HETEROCYCLE-SUBSTITUTED, N-PHENYL-PHTHALAMIDE DERIVATIVES, RELATED COMPOUNDS AND THEIR USE AS INSECTICIDES

Abstract

Novel benzenedicarboxamides of the formula (I) wherein X represents hydrogen, halogen atom, nitro, C1-6alkylsulfonyloxy, C1-6alkylsulfinyl, C1-6alkylsulfenyl or C1-6alkylsulfonyl, R1 represents C1-6alkyl, C1-6alkylthio-C1-6alkyl, C1-6alkylsulfinyl-C1-6alkyl or C1-6 alkylsulfonyl-C1-6alkyl, Y represents halogen or C1-6alkyl, 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; processes for their preparation, their intermediates and their use as insecticides.

Description

The present invention relates to novel benzenedicarboxamides, processes for the preparation thereof, their intermediates and their use as insecticides.

It was already 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 (I)

wherein

• X represents hydrogen, halogen atom, nitro, C_1-6alkylsulfonyloxy, C_1-6alkylsulfinyl, sulfenyl or C_1-6alkylsulfonyl,
  • R¹ represents C_1-6alkyl, C_1-6alkylsulfinyl-C_1-6alkyl or C_1-4 alkylsulfonyl-C_1-6alkyl,
• Y represents halogen or C_1-6alkyl,
• 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 (I), according to the invention, can be obtained by

• (a) reacting compounds of the formula (II)

• • wherein R¹ and X have the same definitions as aforementioned,
  • with compounds of the formula (III)

• • 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,
    or
• (b) reacting compounds of the formula (IV)

• • wherein X, Y, A, m and Q have the same definitions as aforementioned,
  • with 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
• (c) reacting compounds of the formula (VI)

• • wherein X and R¹ have the same definitions as aforementioned,
  • with the compounds of the formula (III),

• • 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,
    or
• (d) reacting compounds of the formula (VII)

• • 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 (VIII)

• • wherein X, Y, A, in 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
• (f) in the case that R¹ represents C_1-6alkylsulfinyl-C_1-6alkyl or C_1-6alkylsulfonyl-C_1-6alkyl in the formula (I), reacting compounds of the formula (If)

• • wherein
  • R^1f represents C_1-6alkylthio-C_1-6alkyl, and
  • X, Y, A, in 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 of the formula (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.

“Alkyl” represents straight chain or branched chain C_1-12alkyl, 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 C_1-6alkyl.

As each alkyl part in “alkylsulfonyloxy”, “alkylsulfenyl”, “alkylthioalkyl”, “alkylsulfinylalkyl”, “alkylsulfonylalkyl”, “alkoxy”, “alkylthio”, “alkylsulfinyl”, “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 N 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 (I), according to the invention, the compounds in case that

• X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, C_1-4 alkylsulfonyloxy, C_1-4alkylsulfinyl, C_1-4 alkylsulfenyl or C_1-4 alkylsulfonyl,
• R¹ represents C_1-4alkyl, C_1-4alkylthio-C_1-4alkyl, C_1-4alkylsulfinyl-C_1-4alkyl or C_1-4alkylsulfonyl-C_1-4alkyl,
• Y represents fluorine, chlorine, bromine or C_1-4alkyl,
• m represents 0 or 1,
• A represents O, S, SO, SO₂, CH₂ or CH(CH₃), and
• Q represents 5-membered or 6-membered heterocyclic group that contains at least one hetero atom selected from a group consisting of N, O and S and can be optionally substituted by at least one selected from a group consisting of C_1-6alkyl, C_1-6alkoxy, C_1-6alkylthio, C_1-6alkylsulfinyl, C_1-6alkylsulfonyl, C_1-10haloalkoxy, C_1-6haloalkoxy, C_1-6haloalkylthio, C_1-6haloalkylsulfinyl, C_1-6haloalkylsulfonyl, C_1-6haloalkylcarbonyl, 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, C_1-2 alkylsulfenyl or C_1-2 alkylsulfonyl,
• R¹ represents isopropyl, C_1-2alkylthio-C_3-4alkyl, C_1-2alkylsulfinyl-C_3-4alkyl or C_1-2alkylsulfonyl-C_3-4alkyl,
• Y represents fluorine, chlorine or methyl,
• m represents 0 or 1,
• A represents O, S, SO, SO₂, CH₂ or CH(CH₃), and
• Q represents heterocyclic group, selected from a group consisting of pyrazolyl, triazolyl, pyrazolinyl, imidazolyl, thiazolyl, pyrrolyl, oxadiazolyl and pyrimidinyl, that can be optionally substituted by at least one selected from the group consisting of C_1-4alkyl, C_1-4alkoxyl, C_1-4alkylthio, C_1-4alkylsulfinyl, C_1-4alkylsulfonyl, C_1-8haloalkyl, C_1-4haloalkoxy, C_1-4haloalkylthio, C_1-4haloalkylsulfinyl, C_1-4haloalkylsulfonyl, C_1-4haloalkylcarbonyl, fluorine, chlorine, bromine, iodine, oxo and hydroxy 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-(1,1-dimethyl-2-methylthioethylimino)-4-iodo-3H-isobenzofuran-1-one and 1-(4-amino-3-methylbenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole are used as starting materials.

