene pests and pests of stored products, the active compounds of the present invention have a good stability against alkali on limed .substrates and further show an excellent residual effectiveness on wood and soil. As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms),, and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above. Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having certain properties ("traits") which have been obtained ;by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("syneigistic") effects. Thus, for example, reduced application rates and/or a widening of the activity jpctrum and/or an increase in the activity of the substances and compositions to be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were-actually to be expected. The transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are preferably to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful traits to these plants. Examples of such trails are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbialpests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized are in particular increased defence of the plants against insects,' arachnids, nematodes and worms by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryllA, CrylUA, CryHIB2, Cry9c, Cry2Ab, CrySBb and CryEF and also combinations thereof) (hereinbelow referred to as "Bt plants")- Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexius, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the 'TAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize,-cotton, .soya .beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya'bean varieties which are sold under the trade names Roundup Ready© (tolerance to glyphosate, for example maize, cotton., soya bean), Liberty Link® (tolerance to p\|«sphinotricinj for example oilseed rape), IMT® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plants will be developed and/or marketed in the future. The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula I and/or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text. Then the present invention will be described more specifically by examples. The present invention, however, should not be restricted only to them in any way. Synthesis Examples Synthesis Example 1 3-(14-Dimethyl-2-methylsulfanyl-ethylimino)^-iodo-3H-isobenzofuran-l-one (0.53 g) and l-(3-methyl4- aminobenzyl)-3,5-bis(trifluoromethyl)-lH-pyrazole (0.45 g) were dissolved in acetonitrile (15 ml), to which p-toluenesulfonic acid nionohydrate (0.01 g) was added and the mixture was stirred at 60°C for 3 hours. After finishing the reaction, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain N'S-bislrifluorome& ylpyrazol-l-ylmemyl)-2-methylpte amide (0.91 g). mp. 83-87°C. Synthesis Example 2 sulfanylethyl)-3-iodophthalamide (0.5 g) was dissolved in dichloromethane, to which m-chloroperbenzoic acid (0.26 g) was added and the mixture was stirred for 5 hours under ice cooling. After finishing the reaction, the mixture was washed successively with aqueous solution of sodium thiosulfate, saturated aqueous solution of sodium bicarbonate and saturated aqueous solution of sodium chloride, and dried with anhydrous magnesium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtain NI-{4-[3,5-bis(trifluoromethyl)-lH-pyrazoll- ylmethyl]-2-methylphenyl}-N2- (2-meihanesdfmyl-l,l-dimethylethyl)-3-iodoph1halainide (0.30 g). 'H-NMR (CDC]3, ppm): 1.57 (3H, s), 1.60 (3H, s), 2.20 (3H. s), 2.30 (3H, s), 2.93 (2H, dd), 5.43 (2H3 s), 6.57 (1H, s), 6.90 (1H, s), 7.0-8.2 (7H, m). thesis .Example N1-{4-[3,5-Bis(1rifluorome%l)-lH-pyrazol-l-ylme%l]-2-methylplienyl}-N2- (l,l-dimethyl-2-methylsulfanylethyl)- 3-iodophthalarnide (0.30 g) was dissolved in dichloromethane, to which m-chloroperbenzoic acid (0.26 g) was added and the mixture was stirred at room temperature for 5 hours. After finishing the reaction, the mixture was washed successively with aqueous solution of sodium thiosulfate, saturated aqueous solution of sodium bicarbonate and saturated aqueous solution of sodium chloride, and dried with anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude crystals were washed with petroleum ether.to obtain N^4-[3,54)is(trifluoromet^^ me1hylphenyl}-34odo-N2-(2-meth (0.25 g). rap. 104-107°C. Synthesis Example 4 (Figure Removed) A dioxane solution (15 ml) of 2-{4-[3,5-bis(triiluoromethyl)-lH-pyrazol-l- ylmethyl]-2-methylphenyl}- 4-fluoroisoindole-l,3-dione (0.94 g), (S)-l-me1h.yl-2-methylsulfanylethylamine (0.63 g) and acetic acid (0.12 g) was refluxed for 18 hours. After cooling to room temperature, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain N1-{4-[3,5-bis(trifluorome1iiyl)4H-pyrazol4-ylme%l]-2-methylphenyl}-3-fluoro-N2-[l-(S)-lmethyl- 2-methylsulfanyl-ethyl]-phthalamide (0.19 g) (compoundNo. 549). rnp. 66-68°C. Jtetbesis Example 5 3-Iodo-N-(l,l-dimethyl-2-methylsulfanyl-ethyl)-phthalamic acid (0.39 g) and N-(3-dimethylaminopropyty- N^ethylcarbonyl diimidazole hydrochloride (0.19 g) were stirred in dichloromethane (10 ml) at room temperature for 30 minutes. Then, 2-memyM-[l-(3-trifluororneuiyl-lH-pyrazol-l-yl)-ethyl]- aniline (0.30 g) and p-toluenesulphonic acid monohydrate (0.02 g) were added thereto and the mixture was stirred at room temperature for 3 hours. After distilling off the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography to obtain N21,1-dimethyl-2-methylsulfanyl -yl)-ethyl]-phenyl}-phthalamide (0.38 g) (compound No. 558). mp. 79-86°C. The compounds of the formula (I), according to the present invention, which can be obtained in the same manner as the above-mentioned Synthesis Examples 1 to 5 are shown in Table 1, together with the compounds obtained in the above-mentioned Synthesis Examples 1 to 5. NMR. data of the compounds, whose mp. column is marked as *, are collectively shown in Table 2, separately from Table 1. (Figure Removed) Synthesis Example 6 (Starting material) 3-Methyl-4-nitrobenzyl chloride (1.81 g), 3,5-bis(trifluoromethyl)-lH-pyrazole (2.0 g) and potassium carbonate (1.63 g) were stirred in DMF (20 ml) at 60°C for 1 hour. After finishing the reaction, water (100 ml) was added thereto and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride (100 ml) and dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chrornatography to obtain l-(3-me1hyl-4-nitroben2yl)-335-bis-(trifluoromethyl)-lH-pyrazole (3.3 g). JH-NMR (CDC13, ppm): 2.59 (3H, s), 5.50 (2H, s), 6.90 (1H, s), 7.1-7.2 (2H, m), 8.00 (1H, d). Synthesis Example 7 Starting material") CH3 CF, To a mixture of l-(3-methyi-4-nitrobenzyl)-3,5-his(trifluoromethyl)-lH-pyrazole (1.4 g), ammonium acetate (30.5 g), acetone (60 ml) and water (30 ml), 20% aqueous solution of titanium trichloride (27.5 g) was added at room temperature and the mixture was stirred at room temperature for 12 hours. After finishing the reaction, the mixture was extracted with ethyl acetate, washed with saturated aqueous solution of sodium chloride and dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtain l-(3-metiiyM-ammobenzyl)-3,5-bis(trifluoromethyl)-lH-pyrazole (1.19 g). 'H-NMR (CDC13, ppm): 2.14 (3H, s), 3.66 (2H, m), 5.32 (2H, s), 6.62 (1H, d), 6.89 (1H, s), 6.8-7.1 (2H,m). Synthesis Example 8 (Starting material) ,CF, l-(3-Methyl-4-nitrobenzyl)-3,5-bis (trifluoromethyl)-lH-pyrazole (17.66 g) and iron powder (13.69 g) were heated and stirred in acetic acid (150 ml) at 40°C for 5 hours. After finishing the reaction, an insoluble matter was filtered with Celite and the filtrate was concentrated under the reduced pressure. To the residue, IN aqueous solution of sodium hydrate (200 ml) and ethyl acetafe (200 ml) were added. The organic layer was separated, washed with water, and then, dried with anhydrous magnesium sulfate. After distilling off the solvent, l-(3-memyl-4-arninobenzyl)-3,5-bis(trifluoromethyl)- lH-pyrazole (13.0 g), which was the same as that obtained in S3Tithesis Example 7, was obtained. Synthesis Example 9 (Starting material) 3-FluoTophthalic anhydride (4.98 g) and l-(3-methyl-4-aminobenz)'l)-3,5-bis(trifluoromethyl)-lHpyrazole (9.70 g) were refluxed in acetic acid (43 ml) for 3 hours. After finishing the reaction, the acid was distilled oif under the reduced pressure and the obtained crude crystals were washed with t-butyl methyl ether to obtain the aimed 2-{4-[3,5-bis (trifluoromethyl)-lH-pyrazbl-l-ylmethyl]- 2- methylphenyl}-4-fluoroisoindol-l,3-dione (10.80 g).mp. 158-159°C. Synthesis Example 10 (Starting material 3-Methy]-4-nitrobenzyl chloride (0.56 g), 5difluorome%I)-l,2-dihydro-2-methyl-3H-lA4-(triazol)- 3-one (0.45 g) and potassium carbonate (0.61 g) were stirred in DMF (10 ml) at 50°C for 5 hours. After finishing the reaction, the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under the reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain the aimed 5-difiuoromethyl-2-methyl-4- (3- methyl-4-riitrobenzyl)-2,4-dihydro-[l,2.,4]triazol-3-one (0.45 g). JH-NMR (CDC13, ppm): 2.5 (3H, s), 3.5 (3H, s), 4.9 (2H, s), 6.4 (IE, t), 7.2-7.3 (2H, m), 7.8-7.9 (1H, m). Synthesis Example 11 (Starting material) CH3 3-Methyl-4-nitrobenzyl chloride (0.43 g), S-heptafluoropropylsutfanyl-S-trifluoromethyl-lHtriazole (0.70 g), tetrabutylammonium iodide(0.09 g), 18-crown-6 (0.06 g) and potassium carbonate (0.48 g) were refluxed in acetonitrile (10 ml) for 2 hours. After cooling, the reaction solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 3-heptafluoropropylsulfanyl- l-(3-me1hyW-niirobenzyl)-5-1rifluorometbyl-lH-(l,2,4)-triazole(0.30g). 'H-NMR (CDC13, ppm): 2.64 (3H, s), 5.62 (2H, s), 7.31-7.25 artihesis Example 12 (Starting material) SC3F7-n To a mixture of 3-heptafluoropropylsiilfanyl-l-(3-me1hyW-nilTophenyl)-5-trifluoromethyl-lH-(l.J2,4)- triazole (0.3 g), ammonium acetate (4.8 g), acetone (20 ml) and water (10 ml), 20% aqueous solution of titanium trichloride (4.3 g) was added at room temperature and the mixture was stirred at room temperature for 12 hours. After finishing the reaction, the mixture was extracted with ethyl acetate, washed with saturated aqueous solution of sodium chloride and dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtam 4-(3-hepMuoropropylsulfanyl-5-1rifluorom amine (0.28 g) 'H-NMR (CDC13, ppm): 2.17 (3H, s), 4.16 (1H, hre), 5.40 (2H, s), 6.63-6.59 (2H, m), 7.13-6.99 (1H, Synthesis Example 13 (Starting material) (Figure Removed) An acetonitrile solution (30 ml) of 3-trifluoromethyl-lH-pyrazole (5.0 g), dicerium ammonium nitrate (10.0 g) and iodine (5.6 g) was refluxed for 1 hour. After cooling, the reaction solution was washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under thereduced pressure to obtain 4-iodo-3-trifluoromethyl-lH-pyrazole (9.3 g). 'H-NMR (CDC13, ppm): 7.77 (1H, s). Synthesis Example 14 (Starting material) 3-Methyl-4-nitroben2yl chloride (0.77 g), 4-iodo-3-trifluoromethyl-lH-pyrazole {0.99 g) and potas- .sium carbonate (0.63 g) were stirred in DMF (10 ml) at 60°.C for 1 hour. After cooling, the reaction solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off miner the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 4-iodo-l- (3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (1.0 g). 'H-NMR (CDda, ppm): 2.62 (3H, s), 5.36 (2H, s), 7.21-7.18 (2H, m), 7.52 (1H, s), 7.98 (1H, d). Synthesis Example 15 (Starting material) 4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (2.06 g), copper powder (0.95 g), iodopentafluoroethane (4.92 g) and DMF (13 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining the inside temperature of 130-135°C. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (50 ml) and an insoluble matter was filtered with Celite and washed with ethyl acetate. The filtrate was concentrated under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)- 4-pentafluoroethyl-3-trifluoromethyl-lH-pyrazole (1 .39 g) JH-NMR (CDC13, ppm): 2.63 (3H, s), 5.38 (2H, s), 7.21-7.27 (2H, m), 7.74 (1H, s), 8.00 (1H, d). Synthesis Example 16 (Starting material') 3-Methyl-4-nitrobenzyl chloride (8.57 g), 4-iodo-3-pentafluoroethyl-lH-pyrazole (16.00 g) and potassium carbonate (7.66 g) were stirred in DMF (70 ml) at 70°C for 1 hour. After cooling, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with sodium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 4-iodo-l-(3-methyl-4-mtrobenzyl)-3-pentafluoroethyl- lH-pyrazole (4.60 g). 'H-NMR (CDC13, ppm): 2.60 (3H, s), 5.38 (2H, s), 7.22-7.15 (2H, m), 7.53 (1H, s), 7.98 (1H, d). Synthesis Example 17 (Starting material) 4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl-lH-pyrazole (1.84g), (trifluoromethyl)trimethylsilane (1.14g), copper® iodide (1.52g), potassium fluoride (0.28g) were stirred in DMF (8 ml) at 100°C for 8 hours. After cooling, the mixture was poured into water and extracted with ethyl acetate . 'Me combined organic phase was washed with saturated aqueous solution of sodium chloride. After drying the organic layer with sodium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel c'olurm chromatography to obtain l-(3-methyM- ni1ro-benzyl)-3-pentafluoroethyl^-triiluorome1:hyl-lH-pyrazole(0.32g). 'H-NMR (CDC13, ppm): 2.61 (3H, s), 5.41 .(2H, s), 7.31-7.18 (2H3 m), 7.78 (1H3 s), 8.00 (1H, d). Synthesis Example 18 (Starling material) F 4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (2.06 g), copper powder (0.95 g), heptafluoro-1-iodopropane (2.96 g) and DMF (14 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining the inside temperature of 130-135°C. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (50 ml) and an insoluble matter was filtered with Celite and washed with ethyl acetate. The filtrate was concentrated under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)- 4-pentafluoropropyl-3- trifluoromethyl-lH-pyrazole (0.80 g). 'H-NMR (CDC13, ppm): 2.62 (3H, s), 5.42 (2H, s), 7,19-7.20 (2H, m), 7.74 (1H, s), 8.02 (1H, d). Synthesis Example 19 (Starting material) 4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (2.47 g), copper powder (1.14 g), nonafluoro-1-iodobutane (4.15 g) and DMF (16 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining the inside temperature of 130-135°C. After cooling to room temperature, the reaction mixture was diluted with toluene (50 ml) and an insoluble matter was filtered with Celite and washed with toluene. The filtrate was concentrated under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)- 4-nonafluorobutyl-3- trifluoromethyl-lH-pyrazole (1.50g). 'H-NMR (CDC13, ppm): 2.62 (3H, s), 5.42 (2H/s), 7.18-7:24 (2^3^,7^74(113, s), 8.00 (1H, d). sis Example 20 (Starting material) NH An acetonitrile solution (20 ml) of 3-trifluoromethyl-lH-pyrazole (1.0 g), dicerium ammonium nitrate (2.0 g) and bromine (0.7 g) was refluxed for 2 hours. After cooling, the reaction solution was washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure to obtain 4-bromo-3-trifluoromethyl-lH-pyrazole (1.6 g). 'H-NMR (CDC13, ppm): 7.73 (1H, s), 12.86 (1H, brs). Synthesis Example 21 (Starting material) 3-Methyl-4-nitroberi2yl chloride (0.77 g), 4-bromo-3-trifluoromethyl-lH-pyrazole (0.90 g) and potassium carbonate (0.57 g) were stirred in DMF (10 ml) at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain lr(3-methyl-4-ni1robenzyl)-4-bromo-3-trifluoromethyl-lH-pvrazole (0.9 g). 'H-NMR (CDC13, ppm): 2.58 (3H, s), 5.35 (2H, s), 7.24-7.21 (2H, m), 7.49 (1H, s),: 7.98 (1H, d). Synthesis Example 22 (Starting material) An acetonitrile solution (20 ml) of 3-trifluoromethyl-lH-pyrazole (0.5 g), dicerium ammonium nitrate (1.0 g) and N-chlorosuccinimide (0.7 g) was refluxed for 3 hours. After cooling, the reaction solution was washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride. After drying an organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure to obtain 4-cMoro-3-trifluoromethyl-lH-pvrazole (0.9 g). 'H-NMR (CDC13, ppm): 7.80 (1H, s). Synthesis Example 23 (Starting material) 3-Methyl-4-nitrobenzyl chloride (0.82 g), 4-chloro-3-trifluoromethyl-lH- pyrazole (0.63 g) and potassium carbonate (0.61 g) were stirred in DMF (10 ml) at room temperature for 2 hours. The reaction solution was diluted with eiiyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with, magnesium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain l-(3-memyM-nitrobenzyl)-4-chloro-3-trifluoromethyl- IH-pyrazole (0.98 g). 'H-NMR (CDC13, ppm): 2.62 (3H3 s), 5.33 (2H, s), 7.21-7.19 (2H, m), 7.46 (1H, s), 7.98 (IB, d). Synthesis Example 24 (Starting material) o' 2-(Trifluroaceryl)-lH-pyrrole (0.97 g) was added to DMF solution (10 ml) of 60% sodium hydride (0.16 g)'and the mixture was stirred at room temperature for 30 minutes. 3-Metnyl-4-nitrobenzyl chloride (1.0 g) was added thereto and the mixture was stirred at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)-2- (trifluoroacetyl)-lH-pvrrole (1 .53 g). 'H-NMR (CDC13, ppm): 2.55 (3H, s), 5.59 (2H, s), 6.44-6.41 (1H, m), 6.99 (1H, d), 7.04 (1H, s), 7.22-7.19 (1H, m), 7.35-7.32 (lH,m), 7.93 (1H, d). Synthesis Example 25 (Starting material) An acetonitrile solution (20 ml) of 2-(trifluoroacetyl)-lH-pyrrolei(p.5 g), dicerium ammonium nitrate (0.84 g) and iodine (0.47 g) was refluxed for 2 hours. After cqoling, the reaction solution was washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure to obtain 4-iodo-2- (trifluoroaceryl)-lH-pyrrole (0.6 g). 'H-NMR (CDC13, ppm): 7.28-7.35 (211, m), 9.52 (1H, brs). 1 mtfaesis Example 26 (Starting material) 02N 3-Methyl-4-nitrobenzyl chloride (0.63 g), 4-iodo-2- (trifiuoroaceryl) pyrrole (0.89 g) and potassium carbonate (0.57 g) were stirred in DMF (10 ml) at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 4-iodo-l- (3-methyl-4-nitroben2yl)-2-trifluoroacetyl- IH-pyrrole (0.45 g). 'H-NMR (CDC13, ppm):.2.60 (3H, s), 5.56 (2H, s), 7.05-7.12 (2H, m), 7.21 (1H, d), 7.39 (1H, s), 7.94 Synthesis Example 27 (Starting material) O2N. 4-Iodo-l-(3-methyl-4-nitrobenzyl)-2-1riiluoroaceiyl-lH-pyrrole (1.75 g), copper powder (5.08 g), iodopentafluoroethane (5.92 g) and DMSO (6 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining the inside temperature of 120°C. After finishing the reaction, the reaction mixture was poured into ice water and an insoluble matter was filtered with Celite, and then, it was extracted with ethyl acetate. The extracted solution was washed with water and then dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitr6phenyl)-4-peniafluoroethyl-lH-pyrrole (1.35 g). 'H-NMR (CDC13, ppm): 2.59 (3H, s), 5.62 (2H, s), 7.00-7.10 (2H, m), 7.43-7.50 (2H, m), 7.96 (1H, d). Some specific examples of other processes to synthesize the compounds of the aforementioned formula (IX) are shown below. Synthesis Example 28 (Starting material) TO a toluene suspension of ethyl 4,4,4-trifluoroacetoacetate (5.0 g), sodium hydride (1,1 g) was slowly added and the mixture was stirred for 1 hour. After adding 4-chloromethyl-2-methyl- 1-nitre-benzene (5.5 g) and potassium iodide dissolved in acetone (0.5 g), the reaction solution was refluxed for 5 hours. After cooling, the solvent was distilled off under reduced pressure. The residue was suspended in ethyl acetate and washed with IN aqueous solution of hydrochloric acid. After drying the organic layer with sodium sulfate, the solvent was distillea off and the obtained residue was purified by silica gel column chromatography to obtain ethyl 4,4,4-trifluoro-2- (3-methyl-4-nitro-benzyl)-3-oxo-butyrate(6.3 g).nD 20 1.4970 Synthesis Example 29 (Starting material) H3C Ethyl 4,4,4-trifluoro-2- (3-methyl-4-nitro-benzyl)-3-oxo-buryrate (2.0 g), hydrazine monohydrate (0.5 g) and a small amount of p-toluenesulfonic acid were dissolved in toluene, and the mixture was refluxed for 4 hours. After cooling, the solvent was distilled off under reduced pressure. The residue was suspended in ethyl acetate, and washed with IN aqueous solution of hydrochloric acid. After drying the organic layer with sodium sulfate, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain 4-(3-methyl-4-nitro-benzyl)-5-trifluoromethyl- 2,4-dihydro-pyrazol-3-one (1.0 g). 'H-NMR (DMSO-dfo 90MHz): 62.2 (3H, s), 3.8 (2H, s), 7.0 (1H, d, J=5.5Hz), 7.2 (1H, s), 7.8 (1H, d, J=5.5Hz), 11.2(lH,brs). Synthesis Example 30 (Starting material) (Figure Removed) To a DMF suspension of 4-(3-methyl-4-nitro-benzyl)-5-trifluoromethyl-2,4-dihydro-pyrazol-3-one (1.0 g) and potassium carbonate (1.5 g), chlorodifluoromethane (5.7 g) was sealed in by using a balloon. After 5 hours, after the gas in the solution was saturated, the vessel was tightly closed and the mixture was stirred at 50°C for 5 hours. After cooling, the solvent was distilled off and the obtained residue was dissolved in ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the organic layer with sodium sulfate, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain 5-difluoromethoxy-l-difluoromethyl-4-(3- 80 ethyl-nitro-benzyl)-3-trifluoromethyl-lH-pyrazole (IX-1) (0.5 g) and3-difluoromethoxy-l-difluoromethyl- 4- (3-nie1hylnitro-ben2yl)-5-trifluoromethyl-lH-pyrazole (K-2) (0.4 g) respectively. (EX-1): nD°1.4780, (K-2): nD 201.4855. Synthesis Example 31 (Starting material') (3-Methyl-4-nitrophenyl)-hydrazine (3.0 g) and hexafluoroacetylacetone (3.7 g) were dissolved in toluene and the solution was refluxed for 6 hours. After cooling, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitropheriyl)- 3,5- bis(trifluoromethyl)-lH-pyrazole (5.6 g). nD 201.4890. Synthesis Example 32 (Starting material) CF2CF3 "3° !? \V-CF2CF3 (3-Methyl-4-nitro-phenyl)-hydrazine (2.0 g).and 1,1, 1,5,5,6, 6,6-octafluoro-2,4-hexanedione (3.1 g) were dissolved in toluene and the solution was refluxed for 6 hours. After cooling, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain l'(3-methyl-4-nitro-phenyl)-3- pentafluoroethyl-5-trifluoromethyl-lH-pyrazole (K-3)~ (3.0 g) and 2-(3-mernyW-mfro-phenyl)-5-pentafluoroethyl-3- (TX-4) (0.5 g), respectively. CK-3):nD 20 1.4690, (K-4): 'H-NMR (CDC13, 90MHz): 82.6 (3H, s), 3.3 (1H, br d, J=16Hz), 3.7 (1H, br d, J=16Hz), 4.1 (1H, s), 7.2 (2H, m), 7.8 (1H, d, J=7.8Hz). Synthesis Example 33 (Starting material) To a THF suspension of l-(3-meihyl-4-nitrQ-phenyl)-ethanone (2.0 g), sodium hydride (0.6 g) was slowly added and the mixture was stirred for 1 hour. After adding ethyl trifluoroacetate (1.6 g), the reaction mixture was refluxed for 5 hours. After cooling, the solvent was distilled off under reduced 81 pressure. The residue was suspended in, ethyl acetate and washed with IN aqueous solution of hydrochloric acid. After drying the organic layer with sodium sulfate, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain 4,4,4-trifluoro-l- (3-methyl-4-nitro-phenyl)-butane-l,3- dione (2.5 g). 'H-NMR (CDOa, 90MHz): 62.6 (3H, s), 6.5 (1H, s), 7.7-8.1 (3H, m). Synthesis Example 34 (Starting material) (IX-5) (IX-6) A toluene solution of 4,4J 4-trifluoro-l-(3-methyl^-nitro-phenyl)-butane-lJ3-dione (1.8 g), 2,2,2-trifluoroethylhydrazine (1.2 g) and a catalytic amount of p-toluenesulfonic acid were refluxed for 6 hours. After cooling, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain 3-(3-me1hyM-mtro-phenyl)-l^2,2}2-1rifluoro^thyl)-5-1rifluoro-methyl-lHpyrazole (K-5) (1.1 g) and 5-(3-methyl-4-nitro-phenyl)-l- (2,2,2-trifluoro-etbyl)-3-trifluoromethyl-lHpyrazole (K-6) (0.5 g), respectively. (K-5) mp; 98-104°C, (K-6)mp; 50-53°C. Synthesis Example 35 (Starting material") o o To a dichloromethane solution of 2,2-dimethyl-l,3-dioxane-4,6-dione (10 g) and dimethylaminopyridine (17 g), a dichloromethane solution of S-methyM-nitro-benzoyI chloride (14 g) was added dropwise under ice cooling. After stirring at room temperature for 3 hours and then adding 100 ml of ethanol, the mixture was refluxed for 2 hours. After cooling, the solvent was distilled off under the reduced pressure. The residue was dissolved in ethyl acetate and washed with IN aqueous solution of hydrochloric acid. After drying the organic layer with sodium sulfate, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain ethyl -3-(3-methyl- 4-nitro-phenyl)-3-oxo- propionate (12.4 g). mp; 207-211°C. mthesis Example 36 CStarting material) N To an ethanol solution of ethyl 3-(3-methyl-4-nitro-phenyl)-3-oxo-propionate (3.0 g), hydrazine monohydrate (0.9 g) and a small amount of p-toluenesulfonic acid were added and the mixture was refluxed for 5 hours. After cooling, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 5-(3-methyl-4-mtro-phenyl2,4- dihydro-pyrazol-3-one (2.6 g). mp; 218-219°C. Synthesis Example 37 (Starting material) (Figure Removed) To a DMF suspension of S^S-methyM-nitro-pheny^^^-dihydro-lH-pyrazol-S-one, (2.0 g) and potassium carbonate (6.3 g), chlorodifluoromethane (8.7 g) was sealed in by using a balloon. After 5 hours, after the gas in the solution was saturated, the vessel was tightly closed and the mixture was stirred at 50°C for 5 hours. After cooling, the solvent was distilled off and the obtained residue was. dissolved in ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying with sodium sulfate, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain 5-difluoromerhoxy-l-diiluoromethyl-3-(3-methyl- nitro-phenyl)-lH-pyrazole (IX-7) (0.7 g) and 3-difluoromethoxy-l-difluoromethyl-5-(3-methyl-4- nitro-phenyl)-lH- pyrazole (TX-8) (0.5 g), respectively. (IX-7) mp; 80-82°C, (Dt-8) mp; 99-100°C. Synthesis Example 38 (Starting material) To an ethanol solution (60 ml) of hydrazine monohydrate (5.00 g), an ethanol solution (20 ml) of 3-methyl-4-nitrobenzyl chloride (3.71 g) was added dropwise while refluxingit, and the mixture was continuously refluxed for 6 hours. After finishing the reaction, the solvent was distilled off and (3-methyl-4-nitrobenzyl)- hydrazine (3.50 g) was obtained. 'H-NMR (CDC13, ppm): 2.60 (3H, s), 2.65-3.35 (3H, m), 3.95 (2H, s), 7.20-7.40 (2H, m), 7.98 (1H, d). Svofhesis Example 39 ("Starting material') (Figure Removed) (3-Methyl-4-nitrobenzyl)-hydrazine (1.81 g) and 5-emoxy-l,l,l,2,2-pentafluoro-4-penten-3-one (2.18 g) were refluxed in ethanol (60 ml) for 8 hours., and p-toluenesulfonic acid (0.10 g) was added thereto and the mixture was further refluxed for 6 hours. After finishing the reaction, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography (mixed solvent of n-hexane and ethyl acetate) to obtain l-(3-methyl-4-nitrobenzyl)-5-pentafluoroethyl- lH-pyrazole (0.96 g) as the first elution portion and l-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl- lH-pyrazole (0.50 g) as the second elution portion. OK-9): 'H-NMR (CDC13, ppm): 2.61 (3H, s), 5.49 (2H, s), 6.70 (IB, bs), 7.05-7.15 (2H, m), 7.66 (IB, bs), 7.94 (IB, d). (K-10): 'H-NMR (CDC13, ppm): 2.64 (3H, s), 5.40 (2H, s), 6.63 (1H, d), 7.07-7.20 (2H, m), 7.52 (1H, d), 7.9.5 (IE, d). Synthesis Example 40 (Starting material) A mixture of 5-fluoro-2-nitrotoluene (2.33 g), 4-iodo-lH-pyrazole (2.91 g) and potassium carbonate (2.49 g) was heated and stirred in DMF (30 ml) at 140°C for 4 hours. After cooling to room temperature, the reaction mixture was poured into ice water to separate out crystals. The obtained crystals were filtered, washed with water and dried, and 4-iodo-l-(3-methyl-4-nitrophenyl)- lH-pyrazole (4.60 g) was obtained. 'H-NMR(CDC13,ppm): 2.70 (3H, s), 7.50-7.70(3H,m),7.95-8.15 (2H,m). Synthesis Example 41 (Starting material) 4-Iodo-l-(3-methyl-4-nitrophenyl)-lH-pyrazole (1.98 g), copper powder (1.14 g), iodopentafluoroethane (8.85 g) and DMSO (9 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining the inside temperature of 100°C. After finishing the reaction, the reaction mixture was poured into ice water and an insoluble matter was filtered with Celite, and then, it was extracted with ethyl £tate. The extracted solution was washed with water and dried with anhydrous sodium sulfate., After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrophenyl)-4-pentafluoroe1iiyl- IH-pyrazple (0.72 g). 'H-NMR (CDC13, ppm): 2.70 (3H, s), 7.60-7.73 (2H, m), 7.93 (1H, s), 8.13 (1H, d), 8.23 (1H, s). Synthesis Example 42 (Starting material') To a suspension of methanol (300 ml) of 3-methyl-4-nitroacetophenone (26.88 g), sodium borohydride (8.51 g) was added at 0°C over a period of 1 hour. The mixture was further stirred at room temperature for 8 hours. After finishing the reaction, the reaction mixture was poured into ice water (1,000 ml) and extracted with ether. The organic layer was washed with saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. After distilling off the solvent, the aimed l-(3-methyl-4-nitrophenyl)-ethanol (23.33 g) was obtained. 'H-NMR (CDC13, ppm): 1.51 (3H, d), 1.98 (1H, d), 2.62 (3H, s), 4.90-5.01 (1H, m), 7.28-7.35 (2H, m), 7.98 (1H, d). Synthesis Example 43 (Starting material) (Figure Removed) Into a THF solution (35 ml) of l-(3-methyl-4-nitrophenyl)-ethanol (5.44 g) and trieihylamine (3.95 g), a THF solution (10 ml) of methanesulfonyl chloride (3.48 g) was added dropwise at 5°C over a period of 30 minutes. Further, the mixture was stirred at room temperature for 8 hours. After finishing the reaction, the solvent was distilled off and the residue was dissolved in ethyl acetate (100 ml). It was washed with 2N aqueous solution of hydrochloric acid and saturated aqueous solution of sodium bicarbonate and then dried with anhydrous magnesium sulfate. After distilling off the solvent, the aimed l-(3-methyl-4-nitrophenyl)-ethyl methanesulfonate (5.80 g) was obtained. 'H-NMR (CDC13, ppm): 1.74 (3H, d), 2.65 (3H, s), 2.95 (3H, s), 5.76 (1H, q), 7.35-7.45 (2H, m), 8.01 (1H, d). vfeffhesis Example 44 ("Starting material) O2N l-(3-MeHiyl-4-nitrophenyl)-ethyl methanesulfonate (2.59 g), 3-trifluoromethyl-lH-pyrazole (1.09 g), potassium carbonate (1.66 g) and 18-crown-6 (0.26 g) were refluxed in acetonitrile (100 ml) for 6 hours. After finishing the reaction, water (100 ml) was added to the mixture and extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium bicarbonate and then dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography to obtain l-[l-(3-methyl-4-nitrophenyl)-ethyl]-3-trifluorornethyl- IH-pyrazole (1.60 g). • 'H-NMR (CDC13, ppm): 1.95 (3H, d), 2.59 (3H, s), 5.59 (1H, q), 6.57 (1H, bs), 7.13-7.20 (2H, m), 7.47 (lH,bs), 8.00 (1H, d). Synthesis Example 45 (Starting material') HN Ethyl :pentafluoropropylenate (14.6 g) and hydrazine monohydrate (3.6 g) were refluxed in tetrahydrofuran (300 ml) for 1 hour. After cooling to room temperature, trifluoroacetamidine (10.0 g) was added dropwise to the mixture and it was refluxed for 3 hours. After finishing the reaction, saturated aqueous solution of sodium hydrogen carbonate was added thereto and the mixture was extracted with ethyl acetate. After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off to obtain crude 3-pentafluoroethyl-5-trifluoromethyl-lH- (l,2,4)-triazole (7.9 g). Synthesis Example 46 ("Starting material) (IX-11) on3 "2 5 (IX-12) l-(3-Memyl-4-nitrophenyl)-ethyl mernanesulfonate (2.5 g), 3-pentafluoroethyl-5-trifluoromemyl-lH- (l,2,4)-triazblev(2;2 g),-pVtassiurh carbonate (1.6 g) and 18-crown-6 (0.26 g) were refluxed in acetonitrile (100 ml) for 6 hours. After finishing the reaction, water (100 ml) was added thereto and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride (100 ml) and then dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column chromatography (mixed Invent of n-hexane and ethyl acetate) to obtain (K-ll) l-([l-(3-methyl-4-nitro-phenyl)-ethyl]-5- pentafluoroethyl-3-trifluoromethyl- lH-(l,2,4)-triazole (0.95 g) as the first elution portion and (EX-12) l-([l-(3-methyl-4- nitro-phenyO-ethylJ-S-pentafluoroethyl-S-trifluorometiiyl-lH-C1-6-triazole (1.35 g) as the second elution portion. (K-ll) 'H-NMR (CDC13)5: 8.03-7.97 (1H, m), 7.37 (2H, t, J=5.4Hz), 5.86 (1H, q, J=7.0Hz), 2.62 (3H, s), 2.00(3H,d,J=7.0Hz). (K-12) ]H-NMR (CDC13) 6: 7.98 (1H, d; J=8.2Hz), 7.34 (2H, t, J=7.1Hz), 5.81 (1H, q, J=7.0Hz), 2.63 (3H, s), 2.01 (3H, d, J=7.0Hz). Synthesis Example 47 (Starting material) Sodium hydride (0.10 g) was added to a DMF solution (12 ml) of 4-methyl-5-pentafluoroethyl- 4H-[l,2,4]triazol-3-thiol (0.70 g), and the mixture was stirred at room temperature until the generation of hydrogen .gas stopped. Continuously, 5-fluoro-2-nitrotoluene (0.47 g) was added thereto and the mixture was further stirred at room temperature for 1 hour. After cooling to room temperature, the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride and then dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was purified by; silica gel column chromatography (mixed solvent of n-hexane and ethyl acetate) to obtain the aimed 4-methyl-3- (3- methyl-4rnitrophenyl sulfanyl)-5-pentafluoroethyl-4H-(l,2,4)-triazole (0.55 g). 'H-NMR (CDC13, ppm): 2.70 (3H, s), 3.80 (3H, s), 8.10-8.30 (3H, m). Synthesis Example 48 (Starting material) A mixture of 2-memylmelcapto^.6-bistrifluoromemyl-pyrimidine (36 g), oxone (126 g), water (500 ml) and chloroform (110 ml) was refluxed for 2 days. After cooling to room temperature., the mixture was extracted with dichloromethane. The obtained organic layer was washed with water and then dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained crude crystals were washed with petroleum ether to obtain 2-methanesulfonyl-4.6-bistrifJuoromethyl-pyrimidine (7.5 g). 'H-NMR (CDC13, ppm): 3.48 (3H, s), 8.19 (1H, s). Example 49 (Starting material^) 4-Nitro-m-cresol (0.77 g), 2-methanesulfonyl-4, 6-bistrifluoromethyl- pyrirnidine (1.77 g) and potassium carbonate (1.04 g) were refluxed in acetonitrile (15 ml) for 5 hours. After finishing the reaction, the reaction mixture was poured into ice to separate out crystals. The obtained crystals were filtered and dried to obtain 2-(3-methyl-4-nitrophenoxy)- 4,6-bistrifluoromethyl-pyrimidine (1.03 g). 'H-NMR (CDC13, ppm): 2.60 (3H, s), 7.1-7.3 (2H, m), 7.67 (1H, s), 8.10 (1H5 d). Synthesis Example 50 (Starting material) CH, (3-Methyl-4-nitrophenyl)-acetonitrile(3.52g) was dissolved in pyridine (30 ml), thereto excess H2S was bubbled into at room temperature for 3 hours. Then the mixture was poured onto ice. The precipitate was collected by suction, washed with water and dried to obtain 2-(3 -methyl-4-nitro-phenyl)- thioacetamide (1.69 g). ): 2.60 (3H, s),4.06 (2H, s), 6.40-8.00 (5H, m) Synthesis Example 51 (Starting material) CHQ 2-(3-Methyl-4-nitrophenyl)-thioacetamide (1.00 g), l-bromo-333,4,4,4-pentafluoro-2-butanone (1.15 g) and potassium carbonate (0.79 g) were stirred in DMF (10 ml) at room temperature for 1 hour. The reaction solution was diluted with ethyl acetate and washed witii water and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 2-(3-Methyl-4-nitro-phenyl)-thioacetimidic acid 3,3,4,4,4-pentafluoro- 2-oxo-butyl ester (1.30 g). 'H-NMR(CDC13)ppm):2.55 C3H, s), 3.57 (2H, dd), 3.90;(2Et, d), 72722-2H,rn),7-91^.89 (lH,m) Example 52 (Starting material) Trifluoroacetic anhydride(1.47g) was added to 2-(3-Methyl-4-nitro-pheny])-thioacetimidic acid 3,3,4,44-pentafluoro-2-oxo-butyl ester (1.30 g) and triethylamine (0.71 g) in dichloromethane (10 ml), and stirred at room temperature for 20 minutes. The reaction solution was washed with water, and the solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 2-(3-memyM-rjitro-benzyl)-4-perfluoroethyl-thiazole (0.70 g). 'H-NMR (CDC13, ppm): 2.63 (3H, s), 4.43 (2H, s), 7.30-7.28 (2H, m), 7.75 (1H, s), 7.98 (1H, d) Synthesis Example 53 rStarting material) An acetonitrile solution (20 ml) of 3-pentafluoroethyl-lH-pyrazole (2.0 g), dicerium ammonium nitrate (3.0 g) and iodine (1.6 g) was refluxed for 3 hours. After cooling, the reaction solution was washed with saturated aqueous solution of sodium thipsulfate and .saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure to obtain 4-iodo-3- pentafluoroethyl-lH-pyrazole (3.2 g). 'H-NMR (CDC13, ppm): 7.77 (1H, s), 11.11(1H, m) Synthesis Example 54 (Starting material) F2HCF2C C2F5 (Figure Removed) 4-Iodo-3-pentafluoroethyl-lH-pyrazole (6.24 g), copper powder (3.81 g), Iodo-l,l,2,2-tetrafluoroetharie (9.12 g) and DMF (30 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining the inside temperature of 120-125°C. After cooling to room temperature, the insoluble material was filtered off through Celite and washed with diethyl ether. The filtrate was diluted with water and extracted with diethyl ether. The organic phase was washed wMi water and dried over sodium sulfate, and concentrated under the reduced pressure. The crude product was distilled under reduced pressure to obtain 3-pentafluoroethyl-4-(l,l,2,2-tetrafluoroethyl)-lH-pyrazole (0.60 g), bp. 125-135°C/20mbar. 'H-NMR (CDC13, ppm): 5.98 (1H, tt), 7.96 (IB, s), 12.22 (IB, m) Synthesis Example 55 (Starting material) 4-Iodo-3-pentafluoroethyl-lH-pyrazole (12.48 g), copper powder (7.63 g), iodopentafluoroethane (29.50 g) and DMF (60 ml) were set in an autoclave and heated and stiired for 8 hours, maintaining the inside temperature of 120-125°C. After cooling to room temperature, the insoluble material was filtered off through Celite and washed with diethyl ether. The filtrate was diluted with water and extracted with diethyl ether. The organic phase was washed with water and dried over sodium sulfate, and concentrated under the reduced pressure/The crude product was distilled under reduced pressure to obtain 3,4-bis-pentafluoroethyl-lH-pyrazole (1.20 g), bp. 110-115°C/20 mbar. 'H-NME. (CDC13, ppm):.7.99 (1H, s), 12.31 (1H, m). Synthesis Example 56 (Starting material) An acetonitrile solution (20 ml) of 4-methyl-lH-pyrazole (0.5 g), dicerium ammonium nitrate (1.7 g) and iodine (1.9 g) was refluxed for 3 hours. After cooling, the reaction solution was washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced pressure to obtain 3,5-diiodo~4- methyl- IH-pyrazole (1.2 g). JH-NMR (CDC13, ppm): 2.03 (3H, s), 6.96 (IE, br s) Synthesis Example 57 (Starting material) 5-Trifluoromethyl-lH-(l,2,4)-triazole-3-thiol(1.0g), heptafluoro-1-iodopropane (3.5 g) and triethylamine (0.90 g) were stirred in DMF (10 ml) at 90°C for 24 hours. After cooling to room temperature, he reaction mixture was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride. After drying the "organic layer with magnesium .'sulfate/the solvent was distilled" off 'under the reduced pressure to obtain '3-heptaflubfc)pr6pylsulfanyl-5-tnfluoromethyl- lH-(l,2,4)-1riazole(0.70g). 90 : examples Biological Test Example 1: Test against larva of Spodoptera litura Preparation of test solution: Solvent: Dimethylformamide : 3 parts by weight Emulsifier: Polyoxyethylene alkyl phenyl ether: 1 part by weight In order to make an appropriate formulation of an active compound, 1 part by weight of the active compound was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier and the mixture was diluted with water to a prescribed concentration. Test method: Leaves of sweet potato were soaked in the test solution diluted to a prescribed concentration with water, dried in the air and put in a dish of 9 cm diameter. 10 larvae ofSpodoptera litura at the third instar were placed on the leaves and kept in a room at the constant temperature of 25°C. After 2 and 4 days further leaves of sweet potato were added and after 7 days the number of dead larvae was counted and the rate of death was calculated. In this test the results of 2 dishes at 1 section were averaged. Biological Test Example 2: Test against larva of Cnaplialocrocis medinalis Guenee Testmethod: Paddy rice (variety: Tamanishiki) planted in a pot was treated by spraying 50ml per pot of the diluted aqueous solution of the prescribed concentration of the active compound prepared in the same manner as in the above-mentioned Biological Test Example 1. After the treated rice plant was dried in the air, their foliage part was cut in 4-5 cm length, which were put in a dish with 9 cm diameter with a sheet of filter paper and 2 ml of water. Five larvae of Cnaplialocrocis medinalis Guenee at the second instar were put in the dish that was placed in a room at the constant temperature of 25°C. After 2 and 4 days,' each rest (each 1/3 amount) of foliage parts of rice plant were cut in the same manner and added to the dish. After 7 days the number of dead larvae was counted and the rate of death was calculated. In this test the results of 2 dishes at 1 section were averaged. Test results: In the above BiologicaJ.Jlest.JbxampJles,;1ancl.2, as;specific, examples, the compounds, pi Jhe . aforementioned compound Nos. 8, 9,10,11,12,13,14,15,16,45, 47,48,49, 51, 52, 53, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 93, 103, 107, 116, 128, 132, 137, 138, 139, 140,141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 153, 155, 157, 174, 176, 177, 178, 180, 181, 182,210,211,212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 226, 227, 229, 230, 231, 238., 239, 242, 243, 251, 253; . 264, 268, 270, 281, 299, 308, 310, 318, 322, 413,414, 417,422, 434, 446, 448, 473, 475, 492, 50T; 508, 512, 518, 520, 539, 543, 544, 545, 546, 547, 548, 549, 552, 554, 559, 561, 562, 563, 564, 565, 566, 567, 568, 570, 571, 572, 573, 574, 578, 579, 580, 626, 637, 638, 639, 640, 641, 642, 643, 644, 645, 646, 647, 648, 649, 650, 655, 656, 657, 658, 659, 660, 661, 662, 663, 664, 665, 666, 667, 668, 669, 670, 671, 672, 681, 761, 762, 763, 804 and 920 showed controlling effect of 100% of rate of death at 20 ppm concentration of the active component. Biological Test Example 3: Test against Mvzus persicae resistant to organophosphorous agents and carbamates Test method: About 30 bred Myzus persicae resistant to organophosphorous agents and carbamates were inoculated per 1 seedling of eggplant planted in a vinyl pot of 6 cm diameter. One day after the inoculation, a sufficient amount of a diluted aqueous solution of a prescribed concentration of an active compound prepared as mentioned above, was sprayed by using a spray gun. After spraying it was placed in a green house of 28°C and the rate of death was calculated 7 days after the spraying. Test was repeated twice. Test results The compounds of the aforementioned compound Nos. 140, 141, 144, 146, 147, 148, 174, 176, 177, 178, 180, 181, 211, 213, 214, 215, 218, 220, 222, 226, 239, 243, 569, 570, 572, 579, 761, 797 and 920 offered to the test as specific examples showed controlling effect of 100% of rate of death at 100 ppm concentration of the effective component. Formulation Example 1 (Granule1) To a mixture of 10 parts of the compound of the present invention (No. 8), 30 parts of bentonite (montniorillomte), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water are added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules. Formulation Example 2 ("Granules') 95 Parts of clay mineral particles having particle diameter distribution in the range of 0.2-2 mm are put in a rotary mixer. While rotating it, 5 parts of the compound of the present invention (No. 11) are sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules. Ihnnulation Example 3 (Emulsifiable concentrate) 30 Parts of the compound of the present invention (No. 12), 55 parts of xylene, 8 parts of polyoxyethylene aliyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsifiable concentrate. Formulation Example 4 (Wettable powder) 15 Parts of the compound of the present invention (No. 15), 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate-formaHn-condensate are crushed and mixed to make a wettable powder. Formulation Example 5 (Water dispersible granule) 20 Parts of the compound of the present invention (No. 16), 30 parts of sodium ligninsulfonate, parts of bentonite and 35 parts of calcined diatomaceous earth powder are well mixed, added with water, extruded with 0.3 mm screen and dried to obtain water dispersible granules. WE CLAIM: 1. N1-(pyrazol-l-ymethyl)-2-methylphenyl)-phatalamide derivatives of the formula (I) (Formula Removed) wherein X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-4alkylsulfonyloxy, C1-4alkylsulfinyl, C1-4alkylsulfenyl or C1-4alkylsulfonyl, R1 represents C1-4alkyl, C1-4alkylthio-C1-4alkyl, C1-4alkylsulfinyl-C1-4alkyl or C1-4alkylsulfonyl-C1-4alkyl, Y represents fluorine, chlorine, bromine or Ci^alkyl, m represents 1, A represents CH2 or CH(CH3), and Q represents 5-membered or 6-membered heterocyclic group containing one to three N-atoms and which heterocyclic group can be optionally substituted by at least one selected from a group consisting of C1-6alkyl, C1-6alkoxy, C1-6alkylthio, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-10haloalkyl, C1-6haloalkoxy, C1-6haloalkylthio, C1-6haloalkylsulfinyl, C1-6haloalkylsulfonyl, C1-6haloalkylcarbonyl, halogen, oxo and hydroxy. 2. The compounds as claimed in claim 1, wherein X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, methanesulfonyloxy, C1-2alkylsulfinyl, C1-2alkylsulfenyl or C1-2 alkylsulfonyl, R1 represents isopropyl, C1-2alkylthio-C3-4alkyl, C1-2alkylsulfinyl-C3-4alkyl or Cl-2aikylsulfonyl-C3-4alkyl, Y represents fluorine, chlorine or methyl, m represents 1, A represents CH2 or CH(CH3), and Q represents a heterocyclic group, selected from a group consisting of pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, pyrrolyl, and pyrimidinyl and which heterocyclic group can be optionally substituted by at least one selected from the group consisting of C1-4alkyl, C1-4alkoxy, C1-4alkylthio, C1-4alkylsulfinyl, C1-4alkylsulfonyl, C1-8haloalkyl, C1-4haloalkoxy, C1-4haloalkylthio, C1-4haloalkylsulfinyl, C1-4haloalkylsulfonyl, C1-4haloalkylcarbonyl, fluorine, chlorine, bromine, iodine, oxo and hydroxy. 3. Processes for the preparation of the compounds as claimed in claim 1, wherein (a) compounds of the formula (II) (Formula Removed) wherein R1 and X are as defined in claim 1 , are reacted with compounds of the formula (III) (Formula Removed) wherein Y, A, m and Q are as defined in claim 1, in the presence of inert solvents, of the kind such as herein described and, if appropriate, in the presence of an acid catalyst, of the kind such as herein described, wherein the reaction can be in a temperature range from -20 °C to 100 °C. 4. The compound as claimed in claim 1 or 2, whenever used as an insecticida! composition comprising at least one benzenedicarboxamide compound 0.1-95% by weight.

Full Text

• ( (PYRAZOL-l-yMETHYL)-2-METHYIjPHENyL)~ PHATALAMIDE DERIVATIVES AND RELATED
COMPOUNDS INSECTICIDES
The present invention relates to novel benzenedicarboxamides, processes for the preparation thereof,
their intermediates and their use as insecticides.
It was akeady known that phthalamide derivatives are useful-as insecticides [see JP-A 11-240857
(1999), JP-A 2001-64258, JP-A 2001-64268, JP-A 2001-131141, JP-A 2003-40864, WO 01/21576
and WO 03/11028], and also that they show medicinal function [see JP-A 59-163353 (1984)].
There have now been found novel benzenedicarboxamides of the formula (T)
(Figure Removed)
wherein
X represents hydrogen, halogen atom, nitro, Ci.6alkylsulfonyloxy, Q-ealkvlsulfinyl,
sulfenyl or Ci.6alkylsulfonyl,
R1 represents CMalkyl, Ci.6alkylthio-Cwa]]cyl, Ci^alkylsulfinyl-Q-fialkyl or Cw alkylsulfo-
Y represents halogen or
m represents 0 or 1,
A represents O, S, SO, SO2, CH2 or CH(CH3), and
Q • represents a 5- or 6-membered heterocyclic group that contains at least one hetero atom
selected from the group consisting of N, O and S and can be optionally substituted.
The compounds of the formula 0), according to the invention, can be obtained by
(a) reacting compounds of the formula (U)
wherein R and X have the same definitions as aforementioned,
with compounds of the formula (HI)
(Figure Removed)
wherein Y, A, m and Q have the same definitions as aforementioned,
in the presence of inert solvents, and if appropriate in the presence of an acid catalyst,
reacting compounds of the formula (IV)
(Figure Removed)
wherein X, Y, A, m and Q have the same definitions as aforementioned,
wilh compounds of the formula (V)
H2N-R1 (V)
wherein R1 has the same definitions as aforementioned,
in the presence of inert solvents, and if appropriate in the presence of an acid catalyst,
reacting compounds of the formula (VI)
(Figure Removed)
wherein X and R1 have the same definitions as aforementioned,,
with the compounds of the formula (HT),
wherein Y, A, m and Q have the same definitions as aforementioned,
in the presence of inert solvents, and if appropriate in the presence of an acid catalyst,
reacting compounds of the formula (VTQ
(Figure Removed)
wherein X, Y, A, m and Q have the same definitions as aforementioned,
with the compounds of the formula (V),
H2N-R1 (V)
wherein R1 has the same definitions as aforementioned,
in the presence of inert solvents, and if appropriate in the presence of an acid catalyst,
or
(e) • compounds of the formula (VET)
wherein X, Y, A, m and Q have the same definitions as aforementioned,
are reacted with the compounds of the formula (V),
H2N-R1 (V)
wherein R1 has the same definitions as aforementioned,
in the presence of inert solvents, and if appropriate in the presence of an acid catalyst,
or
(i) in the case that R1 represents C1-6alkylsulfinyl-C1-6allcyl orC1-6alkylsulfonyl-C1-6alkyl in the
fonnula (I), reacting compounds of the formula (If)
(Figure Removed)
wherein
RIf represents C1-6alkylthio-C1-6alkyl, and
X, Y, A, m and Q have the same definitions as aforementioned,
with an oxidizing agent in the presence of inert solvents.
According to, the present invention, the benzenedicarboxamides^pf the fonnula (I) show a strong
insecticidal action.
The compounds of the formula (I) are conceptually embraced in the general formula described in the
aforementioned JP-A 11-240857 (1999). But they are not specifically disclosed at all in it and new
compounds. Surprisingly, they show particularly remarkable insecticidal -action compared with
similar compounds described in the known prior art
In the present specification:
"Halogen" represents fluorine, chlorine, bromine and iodine., and preferably represents fluorine,
chlorine and bromine.
"Alky!" represents straight chain or branched chain Chalky!, for example, methyl, ethyl, n- or
iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl,
n-dodecyl, etc. and preferably represents Ci^alkyl.
As each alkyl part in "alkylsulfonyloxy", "alkylsulfenyl", "alkylthioalkyl", "alkylsulfinylalkyl", .
"alkylsulfonylalkyl", "alkoxy", "alkylthio", "alkylsulfmyr, "alkylsulfonyl", "haloalkyl",
"haloalkoxy", "haloalkylthio", "haloalkylsulfinyl", "haloalkylsulfonyl" and "haloalkylcarbonyl",
there can be mentioned the same as described in the above-mentioned "alkyl" as examples.
As each halogen part in "haloalkyl", "haloalkoxy", "haloalkylthio", "haloalkylsulfinyl".,
"haloalkylsulfonyl" and "haloalkylcarbonyl", there can be mentioned the same as described in the
above-mentioned "halogen" as examples.
"5- or 6-membered heterocyclic group" contains at least one hetero atom selected from the group
consisting of N, O and S, and preferably represents a heterocyclic group containing "one to three
atoms", or "one O atom", or "one S atom", or "both one S atom and one to two N atoms", or "both
one O atom and one to two N atoms", and as specific examples thereof, pyrazolyl, triazolyl,
pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl, furyl, thienyl, oxadiazolyl and pyrimidinyl, and moreover
as most preferable examples thereof, pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl,
oxadiazolyl and pyrimidinyl are exemplified.
In the compounds of the formula (T), according to the invention, the compounds in case that
X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, CM alkylsulfonyloxy,
C1-6alkylsulfinyl, C1-6alkylsulfenyl or C1-6alkylslfonyl,
R1 represents C1-6alky!, C1-6alkylthio-C1-6alkyl, C1-6alkylsulfinyl-C1-6alkyl or C1-6alkylsulfo-
Y represents fluorine, chlorine, bromine or CMalkyl,
m represents 0 or 1,
A represents O, S, SO, S02, CH? or CH(CH3), and
Q represents 5-meinbered dr~6-membefed heterocyclic group that contains at least one hetero
atom selected from a group consisting of N, 0 and S and can be optionally substituted by at
least one selected from a group consisting of C1-6alkyl, C1-6alkoxy, C1-6alkyltbio, C1-6
finyl, C1-6alkylsulfonyl5 C1-60haloalkyl, C1-6haloalkoxy, C1-6haloalkylthio,C1-6haloalkylsulfinyl,
C1-6haloalkylsulfonyl, C1-6shaloalkylcarbonyl, halogen, oxo and hydroxy group, •
can be mentioned as preferable.
Above all, in the compounds of the formula (I), the compounds in case that
X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, methanesulfonyloxy,
C1-6alllsulfinyl, C1-6alkylsulfenyl or C1-6alkylslfonyl}
R1 represents isopropyl, Ci.2alkylthio-C1-64alkyl, C1-6alkylsulfinyl-C1-6alkyl or C1-6alkylsulfonyl-
C1-6alkyl,
Y represents fluorine, chlorine or methyl,
m represents 0 or 1,
A represents O, S, SO, SO2s CH2 or CH(CH3), and
Q represents heterocyclic group, selected from a group consisting of pyrazolyl, triazolyl,
pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl, oxadiazolyl andpyrimidinyl, that can be optionally
substituted by at least one selected from the group consisting of Chalky!, C1-6alkoxy,
C1-6alkylthio, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-68haloalkyl, C1-6haloalkoxy, C1-6haloalkylthio,
C1-6haloalkylsulfinyl, C1-6aloalkylsulfonyl,C1-6thaloalkylcarbonyl, fluorine, chlorine,
bromine, iodine, oxo andhydroxy group,
are particularly preferable.
The compounds of the'formula (I), according to the present invention, include stereo isomers (R/S
configuration) in case that the group R1 has an asymmetric carbon.
The aforementioned process (a) can be illustrated by the following reaction scheme, in case that, for
example, 3-(l,l-dimethyl-2-mettiylthioemylimino)^-iodo-3H-isoberizofuran-l-one and l-(4-amino-3-
methylbenzyl)-3,5-bis (trifluoromethyl)-lH-pyrazole are used as starting materials.
SCH3
He.aforementioned preparation process (b) can be illustrated by the following reaction.scheme_in
case that, for example, 2-{4-[335-bis (trifluoromethy3)pyrazo]e-l-yknethyl]-2-methylpheny3}-4-fJuoroisoindole-
l,3-clione and (S)-l-me'thyl-2-methylthioe'thylamine are used as starting materials.
The aforementioned preparation process (c) can be illustrated by the following reaction scheme in
case that, for example, 3-iodo-N-(l,l-dimethyl-2-niethylthioethyl)-phthalamic acid and 2-methyl-
[l-(3-trifluoromethylpyrazole-l-yl)-ethyl]-aniline are used as starting materials.
The aforementioned preparation process (d) can be illustrated by the following reaction scheme in case
that, for example, l-[4-(4-iodo-3-oxo-3H4sobenzofuran-l-yHdenearnino)-3-me1hyl-benzyl]-3,5-bis (trifluoromethyl)-(
l,2,4)-triazol and l-methyl-2-methylthioethylamine are used as starting materials.
SCH,
The aforementioned preparation process (e) can be illustrated by the following reaction scheme in case
that, for example, N-{4-[3,5-bis (trifluoromemyl)-lH-pyrazoI-l-ylmethyl]-2-mel:hyl-phenyl}-6-iodophthalamic
acid and l-methyl-2-methylthioethylamine are used as starting materials.
(Figure Removed)
SOH,
The aforementioned process (f) can be illustrated by the following reaction scheme in case that, for
example, N2-(l-memyl-2-memyl1hioefliyl)-3-iodo-NM2-m^
zol-l-ylmethyl]phenyl}prithalamide and m-chloroperbenzoic acid are used as starting materials.
SCH3
+ m-chloroperbenzoic acid
S02CH3
The compounds of the formula (IT)., used as starting materials in the above-mentioned preparation
process (a), are per se known compounds and can be easily prepared according to the process
described in, for example, JP-A11-240857 (1999), JP-A 2001-131141.
As specific examples of the compounds of the formula (DQ, used as starting materials in the
preparation process (a), there can be mentioned the following:
3-isopropylimino-3H-isobenzofuran-l-one,
4-fluoro-3-isopropylirrjino-3H-isobenzofuran-l-one,
4-chloro-3 -isopropylimino-3H-isobenzofuran-l -one,
4-bromo-3-isopropylimino-3H-isobenzoruran-l-one,
4-iodo-3-isopropylimin6-3H-isobenzofuran-1 -one,
3-(l-me(hyl-2-memylsulfanyl-ethylirnino)-3H-isobenzofuran-l-one,
4-fluoro-3-(l-memyl-2-memylsiufanyl-emymnmo)-3H-isobenzofuran-l-one,
4~cnl6ro-3-(l-memyl-2- ;"
4-bromo-3-(l -methyl-2-methylsulfanyi-emylimmo)-3H-is6berizofuran-l -one,
4-iodo-3-(l -methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-l -one,
3-(l,l-dimemyl-2-methylsulfanyl-emylirr±io)-3H-isobenzofuran-l-one,
3-(l, 1 -diniethyl-2-methylsulfanyl-etliylimino)-4-f!uoro-3H-isobenzofiiran-l -one
-%hloro-3-(l, 1 -dimemyl-2-memylsulfanyl-emyHmino)-3H-isobenzofuran-l -one,
4-bromo-3-(l, 1 -dimemyl-2-memylsulfanyl-emylimino)-3H-isobenzofuran-l -one,
3-(l,lHiime1hyl-2-me1hy]sulfanyl-emylir^
3-isopropylirnino-l-oxo-l,3-dmydro-isoberizofuran-4-ylmethanesulfonate
3-(l-memyl-2-memylsiilfanyl-emyliinmo)-l-oxo-^
3-(l,l-dimemyl-2-memylsulfanyl-ethylirn^
rnethanesulfonate and so on.
The compounds of the formula (ID), used as starting materials in the above-mentioned preparation
process (a), which are partly novel compounds that are not described in the existing literature yet, can
be obtained, for example, by reducing compounds of the formula (IX)
wherein Y, A, m and Q have the same definitions as aforementioned,
according to the catalytic hydrogen reduction process, a well-known process in the field of organic
chemistry, with hydrogen in the presence of a catalytic reduction catalyst, for example, palladium
carbon, Raney nickel, platinum oxide, etc.
The above-mentioned catalytic hydrogen reduction process can be conducted in an adequate diluent
As examples of the diluent used in that case there can be mentioned ethers, for example, ethyl ether,
methyl ethyl ether, isopropyl ether, butyl ether, dioxane, tetrahydrofuran (THF), etc,; alcohols, for
example, methanol, ethanol, isopropanol, butanol, ethylerie glycol, etc. and as catalytic reduction
catalyst there can be mentioned, palladium carbon, Raney nickel, platinum oxide, etc.
The reaction can be conducted at the temperatures generally from about 0 to about 100°C, preferably
from room temperature (20°C) to about 80°C.
Said reaction can be conducted usually under normal pressure but can be operated optionally also
under elevated pressure.
For example, a compound of the formula (ID) can be obtained by hydrogenating the compounds of the
formula (EX) in a diluent, for example, ethanol, in the presence of 0.1-10% (w/w) palladium carbon.
Also by a reduction reaction using metals etc. instead of catalytic hydrogen reduction, the compounds
of the formula (ID) can be obtained from the compounds of the formula (IX).
As. a reduction process using metals, etc., there can be mentioned, for example, a process of reacting iron
pdWder in acetic acid, a process of reacting zinc dust under neutral condition (Organic Syntheses Collective
Vol. It, p. 447), a process of reacting stannic chloride under acidic condition (Organic Syntheses
Collective Vol. n, p. 254), a process of reacting titanium trichloride under neutral condition, etc.
The compounds of the formula (K) are novel compounds and can be obtained by reacting the
compounds of the formula (DC) wherein A represents other than oxygen atom, for example,
compounds of the formula (X)
wherein
Y and m have the same definitions as aforementioned,
A1 represents S, SO, S02, CH2 or CH(CH3), and
M represents chlorine, bromine or methanesulfonyloxy,
with compounds of the formula (XT)
H-Q (XT)
wherein Q has the same definition as aforementioned.
The compounds of the formula (X), are are well known in the field of organic chemistry and described
in publications, for example, Chem. Abstr., Vol. 58, 3444e (1963); Bull. Soc. Chim. Fr.
(1934), p. 539-545; J. Chem. Res. Miniprint, Vol. 8 (1987), p. 2133-2139; J. Chem. Soc. B (1967), p.
1154-1158; J. Chem. Soc. (1961), p. 221-222; J. Amer. Chem. Soc., Vol. Ill (1989), p. 5880-5886;
J. Amer. Chem. Soc., Vol. 96 (1974), p. 7770-7781; Can. J. Chem., Vol. 68 (1999), p. 1450-1455,
Tetrahedron Letter, vol. 35 (1994), p. 7391-7394.
As specific examples of the compounds of the formula (X), there can be mentioned specifically
2-methyl-4-nitrobenzyl chloride,
3-methyl-4-nitroben2yl chloride
4-nitrobenzyl methanesulfonate
2-methyl-4-nitroben2yl methanesulfonate
3-methyl-4-nitrobenzyl methanesulfonate,
4-nitrobenzenesulfenyl chloride,
4-nitrobenzenesulfrnyl chloride,
4-nitrobenzenesulfdnyl chloride,
4-nitro-3 -methylbenzenesulfonyl chloride,
3-fiuoro-4-nitrobensyl bromide,
i^hloro-4-nitrobenzyl chloride and so on.
The nitro-substituted benzoic acids and their esters, starting materials of the compounds of the
formula (X), are known compounds described in, for example, Chem. Ber., Vol. 52 (1919), p. 1083;
Bull. Soc. Chim. Fr. (1962), p. 2255-2261; Tetrahedron (1985), p. 115-118; Chem. Pharm. Bull,
41 (1993), p. 894-906; WO 2001/042227.
The compounds of the formula (XT) include known compounds and as their specific examples., there
can be mentioned:
3,5-bis (trifluoromethyl)-lH-pyrazole,
5-difluoromethoxy-3-trifluoromethyl-lH-pyrazole,
4-pentafluoroethyl-lH-pyrazole,
5-hexafluoro-n-propyl-lH-pyrazole,
3,5-bis (trifluoromethyl)-lH-(l,2,4)-triazole,
5-pentafluoroethyl-3-trifluoromethyl-lH-(l,2,4)-triazole, .
5-difluoromethyl-3-trifluoromethyl-lH-(l,2,4)-triazole,
5-hydroxy-3,5-bis (trifluoromethyl)-lH-4,5-dihydropyrazole,
2,4-bis (trifluoromethyl)-lH-imidazole,
3-(2,2,24rifluoroethyl)-5-trifluoromethyl-l, 2-dihydro-(l,3,4)-triazol-2-one,
2,5-bis(trifluoromethyl)-(l,3,4)-triazole,
5-pentafluoroethyl-lH-pyrazole,
3-pentafluoroethyl-lH-pyrazole,
4-brpmo-3-trifIuoromethyl-lH-pyrazole,
3-trifluoromethyl-lH-pyrazole,
5-(difluorome1hyl)-l,2-dihydro-2-methyl-3H-(l,2,4)-triazol-3-one,
4-(trifluoromethyl)-2H-l,2,3-triazole,
4-iodo-3- pentafluoroethyl-lH-pyrazole,
3-pentafluoroethyl-4-(l,l,2,2-tetrafluoroethyl)-lH-pyrazole,
3,4-bis-pentafluoroethyl-lH-pyrazole,
3,5-diiodo-4-methyl-lH-pyrazole,
3 -Heptafluoropropylsulfanyl-5 -trifluoromethyl-1 H-( 1,2,4)-triazole,
3,5-bis(pentafluoroethyl)-lH-(l,,2,4)-triazole and so on.
formula (XT) can be conducted in an adequate diluent.
A%*xamples of the diluent used in that case there can be mentioned, for example, aliphatic, alicyclic
anoaromatic hydrocarbons (maybe optionally chlorinated), for example, pentane, hexane, cyclohexarie,
petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, etc.; ethers, for example, ethyl
ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME)5
tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone,
methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for
example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate,
etc.; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA),
N-methylpyrrolidone, l,3-dimethyl-2-imidazoh'dinone, hexamethyl phosphoric triamide (BMPA), etc.
The reaction can be conducted in the presence of an acid binder and as said acid binder there can be
mentioned, for example, as inorganic base, hydrides, hydroxides, carbonates, bicarbonates, etc. of alkali
metals or alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen
carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide,
sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; inorganic alkali metal amides, for
example, lithium amide, sodium amide, potassium amide, etc.; as organic base, alcoholates, tertiary
amines, dialkylarninoanilines and pyridines, for example," triethylamine, 1,1,4,4-tetramethylethylenediamine
(TMEDA), N,N-dimethylaniUne, N,N-diethylaniline, pyridine, 4-dimemylarninopyridine
(DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
The above-mentioned reaction can also be conducted by a process using a phase transfer catalyst in
the presence of a diluent. As examples of the diluent used in that case there can be mentioned water;
aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane,
hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, etc.; ethers, for example,
ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME),
tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc. As examples of the phase
transfer catalyst, quaternary ions, for example, tetramethylammonium bromide,
tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium bissulfate,
tetrabutylammonium iodide, trioctylmethylammonium chloride, benz>'ltriethylammonium bromide,
butylpyridinium bromide, heptylpyridinium bromide, benzyltriethylammonium chloride, etc.; crown
ethers, for example, dibenzo-lS-crown-6, dicyclohexyl-18-crown-6, 18-crown-6, etc.; cryptands, for
example, [2.2.2]-cryptate, [2.1.1]-cryptate, [2.2.1]-cryptate, [2.2.B]-cryptate, [3.2.2]-cryptate, etc.
The above-mentioned reaction can be conducted in a substantially wide range of temperature. It is
adequate to conduct it at the temperatures in a range of generally from about 0 to about 200°C,
preferably from room temperature (20°C) to about 150°C.
jjphough said reaction is conducted desirably under normal pressure, it can-be operated also under
elevated pressure or under reduced pressure.
In conducting the above-mentioned reaction, the aimed compounds of the formula (TX) can be
obtained, for example, by reacting 1 mole to a little excess mole amount of the compounds of the
formula (XT) to 1 mole of the compounds of the formula (X) in a diluent, for example, DMF, in the
presence of potassium carbonate.
As the compounds of the formula (IX) obtained according to the above-mentioned process, there can
be mentioned, for example, the corresponding 4-nitrobenzyl derivatives to the 4-aminobenzyl
derivatives of the formula (HI) mentioned hereinafter. And, as one typical example,
l-(3-memyl4-nitroben2yl)-3,5-bis-(trifluorornethyl)-lH-pyrazQle can be mentioned. .
Furthermore, in a case where Q represents 2-thiazolyl in 'the formula (K), as a specific example,
2-(3-methyl-4T-nitrobenzyl)-4-pentafluoroethyl-thiazole can be prepared by the following way in
which a known compound, 3-methyl-4-nitroben2ylcyanide (see J. Chem. Soc., vol. 97 (1910), p.
2260) is reacted with hydrogen sulfide, and then the product, 3-methyl-4-nitro-benzylthioamide is
reacted with a commercial product, l-bromo-3,3,4,4,4-pentafluoro-2-butanone and then cyclized,
according to a method described in J. Heterocycl. Chem., vol. 28 (1991) p. 907 to 911.
In a case where Q represents l,3,4-oxadiazol-2-yl in the formula (IX), as a specific example,
2-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-l,3,4-oxazole can easily be obtained, according to a
method described in Heterocycles, (1994), vol. 38, p. 981 to 990, from the corresponding aldoxime as
a starting material which can be prepared by a method described in Justus Liebigs Ann. Chem.,
(1927) vol. 45, p. 166.
And, as another specific example, 2-(3-memyl-4-ni1robenzyl)-5-trifluorornethyl-l,3,4-oxazo}e can
easily be obtained, according to a method described in Heterocycles, (1994) vol. 38, p. 981 to 990,
from the corresponding 3-memyl-4-ni1xobenzaldehyde oxime. In the above preparation, the oxime
can be obtained from a known 3-methyl-4-nitrobenzaldehyde [see J. Chem. Soc. B, (1967) p; 1154 to
1158] as a starting material, according to methods described in J. Chem. Soc. C, (1969) p. 986 to 990
and then Tetrahedron Letter, vol. 35 (1994) p. 9099 to 9100.
In a case where Q represents 2H-l,2,3-triazol-2-yl in the formula (IX), as a specific example,
2-(3-memyW-m'trobenzyl)-2H-4-trifluoromethyl-l,2,3-triazole can easily be prepared by a reaction
of a known 3-methy3-4-nitrobenzyl chloride with a known 2H-4-trifluoromethyl-l,2,3-triazole described
in J. Chem. Soc., Perkin Transaction 2, vol. 10 (1989) p. 1355 to 1375.
where Q represents lH-l,2,4-triazol-l-yl in the fomnila (K), as a specific example,
5-mefcyl-4-mirophenyIsulfanyl)-l-memyW can easily be prepared
by a reaction of lrfluoro-3-memyl-4-nitrobenzene with a known 5-mercapto-l-methyl-3-trifluoromethyl-
lH-l,2,4-triazole described in J. Med. Chem., vol. 35 (1992) p. 2103 to 2112, according to the
same preparation as Synthesis Example 47 hereinafter.
In a case where Q represents l,2,4-oxazol-3-yl in the formula (K), as a specific example,
3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-l,2,4-oxazole can easily be obtained from 3-methyl-
4-nitrobenzamideoxime, according to a method described in J. Qrg. Chem., vol. 68(2), 2003, p.
605-608. And, 3-methyl-4-mtrobenzamideoxime can be prepared by a reaction of a commercial
3-methyl-4-nitrobenzonitrile with hydroxylamine, according to a method described in Chem. Ber.,
vol. 22 (1889), p. 2428.
And, as another specific example, 3-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-l,2,4-oxazole can
easily be obtained from 2-(3-methyl-4-nitrophenyl)-acetamideoxime as well, according to a method
described in J. Org. Chem., vol. 68(2), 2003, p. 605-608. And, 2-(3-methyl-4-nitrophenyl)-
acetamideoxime can be prepared by a reaction of 3-methyl-4-nitrophenyl-acetonitrile with
hydroxylamine, according to a method described in Chem. Ber., vol. 22 (1889), p. 2428.
In a case where Q represents lH-l,2,4-triazol-3-yl in the formula (IX), as specific examples,
l-methyl-3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-lH-l,2,4-triazole can easily be prepared by a
reaction of the above 3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-l,2,4-oxazole with methylhydrazine,
according to a method described in J. Org. Chem., vol. 68(2), 2003, p. 605 - 608, and also
l-methyl-3-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-lH-l,2,4-triazole can be done by a reaction of
the above 3-(3-methyl-4-nitrobenzyI)-5-trifluoromethyl-l,2,4-oxazole with methylhydrazine as well.
The compounds of the formula (IX) can be prepared, besides the above-mentioned preparation
process, also by the process to be mentioned later in Examples as an alternative.
As specific examples of the compounds of the formula (IQ) there can be mentioned, for example, the
following:
l-(4-amino-3-methylbenzyl)-3,5-bis(trifluorornethyl)-lH-pyrazole,
l-(4-ainmp-3-memylbenzyl)-5-difluorometh^
1 -(4-amino-3 -methylbenzyl)-4-pentafiuoroethyl-lH-pyrazole,
1 -(4-amino-3 -methylbenzyl)-5-hexafluoro-n-propyl- IH-pyrazole,
l-(4-amino-3-methylbenzyl)-3,5-bis (trifluoromethyI)-lH-(l,2,4)-triazole,
l-(4-arnmo-3-memylben2yl)-5-pentafluoroethyl-3-trifluoromethyl-lH-(l,2,4)-tria2ole5
)-5-difl
4-(4-aroino-3-methylben2yl)-5-difluoromethoxy-l-difluoroiriethyl-3-trifluorome
4-(4-amino-3-mefhylbenzyl)-3-difluo
l-(4-anmo-3-methylben2yl)-5-h.ydroxy-3, 5-bis (trifluoromethyl)-lH-4,5-dihydropyrazole,
l-(4-anuno-3-methylben2yl)-2.,4-bis(trifluoroniethyl)-lH-imidazole,
4 -3-one,
2 azol-3-one,
l-(4-amino-3-methylbenzyl)-2.,5-bis (trifluoromeihyljS-triazole,