The aforementioned preparation process (b) can be illustrated by the following reaction scheme in case that, for example, 2-{4-[3,5-bis(trifluoromethyl)pyrazole-1-ylmethyl]-2-methylphenyl}-4-fluoroisoindole-1,3-dione and (S)-1-methyl-2-methylthioethylamine 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-(1,1-dimethyl-2-methylthioethyl)-phthalamic acid and 2-methyl-4-[1-(3-trifluoromethylpyrazole-1-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, 1-[4-(4-iodo-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,5-bis(trifluoromethyl)-(1,2,4)-triazol and 1-methyl-2-methylthioethylamine are used as starting materials.

The aforementioned preparation process (e) can be illustrated by the following reaction scheme in case that, for example, N-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methyl-phenyl}-6-iodo-phthalamic acid and 1-methyl-2-methylthioethylamine are used as starting materials.

The aforementioned process (f) can be illustrated by the following reaction scheme in case that, for example, N²-(1-methyl-2-methylthioethyl)-3-iodo-N¹-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]phenyl}phthalamide and m-chloroperbenzoic acid are used as starting materials.

The compounds of the formula (II), 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-A 11-240857 (1999), JP-A 2001-131141.

As specific examples of the compounds of the formula (Ia), used as starting materials in the preparation process (a), there can be mentioned the following:

• 3-isopropylimino-3H-isobenzofuran-1-one,
• 4-fluoro-3-isopropylimino-3H-isobenzofuran-1-one,
• 4-chloro-3-isopropylimino-3H-isobenzofuran-1-one,
• 4-bromo-3-isopropylimino-3H-isobenzofuran-1-one,
• 4-iodo-3-isopropylimino-3H-isobenzofuran-1-one,
• 3-(1-methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 4-fluoro-3-(1-methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 4-chloro-3-(1-methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 4-bromo-3-(1-methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 4-iodo-3-(1-methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 3-(1,1-dimethyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 3-(1,1-dimethyl-2-methylsulfanyl-ethylimino)-4-fluoro-3H-isobenzofuran-1-one,
• 4-chloro-3-(1,1-dimethyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 4-bromo-3-(1,1-dimethyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-1-one,
• 3-(1,1-dimethyl-2-methylsulfanyl-ethylimino)-4-iodo-3H-isobenzofuran-1-one,
• 3-isopropylimino-1-oxo-1,3-dihydro-isobenzofuran-4-yl methanesulfonate
• 3-(1-methyl-2-methylsulfanyl-ethylimino)-1-oxo-1,3-dihydro-isobenzofuran-4-yl methanesulfonate
• 3-(1,1-dimethyl-2-methylsulfanyl-ethylimino)-1-oxo-1,3-dihydro-isobenzofuran-4-yl
  methanesulfonate and so on.

The compounds of the formula (III), 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, ethylene 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 (III) can be obtained by hydrogenating the compounds of the formula (IX) 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 (III) 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 powder in acetic acid, a process of reacting zinc dust under neutral condition (Organic Syntheses Collective Vol. II, p. 447), a process of reacting stannic chloride under acidic condition (Organic Syntheses Collective Vol. II, p. 254), a process of reacting titanium trichloride under neutral condition, etc.

The compounds of the formula (IX) are novel compounds and can be obtained by reacting the compounds of the formula (IX) 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, SO₂, CH₂ or CH(CH₃), and
• M represents chlorine, bromine or methanesulfonyloxy,
  with compounds of the formula (XI)

H-Q  (XI)

wherein Q has the same definition as aforementioned.

The compounds of the formula (X), are well known in the field of organic chemistry and described in publications, for example, Chem. Abstr., Vol. 58, 3444e (1963); Bull. Soc. Claim. 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. 111 (1989), p. 5880-5886; J. Amer. Chem. Soc., Vol. 96 (1974), p. 7770-7781; Can. J. Chem., Vol. 68 (1990), 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-nitrobenzyl chloride
• 4-nitrobenzyl methanesulfonate
• 2-methyl-4-nitrobenzyl methanesulfonate
• 3-methyl-4-nitrobenzyl methanesulfonate,
• 4-nitrobenzenesulfenyl chloride,
• 4-nitrobenzenesulfinyl chloride,
• 4-nitrobenzenesulfonyl chloride,
• 4-nitro-3-methylbenzenesulfonyl chloride,
• 3-fluoro-4-nitrobenzyl bromide,
• 3-chloro-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., Vol. 41 (1993), p. 894-906; WO 2001/042227.