2-(4-amino-3-methylberi2yl)^,6-bis(trifluoromethyl)-pyrimidine,
2-(4-ammo-3-melhylphenoxy)^56-bis(trifluorome1hyl)-pyrirnidme,
l-(4-airuno-3-mefhylph.enyl)-3,5-bis(trifluoroniethyl)-lH-pyrazole,
1 -(4-amino-3 -methylphenyl)-5-pentafluoroe1:hyl- IH-pyrazole,
l-(4-arnino-3-methylphenyl)-3-pentafluoroethyl-lH-pyrazole,
l-(4-amino-3-methylphenyl)-4-pentafluoroethyl-lH-pyrazole,
l-(4-amiao-3-methylphenyl)-3-methyl-5-trifluoromethyl-lH-pyrazole,
!-(4-anrino-3-me1hylphenyl)-5-inethyl-3-trifluoromethyl-lH-pyrazoIe3
l-(4-amino-3-mefliylphenyl)-3-pentafluoroeihyl-5-trifluoromethyl-lH-pyrazole,
l-(4-amino-3-methylphenyl)-4-bromo-3-trifIuoromethyl-lH-pyrazole,
l-(4-airuno-3-methylphenyl)-3-trifluoromet;hyl-lH-pyrazole,
l-(4-an±io-3-methylphenyl)-5-hydroxy-3-(2,2,2-trifluoroe1hyl)-5-trifluoromethyl-lH^,^
, pyrazole,
5-(4-amino-3-mefhylphenyl)-l-(2,2,2-1rifluoroethyl)-3-trifluorome1hyl-pyrazole.,
5-(4-anrino-3-methylphenyl)-l-difluoromethyl-3-trifluorome1hyl-pyrazole,
S^-amino-S-mefhylplieny^-l-difluoroinethyl-S-difluQromethoxy-pyrazole,
l-(4-amino-3-methylbenzyl)-3,4-bis (pentafluoroethyl)-lH-pyrazole,
1 -(4-amino-3-methylbenzyl)-3,5-bis (pentafluoroetliyl)-lH-pyrazole,
l-(4-amino-3-methylbenzyl)-3,4-bis (pentafluoropropyl)-lH-pyrazole,
1 -(4-amino-3 -me£hylbenzyl)-3,5-bis (pentafluoropropyl)-1 H-pyrazole,
l-(4-amino-3-mefhylbenzyl)-3,5-bis(pentafluoroethyl)-lH-(l,2,4)-triazole,
l-(4-amino-3-methylbenzyl)-2J5-bis(pentafluoroethyl)-lH-(l,3,4)-triazole,
2-(4-ari±io-3-me1h3'lphenyl)-5-(trifIuoromethyl)-l,3,4-oxadiazole,
2-(4-amino-3-methy]plieny])-5-(pentafluoroethyl)-l,3J4-oxadiazole3
2-(4-amino-3-methylphenyl)-5-(heptafluoropropyl)-l,3,4-oxadiazole,
2-(4-arQino-3-mefhylbenzyl)-5-(trifluoromethyl)-l3354-oxadiazole,>
2-(4rarQino-3-methylbenzyl)-4-(pentafluoroethyl)-thiazole,
x rr-3-me1hylphenyl)sulfaiiyl-l-me1iiyl-3-(trifluorome1hyl)-lH-l,2/-triazole3
3-(4-arnino-3-rnethylphenyl)-5-(trifluorornethyl)-l,2,4-oxadiazole5
3-(4-ainino-3-methylphenyl)-l-methyl-5-(trifluorome1:hyl)-lH-l,234-1iiazole,
l-(4-amino-3-chlorobenzyl)-3,5-bis (trifluoromethyl)-lH-pyrazole,
l-(4-ainino-3-fluoroben2yl)-3,5-bis(trifluorometh.yl)-lH-pyrazole
and so on.
The compounds of the formula (IV), used as starting materials in the above-mentioned preparation
process (b), are novel compounds and can be easily obtained according to the process described in
Japanese Laid-open Patent Publication No. 61-246161 (1986), for example, by reacting compounds
of the formula (XD)
(Figure Removed)
wherein X has the same definition as aforementioned,
with the compounds of the formula (HI).
Y -OH)
wherein Y, A, m and Q have the same definitions as aforementioned,
The reaction can be conducted in an adequate diluent As the diluent used in that case there can be mentioned,
for example, aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for
example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene,
dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene,
etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane,
dimethoxyethane (DME), tetrahydrofuran (TJ3F), diethylene glycol dimethyl ether (DGM), etc,; esters,
for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylforrnamide (DMF),
dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazoridinone, hexamethyl
phosphoric triamide (HMPA), etc.; acids, for example, acetic acid etc.
The reaction can be conducted in a substantially wide range of temperature. It is adequate to conduct
it at the temperatures in a range of -generally from room temperature (20°C) to about 200°C,
preferably from room temperature to 150°C.
aid reaction is conducted desirably under normal pressure, it can -be operated also under
elevated pressure or under reduced pressure.
In conducting the reaction, the aimed compounds of the formula (IV) can be obtained, for example,
by reacting equimolar to a little excess mole amount of the compounds of the formula (EOT) to 1 mole
• of the compounds of the formula (XH) in a diluent, for example, acetic acid.
Many of the compounds of the above-mentioned formula (XH) are publicly known, and as their
specific examples'there can be mentioned, phthalic anhydride, 3-fluorophthalic anhydride, 3-chlorophthalic
anhydride, 3-bromophthalic anhydride, 3-iodophthalic anhydride, 3-methanesulfonyloxyphthalic
anhydride, etc.
Among the above-mentioned compounds, 3-methanesulfonyloxyphthalic anhydride can be easily
obtained from 3-hydroxyphthalic anhydride and methanesulfonyl chloride according to the process
described in Tetrahedron Letters Vol. 29, p. 5595-8 (1988).
As specific examples of the compounds of the formula (IV), used as starting materials in the
preparation process.(b), there can be mentioned the following:
4-cHoro-2-{2~me1hyW-[3,5-bis(1riflucn:om
2-{2-memyl-4-[3,5~bis(trifluoromeihyl)-lH^
4-cWoro-2-[2-me1hyl-(5-difluoromernoxy-3-1riflu
indole-l,3-dione, .
4-chloro-2-[2-methyl-4-(4-pentafluoroeihyl-lH-pyrazol-l-yl-memyl)-phenyl]-isomdole-l,3-dione,
4-bromo-2-{2-methyM-[3,5-bis(1iifluOTometh
4-bromo-2-[2-methyl-4-(5-difluoromernoxy-3-ta
indole-l,3-dione,
4-bromo-2-[2-methyl4-(4-peoitafluoroethy
4-iodo-2- {2-methyl-4-[3,5-bis(trifluoroniethyl)-lH-pyrazol-l -yl-methyl]-phenyl) -isoindole-1,3-dione,
4-iodo-2-[2-meihyM-(5-difluoromethoxy-34rifluo
-indole-l,3-dione,
4-iodo-2-[2-memyl-4-(4-pentafluoroemyl-lH-pyrazol-l-yl-memyl)-phenyl-]isoindole-l,3-dione,
4-iodo-2-[2-methyM-(5-hexafluoro-n-prqpyl-lH-
4-me1hanesulfonyloxy-2-{2-methyl-4-[3,5-bis(Mfluoromemyl)-lH-pyrazol-l-yl-methyl]-phenyl}-
isoiridole-l,3-dione,s "'
4-chloro-2-{2-me%l-4-[3,5-bis(tiifluorome%l)4H-(l,2,4)-triazol-l-yl-memylJ-phenyl}-isoindole17
isoindole-1,3-dione,
4-cMoro-2-{2-melhyW-[5-difluoroniethoxy-lisoindole-
l,3-dione,
4-iodo-2-{2-methyl-4-[3,5-bis(tifluorome%
dione,
4-iodo-2-{2-methyl-4-[5-penMuoroe1hyl-3-trifl
isoindole-l,3-dione,
4-iodo-2-{2-me%l[5-Muorome%l-3-trifluoro
isoindole-l,3-dione,
4-methanesulfonylo-2-{2-methyl^[3,5-bis(triflucTomeliiyl)-lH-(l,254)-tri
-isoindole-l,3-dione,
4-iodo-2-[2-methyM-(5-difluoromethoxy-l^iflu6romethyl-3-trifluoroinethyl-lH-py
-phenyl]-isoindole-l,3-dione,
4-iodo-2-[2-methyM-(5-hydroxy-3,5-bis(trifluoromethyl)-lH^5^hydropyrazol-l-yl-met
nylj-isoindole-1,3-dione,
4-iodo-2-{2-methyW-[2,4-bis(irifluoromethyl)-lH-imida2ol-l-yl-methyl]-phm
49-3iodo-2-{2-me1hyl4 2,2J2-1rifluoroe%l)-5-1rifluorome%l452-jihydro methyl]-phenyl}-isomdole-l,3-dione5 ,
4-iodo-2-{2-methyH-[4-(2,232-trifluoroe%l)-3-trffluoromeihyMJ5-y
mefhylj-phenyl} -isoindole-1,3-dione,
4-iodo-2-{2-methyl-4-[2,5-bis(lrifluoromethyl)-(l,3,4)-1riazol-l-yl-me
4-iodo-2-{2-methyl-4-[4,6-bis(trifluoromethyl)pyrirnidin-2-yl-me1iiyl]rphenyl}
4-iodo-2-{2-me1hyl4-[4,6-bis(trifluoromethyl)pyrMdin-2-yloxy]-phenyl}-isoffl
4-cMoro-2-{2-rnethyl-4-[3,5-bis(Mfluoromettiyl)-lH-pyrazpl-l-yl]-phenyl}-isoindoie-l,3-dione,
4^hloro-2-[2-methyl-4-(5-penfafluoroethyl-lH-pyrazol-l-yl)-phenyl]-isoindole-l,3-dione,
4-chloro-2-[2-methyl-4-(3-pentafluoroethyl-lH-pyrazol-l -yl)-phenyl]-isoindole-l,3-dione,
4-cUoro-2-[2-methyM-(4-pentafluoroethyl-lH-pyrazol-l-yl)-p]ienyl3-isoindole-l,3-dione,
4-iodo-2-[2-methyl4-[3-me%l-5-trifluoromethyl-lH-pyrazol-l-yl3-pheiiyl]-isoindole-l,3-dioiie,
4-iodo-2-[2-methyM-(5-methyl-3-trifluoromethyl-lH-pyrazol-l-yl)-phenyl]-isoindole-l,3-dione,
4-iodo-2-[2-methyW-(3-pentafluoroethyl-5-trifluorpmethyl-lH-pyrazoI-l-yl)-pheaiyl]-isoindole-l,3-
dione,
4-iodo-2-[2-methyW-(4-bromo-3-1rifluorome1:hyl-lH-pyrazoll-yl)phenyyi
4-iodo-2-[2-methy]-4-(3 -trifluoromethyl- lH-pyrazol-1 -yl)-phenyl] -isoindole-1,3 -dione,
4-iodo-2-{2-me%l-4-[5-hydroxy-3-(2,2,2-tffluoroe%^^
yl]-plienyl}-isoindole-l,3-dione,
dione.,
l-3-difl
4-iodor2-{2-methyM-[3,5-bis(trifluoromethyl)-lH-pyra2ol-l-yl]-phenyl}-isoindole-l,3-di
4-iodo-2-[2-me1hyl^-(5-pentafluoroethyl-lH-pyrazol-l-yl)-phenylJ-isoindole-l,3-diane,
4-iodo-2-[2-methyW-(3-pentafluoroethyl-lH-pyrazol-l-yl)-plienyl]-isoindole-l33-dione,
4-iodo-2-[2-meftyM-(4-pentafluoroethyl-lH-pyrazol-l-yI)-phenyl]-isoindole-l53-dione3
4-bromo-2-{2-methyW-[3,5-bis(trifluoromethyl)-lH-pyrazol-l-yl]-phenyl}-isoindole-lJ3-dioneJ
4-bromo-2-[2-methyW-(5-pentafluoroetfayl-lH-pyrazol-l-yl)-phenyl-isoindole-l,3-dione,
4-bromo-2-[2-methyl^3-pentafluoroe%l-lH-pyrazol-l-yl)-phenyl]-isoindole-l33-dione,
4-bromor2-[2-methyM-(4-pentafluoroethyl-lH-pyrazol-l-yl)-plienyl]-isoindole-l,3-dione,
4hloro-2-{2-mefhyl^[3,4-bis(pentafluoroethyl)-lH-pyrazol-l-y]methyl]-phenyl}-i^^
dione, ,
4^Horo-2-{2-methyM-[3J5-bis(heptafluoropropyl)-lH-pyrazol-l-ylmethyl]-phenyl}-
dione,
4-cHoro-2-[2-methyl-(5-trifluorome1
4-chloro-2-[2-methyl-4-(5-pentafluoroethyl-l ,3,4-oxadiazol-2-yl)-phenyl]-isoindole-l ,3-dione,
4-cUoro-2-[2-methyl-4-(5-heptafluoropropyl-l,3,4-oxadiazol2-yl)-phenyl]-isoindole-l33-dione,"
4-cUoro-2-[2-mefeyW-(5-1rifluorometh^
4-ch]oro-2-[2-methyW-(4-lrifluorome1hyl-2H-l,23-triazol-2-yl-methyl)
4-cWoro-2-[2-me&yM-(4-(pentafluoroethyl)-thiazol-2-yl-methyl)-pheny]]-isoindole-l,
4-ch]oro-2-{2-methyM-[l-methyl-3-(trifluoromefliyl)-lH-l^,4-triazol-5-yl-sufanyl]-ph
indole-l,3-dione,
4;Woro-2-[2-meihyl-4-(5-tri£luorornefhyl-l,234-oxadiazol-3-yl)-phenylJ-isoindole-l,3-dione,
4-cWpro-2-[2-methyW^l-methyl-5-trifluoromethyl-lH-l3234-triazol-3-yI)-pheaiyl]-isoindol^
4-iodo-2-[2-methyl-4-(5-trifluoromethyl-l3334-oxadiazol-2-yl)-phenyl]-isoindole-l,3-dione and so on.
The compounds of the formula (V), used as starting materials in the preparation process (b), are either
compounds well known in the field of organic chemistry or can be synthesized according to the
process described in DE-A 20 45 90531WO 01/23350.
As their specific examples there can be mentioned euiylamine, diethylamine, n-propylamine, isopropylamine,
n-butylainine, sec-butylamine, isobutylamine, t-butylamine, t-amylamine, 2-(methyl19
thio)-ethylamine., 2-(emylmio)-emylamine, l-methyl-2-(methylfhio)-ethylamine3
thfK-(methylthio)-ethylarnine and so on. ' • '
The compounds of the formula (VI)., used as starting materials in the preparation process (c), include
publicly known compounds and can be easily prepared according to the process described in JP-A
11-240857 (1999), JP-A 2001-131141, etc.
As their specific examples there can be mentioned the following:
N-isopropyl-phthalamic acid,
3-fluoro-N-isopropyl-phthalamicacid,
3-chloro-N-isopropyl-phthalamicacid,
3-bromo-N-isopropyl-phthalamicacid,
3-iodo-N-isopropyl-phthalamic acid,
N-(l -methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
3-fluoro-N-(l -methyl-2-methylsulfanyl-ethyl)-phthalarnic acid,
3-cMoro-N-(l-memyl-2-methylsiilfanyl-ethyl)-phmalamic acid,
3-bromo-N-(l -methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
3-iodo-N-(l-methyl-2-methylsulfanyl-ethyl)-phthalamicacid,
N-(l,lrd4methyl-2-memylsulfanyl-emyl)-phmalarnic acid,
N-(l,l-dimethyl-2-methylsulfanyl-ethyl)-3-fluoro-phthalarnic acid,
3-cWoro-N-(l,l-dimemyl-2-methylsiilfanyl-ethyl)-phthalamicacid,
3-bromo-N-(l , 1 -dimemyl-2-memylsulfanyl-ethyl)-phthalatnic acid,
N-(l,l-dimethyl-2-memylsulfanyl-emyl)-3-iodo-phthalamicacid,
N-isopropyl-3-methanesulfonyloxy-phthalamic acid,
N-(l-methyl-2-memylsulfanyl-ethyl)-3-methanesulfonyloxy-phthalamicacid,
N-(l-meihyl-2-me1hylsulfanyl-ethyl)-3-iiitro-phthalamic acid,
3 -chloro-N-(2-ethylsulfanyl- 1 -methyl-ethyl)-phthalamic acid,
3-bromo-N-(2-ethylsulfanyl-l-methyl-ethyl)-phthalamicacid,
N-(2-ethylsulfanyl-l -methyl-ethyl)-3-iodo-phthalarnic acid,
N-(2-ethylsulfanyl-l-methyl-ethyl)-3-nitro-phthalamic acid,
N-(2-etiiylsulfanyl-r-methyl-ethyl)-3-methanesulfonyloxy-phthalamicacid,
N-(l,l-dimethyl-2-memylsulfanyl-ejhyl)-3-methanesulfonyloxy-phthalarnic acid and so on.
The above-mentioned compounds of the formula (VT) can be easily obtained generally by reacting
phthalic anhydrides of the aforementioned formula (XH)
wherein X has the same definition as aforementioned,
with amines of the formula
H2N-R1 pan)
wherein R1 has the same definitions as aforementioned,
The compounds of the above-mentioned formula (XIE) are weU known in the field of organic chemistry
and there can be specifically mentioned, for example, ethylamine, n-propylamine, isopropylamine,
n-butylamine, sec-butylamine, isobutylamine, t-butylamine, t-amylamine, 2-(methylthio)etiiylamine,
2-(ethylthio)ethylamine, l-methyl-2-(methylthio)ethylamine, 1, l-dmefeyl-2-(methyl1m"o)ethylamine,
etc.
These' amines can be easily obtained also by the process described in DE-A 20 45 905, WO 01/23350,
etc.
The above-mentioned reaction of the compounds of the formula (Xn) with the amines of the formula
(X33I) can be conducted according to the process described in, for example, J. Org. Chem., Vol. 46, p.
175 (1981) etc.
Said reaction can be conducted in an adequate diluent, and as examples of the diluent used in that
case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally
chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene,
xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichlordethane, chlorobenzene,
dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether,
dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM),
etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl
isobutyl ketone (MIBK), etc.; nitriles, for example, acetoniirile, propiomtrile, acrylonitrile, etc.; esters,
for example, ethyl acetate, amyl acetate, etc.
The above-mentioned reaction can be conducted in the presence of a base, and as said base there can
be mentioned, for example, tertiary amines, dialkylammbanilines arid pyridines,' for example,
triethylamine, 1,1.,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylanihne, N,N-diethylaniline,
pyridine, 4-dimethylaminopyridine (DMAP)_, l,4-diazabicyclo[2,2,2]octane (DABCO),
l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
Tb£ibove-mentioned reaction can be conducted in a substantially wide range of temperature. It is
adequate to conduct it at the temperatures in a range of generally from about -70 to about 1.00°-C,
preferably from about -50 to about 80°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under
elevated pressure or under reduced pressure.
In conducting the above-mentioned reaction, the aimed compounds of the formula (VI) can be
obtained, for example, by reacting 1-4 moles of the compounds of the formula (XIH) to 1 mole of the
compounds of the formula (XT!) in a diluent, for example, acetonitrile.
The compounds of the formula (VH), used as starting materials in the preparation process (d), are
novel compounds and can be easily obtained, for example, by reacting the compounds of the formula
(VIE), starting materials in the below-mentioned preparation process (e), according to the process
described in J. Med. Chem., Vol. 10, p. 982 (1967) etc. in the presence of a condensing agent.
As specific examples of the compounds of the formula (VH), there can be mentioned the following:
l-[4-(4-iodo-3-oxo-3H-isobenzoiuran-l-yMdeneamino)-3-methyl-benzyl]-3,5-
bis(trifluoromethyl)-lH-pyrazole,:
l-[4-(4-cMoro-3-oxo-3H-isoberizofuran-l-ylideneamino)-3-methyl-benzyl]-3,5-
bis(trifluoromethyl)-lH-pyrazole, :
l-[4-(4-iodo-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-memyl-benzyl]-3,5-
bis(trifluoromethyl)-l,2,4-triazole,
1 -[4-(4-iodo-3-oxo-3H-isobenzofuran-l -ylideneamino)-3-methylpbenyl]-3,5-
bis(trifluoromethyl)-lH-pyrazole,
l-[4-(4-cHoro-3-oxo-3H-isobenzofuran-l-ylideneammo)-3-me1hyl-benzyl]-354
bisfcentafluoroernyty-lH-pyrazole,
l-[4-(4-cUoro-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methyl-ben2yl]-3,5-
bis(pentafluoroethyl)-lH-pyrazole,
l-[4-(4-cMoro-3-oxo-3H-isobenzof\Kan-l-ylideneamino)-3-methyl-benzyl]-3,4-
bis(heptafluoropropyl)-lH-pyrazole,
l-[4-(4-cMoro-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methyl-benzyl]-3,5-
bis(heptafluoropropyl)-lH-pyrazole, ,
2-[4-(4-cHoro-3-oxo-3H-isober^ofOTan-l-ylidenea
oxadiazole,
2-[4-(4-cMoro-3-oxo-3H-isobenzofuran-l-ylide
-oxadiazole,
4-(4-cHoro-3-oxo-3H-isobemzofuran-l-yM
4-oxadiazole,
2-[4-(4-cUoro-3-oxo-3H-isobeffizofuran-l-ylidenearnmo)-3
oxadiazole,
2-[4-(4-chloro-3 -oxo-3H-isobenzofuran-l -ylideneamino)-3-methylben2yl] -4-(trifluoromethyl)-2H-
1,2,3-triazole,
2-[4-(4-cUoro-3H3xo-3H-isobenzofuran-r-y
thiazole,
5-[4-(4-cWoro-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methylphenyl]siilfanyl-l-methyl-3-
fluoromethyl)-lH-l,2,4-triazole,
3-[4-(4-chloro-3-oxo-3H-isobenzofoan-l-ylideneamino)-3-meth)dphenyl]-
5-(trifluoromethyI)-1,2,4-oxadiazole,
3-[4-(4-cUoro-3-oxo-3H-isobenzofi
methyl)-lH-l,2,4-triazole,
2-[4-(4-iodo-3-oxo-3H-isobenzofiffan-l-ylideneainmo)-3-mefo
oxadiazole and so on.
The compounds of the formula (V), similarly used as starting materials in the preparation process (d),
are the same as explained in the aforementioned preparation process (b).
The compounds of the formula (VET), used as starting materials in the preparation process (e), are
novel compounds and can be easily obtained, for example, by reacting phthalic anhydrides of the
aforementioned formula (XS) with the compounds of the aforementioned formula (HI)..
The above-mentioned reaction can be conducted in an adequate diluent, and as examples of the
diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may
be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine,
benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl
ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol
•dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl
isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile,
propionitrile/acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc.
The above-mentioned reaction can be conducted in the presence of a base, and as said base there can
be mentioned tertiary amines, dialkylarninoanilines and pyridines. for example, triethylamine,
1,1,4,4-teframethyleihylenediaimne (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine,
4-aefliylamJnopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and
l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
The above-mentioned reaction can be conducted in a substantially wide range of temperature. It is
adequate to conduct it at the temperatures in a range of generally from about -70 to about 100°C,
preferably from about -50 to about 80°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under
elevated pressure or under reduced pressure.
As specific examples of the compounds of the formula (VEQ), there can be mentioned the following:
N-{4-[3is(trifluorotnethyl)-l
N- {4-[335-bis(trifluoromethyl)-lH-pyrazol-l -yl-mefhyl]-2-methyl-phenyl} -6-chloro-phthalamic acid,
N- {4-[3,5-bis(trifluoromethyl)-(l ,2,4)-triazol-l-yl-methyl]-2-meuiyl-phenyl}-6-iodo-phthalamicacid,
N-{4-[3,5-bis(trifluoromethyl)-lH-pyrazol-l-yl]-2-memyl-phenyl}-6-iodo-phthaIamicacidJ
N-{4-[3,4-bis(pentafluoroethyI)-lH-pyrazol-l-yl-methyl]-phenyl}-6-cWoro-phmalamicacid,
N-{4-[3,5-bis(pe»tafluoroethyl)-lH-pyrazol-l-yl-methyl]-phenyl}-6-chloro-phthalamic acid,
N-{4-[3,4-bis(heptafluoropropyl)-lH-pyrazol-l-yl-methyl]-phenyl}-6-cMoro-phthalamic acid,
N-{4-[3,5-bis(b.eptafluoropropyl)-lH-pyrazol-l-yl-memyl]-phenyl}-6-cMoro-ph1ha]arnic acid,
Nr[2-memyl^5-1rifluorome1hyl-l,3,4-oxadiazol-2-yl)-phenyl]-6-cWoro-phmalannc
N-[2-memyl-4-(5-pentafluoroethyl-l,3,4-oxadiazol-2-yl)-phenyl]-6-chloro-phthalarnic acid,
N-[2-methyl-4-(5-heptafluoropropyl-l,3,4-oxadiazol-2-yl)-phenyl]-6-cHoro-phflialamicacid,
N-p-memyW-(5-1rifluoromemyl-l,3,4-oxadiazol-2-yl-memyl)-phenyl]-6-chloro-ph1i^^ acid,
N-[2-memyM-(4-trifluoromemyl-2H-l,2,3-triazol-2-yl-methyl)-phenylj-6-cMoro-ph^
N-[2-memyM-(4-pentafluoroemyl-thiazol-2-yl-methyl)-phenyl]-6-cMoro-phmalaniicacid,
N-{2-methyl-4-[l-methyl-3-(trifluoro
phthalamic acid, _
N-[2-memyM-(5-trifluoromemyl-l,2,4-oxadiazol-3-yl)-phenyl]-6-cMoro-phmalarm
N-[2-memyl-4-(l-memyl-5-1riiluoromemyl-lH-l,2,4-triazol-3-yl)-phenyl]-6-chloro-phmalan^
N-[2-methyW-(5-1rifluorome%l-l,3,4-oxadiazol-2-yl)-phenyl]-64odo-phmalarnic acid and so on.
The compounds of the formula (V), similarly used as starting materials in the preparation process (e),
can be the same as ones used in the aforementioned preparation processes, (b) and (d)f
The compounds of the formula (If), used as starting materials in the preparation process (f), are
compounds included in the formula (T) of the present invention.
yoxidizing the group R^ in the compounds of the formula (If), namely, C1-6alkylthio-C1.6alkyl, the
compounds of the formula (I), in which the group Rff corresponds to C1-6alkylsulfrnyl-C1-6alkyl or
l, can be obtained.
The compounds of the formula (If) can be prepared by the processes of the aforementioned
preparation processes (a), (b), (c), (d) and/or (e).
As specific examples of the compounds of the formula (If), there can be mentioned the following:
3-iodo-N2l-methyl-2-methylsulfanyl-ethyl)-N1-{2-memyW-[3,5-bis(trifluorom
1-yknelhyl]-phenyl}phthalamide,
N2-(l,l-dime%l~2-me1hylsulfmyl-e^
pyrazol-l-ylmethyl]-phenyl}phthalamide,
3 -iodo-N2-(l -me&yl-2-methylsulfanyl-ethyl)-N'- {2-methyl-4-[3,5-bis(trifluoromethyl)-
(l,2,4)-triazol-l-yhnethyl]-phenyl}phthalamide,
3-cttoro-N2-(l-me%l-2-methylsulf^^
-l-yhnethyl]-phenyl}phthalamide,
3-chloro-N2-( 1 -mernyl-2-methylsuifanyl-ernyl)-N!r {2-methyl-4-[3,4-bis(pentafluoro-ethyl)-lH-pyrazoH-
ylmemyl]-phenyl}phthalamide,
3-cWoro-N2-(l-memyl-2-methylsulfanyzol-l-ylmethyl]-phenyl}phthalamide,
3-chloro-N2Kl-me^l-2Hmeftylsulfanyl
razol-l-yhnethyl]-phenyl}phthalamide,
3-cMoro-N2-(l-memyl-2-memylsulfanyl^myl)-N1-{2-methyl^[3,5-bis(heptafIuoro-propyl)-lH^^
razol-l-ylmethyl]-phenyl}phthalamide and so on
The reaction of the aforementioned preparation process (a) can be conducted in an adequate diluent
singly or mixed. As examples of the diluent used in that case there can be mentioned water; aliphatic, .
alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane,
cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform,
carbon tetrachloride, 1,2-dichIoroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example,
ethyl ether, methyl ethyl ether, isopropyl .ether, butyl ether, dioxane, dimethoxyethane (DME),
tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example,
acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc. r,
The preparation process (a) can be conducted in the presence of an acid catalyst, and as examples of
said acid catalyst there can be mentioned mineral acids, for example, hydrochloric acid and sulfuric
act; organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic
acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.
The preparation process (a) can be conducted in a substantially wide range of temperature. It is
adequate to conduct it at the temperatures in a range of generally from about -20 to about 100°C,
preferably from about 0 to about 100°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under
elevated pressure or under reduced pressure.
In conducting the preparation process (a), the aimed compounds of the formula (I) can be obtained,
for example, by reacting 1 to a little excess mole amount of the compounds of the formula (ID) to 1
mole of the compounds of the formula (IT) in a diluent, for example, 1,2-dichloroethane in the
presence of 0.01-0.1 mole amount of p-toluenesulfonic acid.
The reaction of the aforementionedpreparation process (b) can be conducted in an adequate diluent. As
examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and.aromatic
hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum
ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon .tetrachloride,
1,2-dichloroethane., chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl
ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene
glycol dimethyl ether (DGM), etc.; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for
example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone,
1,3 -dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (BMPA), etc.
The preparation process (b) can be conducted in the presence of an acid catalyst and as examples of
said acid catalyst there can be mentioned mineral acids, for example, hydrochloric acid and sulfuric
acid; organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic
acid, p-toluenesulfonic acid, etc.
The preparation process (b) can be conducted in a substantially.wide range of temperature. It is
adequate to conduct it at the temperatures in a range of generally from about -20 to about 150°C,
preferably from room temperature (20°C) to about 100°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under
elevated pressure or under reduced pressure.
IrFconducting the preparation process (b), the aimed compounds of the formula (I) can be obtained.,
for example, by reacting 1-25 moles of the compounds of the formula (V) to 1 mole of the
compounds of the formula (TV) in a diluent, for example, dioxane in the presence of 0.01-0.5 mole
amount of acetic acid.
The aforementioned preparation processes (c), (d) and (e) can be conducted under the similar
condition as the above-mentioned preparation process (a).
The reaction of the aforementioned preparation process (f) can be conducted in an adequate diluent. As
examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic
hydrocarbons (may be optionally chlorinated), for example, benzene, toluene, xylene, dichloromethane,
chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; alcohols,
for example, methanol, ethanol, isopropanol andbutanol; acids; formic acid, acetic acid, etc.
As the oxidizing agents usable in the aforementioned preparation process (f) there can be mentioned,
for example, m-chloroperbenzoic acid, peracetic acid, potassium metaperiodate, potassium hydrogen
persulfate (oxon), hydrogen peroxide, etc.
The preparation process (f) can be conducted in a substantially .wide range of temperature. It is .
adequate to conduct it at the temperatures in a range of generally firom about —50 to about 150°C,
preferably from about--10 to about 100°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under
elevated pressure or under reduced pressure.
In conducting the preparation process (f), the aimed compounds of the corresponding formula (I) can
be obtained, for example, by reacting 1-5 moles of an oxidizing agent to 1 mole of the compounds of
the formula (If) in a diluent, for example, dichloromethane.
The reaction of the aforementioned preparation process (f) can be conducted, for example, according to
the process described in JIKKENKAGAKU KOZA (Lecture on experimental chemistry) edited by the-
Chemical Society of Japan, 4th ed., Vol. 24, p. 350 (1992) published by MARUZEN or ibid. p. 365.
The compounds of the formula.(!) of the present invention show strong insecticidal action. The
compounds of the formula (I), according to the present invention can, therefore, be used as
insecticidal agents. And the active compounds of the formula (T) of the present invention exhibit
exact controlling effect against harmful insects without giving phytotoxiciiy on cultured plants. And
tbf vompounds of the present invention can be used for controlling a wide variety of pests, for
example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain.pests,
hygienic pests, etc. and applied for their extermination.
As examples of such pests there can be mentioned the following pests:
As insects, there can be mentioned:
Coleqptera pests, for example,
Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata,
Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus
alternatus, Lissorhoptnts oryzophilus, Lyctus bruneiis;
Lepidoptera pests, for example,
Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo
suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella,
Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella;
Hemiptera pests, for example,
Nephqtettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki,; Unaspis yanonensis, Myzus
persicae, Aphis pomi, Aphis gossypii, Khopalosiphum pseudqbrassicas, Stephanitis nashi, Nazara
spp., Trialeurodes vaporariorum, Psylla spp.;
Tfiysanopterapests, for example,
Thrips palmi, Frankliniella occidental;
Orthoptera pests, for example, .
Blatella gennanica, Periplaneia americana, Gryllotalpa africana, Locusta migratoria migratoriodes;
Homoptera pests, for example,
Reticulitermes speratus, Coptotermes formosanus;
Diptera pests, for example,
Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex
tritaeniorhynchus, Liriomyzae trifolii etc.
Moreover, as mites there can be mentioned, for example,
Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemns
spp., etc.
Furthermore, as nematodes there can be mentioned, for example,
Meloidogyne incognita, Biirsaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi,
Heterodera glycines, Pratylenchus spp., etc.
Upldition, in the field of veterinary medicine, the novel compounds of the present invention can be
effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for
example, insects and helrninthes. As examples of such animal-parasitic pests there can be mentioned
the following pests:
As insects there can be mentioned, for example,
Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, Cimex
lectularius etc.
As mites there can be mentioned, for example,
Ornithodoros spp., Jxodes spp., Boophilus spp., etc.
In the present invention, substances having insecticidal action against pests, which include all of them,
are in some cases called as insecticides.
All plants and plant parts can be treated in accordance with the invention. Plants are to be understood
as meaning in the present context all plants and plant populations such as desired and undesired wild
plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can
be obtained by conventional plant breeding and optimization methods or by biotechnological and
genetic engineering methods or by combinations of these methods, including the transgenic plants
and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts
are to be understood as meaning all parts and organs of plants above and below the ground, such as
shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems,
flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested
material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes,
offshoots and seeds.
Treatment according to the invention of the plants and plant parts with the active compounds is
carried out directly or by allowing the compounds to act on the surroundings, environment or storage
space by the customary treatment methods, for example by immersion, spraying, evaporation,
fogging, scattering, painting on and, in the case of propagation material, in particular in the case of
seeds, also by applying one or more coats.
The active compounds; according to the present invention, can :be converted into the customary
formulation forms, when they are used as insecticides. As formulation forms there can be mentioned,
for example, solutions, emulsions, wettable powders, water dispersible granules, suspensions,
powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with
active compound, microcapsules, seed coating agents, formulations used with burning equipment (as
burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold
mist, warm mist], etc.
These formulations can be produced according to per se known methods, for example, by mixing the
active compounds with extenders, namely liquid diluents or carriers; liquefied gas diluents or carriers;
solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or
dispersants and/or foam-forming agents.
In case that water is used as extender, for example, organic solvents can also be used as auxiliary
solvents.
As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for
example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic
hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic
hydroparbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)],
alcohols (for example, butanol, glycols and their ethers, esters, etc.), ketones (for example, acetone,
methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for
example,-dimethylformamide, dimethyl sulfoxide, etc.), and water.
Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure
and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas,
carbon dioxide, halogenated hydrocarbons. .
As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin,
clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic
minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).
As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks
(for example, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic or
organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs,
tobacco stalks, etc.), etc.
As-emulsifiers "and/or Tfoam-forming agents, there can be mentioned, for example, nonionic and
anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid
alcohol ethers (for example, alkylaryl polyglycol ethers), alkylsulfonates, alkylsulfates, arylsulfonates,
etc.], albumin hydrolysis products, etc.
30
Jjl^persants include, for example., lignin sulfite waste liquor and methyl cellulose.
Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said
tacldflers, there can be mentioned, for example, carboxymethyl cellulose, natural or synthetic
polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).
Colorants can also be.used. As said colorants there can be mentioned, for example, inorganic
pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such, as
alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as
salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Said formulations can contain the aforementioned active component of the amount in the range of
generally 0.1-95% by weight, preferably 0.5-90% by weight.
The active compounds of the formula (I) of the present invention can exist also as a mixed agent with
other' active compounds, for example, insecticides, poisonous baits, bactericides, miticides,
nematicides, fungicides, growth regulators or herbicides in the form of their commercially useful
formulations and in the application forms prepared from such formulations. Here, as the
above-mentioned insecticides, there can be mentioned, for example, organophosphorous agents,
carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal
substances produced by microorganisms, etc. .
Further, the active compounds of the formula (I) of the present invention can exist also as a mixed
agent with a synergist, and such formulations and application forms can be mentioned as
commercially useful. Said synergist itself must not be active, but is a compound that enhances the
action of the active compound.
Particularly favourable mixing components are, for example, the following compounds:
Fungicides:
2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos;
ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benalaxyl-
M; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos;
binapacryl; biphenyl; bitertanol; blasticidin-S; boscalid; bromuconazole; bupirimate; buthiobate; butylamine;
calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone;
chinomethionat; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofarnid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram: Dagger G; debacarb;
dichlofluanid; dichlone; dicMorophen; diclocymst; diclorneziiie; dicloran; diethofencarb: difeno31
cbnazple; diflumetorirn; dimethiiimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M;
dinocap; diphenylamine; dipyrithiione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole;
ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenarimol; feribuconazole;
fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; fefbam;
fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluororhide; fluoxastrobin; fluquinconazole;
flurprimidol; 'flusilazole; flusulfairdde; flutolanil; flutriafol; folpet; fosetyl-Al; fosetyl-sodium;
fiiberidazole; furalaxyl; furametpyr; furcarbanil; funnecyclox; guazatine; hexachlorobenzene; hexaconazole;
hymexazol; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate);
iodocafb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione;
kasugamycin; kresoxim-methyl; mancozeb; maneb; rneferimzone; mepanipyrim; mepronil; metalaxyl;
metalaxyl-M; metconazole; methasulfocarb; methfuroxarn; metiram; metominostrobin; metsulfovax;
mildiomycin; myclobutanil; myclozolin; natamycin; mcobifen; nitrothal-isopropyl; noviflumuron; nuarimol;
ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol;
pefurazoate; peneonazole; pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins;
polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole;
propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazopnos; pyrifenox; pyrimethanil;
pyroquilon; pyroxyfur; pyrrolnitrine; quinconazole; qurnoxyfen; quintozene; simeconazole; spiroxamine;
sulfur, tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen;
thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon;
triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumizole;
triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)-N-[2-[4-
[[3-(4-cUprophenyl)-2-propynyl]oxy]-3-methoxyphenyl]emyl]-3-me1hyl-2-[(memylsulfo^
butanamide; l-(l-naphthalenyl)-lH-pyrrol-2,5-dione; 2,335,6-tetrachloro-4-(me1iiylsulfonyl)-pyiidine;
2-arnino-4-me1hyl-N-phenyl-5-traazolecarboxarnide; 2-chloro-N-(2^-dihydro-lJ,3j-trirnethyl-lH-inden-
4-yl)-3-pyridinecarboxamide; SAS-trichloro^^-pyridinedicarbonitrile; actinovate; cis-l-(4-chloroprienyl)-
2-(lH-l,2,4-triazol-l-yl)-cycloheptanol; methyl., l-(2,3-dihydro-232-dimethyl-lH-inden-l-yl)-
lH-imidazole-5-carboxylate; mono potassium carbonate; N-(6-methoxy-3-pyridinyl)-cyclopropane:
cafboxamide; N-butyl-8-(l J-dimethylethyl)-l-oxaspiro[4.5]decan-3-amine; sodium tetrathiocarbonate;
and copper salts and preparations, such as Bordeaux mixture; copper hydroxide; copper naphthenate;
copper oxychloride; copper sulphate; cufraneb; copper oxide; mancopper; oxine-copper.
Bactericides:
bronopol, dichlorophen, nitrapyrin,..nickel dimethyldithio^arbamate, .kasugamycin, octhilinone,
furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper, sulphate and
other copper preparations.
Insecticides / aeari cities / nematicides:
ffAcetylcholinesterase (ACliE) inhibitors
1.1 Cafbamates (e.g. alanycafb, aldicarb, aldoxycarb, allyxycarb, aminocarb, azamethiphos, bendiocarbj
benfuracarb, bufencarb, butacafb, butocarboxim, butoxycafboxim, carbaiyl, carbofuran, carbosulfan,
chloethocarb, coumaphos, cyanofenphos, cyanophos, dimetilan, ethiofencarb, fenobucarb, fenothiocarb,
formetanate, furathiocarb, isoprocarb, metam-sodium, methiocafb, methomyl, metolcarb, oxamyl,
pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, xylylcafb)
1.2 Qrganophosphates (e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl,
bromfenvinfos (-methyl), butalbiofos, cadusafos, carbophenotbion, chlorethoxyfos, chlorfenviaphos,
cblormephos, chloipyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos,
demeton-s-methyl., demeton-s-meth.ylsulpb.on, dialifos, diazinon, dichlofenthion, dichlorvos/ddvp, dicrotophos,
dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, epn, ethion, ethoprophos, etrimfos,
famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan,
fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl o-salicylate,
isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, meyinphos, monocrotophos,
naled, omethoate, oxydemeton-methyl, parathion (-methyl/-ethyl), phenthoate, phorate,
phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (-methyl/-ethyl), profenofos,
propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos,
sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, tbiometon, triazophos,
triclorfon, vamidothion)
2. Sodium channel modulators/voltage dependant sodium channel blockers
2.1 Pyrethroids (e.g. acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin,
bioallethrin-s-cyclopentjd-isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin,
cis-cypermethrin, cis-resmetbrin, cis-permethrin, clocythrin, cycloproflmn, cyfluthrin, cyhalotixtin,
cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, DDT, deltamethrin, empenthrin (IR-isomer),
esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate,
flucythririate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprolhrin,
kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (IR-trans isomer),
prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, lau-fluvalinate,
tefluthrin, terallethrin, tetramethrin (IR-isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins
(pyrethrum))
2.2 Oxadiazine (e.g. indoxacarb)
3. Acetylclioline receptor agonists/-antagonists
3.1 Qilo'rbnicotinyls/nebnicotinbids (e:g. acetamiprid, clothianidin, dinotefuran, ;imidacloprid, :nitenpyram,
rnithiazine, thiacloprid, thiamethoxam)
3.2 nicotine, bensultap, cartap
4. Acetylcholine receptor modulators
4.1 Spinosyns (e.g. spinosad)
5. SABA gated chloride channel antagonists
5.1 Cyclodiene organochlorines (e.g. camphechlor, chlordane, endosulfan/gamma-HCH, HCH,
heptachlor, lindane, methoxycblor
5.2Fiproles (e.g. acetoprole, ethiprole, fipronil, vaniliprole)
6. Chloride channel activators
6.1 Mectins (e.g. abamectin, avermectin, emamectin, emamectin-benzoate, ivermectin, milbemectin,
milbemycin)
7. Juvenile hormone mimics
(e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene)
8. Ecdysone agonists/disrupters
8.1 Diacylhydrazines (e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenoadde)
9. Inhibitors ofchitin biosynthesis
9.1 Benzoylureas (e.g. bistrifluron, cblofluazuron., diflubenzuron, fluazuron, flucycloxuron, flufenoxuron,
hexaflurnuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron)
9.2 buprofezin
9.3 cyromazine
10. Inhibitors ofoxidativephosphorylation, ATP-disruptors
10.1 diafenfhiuron
10.2 Organotins (e.g. azocyclotin, cyhexatin, fenbutatiB-oxide)
11. Decoupler ofoxidativephoshorylation by diruption of Hproton gradient
11.1 Pyrroles (e.g. cblorfenapyr) '
11.2 Dinitrophenoles (e.g. binapacyrl, dinobuton, dinocap, DNOC)
12. Site I electron transport inhibitors
12.1 MEITs (e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad,J:olfenpyrad)
12.2 hydramethylnone
12.3 dicofol
13. Site H electron ti-ansport inhibitors
13.1 rotenone
14. Site ID. electron transport inhibitors
14.1 acequinocyl, fluacrypyrim
15. Microbial disrupters of insect midgut membranes
Bacillus thuringiensis strains
16. Inhibitors of lipid synthesis
16.1 Tetronic acid insecticides (e.g. spirodiclofen, spiromesifen)
16.2 Tetramic acid insecticides [e.g. 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-
en-4-yl ethyl carbonate (alias: carbonic acid, 3-(2,5-dimefhylplienyl)-8-mefhoxy-2-oxo-l-azaspiro[4.5]-
%i-3-en-4-yl ethyl ester, CAS-Reg.-No.: 382608-10-8) and carbonic acid, cis-3-(235-dimethylphenyl)-
8-methoxy-2-oxo-l -azaspiro[4.5]dec-3-en-4-yl ethyl ester (CAS-Reg.-No.: 203313-25-1)] '
17. Carboxamides
(e.g. flonicamid)
18. Octopaminergic agonists
(e.g. amitraz)
19. Inhibitors of magnesium stimulated ATPase
(e.g. propargite)
20. Phthalamides
(e.g. NMU-dimethyl-2-(memylsulf
methyl)ethyl]phenyl]-l,2-benzenedicafboxamide (CAS-Reg.-No.: 272451-65-7, flubendiamide))
21. Nereistoxin analogues
(e.g. thiocyclam hydrogen oxalate, thiosultap-sodium)
22. Biologica, hormones orpheromones
(e.g. azadirachtin, Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec., Paecilomyces
spec.,- thuringiensin, Verticillium spec.)
23. Compounds of unknown or non-specific mode of action
23.1 Fumigants (e.g.' aluminium phosphide, methyl bromide, sulfuryl fluoride)
23.2 Selective feeding blockers (e.g. cryolite, flonicamid, pymetrozine) . .
23.3 Mite growth inhibitors (e.g. clofentezine, etoxazole, hexythiazox)
23.4 amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, chinomethionat,
chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil,
fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone, japonilure,
metoxadiazone, petroleum, piperonyl butoxide, potassium oleate, pyrafluprole, pyridalyl, pyriprole,
sulfluramid, tetradifon, tetrasul, triarathene, vefbutin
further the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3-(5-chloro-3-
pyridinyl)-8-(232J2-trifluoroemyl)-8-azabicyclo[3.2.1]octan-3-carbonitrile(CAS-Reg.-Nr. 185982-80-3)
and the corresponding 3-endo isomer (CAS-Reg.-Nr. 185984-60-5) (cf. WO 96/37494, WO 98/25923),
and preparations comprising insecticidal active plant extracts, nematodes, fungi or viruses.
A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators,
safeners and/or semiochemicals is also possible.
When used as insecticides, the active compounds according to the invention can furthermore be
present in their commercially available formulations and in the use forms, prepared from these
formulations, as a mixture with synergistic agents. Synergistic agents are compounds, which increase
%•. action of the active compounds, without it being necessary for the synergistic agent added to be
active itself.
When used as insecticides, the active compounds according to the invention can furthermore be
present in their commercially available formulations and in the use forms, prepared from these
formulations, as a mixture with inhibitors which reduce degradation of the active compound after use
in the vicinity of the plant, on the surface of parts of plants or in plant tissues.
The content of the active compounds of the formula (T) of the present invention in a commercially
useful application form can be varied in a wide range.
The concentration of the active compounds of the formula (!) of the present invention at the time of
actual usage can be, for example, in the range of 0.0000001-100% by weight, preferably 0.00001-1%
byweight. .
The pompounds of the formula (I) of the present invention can be applied by usual methods suitable
to the application forms.
In case of application against hygiene pests and pests of stored products, the active compounds of the
present invention have a good stability against alkali on limed .substrates and further show an
excellent residual effectiveness on wood and soil.
As already mentioned above, it is possible to treat all plants and their parts according to the invention. In
a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional
biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a
further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if
appropriate in combination with conventional methods (Genetically Modified Organisms),, and parts
thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.
Particularly preferably, plants of the plant cultivars which are in each case commercially available or
in use are treated according to the invention. Plant cultivars are to be understood as meaning plants
having certain properties ("traits") which have been obtained ;by conventional breeding, by
mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate,
vegetation period, diet), the treatment according to the invention may also result in superadditive
("syneigistic") effects. Thus, for example, reduced application rates and/or a widening of the activity
jpctrum and/or an increase in the activity of the substances and compositions to be used according to
the invention, better plant growth, increased tolerance to high or low temperatures, increased
tolerance to drought or to water or soil salt content, increased flowering performance, easier
harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional
value of the harvested products, better storage stability and/or processability of the harvested products
are possible which exceed the effects which were-actually to be expected.
The transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are preferably
to be treated according to the invention include all plants which, in the genetic modification, received
genetic material which imparted particularly advantageous useful traits to these plants. Examples of
such trails are better plant growth, increased tolerance to high or low temperatures, increased tolerance
to drought or to water or soil salt content, increased flowering performance, easier harvesting,
accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the
harvested products, better storage stability and/or processability of the harvested products. Further and
particularly emphasized examples of such traits are a better defence of the plants against animal and
microbialpests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also
increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic
plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya
beans, potatoes, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus
fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and
oilseed rape. Traits that are emphasized are in particular increased defence of the plants against insects,'