The compounds of the formula (XI) include known compounds and as their specific examples, there can be mentioned:

• 3,5-bis(trifluoromethyl)-1H-pyrazole,
• 5-difluoromethoxy-3-trifluoromethyl-1H-pyrazole,
• 4-pentafluoroethyl-1H-pyrazole,
• 5-hexafluoro-n-propyl-1H-pyrazole,
• 3,5-bis(trifluoromethyl)-1H-(1,2,4)-triazole,
• 5-pentafluoroethyl-3-trifluoromethyl-1H-(1,2,4)-triazole,
• 5-difluoromethyl-3-trifluoromethyl-1H-(1,2,4) triazole,
• 5-hydroxy-3,5-bis(trifluoromethyl)-1H-4,5-dihydropyrazole,
• 2,4-bis(trifluoromethyl)-1H-imidazole,
• 3-(2,2,2-trifluoroethyl)-5-trifluoromethyl-1,2-dihydro-(1,3,4)-triazol-2-one,
• 2,5-bis(trifluoromethyl)-(1,3,4)-triazole,
• 5-pentafluoroethyl-1H-pyrazole,
• 3-pentafluoroethyl-1H-pyrazole,
• 4-bromo-3-trifluoromethyl-1H-pyrazole,
• 3-trifluoromethyl-1H-pyrazole,
• 5-(difluoromethyl)-1,2-dihydro-2-methyl-3H-(1,2,4)-triazol-3-one,
• 4-(trifluoromethyl)-2H-1,2,3-triazole,
• 4-iodo-3-pentafluoroethyl-1H-pyrazole,
• 3-pentafluoroethyl-4-(1,1,2,2-tetrafluoroethyl)-1H-pyrazole,
• 3,4-bis-pentafluoroethyl-1H-pyrazole,
• 3,5-diiodo-4-methyl-1H-pyrazole,
• 3-Heptafluoropropylsulfanyl-5-trifluoromethyl-1H-(1,2,4)-triazole,
• 3,5-bis(pentafluoroethyl)-1H-(1,2,4)-triazole and so on.

The above-mentioned reaction of the compounds of the formula (X) with the compounds of the formula (XI) can be conducted in an adequate diluent.

As examples of 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, 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.; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA), 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, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-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 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, benzyltriethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, benzyltriethylammonium chloride, etc.; crown ethers, for example, dibenzo-18-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.

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 (IX) can be obtained, for example, by reacting 1 mole to a little excess mole amount of the compounds of the formula (XI) 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 (III) mentioned hereinafter. And, as one typical example, 1-(3-methyl-4-nitrobenzyl)-3,5-bis-(trifluoromethyl)-1H-pyrazole can be mentioned.

Furthermore, in a case where Q represents 2-thiazolyl in the formula (IX), as a specific example, 2-(3-methyl-4-nitrobenzyl)-4-pentafluoroethyl-thiazole can be prepared by the following way in which a known compound, 3-methyl-4-niirobenzylcyanide (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, 1-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 1,3,4-oxadiazol-2-yl in the formula (IX), as a specific example, 2-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-1,3,4-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-methyl-4-nitrobenzyl)-5-trifluoromethyl-1,3,4-oxazole can easily be obtained, according to a method described in Heterocycles, (1994) vol. 38, p. 981 to 990, from the corresponding 3-methyl-4-nitrobenzaldehyde 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-1,2,3-triazol-2-yl in the formula (IX), as a specific example, 2-(3-methyl-4-nitrobenzyl)-2H-4-trifluoromethyl-1,2,3-triazole can easily be prepared by a reaction of a known 3-methyl-4-nitrobenzyl chloride with a known 2H-4-trifluoromethyl-1,2,3-triazole described in J. Chem. Soc., Perkin Transaction 2, vol. 10 (1989) p. 1355 to 1375.

In a case where Q represents 1H-1,2,4-triazol-1-yl in the formula (IX), as a specific example, 5-(3-methyl-4-nitrophenylsulfanyl)-1-methyl-3-trifluoromethyl-1H-1,2,4-triazole can easily be prepared by a reaction of 1-fluoro-3-methyl-4-nitrobenzene with a known 5-mercapto-1-methyl-3-trifluoromethyl-1H-1,2,4-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 1,2,4-oxazol-3-yl in the formula (IX), as a specific example, 3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-1,2,4-oxazole can easily be obtained from 3-methyl-4-nitrobenzamideoxime, according to a method described in 3. Org. Chem., vol. 68(2), 2003, p. 605-608. And, 3-methyl-4-nitrobenzamideoxime 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-1,2,4-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 1H-1,2,4-triazol-3-yl in the formula (IX), as specific examples, 1-methyl-3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-1H-1,2,4-triazole can easily be prepared by a reaction of the above 3-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-1,2,4-oxazole with methylhydrazine, according to a method described in J. Org. Chem., vol. 68(2), 2003, p. 605-608, and also 1-methyl-3-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-1H-1,2,4-thiazole can be done by a reaction of the above 3-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-1,2,4-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 (III) there can be mentioned, for example, the following:

• 1-(4-amino-3-methylbenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-5-difluoromethoxy-3-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-4-pentafluoroethyl-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-5-hexafluoro-n-propyl-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-3,5-bis(trifluoromethyl)-1H-(1,2,4)-triazole,
• 1-(4-amino-3-methylbenzyl)-5-pentafluoroethyl-3-trifluoromethyl-1H-(1,2,4)-triazole,
• 1-(4-amino-3-methylbenzyl)-5-difluoromethyl-3-trifluoromethyl-1H-(1,2,4)-triazole,
• 4-(4-amino-3-methylbenzyl)-5-difluoromethoxy-1-difluoromethyl-3-trifluoromethyl-1H-pyrazole,
• 4-(4-amino-3-methylbenzyl)-3-difluoromethoxy-1-difluoromethyl-5-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-5-hydroxy-3,5-bis(trifluoromethyl)-1H-4,5-dihydropyrazole,
• 1-(4-amino-3-methylbenzyl)-2,4-bis(trifluoromethyl)-1H-imidazole,
• 4-(4-amino-3-methylbenzyl)-2-(2,2,2-trifluoroethyl)-5-trifluoromethyl-2,4-dihydro-3H-(1,2,4)-triazol-3-one,
• 2-(4-amino-3-methylbenzyl)-4-(2,2,2-trifluoroethyl)-5-trifluoromethyl-2,4-dihydro-3H-(1,2,4)-triazol-3-one,
• 1-(4-amino-3-methylbenzyl)-2,5-bis(trifluoromethyl)-1,3,4-triazole,
• 2-(4-amino-3-methylbenzyl)-4,6-bis(trifluoromethyl)-pyrimidine,
• 2-(4-amino-3-methylphenoxy)-4,6-bis(trifluoromethyl)-pyrimidine,
• 1-(4-amino-3-methylphenyl)-3,5-bis(trifluoromethyl)-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-5-pentafluoroethyl-1H-pyrazole,
• 1-(4-amino-3,7-methylphenyl)-3-pentafluoroethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-4-pentafluoroethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-3-methyl-5-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-5-methyl-3-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-3-pentafluoroethyl-5-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-4-bromo-3-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-3-trifluoromethyl-1H-pyrazole,
• 1-(4-amino-3-methylphenyl)-5-hydroxy-3-(2,2,2-trifluoroethyl)-5-trifluoromethyl-1H-4,5-dihydropyrazole,
• 5-(4-amino-3-methylphenyl)-1-(2,2,2-trifluoroethyl)-3-trifluoromethyl-pyrazole,
• 5-(4-amino-3-methylphenyl)-1-difluoromethyl-3-trifluoromethyl-pyrazole,
• 3-(4-amino-3-methylphenyl)-1-difluoromethyl-3-difluoromethoxy-pyrazole,
• 1-(4-amino-3-methylbenzyl)-3,4-bis(pentafluoroethyl)-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-3,5-bis(pentafluoroethyl)-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-3,4-bis(pentafluoropropyl)-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-3,5-bis(pentafluoropropyl)-1H-pyrazole,
• 1-(4-amino-3-methylbenzyl)-3,5-bis(pentafluoroethyl)-1H-(1,2,4)-triazole,
• 1-(4-amino-3-methylbenzyl)-2,5-bis(pentafluoroethyl)-1H-(1,3,4)-triazole,
• 2-(4-amino-3-methylphenyl)-5-(trifluoromethyl)-1,3,4-oxadiazole,
• 2-(4-amino-3-methylphenyl)-5-(pentafluoroethyl)-1,3,4-oxadiazole,
• 2-(4-amino-3-methylphenyl)-5-(heptafluoropropyl)-1,3,4-oxadiazole,
• 2-(4-amino-3-methylbenzyl)-5-(trifluoromethyl)-1,3,4-oxadiazole,
• 2-(4-amino-3-methylbenzyl)-4-(trifluoromethyl)-2H-1,2,3-triazole,
• 2-(4-amino-3-methylbenzyl)-4-(pentafluoroethyl)-thiazole,
• 5-(4-amino-3-methylphenyl)sulfanyl-1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazole,
• 3-(4-amino-3-methylphenyl)-5-(trifluoromethyl)-1,2,4-oxadiazole,
• 3-(4-amino-3-methylphenyl)-1-methyl-5-(trifluoromethyl)-1H-1,2,4-triazole,
• 1-(4-amino-3-chlorobenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole,
• 1-(4-amino-3-fluorobenzyl)-3,5-bis(trifluoromethyl)-1H-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)

wherein X has the same definition as aforementioned,
with the compounds of the formula (III).

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, ligroin, 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 (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.

Although said 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 (II) to 1 mole of the compounds of the formula (XII) in a diluent, for example, acetic acid.