arachnids, nematodes and worms by toxins formed in the plants, in particular those formed in the plants
by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b),
CryIA(c), CryllA, CrylUA, CryHIB2, Cry9c, Cry2Ab, CrySBb and CryEF and also combinations
thereof) (hereinbelow referred to as "Bt plants")- Traits that are also particularly emphasized are the
increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance
(SAR), systemin, phytoalexius, elicitors and resistance genes and correspondingly expressed proteins
and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants
to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or
phosphinotricin (for example the 'TAT" gene). The genes which impart the desired traits in question
can also be present in combination with one another in the transgenic plants. Examples of "Bt plants"
which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties
which are sold under the trade names YIELD GARD® (for example maize,-cotton, .soya .beans),
KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn®
(cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are
maize varieties, cotton varieties and soya'bean varieties which are sold under the trade names Roundup
Ready© (tolerance to glyphosate, for example maize, cotton., soya bean), Liberty Link® (tolerance to
p|«sphinotricinj for example oilseed rape), IMT® (tolerance to imidazolinones) and STS® (tolerance to
sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner
for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield®
(for example maize). Of course, these statements also apply to plant cultivars having these genetic traits
or genetic traits still to be developed, which plants will be developed and/or marketed in the future.
The plants listed can be treated according to the invention in a particularly advantageous manner with
the compounds of the general formula I and/or the active compound mixtures according to the
invention. The preferred ranges stated above for the active compounds or mixtures also apply to the
treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds
or mixtures specifically mentioned in the present text.
Then the present invention will be described more specifically by examples. The present invention,
however, should not be restricted only to them in any way.
Synthesis Examples
Synthesis Example 1
3-(14-Dimethyl-2-methylsulfanyl-ethylimino)^-iodo-3H-isobenzofuran-l-one (0.53 g) and l-(3-methyl4-
aminobenzyl)-3,5-bis(trifluoromethyl)-lH-pyrazole (0.45 g) were dissolved in acetonitrile
(15 ml), to which p-toluenesulfonic acid nionohydrate (0.01 g) was added and the mixture was stirred
at 60°C for 3 hours. After finishing the reaction, the solvent was distilled off under reduced pressure
and the residue was purified by silica gel column chromatography to obtain N'S-bislrifluorome&
ylpyrazol-l-ylmemyl)-2-methylpte
amide (0.91 g). mp. 83-87°C.
Synthesis Example 2
sulfanylethyl)-3-iodophthalamide (0.5 g) was dissolved in dichloromethane, to which m-chloroperbenzoic
acid (0.26 g) was added and the mixture was stirred for 5 hours under ice cooling. After finishing
the reaction, the mixture was washed successively with aqueous solution of sodium thiosulfate, saturated
aqueous solution of sodium bicarbonate and saturated aqueous solution of sodium chloride, and
dried with anhydrous magnesium sulfate. After distilling off the solvent, the obtained residue was purified
by silica gel column chromatography to obtain NI-{4-[3,5-bis(trifluoromethyl)-lH-pyrazoll-
ylmethyl]-2-methylphenyl}-N2- (2-meihanesdfmyl-l,l-dimethylethyl)-3-iodoph1halainide (0.30 g).
'H-NMR (CDC]3, ppm): 1.57 (3H, s), 1.60 (3H, s), 2.20 (3H. s), 2.30 (3H, s), 2.93 (2H, dd), 5.43 (2H3
s), 6.57 (1H, s), 6.90 (1H, s), 7.0-8.2 (7H, m).
thesis .Example
N1-{4-[3,5-Bis(1rifluorome%l)-lH-pyrazol-l-ylme%l]-2-methylplienyl}-N2- (l,l-dimethyl-2-methylsulfanylethyl)-
3-iodophthalarnide (0.30 g) was dissolved in dichloromethane, to which m-chloroperbenzoic
acid (0.26 g) was added and the mixture was stirred at room temperature for 5 hours. After
finishing the reaction, the mixture was washed successively with aqueous solution of sodium thiosulfate,
saturated aqueous solution of sodium bicarbonate and saturated aqueous solution of sodium chloride,
and dried with anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude crystals
were washed with petroleum ether.to obtain N^4-[3,54)is(trifluoromet^^
me1hylphenyl}-34odo-N2-(2-meth (0.25 g). rap. 104-107°C.
Synthesis Example 4
(Figure Removed)
A dioxane solution (15 ml) of 2-{4-[3,5-bis(triiluoromethyl)-lH-pyrazol-l- ylmethyl]-2-methylphenyl}-
4-fluoroisoindole-l,3-dione (0.94 g), (S)-l-me1h.yl-2-methylsulfanylethylamine (0.63 g) and
acetic acid (0.12 g) was refluxed for 18 hours. After cooling to room temperature, the solvent was
distilled off and the obtained residue was purified by silica gel column chromatography to obtain
N1-{4-[3,5-bis(trifluorome1iiyl)4H-pyrazol4-ylme%l]-2-methylphenyl}-3-fluoro-N2-[l-(S)-lmethyl-
2-methylsulfanyl-ethyl]-phthalamide (0.19 g) (compoundNo. 549). rnp. 66-68°C.
Jtetbesis Example 5
3-Iodo-N-(l,l-dimethyl-2-methylsulfanyl-ethyl)-phthalamic acid (0.39 g) and N-(3-dimethylaminopropyty-
N^ethylcarbonyl diimidazole hydrochloride (0.19 g) were stirred in dichloromethane (10 ml)
at room temperature for 30 minutes. Then, 2-memyM-[l-(3-trifluororneuiyl-lH-pyrazol-l-yl)-ethyl]-
aniline (0.30 g) and p-toluenesulphonic acid monohydrate (0.02 g) were added thereto and the
mixture was stirred at room temperature for 3 hours. After distilling off the solvent under reduced
pressure, the obtained residue was purified by silica gel column chromatography to obtain
N21,1-dimethyl-2-methylsulfanyl
-yl)-ethyl]-phenyl}-phthalamide (0.38 g) (compound No. 558). mp. 79-86°C.
The compounds of the formula (I), according to the present invention, which can be obtained in the
same manner as the above-mentioned Synthesis Examples 1 to 5 are shown in Table 1, together with
the compounds obtained in the above-mentioned Synthesis Examples 1 to 5.
NMR. data of the compounds, whose mp. column is marked as ***, are collectively shown in Table 2,
separately from Table 1.
(Figure Removed)
Synthesis Example 6 (Starting material)
3-Methyl-4-nitrobenzyl chloride (1.81 g), 3,5-bis(trifluoromethyl)-lH-pyrazole (2.0 g) and potassium
carbonate (1.63 g) were stirred in DMF (20 ml) at 60°C for 1 hour. After finishing the reaction, water
(100 ml) was added thereto and the mixture was extracted with ethyl acetate. The organic layer was
washed with saturated aqueous solution of sodium chloride (100 ml) and dried with anhydrous
sodium sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column
chrornatography to obtain l-(3-me1hyl-4-nitroben2yl)-335-bis-(trifluoromethyl)-lH-pyrazole (3.3 g).
JH-NMR (CDC13, ppm): 2.59 (3H, s), 5.50 (2H, s), 6.90 (1H, s), 7.1-7.2 (2H, m), 8.00 (1H, d).
Synthesis Example 7 Starting material")
CH3 CF,
To a mixture of l-(3-methyi-4-nitrobenzyl)-3,5-his(trifluoromethyl)-lH-pyrazole (1.4 g), ammonium
acetate (30.5 g), acetone (60 ml) and water (30 ml), 20% aqueous solution of titanium trichloride
(27.5 g) was added at room temperature and the mixture was stirred at room temperature for 12 hours.
After finishing the reaction, the mixture was extracted with ethyl acetate, washed with saturated
aqueous solution of sodium chloride and dried with anhydrous sodium sulfate. After distilling off the
solvent, the obtained residue was purified by silica gel column chromatography to obtain
l-(3-metiiyM-ammobenzyl)-3,5-bis(trifluoromethyl)-lH-pyrazole (1.19 g).
'H-NMR (CDC13, ppm): 2.14 (3H, s), 3.66 (2H, m), 5.32 (2H, s), 6.62 (1H, d), 6.89 (1H, s), 6.8-7.1
(2H,m).
Synthesis Example 8 (Starting material)
,CF,
l-(3-Methyl-4-nitrobenzyl)-3,5-bis (trifluoromethyl)-lH-pyrazole (17.66 g) and iron powder (13.69
g) were heated and stirred in acetic acid (150 ml) at 40°C for 5 hours. After finishing the reaction, an
insoluble matter was filtered with Celite and the filtrate was concentrated under the reduced pressure.
To the residue, IN aqueous solution of sodium hydrate (200 ml) and ethyl acetafe (200 ml) were
added. The organic layer was separated, washed with water, and then, dried with anhydrous
magnesium sulfate. After distilling off the solvent, l-(3-memyl-4-arninobenzyl)-3,5-bis(trifluoromethyl)-
lH-pyrazole (13.0 g), which was the same as that obtained in S3Tithesis Example 7, was
obtained.
Synthesis Example 9 (Starting material)
3-FluoTophthalic anhydride (4.98 g) and l-(3-methyl-4-aminobenz)'l)-3,5-bis(trifluoromethyl)-lHpyrazole
(9.70 g) were refluxed in acetic acid (43 ml) for 3 hours. After finishing the reaction, the
acid was distilled oif under the reduced pressure and the obtained crude crystals were washed
with t-butyl methyl ether to obtain the aimed 2-{4-[3,5-bis (trifluoromethyl)-lH-pyrazbl-l-ylmethyl]-
2- methylphenyl}-4-fluoroisoindol-l,3-dione (10.80 g).mp. 158-159°C.
Synthesis Example 10 (Starting material
3-Methy]-4-nitrobenzyl chloride (0.56 g), 5difluorome%I)-l,2-dihydro-2-methyl-3H-lA4-(triazol)-
3-one (0.45 g) and potassium carbonate (0.61 g) were stirred in DMF (10 ml) at 50°C for 5
hours. After finishing the reaction, the reaction mixture was poured into ice water and extracted with
ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride and
then dried with anhydrous magnesium sulfate, and the solvent was distilled off under the reduced
pressure. The obtained residue was purified by silica gel column chromatography to obtain the aimed
5-difiuoromethyl-2-methyl-4- (3- methyl-4-riitrobenzyl)-2,4-dihydro-[l,2.,4]triazol-3-one (0.45 g).
JH-NMR (CDC13, ppm): 2.5 (3H, s), 3.5 (3H, s), 4.9 (2H, s), 6.4 (IE, t), 7.2-7.3 (2H, m), 7.8-7.9 (1H,
m).
Synthesis Example 11 (Starting material)
CH3
3-Methyl-4-nitrobenzyl chloride (0.43 g), S-heptafluoropropylsutfanyl-S-trifluoromethyl-lHtriazole
(0.70 g), tetrabutylammonium iodide(0.09 g), 18-crown-6 (0.06 g) and potassium carbonate
(0.48 g) were refluxed in acetonitrile (10 ml) for 2 hours. After cooling, the reaction solution was
diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium chloride.
After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced
pressure and the obtained residue was purified by silica gel column chromatography to obtain 3-heptafluoropropylsulfanyl-
l-(3-me1hyW-niirobenzyl)-5-1rifluorometbyl-lH-(l,2,4)-triazole(0.30g).
'H-NMR (CDC13, ppm): 2.64 (3H, s), 5.62 (2H, s), 7.31-7.25 artihesis Example 12 (Starting material)
SC3F7-n
To a mixture of 3-heptafluoropropylsiilfanyl-l-(3-me1hyW-nilTophenyl)-5-trifluoromethyl-lH-(l.J2,4)-
triazole (0.3 g), ammonium acetate (4.8 g), acetone (20 ml) and water (10 ml), 20% aqueous solution of
titanium trichloride (4.3 g) was added at room temperature and the mixture was stirred at room
temperature for 12 hours. After finishing the reaction, the mixture was extracted with ethyl acetate,
washed with saturated aqueous solution of sodium chloride and dried with anhydrous sodium sulfate.
After distilling off the solvent, the obtained residue was purified by silica gel column chromatography
to obtam 4-(3-hepMuoropropylsulfanyl-5-1rifluorom
amine (0.28 g)
'H-NMR (CDC13, ppm): 2.17 (3H, s), 4.16 (1H, hre), 5.40 (2H, s), 6.63-6.59 (2H, m), 7.13-6.99 (1H,
Synthesis Example 13 (Starting material)
(Figure Removed)
An acetonitrile solution (30 ml) of 3-trifluoromethyl-lH-pyrazole (5.0 g), dicerium ammonium
nitrate (10.0 g) and iodine (5.6 g) was refluxed for 1 hour. After cooling, the reaction solution was
washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of
sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off
under thereduced pressure to obtain 4-iodo-3-trifluoromethyl-lH-pyrazole (9.3 g).
'H-NMR (CDC13, ppm): 7.77 (1H, s).
Synthesis Example 14 (Starting material)
3-Methyl-4-nitroben2yl chloride (0.77 g), 4-iodo-3-trifluoromethyl-lH-pyrazole {0.99 g) and potas-
.sium carbonate (0.63 g) were stirred in DMF (10 ml) at 60°.C for 1 hour. After cooling, the reaction
solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of
sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off
miner the reduced pressure and the obtained residue was purified by silica gel column chromatography
to obtain 4-iodo-l- (3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (1.0 g).
'H-NMR (CDda, ppm): 2.62 (3H, s), 5.36 (2H, s), 7.21-7.18 (2H, m), 7.52 (1H, s), 7.98 (1H, d).
Synthesis Example 15 (Starting material)
4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (2.06 g), copper powder (0.95 g),
iodopentafluoroethane (4.92 g) and DMF (13 ml) were set in an autoclave and heated and stirred for 8
hours, maintaining the inside temperature of 130-135°C. After cooling to room temperature, the
reaction mixture was diluted with ethyl acetate (50 ml) and an insoluble matter was filtered with
Celite and washed with ethyl acetate. The filtrate was concentrated under the reduced pressure and
the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)-
4-pentafluoroethyl-3-trifluoromethyl-lH-pyrazole (1 .39 g)
JH-NMR (CDC13, ppm): 2.63 (3H, s), 5.38 (2H, s), 7.21-7.27 (2H, m), 7.74 (1H, s), 8.00 (1H, d).
Synthesis Example 16 (Starting material')
3-Methyl-4-nitrobenzyl chloride (8.57 g), 4-iodo-3-pentafluoroethyl-lH-pyrazole (16.00 g) and potassium
carbonate (7.66 g) were stirred in DMF (70 ml) at 70°C for 1 hour. After cooling, the reaction
solution was poured into water and extracted with ethyl acetate. The organic phase was washed with
water and saturated aqueous solution of sodium chloride. After drying the organic layer with sodium
sulfate, the solvent was distilled off under the reduced pressure and the obtained residue was purified
by silica gel column chromatography to obtain 4-iodo-l-(3-methyl-4-mtrobenzyl)-3-pentafluoroethyl-
lH-pyrazole (4.60 g).
'H-NMR (CDC13, ppm): 2.60 (3H, s), 5.38 (2H, s), 7.22-7.15 (2H, m), 7.53 (1H, s), 7.98 (1H, d).
Synthesis Example 17 (Starting material)
4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl-lH-pyrazole (1.84g), (trifluoromethyl)trimethylsilane
(1.14g), copper® iodide (1.52g), potassium fluoride (0.28g) were stirred in DMF (8 ml) at
100°C for 8 hours. After cooling, the mixture was poured into water and extracted with ethyl acetate .
'Me combined organic phase was washed with saturated aqueous solution of sodium chloride. After
drying the organic layer with sodium sulfate, the solvent was distilled off under the reduced pressure
and the obtained residue was purified by silica gel c'olurm chromatography to obtain l-(3-methyM-
ni1ro-benzyl)-3-pentafluoroethyl^-triiluorome1:hyl-lH-pyrazole(0.32g).
'H-NMR (CDC13, ppm): 2.61 (3H, s), 5.41 .(2H, s), 7.31-7.18 (2H3 m), 7.78 (1H3 s), 8.00 (1H, d).
Synthesis Example 18 (Starling material)
F
4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (2.06 g), copper powder (0.95 g),
heptafluoro-1-iodopropane (2.96 g) and DMF (14 ml) were set in an autoclave and heated and stirred
for 8 hours, maintaining the inside temperature of 130-135°C. After cooling to room temperature, the
reaction mixture was diluted with ethyl acetate (50 ml) and an insoluble matter was filtered with
Celite and washed with ethyl acetate. The filtrate was concentrated under the reduced pressure and
the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)-
4-pentafluoropropyl-3- trifluoromethyl-lH-pyrazole (0.80 g).
'H-NMR (CDC13, ppm): 2.62 (3H, s), 5.42 (2H, s), 7,19-7.20 (2H, m), 7.74 (1H, s), 8.02 (1H, d).
Synthesis Example 19 (Starting material)
4-Iodo-l-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-lH-pyrazole (2.47 g), copper powder (1.14 g),
nonafluoro-1-iodobutane (4.15 g) and DMF (16 ml) were set in an autoclave and heated and stirred
for 8 hours, maintaining the inside temperature of 130-135°C. After cooling to room temperature, the
reaction mixture was diluted with toluene (50 ml) and an insoluble matter was filtered with Celite and
washed with toluene. The filtrate was concentrated under the reduced pressure and the obtained
residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)-
4-nonafluorobutyl-3- trifluoromethyl-lH-pyrazole (1.50g).
'H-NMR (CDC13, ppm): 2.62 (3H, s), 5.42 (2H/s), 7.18-7:24 (2^3^,7^74(113, s), 8.00 (1H, d).
sis Example 20 (Starting material)
NH
An acetonitrile solution (20 ml) of 3-trifluoromethyl-lH-pyrazole (1.0 g), dicerium ammonium
nitrate (2.0 g) and bromine (0.7 g) was refluxed for 2 hours. After cooling, the reaction solution was
washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of
sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off
under the reduced pressure to obtain 4-bromo-3-trifluoromethyl-lH-pyrazole (1.6 g).
'H-NMR (CDC13, ppm): 7.73 (1H, s), 12.86 (1H, brs).
Synthesis Example 21 (Starting material)
3-Methyl-4-nitroberi2yl chloride (0.77 g), 4-bromo-3-trifluoromethyl-lH-pyrazole (0.90 g) and potassium
carbonate (0.57 g) were stirred in DMF (10 ml) at room temperature for 2 hours. The reaction
solution was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium
chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off
under the reduced pressure and the obtained residue was purified by silica gel column chromatography
to obtain lr(3-methyl-4-ni1robenzyl)-4-bromo-3-trifluoromethyl-lH-pvrazole (0.9 g).
'H-NMR (CDC13, ppm): 2.58 (3H, s), 5.35 (2H, s), 7.24-7.21 (2H, m), 7.49 (1H, s),: 7.98 (1H, d).
Synthesis Example 22 (Starting material)
An acetonitrile solution (20 ml) of 3-trifluoromethyl-lH-pyrazole (0.5 g), dicerium ammonium
nitrate (1.0 g) and N-chlorosuccinimide (0.7 g) was refluxed for 3 hours. After cooling, the reaction
solution was washed with saturated aqueous solution of sodium thiosulfate and saturated aqueous
solution of sodium chloride. After drying an organic layer with magnesium sulfate, the solvent was
distilled off under the reduced pressure to obtain 4-cMoro-3-trifluoromethyl-lH-pvrazole (0.9 g).
'H-NMR (CDC13, ppm): 7.80 (1H, s).
Synthesis Example 23 (Starting material)
3-Methyl-4-nitrobenzyl chloride (0.82 g), 4-chloro-3-trifluoromethyl-lH- pyrazole (0.63 g) and potassium
carbonate (0.61 g) were stirred in DMF (10 ml) at room temperature for 2 hours. The reaction
solution was diluted with eiiyl acetate and washed with water and saturated aqueous solution of
sodium chloride. After drying the organic layer with, magnesium sulfate, the solvent was distilled off
under the reduced pressure and the obtained residue was purified by silica gel column chromatography
to obtain l-(3-memyM-nitrobenzyl)-4-chloro-3-trifluoromethyl- IH-pyrazole (0.98 g).
'H-NMR (CDC13, ppm): 2.62 (3H3 s), 5.33 (2H, s), 7.21-7.19 (2H, m), 7.46 (1H, s), 7.98 (IB, d).
Synthesis Example 24 (Starting material)
o'
2-(Trifluroaceryl)-lH-pyrrole (0.97 g) was added to DMF solution (10 ml) of 60% sodium hydride
(0.16 g)'and the mixture was stirred at room temperature for 30 minutes. 3-Metnyl-4-nitrobenzyl
chloride (1.0 g) was added thereto and the mixture was stirred at room temperature for 2 hours. The
reaction solution was diluted with ethyl acetate and washed with water and saturated aqueous solution
of sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled
off under the reduced pressure and the obtained residue was purified by silica gel column chromatography
to obtain l-(3-methyl-4-nitrobenzyl)-2- (trifluoroacetyl)-lH-pvrrole (1 .53 g).
'H-NMR (CDC13, ppm): 2.55 (3H, s), 5.59 (2H, s), 6.44-6.41 (1H, m), 6.99 (1H, d), 7.04 (1H, s),
7.22-7.19 (1H, m), 7.35-7.32 (lH,m), 7.93 (1H, d).
Synthesis Example 25 (Starting material)
An acetonitrile solution (20 ml) of 2-(trifluoroacetyl)-lH-pyrrolei(p.5 g), dicerium ammonium nitrate
(0.84 g) and iodine (0.47 g) was refluxed for 2 hours. After cqoling, the reaction solution was washed
with saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium
chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under
the reduced pressure to obtain 4-iodo-2- (trifluoroaceryl)-lH-pyrrole (0.6 g).
'H-NMR (CDC13, ppm): 7.28-7.35 (211, m), 9.52 (1H, brs).
1 mtfaesis Example 26 (Starting material)
02N
3-Methyl-4-nitrobenzyl chloride (0.63 g), 4-iodo-2- (trifiuoroaceryl) pyrrole (0.89 g) and potassium
carbonate (0.57 g) were stirred in DMF (10 ml) at room temperature for 2 hours. The reaction solution
was diluted with ethyl acetate and washed with water and saturated aqueous solution of sodium
chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off under
the reduced pressure and the obtained residue was purified by silica gel column chromatography to
obtain 4-iodo-l- (3-methyl-4-nitroben2yl)-2-trifluoroacetyl- IH-pyrrole (0.45 g).
'H-NMR (CDC13, ppm):.2.60 (3H, s), 5.56 (2H, s), 7.05-7.12 (2H, m), 7.21 (1H, d), 7.39 (1H, s), 7.94
Synthesis Example 27 (Starting material)
O2N.
4-Iodo-l-(3-methyl-4-nitrobenzyl)-2-1riiluoroaceiyl-lH-pyrrole (1.75 g), copper powder (5.08 g), iodopentafluoroethane
(5.92 g) and DMSO (6 ml) were set in an autoclave and heated and stirred for 8 hours,
maintaining the inside temperature of 120°C. After finishing the reaction, the reaction mixture was
poured into ice water and an insoluble matter was filtered with Celite, and then, it was extracted with
ethyl acetate. The extracted solution was washed with water and then dried with anhydrous sodium
sulfate. After distilling off the solvent, the obtained residue was purified by silica gel column
chromatography to obtain l-(3-methyl-4-nitr6phenyl)-4-peniafluoroethyl-lH-pyrrole (1.35 g).
'H-NMR (CDC13, ppm): 2.59 (3H, s), 5.62 (2H, s), 7.00-7.10 (2H, m), 7.43-7.50 (2H, m), 7.96 (1H, d).
Some specific examples of other processes to synthesize the compounds of the aforementioned
formula (IX) are shown below.
Synthesis Example 28 (Starting material)
TO a toluene suspension of ethyl 4,4,4-trifluoroacetoacetate (5.0 g), sodium hydride (1,1 g) was
slowly added and the mixture was stirred for 1 hour. After adding 4-chloromethyl-2-methyl-
1-nitre-benzene (5.5 g) and potassium iodide dissolved in acetone (0.5 g), the reaction solution
was refluxed for 5 hours. After cooling, the solvent was distilled off under reduced pressure. The
residue was suspended in ethyl acetate and washed with IN aqueous solution of hydrochloric acid.
After drying the organic layer with sodium sulfate, the solvent was distillea off and the obtained
residue was purified by silica gel column chromatography to obtain ethyl 4,4,4-trifluoro-2-
(3-methyl-4-nitro-benzyl)-3-oxo-butyrate(6.3 g).nD
20 1.4970
Synthesis Example 29 (Starting material)
H3C
Ethyl 4,4,4-trifluoro-2- (3-methyl-4-nitro-benzyl)-3-oxo-buryrate (2.0 g), hydrazine monohydrate (0.5
g) and a small amount of p-toluenesulfonic acid were dissolved in toluene, and the mixture was
refluxed for 4 hours. After cooling, the solvent was distilled off under reduced pressure. The residue
was suspended in ethyl acetate, and washed with IN aqueous solution of hydrochloric acid. After
drying the organic layer with sodium sulfate, the solvent was distilled off and the obtained residue
was purified by silica gel column chromatography to obtain 4-(3-methyl-4-nitro-benzyl)-5-trifluoromethyl-
2,4-dihydro-pyrazol-3-one (1.0 g).
'H-NMR (DMSO-dfo 90MHz): 62.2 (3H, s), 3.8 (2H, s), 7.0 (1H, d, J=5.5Hz), 7.2 (1H, s), 7.8 (1H, d,
J=5.5Hz), 11.2(lH,brs).
Synthesis Example 30 (Starting material)
(Figure Removed)
To a DMF suspension of 4-(3-methyl-4-nitro-benzyl)-5-trifluoromethyl-2,4-dihydro-pyrazol-3-one
(1.0 g) and potassium carbonate (1.5 g), chlorodifluoromethane (5.7 g) was sealed in by using a balloon.
After 5 hours, after the gas in the solution was saturated, the vessel was tightly closed and the mixture
was stirred at 50°C for 5 hours. After cooling, the solvent was distilled off and the obtained residue was
dissolved in ethyl acetate and washed with water and saturated aqueous solution of sodium chloride.
After drying the organic layer with sodium sulfate, the solvent was distilled off and the obtained residue
was purified by silica gel column chromatography to obtain 5-difluoromethoxy-l-difluoromethyl-4-(3-
80
ethyl-nitro-benzyl)-3-trifluoromethyl-lH-pyrazole (IX-1) (0.5 g) and3-difluoromethoxy-l-difluoromethyl-
4- (3-nie1hylnitro-ben2yl)-5-trifluoromethyl-lH-pyrazole (K-2) (0.4 g) respectively.
(EX-1): nD°1.4780, (K-2): nD
201.4855.
Synthesis Example 31 (Starting material')