Many of the compounds of the above-mentioned formula (XII) 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-chloro-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]phenyl}-isoindole-1,3-dione,
• 2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-difluoromethoxy-3-trifluoromethyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(4-pentafluoroethyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-bromo-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-bromo-2-[2-methyl-4-(5-difluoromethoxy-3-trifluoromethyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-bromo-2-[2-methyl-4-(4-pentafluoroethyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-difluoromethoxy-3-trifluoromethyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(4-pentafluoroethyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-hexafluoro-n-propyl-1H-pyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-methanesulfonyloxy-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[5-pentafluoroethyl-3-trifluoromethyl-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[5-difluoromethoxy-1-difluoromethyl-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[5-pentafluoroethyl-3-trifluoromethyl-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[5-difluoromethyl-3-trifluoromethyl-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-methanesulfonyloxy-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-(1,2,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-difluoromethoxy-1-difluoromethyl-3-trifluoromethyl-1H-pyrazol-4-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-hydroxy-3,5-bis(trifluoromethyl)-1H-4,5-dihydropyrazol-1-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[2,4-bis(trifluoromethyl)-1H-imidazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[3-(2,2,2-trifluoroethyl)-5-trifluoromethyl-1,2-dihydro-(1,3,4)-triazol-2-on-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[3-(2,2,2-trifluoroethyl)-3-trifluoromethyl-4,5-dihydro-(1,2,4)-triazol-5-on-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[2,5-bis(trifluoromethyl)-(1,3,4)-triazol-1-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[4,6-bis(trifluoromethyl)pyrimidin-2-yl-methyl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[4,6-bis(trifluoromethyl)pyrimidin-2-yloxy]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(3-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(4-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-[3-methyl-5-trifluoromethyl-1H-pyrazol-1-yl]-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(3-pentafluoroethyl-5-trifluoromethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(4-bromo-3-trifluoromethyl-1H-pyrazol-1-yl)phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(3-trifluoromethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[5-hydroxy-3-(2,2,2-trifluoroethyl)-5-trifluoromethyl-1H-4,5-dihydropyrazol-1-yl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[1-(2,2,2-trifluoroethyl)-3-trifluoromethyl-pyrazol-5-yl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(1-difluoromethyl-3-trifluoromethyl-pyrazol-5-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4 (1-difluoromethyl-3-difluoromethoxy-pyrazol-3-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]-phenyl}-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(3-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(4-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-bromo-2-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]-phenyl}-isoindole-1,3-dione,
• 4-bromo-2-[2-methyl-4-(5-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-bromo-2-[2-methyl-4-(3-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-bromo-2-[2-methyl-4-(4-pentafluoroethyl-1H-pyrazol-1-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[3,4-bis(pentafluoroethyl)-1H-pyrazol-1-ylmethyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[3,5-bis(pentafluoroethyl)-1H-pyrazol-1-ylmethyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[3,4-bis(heptafluoropropyl)-1H-pyrazol-1-ylmethyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[3,5-bis(heptafluoropropyl)-1H-pyrazol-1-ylmethyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-trifluoromethyl-1,3,4-oxadiazol-2-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-pentafluoroethyl-1,3,4-oxadiazol-2-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-heptafluoropropyl-1,3,4-oxadiazol-2-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-trifluoromethyl-1,3,4-oxadiazol-2-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(4-trifluoromethyl-2H-1,2,3-triazol-2-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(4-(pentafluoroethyl)-thiazol-2-yl-methyl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-{2-methyl-4-[1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl-sulfanyl]-phenyl}-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)-phenyl]-isoindole-1,3-dione,
• 4-chloro-2-[2-methyl-4-(1-methyl-5-trifluoromethyl-1H-1,2,4-triazol-3-yl)-phenyl]-isoindole-1,3-dione,
• 4-iodo-2-[2-methyl-4-(5-trifluoromethyl-1,3,4-oxadiazol-2-yl)-phenyl]-isoindole-1,3-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 45 905, WO 01/23350.

As their specific examples there can be mentioned ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, t-amylamine, 2-(methylthio)-ethylamine, 2-(ethylthio)-ethylamine, 1-methyl-2-(methylthio)-ethylamine, 1,1-dimethyl-2-(methylthio)-ethylamine 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), JPA 2001-131141, etc.

As their specific examples there can be mentioned the following:

• N-isopropyl-phthalamic acid,
• 3-fluoro-N-isopropyl-phthalamic acid,
• 3-chloro-N-isopropyl-phthalamic acid,
• 3-bromo-N-isopropyl-phthalamic acid,
• 3-iodo-N-isopropyl-phthalamic acid,
• N-(1-methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• 3-fluoro-N-(1-methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• 3-chloro-N-(1-methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• 3-bromo-N-(1-methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• 3-iodo-N-(1-methyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-3-fluoro-phthalamic acid,
• 3-chloro-N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• 3-bromo-N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-phthalamic acid,
• N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-3-iodo-phthalamic acid,
• N-isopropyl-3-methanesulfonyloxy-phthalamic acid,
• N-(1-methyl-2-methylsulfanyl-ethyl)-3-methanesulfonyloxy-phthalamic acid,
• N-(1-methyl-2-methylsulfanyl-ethyl)-3-nitro-phthalamic acid,
• 3-chloro-N-(2-ethylsulfanyl-1-methyl-ethyl)-phthalamic acid,
• 3-bromo-N-(2-ethylsulfanyl-1-methyl-ethyl)-phthalamic acid,
• N-(2-ethylsulfanyl-1-methyl-ethyl)-3-iodo-phthalamic acid,
• N-(2-ethylsulfanyl-1-methyl-ethyl)-3-nitro-phthalamic acid,
• N-(2-ethylsulfanyl-1-methyl-ethyl)-3-methanesulfonyloxy-phthalamic acid,
• N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-3-methanesulfonyloxy-phthalamic acid and so on.

The above-mentioned compounds of the formula (VI) can be easily obtained generally by reacting phthalic anhydrides of the aforementioned formula (XII)

wherein X has the same definition as aforementioned,
with amines of the formula

H₂N—R¹  (XIII)

wherein R¹ has the same definitions as aforementioned,

The compounds of the above-mentioned formula (XIII) are well 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)ethylamine, 2-(ethylthio)ethylamine, 1-methyl-2-(methylthio)ethylamine, 1,1-dimethyl-2-(methylthio)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 (XII) with the amines of the formula (XIII) 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-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (TIM, 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, for example, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-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.

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 (XIII) to 1 mole of the compounds of the formula (XII) in a diluent, for example, acetonitrile.

The compounds of the formula (VII), 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 (VIII), 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 (VII), there can be mentioned the following:

• 1-[4-(4-iodo-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,5-bis(trifluoromethyl)-1H-pyrazole,
• 1-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,5-bis(trifluoromethyl)-1H-pyrazole,
• 1-[4-(4-iodo-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,5-bis(trifluoromethyl)-1,2,4-triazole,
• 1-[4-(4-iodo-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-3,5-bis(trifluoromethyl)-1,1-pyrazole,
• 1-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,4-bis(pentafluoroethyl)-1H-pyrazole,
• 1-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,5-bis(pentafluoroethyl)-1H-pyrazole,
• 1-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,4-bis(heptafluoropropyl)-1H-pyrazole,
• 1-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methyl-benzyl]-3,5-bis(heptafluoropropyl)-1H-pyrazole,
• 2-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-5-(trifluoromethyl)-1,3,4-oxadiazole,
• 2-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-5-(pentafluoroethyl)-1,3,4-oxadiazole,
• 2-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-5-(heptafluoropropyl)-1,3,4-oxadiazole,
• 2-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylbenzyl]-5-(trifluoromethyl)-1,3,4-oxadiazole,
• 2-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylbenzyl]-4-(trifluoromethyl)-2H-1,2,3-triazole,
• 2-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylbenzyl]-4-(pentafluoroethyl)-thiazole,
• 5-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]sulfanyl-1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazole,
• 3-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole,
• 3-[4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-1-methyl-5-(trifluoromethyl)-1H-1,2,4-triazole,
• 2-[4-(4-iodo-3-oxo-3H-isobenzofuran-1-ylideneamino)-3-methylphenyl]-5-(trifluoromethyl)-1,3,4-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 (VIII), 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 (XII) with the compounds of the aforementioned formula (III).

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, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-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 (VIII), there can be mentioned the following:

• N-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl-methyl]-2-methyl-phenyl}-6-iodo-phthalamic acid,
• N-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl-methyl]-2-methyl-phenyl}-6-chloro-phthalamic acid,
• N-{4-[3,5-bis(trifluoromethyl)-(1,2,4)-triazol-1-yl-methyl]-2-methyl-phenyl}-6-iodo-phthalamic acid,
• N-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]-2-methyl-phenyl}-6-iodo-phthalamic acid,
• N-{4-[3,4-bis(pentafluoroethyl)-1H-pyrazol-1-yl-methyl]phenyl}-6-chloro-phthalamic acid,
• N-{4-[3,5-bis(pentafluoroethyl)-1H-pyrazol-1-yl-methyl]-phenyl}-6-chloro-phthalamic acid,
• N-{4-[3,4-bis(heptafluoropropyl)-1H-pyrazol-1-yl-methyl]-phenyl}-6-chloro-phthalamic acid,
• N-(4-[3,5-bis(heptafluoropropyl)-1H-pyrazol-1-yl-methyl]-phenyl)-6-chloro-phthalamic acid,
• N-[2-methyl-4-(5-trifluoromethyl-1,3,4-oxadiazol-2-yl)-phenyl]-6-chloro-phthalamic acid,
• N-[2-methyl-4-(5-pentafluoroethyl-1,3,4-oxadiazol-2-yl)-phenyl]-6-chloro-phthalamic acid,
• N-[2-methyl-4-(5-heptafluoropropyl-1,3,4-oxadiazol-2-yl)-phenyl]-6-chloro-phthalamic acid,
• N-[2-methyl-4-(5-trifluoromethyl-1,3,4-oxadiazol-2-yl-methyl)-phenyl]-6-chloro-phthalamic acid,
• N-[2-methyl-4-(4-trifluoromethyl-2H-1,2,3-triazol-2-yl-methyl)-phenyl]-6-chloro-phthalamic acid,
• N-{2-methyl-4-(4-pentafluoroethyl-thiazol-2-yl-methyl)-phenyl}-6-chloro-phthalamic acid,
• N-{2-methyl-4-[1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl-sufanyl]-phenyl}-6-chlorophthalamic acid,
• N-[2-methyl-4-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)-phenyl]-6-chloro-phthalamic acid,
• N-[2-methyl-4-(1-methyl-5-trifluoromethyl-1H-1,2,4-triazol-3-yl)-phenyl]-6-chloro-phthalamic acid,
• N-[2-methyl-4-(5-trifluoromethyl-1,3,4-oxadiazol-2-yl)-phenyl]-6-iodo-phthalamic 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).

The compounds of the formula (If), used as starting materials in the preparation process (f), are compounds included in the formula (I) of the present invention.