(3-Methyl-4-nitrophenyl)-hydrazine (3.0 g) and hexafluoroacetylacetone (3.7 g) were dissolved in
toluene and the solution was refluxed for 6 hours. After cooling, the solvent was distilled off and the
obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitropheriyl)-
3,5- bis(trifluoromethyl)-lH-pyrazole (5.6 g). nD
201.4890.
Synthesis Example 32 (Starting material)
CF2CF3 "3° !? \V-CF2CF3
(3-Methyl-4-nitro-phenyl)-hydrazine (2.0 g).and 1,1, 1,5,5,6, 6,6-octafluoro-2,4-hexanedione (3.1 g)
were dissolved in toluene and the solution was refluxed for 6 hours. After cooling, the solvent was
distilled off and the obtained residue was purified by silica gel column chromatography to obtain
l'(3-methyl-4-nitro-phenyl)-3- pentafluoroethyl-5-trifluoromethyl-lH-pyrazole (K-3)~ (3.0 g) and
2-(3-mernyW-mfro-phenyl)-5-pentafluoroethyl-3- (TX-4)
(0.5 g), respectively.
CK-3):nD
20 1.4690,
(K-4): 'H-NMR (CDC13, 90MHz): 82.6 (3H, s), 3.3 (1H, br d, J=16Hz), 3.7 (1H, br d, J=16Hz), 4.1
(1H, s), 7.2 (2H, m), 7.8 (1H, d, J=7.8Hz).
Synthesis Example 33 (Starting material)
To a THF suspension of l-(3-meihyl-4-nitrQ-phenyl)-ethanone (2.0 g), sodium hydride (0.6 g) was
slowly added and the mixture was stirred for 1 hour. After adding ethyl trifluoroacetate (1.6 g), the
reaction mixture was refluxed for 5 hours. After cooling, the solvent was distilled off under reduced
81
pressure. The residue was suspended in, ethyl acetate and washed with IN aqueous solution of
hydrochloric acid. After drying the organic layer with sodium sulfate, the solvent was distilled off and
the obtained residue was purified by silica gel column chromatography to obtain 4,4,4-trifluoro-l-
(3-methyl-4-nitro-phenyl)-butane-l,3- dione (2.5 g).
'H-NMR (CDOa, 90MHz): 62.6 (3H, s), 6.5 (1H, s), 7.7-8.1 (3H, m).
Synthesis Example 34 (Starting material)
(IX-5) (IX-6)
A toluene solution of 4,4J
4-trifluoro-l-(3-methyl^-nitro-phenyl)-butane-lJ3-dione (1.8 g), 2,2,2-trifluoroethylhydrazine
(1.2 g) and a catalytic amount of p-toluenesulfonic acid were refluxed for 6 hours.
After cooling, the solvent was distilled off and the obtained residue was purified by silica gel column
chromatography to obtain 3-(3-me1hyM-mtro-phenyl)-l^2,2}2-1rifluoro^thyl)-5-1rifluoro-methyl-lHpyrazole
(K-5) (1.1 g) and 5-(3-methyl-4-nitro-phenyl)-l- (2,2,2-trifluoro-etbyl)-3-trifluoromethyl-lHpyrazole
(K-6) (0.5 g), respectively.
(K-5) mp; 98-104°C, (K-6)mp; 50-53°C.
Synthesis Example 35 (Starting material")
o o
To a dichloromethane solution of 2,2-dimethyl-l,3-dioxane-4,6-dione (10 g) and dimethylaminopyridine
(17 g), a dichloromethane solution of S-methyM-nitro-benzoyI chloride (14 g) was added
dropwise under ice cooling. After stirring at room temperature for 3 hours and then adding 100 ml of
ethanol, the mixture was refluxed for 2 hours. After cooling, the solvent was distilled off under the
reduced pressure. The residue was dissolved in ethyl acetate and washed with IN aqueous solution of
hydrochloric acid. After drying the organic layer with sodium sulfate, the solvent was distilled off and
the obtained residue was purified by silica gel column chromatography to obtain ethyl -3-(3-methyl-
4-nitro-phenyl)-3-oxo- propionate (12.4 g). mp; 207-211°C.
mthesis Example 36 CStarting material)
N
To an ethanol solution of ethyl 3-(3-methyl-4-nitro-phenyl)-3-oxo-propionate (3.0 g), hydrazine
monohydrate (0.9 g) and a small amount of p-toluenesulfonic acid were added and the mixture was
refluxed for 5 hours. After cooling, the solvent was distilled off under the reduced pressure and the
obtained residue was purified by silica gel column chromatography to obtain
5-(3-methyl-4-mtro-phenyl2,4- dihydro-pyrazol-3-one (2.6 g). mp; 218-219°C.
Synthesis Example 37 (Starting material)
(Figure Removed)
To a DMF suspension of S^S-methyM-nitro-pheny^^^-dihydro-lH-pyrazol-S-one, (2.0 g) and potassium
carbonate (6.3 g), chlorodifluoromethane (8.7 g) was sealed in by using a balloon. After 5
hours, after the gas in the solution was saturated, the vessel was tightly closed and the mixture was
stirred at 50°C for 5 hours. After cooling, the solvent was distilled off and the obtained residue was.
dissolved in ethyl acetate and washed with water and saturated aqueous solution of sodium chloride.
After drying with sodium sulfate, the solvent was distilled off and the obtained residue was purified
by silica gel column chromatography to obtain 5-difluoromerhoxy-l-diiluoromethyl-3-(3-methyl-
nitro-phenyl)-lH-pyrazole (IX-7) (0.7 g) and 3-difluoromethoxy-l-difluoromethyl-5-(3-methyl-4-
nitro-phenyl)-lH- pyrazole (TX-8) (0.5 g), respectively.
(IX-7) mp; 80-82°C, (Dt-8) mp; 99-100°C.
Synthesis Example 38 (Starting material)
To an ethanol solution (60 ml) of hydrazine monohydrate (5.00 g), an ethanol solution (20 ml) of
3-methyl-4-nitrobenzyl chloride (3.71 g) was added dropwise while refluxingit, and the mixture was
continuously refluxed for 6 hours. After finishing the reaction, the solvent was distilled off and
(3-methyl-4-nitrobenzyl)- hydrazine (3.50 g) was obtained.
'H-NMR (CDC13, ppm): 2.60 (3H, s), 2.65-3.35 (3H, m), 3.95 (2H, s), 7.20-7.40 (2H, m), 7.98 (1H, d).
Svofhesis Example 39 ("Starting material')
(Figure Removed)
(3-Methyl-4-nitrobenzyl)-hydrazine (1.81 g) and 5-emoxy-l,l,l,2,2-pentafluoro-4-penten-3-one
(2.18 g) were refluxed in ethanol (60 ml) for 8 hours., and p-toluenesulfonic acid (0.10 g) was added
thereto and the mixture was further refluxed for 6 hours. After finishing the reaction, the solvent was
distilled off and the obtained residue was purified by silica gel column chromatography (mixed
solvent of n-hexane and ethyl acetate) to obtain l-(3-methyl-4-nitrobenzyl)-5-pentafluoroethyl-
lH-pyrazole (0.96 g) as the first elution portion and l-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl-
lH-pyrazole (0.50 g) as the second elution portion.
OK-9): 'H-NMR (CDC13, ppm): 2.61 (3H, s), 5.49 (2H, s), 6.70 (IB, bs), 7.05-7.15 (2H, m), 7.66 (IB,
bs), 7.94 (IB, d).
(K-10): 'H-NMR (CDC13, ppm): 2.64 (3H, s), 5.40 (2H, s), 6.63 (1H, d), 7.07-7.20 (2H, m), 7.52 (1H,
d), 7.9.5 (IE, d).
Synthesis Example 40 (Starting material)
A mixture of 5-fluoro-2-nitrotoluene (2.33 g), 4-iodo-lH-pyrazole (2.91 g) and potassium carbonate
(2.49 g) was heated and stirred in DMF (30 ml) at 140°C for 4 hours. After cooling to room
temperature, the reaction mixture was poured into ice water to separate out crystals. The obtained
crystals were filtered, washed with water and dried, and 4-iodo-l-(3-methyl-4-nitrophenyl)-
lH-pyrazole (4.60 g) was obtained.
'H-NMR(CDC13,ppm): 2.70 (3H, s), 7.50-7.70(3H,m),7.95-8.15 (2H,m).
Synthesis Example 41 (Starting material)
4-Iodo-l-(3-methyl-4-nitrophenyl)-lH-pyrazole (1.98 g), copper powder (1.14 g), iodopentafluoroethane
(8.85 g) and DMSO (9 ml) were set in an autoclave and heated and stirred for 8 hours, maintaining
the inside temperature of 100°C. After finishing the reaction, the reaction mixture was poured
into ice water and an insoluble matter was filtered with Celite, and then, it was extracted with ethyl
£tate. The extracted solution was washed with water and dried with anhydrous sodium sulfate.,
After distilling off the solvent, the obtained residue was purified by silica gel column chromatography
to obtain l-(3-methyl-4-nitrophenyl)-4-pentafluoroe1iiyl- IH-pyrazple (0.72 g).
'H-NMR (CDC13, ppm): 2.70 (3H, s), 7.60-7.73 (2H, m), 7.93 (1H, s), 8.13 (1H, d), 8.23 (1H, s).
Synthesis Example 42 (Starting material')
To a suspension of methanol (300 ml) of 3-methyl-4-nitroacetophenone (26.88 g), sodium borohydride
(8.51 g) was added at 0°C over a period of 1 hour. The mixture was further stirred at room
temperature for 8 hours. After finishing the reaction, the reaction mixture was poured into ice water
(1,000 ml) and extracted with ether. The organic layer was washed with saturated aqueous solution of
sodium chloride and dried with anhydrous magnesium sulfate. After distilling off the solvent, the
aimed l-(3-methyl-4-nitrophenyl)-ethanol (23.33 g) was obtained.
'H-NMR (CDC13, ppm): 1.51 (3H, d), 1.98 (1H, d), 2.62 (3H, s), 4.90-5.01 (1H, m), 7.28-7.35 (2H,
m), 7.98 (1H, d).
Synthesis Example 43 (Starting material)
(Figure Removed)
Into a THF solution (35 ml) of l-(3-methyl-4-nitrophenyl)-ethanol (5.44 g) and trieihylamine (3.95 g),
a THF solution (10 ml) of methanesulfonyl chloride (3.48 g) was added dropwise at 5°C over a
period of 30 minutes. Further, the mixture was stirred at room temperature for 8 hours. After finishing
the reaction, the solvent was distilled off and the residue was dissolved in ethyl acetate (100 ml). It
was washed with 2N aqueous solution of hydrochloric acid and saturated aqueous solution of sodium
bicarbonate and then dried with anhydrous magnesium sulfate. After distilling off the solvent, the
aimed l-(3-methyl-4-nitrophenyl)-ethyl methanesulfonate (5.80 g) was obtained.
'H-NMR (CDC13, ppm): 1.74 (3H, d), 2.65 (3H, s), 2.95 (3H, s), 5.76 (1H, q), 7.35-7.45 (2H, m),
8.01 (1H, d).
vfeffhesis Example 44 ("Starting material)
O2N
l-(3-MeHiyl-4-nitrophenyl)-ethyl methanesulfonate (2.59 g), 3-trifluoromethyl-lH-pyrazole (1.09 g),
potassium carbonate (1.66 g) and 18-crown-6 (0.26 g) were refluxed in acetonitrile (100 ml) for 6
hours. After finishing the reaction, water (100 ml) was added to the mixture and extracted with ethyl
acetate. The organic layer was washed with saturated aqueous solution of sodium bicarbonate and
then dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained residue was
purified by silica gel column chromatography to obtain l-[l-(3-methyl-4-nitrophenyl)-ethyl]-3-trifluorornethyl-
IH-pyrazole (1.60 g). •
'H-NMR (CDC13, ppm): 1.95 (3H, d), 2.59 (3H, s), 5.59 (1H, q), 6.57 (1H, bs), 7.13-7.20 (2H, m),
7.47 (lH,bs), 8.00 (1H, d).
Synthesis Example 45 (Starting material')
HN
Ethyl :pentafluoropropylenate (14.6 g) and hydrazine monohydrate (3.6 g) were refluxed in
tetrahydrofuran (300 ml) for 1 hour. After cooling to room temperature, trifluoroacetamidine (10.0 g)
was added dropwise to the mixture and it was refluxed for 3 hours. After finishing the reaction, saturated
aqueous solution of sodium hydrogen carbonate was added thereto and the mixture was extracted
with ethyl acetate. After drying the organic layer with anhydrous magnesium sulfate, the solvent
was distilled off to obtain crude 3-pentafluoroethyl-5-trifluoromethyl-lH- (l,2,4)-triazole (7.9 g).
Synthesis Example 46 ("Starting material)
(IX-11) on3 "2 5 (IX-12)
l-(3-Memyl-4-nitrophenyl)-ethyl mernanesulfonate (2.5 g), 3-pentafluoroethyl-5-trifluoromemyl-lH-
(l,2,4)-triazblev(2;2 g),-pVtassiurh carbonate (1.6 g) and 18-crown-6 (0.26 g) were refluxed in acetonitrile
(100 ml) for 6 hours. After finishing the reaction, water (100 ml) was added thereto and the
mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous
solution of sodium chloride (100 ml) and then dried with anhydrous sodium sulfate. After distilling
off the solvent, the obtained residue was purified by silica gel column chromatography (mixed
Invent of n-hexane and ethyl acetate) to obtain (K-ll) l-([l-(3-methyl-4-nitro-phenyl)-ethyl]-5-
pentafluoroethyl-3-trifluoromethyl- lH-(l,2,4)-triazole (0.95 g) as the first elution portion and
(EX-12) l-([l-(3-methyl-4- nitro-phenyO-ethylJ-S-pentafluoroethyl-S-trifluorometiiyl-lH-C1-6-triazole
(1.35 g) as the second elution portion.
(K-ll)
'H-NMR (CDC13)5: 8.03-7.97 (1H, m), 7.37 (2H, t, J=5.4Hz), 5.86 (1H, q, J=7.0Hz), 2.62 (3H, s),
2.00(3H,d,J=7.0Hz).
(K-12)
]H-NMR (CDC13) 6: 7.98 (1H, d; J=8.2Hz), 7.34 (2H, t, J=7.1Hz), 5.81 (1H, q, J=7.0Hz), 2.63 (3H, s),
2.01 (3H, d, J=7.0Hz).
Synthesis Example 47 (Starting material)
Sodium hydride (0.10 g) was added to a DMF solution (12 ml) of 4-methyl-5-pentafluoroethyl-
4H-[l,2,4]triazol-3-thiol (0.70 g), and the mixture was stirred at room temperature until the
generation of hydrogen .gas stopped. Continuously, 5-fluoro-2-nitrotoluene (0.47 g) was added thereto
and the mixture was further stirred at room temperature for 1 hour. After cooling to room temperature,
the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was
washed with saturated aqueous solution of sodium chloride and then dried with anhydrous sodium
sulfate. After distilling off the solvent, the obtained residue was purified by; silica gel column
chromatography (mixed solvent of n-hexane and ethyl acetate) to obtain the aimed 4-methyl-3- (3-
methyl-4rnitrophenyl sulfanyl)-5-pentafluoroethyl-4H-(l,2,4)-triazole (0.55 g).
'H-NMR (CDC13, ppm): 2.70 (3H, s), 3.80 (3H, s), 8.10-8.30 (3H, m).
Synthesis Example 48 (Starting material)
A mixture of 2-memylmelcapto^.6-bistrifluoromemyl-pyrimidine (36 g), oxone (126 g), water (500
ml) and chloroform (110 ml) was refluxed for 2 days. After cooling to room temperature., the mixture
was extracted with dichloromethane. The obtained organic layer was washed with water and then
dried with anhydrous sodium sulfate. After distilling off the solvent, the obtained crude crystals were
washed with petroleum ether to obtain 2-methanesulfonyl-4.6-bistrifJuoromethyl-pyrimidine (7.5 g).
'H-NMR (CDC13, ppm): 3.48 (3H, s), 8.19 (1H, s).
Example 49 (Starting material^)
4-Nitro-m-cresol (0.77 g), 2-methanesulfonyl-4, 6-bistrifluoromethyl- pyrirnidine (1.77 g) and
potassium carbonate (1.04 g) were refluxed in acetonitrile (15 ml) for 5 hours. After finishing the
reaction, the reaction mixture was poured into ice to separate out crystals. The obtained crystals were
filtered and dried to obtain 2-(3-methyl-4-nitrophenoxy)- 4,6-bistrifluoromethyl-pyrimidine (1.03 g).
'H-NMR (CDC13, ppm): 2.60 (3H, s), 7.1-7.3 (2H, m), 7.67 (1H, s), 8.10 (1H5 d).
Synthesis Example 50 (Starting material)
CH,
(3-Methyl-4-nitrophenyl)-acetonitrile(3.52g) was dissolved in pyridine (30 ml), thereto excess H2S
was bubbled into at room temperature for 3 hours. Then the mixture was poured onto ice. The precipitate
was collected by suction, washed with water and dried to obtain 2-(3 -methyl-4-nitro-phenyl)-
thioacetamide (1.69 g).
): 2.60 (3H, s),4.06 (2H, s), 6.40-8.00 (5H, m)
Synthesis Example 51 (Starting material)
CHQ
2-(3-Methyl-4-nitrophenyl)-thioacetamide (1.00 g), l-bromo-333,4,4,4-pentafluoro-2-butanone
(1.15 g) and potassium carbonate (0.79 g) were stirred in DMF (10 ml) at room temperature for 1
hour. The reaction solution was diluted with ethyl acetate and washed witii water and saturated
aqueous solution of sodium chloride. After drying the organic layer with magnesium sulfate, the
solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel
column chromatography to obtain 2-(3-Methyl-4-nitro-phenyl)-thioacetimidic acid 3,3,4,4,4-pentafluoro-
2-oxo-butyl ester (1.30 g).
'H-NMR(CDC13)ppm):2.55 C3H, s), 3.57 (2H, dd), 3.90;(2Et, d), 72722-2H,rn),7-91^.89 (lH,m)
Example 52 (Starting material)
Trifluoroacetic anhydride(1.47g) was added to 2-(3-Methyl-4-nitro-pheny])-thioacetimidic acid
3,3,4,44-pentafluoro-2-oxo-butyl ester (1.30 g) and triethylamine (0.71 g) in dichloromethane (10 ml),
and stirred at room temperature for 20 minutes. The reaction solution was washed with water, and the
solvent was distilled off under the reduced pressure and the obtained residue was purified by silica gel
column chromatography to obtain 2-(3-memyM-rjitro-benzyl)-4-perfluoroethyl-thiazole (0.70 g).
'H-NMR (CDC13, ppm): 2.63 (3H, s), 4.43 (2H, s), 7.30-7.28 (2H, m), 7.75 (1H, s), 7.98 (1H, d)
Synthesis Example 53 rStarting material)
An acetonitrile solution (20 ml) of 3-pentafluoroethyl-lH-pyrazole (2.0 g), dicerium ammonium
nitrate (3.0 g) and iodine (1.6 g) was refluxed for 3 hours. After cooling, the reaction solution was
washed with saturated aqueous solution of sodium thipsulfate and .saturated aqueous solution of
sodium chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off
under the reduced pressure to obtain 4-iodo-3- pentafluoroethyl-lH-pyrazole (3.2 g).
'H-NMR (CDC13, ppm): 7.77 (1H, s), 11.11(1H, m)
Synthesis Example 54 (Starting material)
F2HCF2C C2F5
(Figure Removed)
4-Iodo-3-pentafluoroethyl-lH-pyrazole (6.24 g), copper powder (3.81 g), Iodo-l,l,2,2-tetrafluoroetharie
(9.12 g) and DMF (30 ml) were set in an autoclave and heated and stirred for 8 hours,
maintaining the inside temperature of 120-125°C. After cooling to room temperature, the insoluble
material was filtered off through Celite and washed with diethyl ether. The filtrate was diluted with
water and extracted with diethyl ether. The organic phase was washed wMi water and dried over
sodium sulfate, and concentrated under the reduced pressure. The crude product was distilled under
reduced pressure to obtain 3-pentafluoroethyl-4-(l,l,2,2-tetrafluoroethyl)-lH-pyrazole (0.60 g), bp.
125-135°C/20mbar.
'H-NMR (CDC13, ppm): 5.98 (1H, tt), 7.96 (IB, s), 12.22 (IB, m)
Synthesis Example 55 (Starting material)
4-Iodo-3-pentafluoroethyl-lH-pyrazole (12.48 g), copper powder (7.63 g), iodopentafluoroethane
(29.50 g) and DMF (60 ml) were set in an autoclave and heated and stiired for 8 hours, maintaining
the inside temperature of 120-125°C. After cooling to room temperature, the insoluble material was
filtered off through Celite and washed with diethyl ether. The filtrate was diluted with water and
extracted with diethyl ether. The organic phase was washed with water and dried over sodium sulfate,
and concentrated under the reduced pressure/The crude product was distilled under reduced pressure
to obtain 3,4-bis-pentafluoroethyl-lH-pyrazole (1.20 g), bp. 110-115°C/20 mbar.
'H-NME. (CDC13, ppm):.7.99 (1H, s), 12.31 (1H, m).
Synthesis Example 56 (Starting material)
An acetonitrile solution (20 ml) of 4-methyl-lH-pyrazole (0.5 g), dicerium ammonium nitrate (1.7 g)
and iodine (1.9 g) was refluxed for 3 hours. After cooling, the reaction solution was washed with
saturated aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride.
After drying the organic layer with magnesium sulfate, the solvent was distilled off under the reduced
pressure to obtain 3,5-diiodo~4- methyl- IH-pyrazole (1.2 g).
JH-NMR (CDC13, ppm): 2.03 (3H, s), 6.96 (IE, br s)
Synthesis Example 57 (Starting material)
5-Trifluoromethyl-lH-(l,2,4)-triazole-3-thiol(1.0g), heptafluoro-1-iodopropane (3.5 g) and triethylamine
(0.90 g) were stirred in DMF (10 ml) at 90°C for 24 hours. After cooling to room temperature,
he reaction mixture was diluted with ethyl acetate and washed with water and saturated aqueous
solution of sodium chloride. After drying the "organic layer with magnesium .'sulfate/the solvent was
distilled" off 'under the reduced pressure to obtain '3-heptaflubfc)pr6pylsulfanyl-5-tnfluoromethyl-
lH-(l,2,4)-1riazole(0.70g).
90
: examples
Biological Test Example 1: Test against larva of Spodoptera litura
Preparation of test solution:
Solvent: Dimethylformamide : 3 parts by weight
Emulsifier: Polyoxyethylene alkyl phenyl ether: 1 part by weight
In order to make an appropriate formulation of an active compound, 1 part by weight of the active
compound was mixed with the above-mentioned amount of solvent containing the above-mentioned
amount of emulsifier and the mixture was diluted with water to a prescribed concentration.
Test method:
Leaves of sweet potato were soaked in the test solution diluted to a prescribed concentration with
water, dried in the air and put in a dish of 9 cm diameter.
10 larvae ofSpodoptera litura at the third instar were placed on the leaves and kept in a room at the
constant temperature of 25°C. After 2 and 4 days further leaves of sweet potato were added and after
7 days the number of dead larvae was counted and the rate of death was calculated.
In this test the results of 2 dishes at 1 section were averaged.
Biological Test Example 2: Test against larva of Cnaplialocrocis medinalis Guenee
Testmethod:
Paddy rice (variety: Tamanishiki) planted in a pot was treated by spraying 50ml per pot of the diluted
aqueous solution of the prescribed concentration of the active compound prepared in the same
manner as in the above-mentioned Biological Test Example 1. After the treated rice plant was dried
in the air, their foliage part was cut in 4-5 cm length, which were put in a dish with 9 cm diameter
with a sheet of filter paper and 2 ml of water. Five larvae of Cnaplialocrocis medinalis Guenee at the
second instar were put in the dish that was placed in a room at the constant temperature of 25°C.
After 2 and 4 days,' each rest (each 1/3 amount) of foliage parts of rice plant were cut in the same
* manner and added to the dish. After 7 days the number of dead larvae was counted and the rate of
death was calculated. In this test the results of 2 dishes at 1 section were averaged.
Test results:
In the above BiologicaJ.Jlest.JbxampJles,;1ancl.2, as;specific, examples, the compounds, pi Jhe .
aforementioned compound Nos. 8, 9,10,11,12,13,14,15,16,45, 47,48,49, 51, 52, 53, 81, 82, 83,
84, 85, 86, 87, 88, 89, 90, 91, 93, 103, 107, 116, 128, 132, 137, 138, 139, 140,141, 142, 143, 144,
145, 146, 147, 148, 149, 150, 153, 155, 157, 174, 176, 177, 178, 180, 181, 182,210,211,212, 213,
214, 215, 216, 217, 218, 219, 220, 221, 222, 226, 227, 229, 230, 231, 238., 239, 242, 243, 251, 253;
. 264, 268, 270, 281, 299, 308, 310, 318, 322, 413,414, 417,422, 434, 446, 448, 473, 475, 492,
50T; 508, 512, 518, 520, 539, 543, 544, 545, 546, 547, 548, 549, 552, 554, 559, 561, 562, 563, 564,
565, 566, 567, 568, 570, 571, 572, 573, 574, 578, 579, 580, 626, 637, 638, 639, 640, 641, 642, 643,
644, 645, 646, 647, 648, 649, 650, 655, 656, 657, 658, 659, 660, 661, 662, 663, 664, 665, 666, 667,
668, 669, 670, 671, 672, 681, 761, 762, 763, 804 and 920 showed controlling effect of 100% of rate
of death at 20 ppm concentration of the active component.
Biological Test Example 3: Test against Mvzus persicae resistant to organophosphorous agents and
carbamates
Test method:
About 30 bred Myzus persicae resistant to organophosphorous agents and carbamates were
inoculated per 1 seedling of eggplant planted in a vinyl pot of 6 cm diameter. One day after the
inoculation, a sufficient amount of a diluted aqueous solution of a prescribed concentration of an
active compound prepared as mentioned above, was sprayed by using a spray gun. After spraying it
was placed in a green house of 28°C and the rate of death was calculated 7 days after the spraying.
Test was repeated twice.
Test results
The compounds of the aforementioned compound Nos. 140, 141, 144, 146, 147, 148, 174, 176, 177,
178, 180, 181, 211, 213, 214, 215, 218, 220, 222, 226, 239, 243, 569, 570, 572, 579, 761, 797 and
920 offered to the test as specific examples showed controlling effect of 100% of rate of death at 100
ppm concentration of the effective component.
Formulation Example 1 (Granule1)
To a mixture of 10 parts of the compound of the present invention (No. 8), 30 parts of bentonite
(montniorillomte), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water are added, well
kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain
granules.
Formulation Example 2 ("Granules')
95 Parts of clay mineral particles having particle diameter distribution in the range of 0.2-2 mm are
put in a rotary mixer. While rotating it, 5 parts of the compound of the present invention (No. 11) are
sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules.
Ihnnulation Example 3 (Emulsifiable concentrate)
30 Parts of the compound of the present invention (No. 12), 55 parts of xylene, 8 parts of
polyoxyethylene aliyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and
stirred to obtain an emulsifiable concentrate.
Formulation Example 4 (Wettable powder)
15 Parts of the compound of the present invention (No. 15), 80 parts of a mixture of white carbon
(hydrous amorphous silicon oxide fine powders) and powder clay (1:5), 2 parts of sodium
alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate-formaHn-condensate are
crushed and mixed to make a wettable powder.
Formulation Example 5 (Water dispersible granule)
20 Parts of the compound of the present invention (No. 16), 30 parts of sodium ligninsulfonate,
parts of bentonite and 35 parts of calcined diatomaceous earth powder are well mixed, added with
water, extruded with 0.3 mm screen and dried to obtain water dispersible granules.

WE CLAIM:
1. N1-(pyrazol-l-ymethyl)-2-methylphenyl)-phatalamide derivatives of the formula (I)
(Formula Removed)
wherein
X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-4alkylsulfonyloxy, C1-4alkylsulfinyl, C1-4alkylsulfenyl or C1-4alkylsulfonyl,
R1 represents C1-4alkyl, C1-4alkylthio-C1-4alkyl, C1-4alkylsulfinyl-C1-4alkyl or C1-4alkylsulfonyl-C1-4alkyl,
Y represents fluorine, chlorine, bromine or Ci^alkyl,
m represents 1,
A represents CH2 or CH(CH3), and
Q represents 5-membered or 6-membered heterocyclic group containing one to three N-atoms and which heterocyclic group can be optionally substituted by at least one selected from a group consisting of C1-6alkyl, C1-6alkoxy, C1-6alkylthio, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-10haloalkyl, C1-6haloalkoxy, C1-6haloalkylthio, C1-6haloalkylsulfinyl, C1-6haloalkylsulfonyl, C1-6haloalkylcarbonyl, halogen, oxo and hydroxy.
2. The compounds as claimed in claim 1, wherein
X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, methanesulfonyloxy, C1-2alkylsulfinyl, C1-2alkylsulfenyl or C1-2 alkylsulfonyl,
R1 represents isopropyl, C1-2alkylthio-C3-4alkyl, C1-2alkylsulfinyl-C3-4alkyl or