By oxidizing the group R^If in the compounds of the formula (If), namely, C_1-6alkylthio-C_1-6alkyl, the compounds of the formula (I), in which the group R^If corresponds to C_1-6 alkylsulfinyl-C_1-6alkyl or C_1-6alkylsulfonyl-C_1-6alkyl, 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-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-phenyl}phthalamide,
• N²-(1,1-dimethyl-2-methylsulfanyl-ethyl)-3-iodo-N¹-{2-methyl-4-[3,5-bis(trifluoro-methyl)-1H-pyrazol-1-ylmethyl]-phenyl}phthalamide,
• 3-iodo-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,5-bis(trifluoromethyl)-(1,2,4)-triazol-1-ylmethyl]-phenyl}phthalamide,
• 3-chloro-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-phenyl}phthalamide,
• 3-chloro-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,4-bis(pentafluoro-ethyl)-1H-pyrazol-1-ylmethyl]-phenyl}phthalamide,
• 3-chloro-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,5-bis(pentafluoro-ethyl)-1H-pyrazol-1-ylmethyl]-phenyl}phthalamide,
• 3-chloro-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,4-bis(heptafluoro-propyl)-1H-pyrazol-1-ylmethyl]-phenyl}phthalamide,
• 3-chloro-N²-(1-methyl-2-methylsulfanyl-ethyl)-N¹-{2-methyl-4-[3,5-bis(heptafluoro-propyl)-1H-pyrazol-1-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-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.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc.

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 acid; 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 (III) to 1 mole of the compounds of the formula (II) 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 aforementioned preparation 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 (Tiff), 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 (HMPA), 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.

In conducting 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 (IV) 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 and butanol; 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 from 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 JIKKEN KAGAKU KOZA (Lecture on experimental chemistry) edited by the Chemical Society of Japan, 4^th ed., Vol. 24, p. 350 (1992) published by MARUZEN or ibid. p. 365.

The compounds of the formula (I) 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 (I) of the present invention exhibit exact controlling effect against harmful insects without giving phytotoxicity on cultured plants. And the compounds 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:

Coleoptera pests, for example, Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus;

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,

Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Trialeurodes vaporariorum, Psylla spp.;

Thysanoptera pests, for example,

Thrips palmi, Frankliniella occidental;

Orthoptera pests, for example,

Blatella gennanica, Periplaneta americana, Gryllotalpa africana, Locusta migratoria migratoriodes;

Homoptera pests, for example,

Reticulitermes speratus, Coptotennes formosanus;

Diptera pests, for example,

Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex tritaeniorlzynchus, Liriomyzae trifolii etc.

Moreover, as mites there can be mentioned, for example,

Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp., etc.

Furthermore, as nematodes there can be mentioned, for example,

Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines, Pratylenchus spp., etc.

In addition, 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 helminthes. 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., Ixodes 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 hydrocarbons [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 foam-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.

Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.

Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tackifiers, 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; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover, flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-A1; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazol; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; penconazole; pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrin; quinconazole; quinoxyfen; 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-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]-butanamide; 1-(1-naphthalenyl)-1H-pyrrol-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; actinovate; cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol; methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; mono potassium carbonate; N-(6-methoxy-3-pyridinyl)-cyclopropane carboxamide; N-butyl-8-(1,1-dimethylethyl)-1-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 dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides/Acaricides/Nematicides:

1. Acetylcholinesterase (AChE) inhibitors

1.1 Carbamates (e.g. alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, azamethiphos, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, chloethocarb, coumaphos, cyanofenphos, cyanophos, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, xylylcarb)

1.2 Organophosphates (e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demeton-s-methyl, demeton-s-methylsulphon, dialifos, diazinon, dichlofenthion, dichloriros/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, isoxatbion, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, 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, thiometon, 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-cyflutbrin, bifenthrin, bioallethrin, bioallethrin-s-cyclopentyl-isomer, bioethanometbrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta), cyphenothrin, DDT, deltamethrin, empenthrin (1R-isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumetbrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans), phenothrin (1R-trans isomer), prallethrin, proflutbrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (1R-isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum))

2.2 Oxadiazine (e.g. indoxacarb)

3. Acetylcholine receptor agonists/-antagonists

3.1 Chloronicotinyls/neonicotinoids (e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam)

3.2 nicotine, bensultap, cartap

4. Acetylcholine receptor modulators

4.1 Spinosyns (e.g. spinosad)

5. GABA gated chloride channel antagonists

5.1 Cyclodiene organochlorines (e.g. camphechlor, chlordane, endosulfan, gamma HCH, HCH, heptachlor, lindane, methoxychlor

5.2 Fiproles (e.g. acetoprole, ethiprole, fipronil, vaniliprole)

6. Chloride channel activators

6.1 Mectins (e.g. abaraectin, avermectin, emamectin, emamectin-benzoate, ivermectin, milbemectin, milbemycin)

7. Juvenile hormone mimics

(e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene)

8. Ecdysone agonists/disruptors

8.1 Diacylhydrazines (e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide)

9. Inhibitors of chitin biosynthesis

9.1 Benzoylureas (e.g. bistrifluoron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluoron, teflubenzuron, tifiumuron)