Cl-2aikylsulfonyl-C3-4alkyl,
Y represents fluorine, chlorine or methyl,
m represents 1,
A represents CH2 or CH(CH3), and
Q represents a heterocyclic group, selected from a group consisting of pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, pyrrolyl, and pyrimidinyl and which heterocyclic group can be optionally substituted by at least one selected from the group consisting of C1-4alkyl, C1-4alkoxy, C1-4alkylthio, C1-4alkylsulfinyl, C1-4alkylsulfonyl, C1-8haloalkyl, C1-4haloalkoxy, C1-4haloalkylthio, C1-4haloalkylsulfinyl, C1-4haloalkylsulfonyl, C1-4haloalkylcarbonyl, fluorine, chlorine, bromine, iodine, oxo and hydroxy.
3. Processes for the preparation of the compounds as claimed in claim 1, wherein
(a) compounds of the formula (II)
(Formula Removed)
wherein R1 and X are as defined in claim 1 , are reacted with compounds of the formula (III)
(Formula Removed)
wherein Y, A, m and Q are as defined in claim 1,
in the presence of inert solvents, of the kind such as herein described and, if appropriate, in the presence of an acid catalyst, of the kind such as herein described, wherein the reaction can be in a temperature range from -20 °C to 100 °C.

4. The compound as claimed in claim 1 or 2, whenever used as an insecticida! composition comprising at least one benzenedicarboxamide compound 0.1-95% by weight.

Documents:

5173-DELNP-2006-Abstract-(14-09-2011).pdf

5173-delnp-2006-abstract.pdf

5173-DELNP-2006-Claims-(05-07-2012).pdf

5173-delnp-2006-Claims-(13-05-2013).pdf

5173-DELNP-2006-Claims-(14-09-2011).pdf

5173-delnp-2006-claims.pdf

5173-delnp-2006-Correspondence Others-(13-05-2013).pdf

5173-delnp-2006-Correspondence Others-(02-08-2011).pdf

5173-DELNP-2006-Correspondence Others-(05-07-2012).pdf

5173-DELNP-2006-Correspondence Others-(14-03-2012).pdf

5173-DELNP-2006-Correspondence Others-(14-09-2011).pdf

5173-delnp-2006-Correspondence-Others-(18-02-2013).pdf

5173-delnp-2006-correspondence-others.pdf

5173-delnp-2006-description (complete).pdf

5173-DELNP-2006-Form-1-(14-09-2011).pdf

5173-delnp-2006-form-1.pdf

5173-delnp-2006-form-18 (05-03-2008).pdf

5173-DELNP-2006-Form-2-(14-09-2011).pdf

5173-delnp-2006-form-2.pdf

5173-delnp-2006-Form-3-(02-08-2011).pdf

5173-DELNP-2006-Form-3-(14-03-2012).pdf

5173-delnp-2006-Form-3-(18-02-2013).pdf

5173-delnp-2006-form-3.pdf

5173-delnp-2006-form-5.pdf

5173-delnp-2006-GPA-(13-05-2013).pdf

5173-DELNP-2006-GPA-(14-09-2011).pdf

5173-delnp-2006-gpa.pdf

5173-delnp-2006-pct-101.pdf

5173-delnp-2006-pct-304.pdf

5173-delnp-2006-pct-306.pdf

5173-DELNP-2006-Petition 137-(14-09-2011).pdf

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Patent Number

257229

Indian Patent Application Number

5173/DELNP/2006

PG Journal Number

38/2013

Publication Date

20-Sep-2013

Grant Date

16-Sep-2013

Date of Filing

08-Sep-2006

Name of Patentee

BAYER CROPSCIENCE AG

Applicant Address

ALFRED-NOBEL-STR. 50, 40789 MONHEIM, GERMANY

Inventors:

#	Inventor's Name	Inventor's Address
1	KATASUAKI WADA	5-12-15 NAKAKUKI, OYAMA-SHI, TOCHIGI 323-0806, JAPAN
2	TAKUYA GOMIBUCHI	4-2-1105 HIGASRIARAI, TSUKUBA-SHI, IBARAKI 305-0051, JAPAN
3	YASUSHI YONETA	1-10-3 DOTE, KAZO-SHI, SAITAMA 347-0056, JAPAN
4	YUICHI OTSU	1-5-7, EKIMINAMI-CHO, OYAMA-SHI, TOCHIGI 323-0822, JAPAN
5	KATSUHIKO SHIBUYA	6-14-4 MIDORI, MINAMIKAWACHI-MACHI, KAWACHI-GUN, TOCHIGI 329-0433, JAPAN
6	NORIHIKO NAKAKURA	3-2-7, GION, MINAMIKAWACHI-MACHI, KAWACHI-GUN, TOCHIGI 329-0434, JAPAN
7	RUDIGER FISCHER	ZU DEN FUSSFALLEN 23, 50259 PULHEIM, GERMANY
8	TETSUYA MURATA	7-16-24-202 JOTO, OYAMA-SHI, TOCHIGI, 323-0807, JAPAN
9	EIICHI SHIMOJO	4-16-1 NISHIJONAN, OYAMA-SHI, TOCHIGI 323-0820, JAPAN

PCT International Classification Number

C07D 231/16

PCT International Application Number

PCT/EP2005/002130

PCT International Filing date

2005-03-01

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2004-70976	2004-03-12	Japan
2	2004-235553	2004-08-12	Japan
3	2005-367994	2004-12-20	Japan