9.2 buprofezin

9.3 cyromazine

10. Inhibitors of oxidative phosphorylation, ATP-disruptors

10.1 diafenthiuron

10.2 Organotins (e.g. azocyclotin, cyhexatin, fenbutatin-oxide)

11. Decoupler of oxidative phoshorylation by diruption of H proton gradient

11.1 Pyrroles (e.g. chlorfenapyr)

11.2 Dinitrophenoles (e.g. binapacyrl, dinobuton, dinocap, DNOC)

12. Site I electron transport inhibitors

12.1 METT's (e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad)

12.2 hydramethyhione

12.3 dicofol

13. Site II electron transport inhibitors

13.1 rotenone

14. Site II electron transport inhibitors

14.1 acequinocyl, fluacrypyrim

15. Microbial disruptors 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-1-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (alias: carbonic acid, 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]-dec-3-en-4-yl ethyl ester, CAS-Reg.-No.: 382608-10-8) and carbonic acid, cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-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. N²-[1,1-dimethyl-2-(methylsulfonyl)ethyl]-3-iodo-N¹-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide (CAS-Reg.-No.: 272451-65-7, flubendiamide))

21. Nereistoxin analogues

(e.g. thiocyclam hydrogen oxalate, thiosultap-sodium)

22. Biologica, hormones or pheromones

(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, sulfa yl 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, verbutin

further the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-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 the 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 (I) 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 (I) 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% by weight.

The compounds 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 (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum 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 traits 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 microbial pests, 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), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF 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 “PAT” 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 phosphinotricin, for example oilseed rape), IMI® (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-(1,1-Dimethyl-2-methylsulfanyl-ethylimino)-4-iodo-3H-isobenzofuran-1-one (0.53 g) and 1-(3-methyl-4-aminobenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole (0.45 g) were dissolved in acetonitrile (15 ml), to which p-toluenesulfonic acid monohydrate (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 obtaining N¹-[4-(3,5-bistrifluoromethylpyrazol-1-ylmethyl)-2-methylphenyl]-N²-(1,1-dimethyl-2-methylsulfanylethyl)-3-iodophthalamide (0.91 g). mp. 83-87° C.

Synthesis Example 2

N¹-{4-[3,5-Bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-N²-(1,1-dimethyl-2-methylsulfanylethyl)-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 N¹-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-N²-(2-methanesulfinyl-1,1-dimethylethyl)-3-iodophthalamide (0.30 g).

¹H-NMR (CDCl₃, ppm): 1.57 (3H, s), 1.60 (3H, s), 2.20 (3H, s), 2.30 (3H, s), 2.93 (2H, dd), 5.43 (2H, s), 6.57 (1H, s), 6.90 (1H, s), 7.0-8.2 (7H, m).

Synthesis Example 3

N¹-{4-[3,5-Bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-N²-(1,1-dimethyl-2-methylsulfanylethyl)-3-iodophthalamide (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 N¹-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-3-iodo-N²-(2-methanesulfonyl-1,1-dimethylethyl)phthalamide (0.25 g). mp. 104-107° C.

Synthesis Example 4

A dioxane solution (15 ml) of 2-{4-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-4-fluoroisoindole-1,3-dione (0.94 g), (S)-1-methyl-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(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-3-fluoro-N²-[1-(S)-1-methyl-2-methylsulfanyl-ethyl]-phthalamide (0.19 g) (compound No. 549). mp. 66-68° C.

Synthesis Example 5

3-Iodo-N-(1,1-dimethyl-2-methylsulfanyl-ethyl)-phthalamic acid (0.39 g) and N-(3-dimethylaminopropyl)-N¹-ethylcarbonyl diimidazole hydrochloride (0.19 g) were stirred in dichloromethane (10 ml) at room temperature for 30 minutes. Then, 2-methyl-4-[1-(3-trifluoromethyl-1H-pyrazol-1-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 N²-(1,1-dimethyl-2-methylsulfanyl-ethyl)-3-iodo-N¹-{2-methyl-4-[1-(3-trifluoromethyl-1H-pyrazol-1-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.

TABLE 1
No.	R1	X	Y	A	m	Q	R2	R3	R4	mp
1	C(CH3)2CH2SCH3	3-H	2-CH3	CH2	1	Q1	CF3	CF3	H	***
2	C(CH3)2CH2SOCH3	3-H	2-CH3	CH2	1	Q1	CF3	CF3	H
3	C(CH3)2CH2SO2CH3	3-H	2-CH3	CH2	1	Q1	CF3	CF3	H	***
4	CH(CH3)CH2SCH3	3-H	2-CH3	CH2	1	Q1	CF3	CF3	H
5	CH(CH3)CH2SOCH3	3-H	2-CH3	CH2	1	Q1	CF3	CF3	H
6	CH(CH3)CH2SO2CH3	3-H	2-CH3	CH2	1	Q1	CF3	CF3	H
7	CH(CH3)2	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
8	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	***
9	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	80-84
10	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	183-186
11	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	***
12	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	76-81
	(S)-isomer
13	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	185-193
14	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	192-194
	(S)-isomer
15	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	***
16	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H	88-93
	(S)-isomer
17	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
18	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
19	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
20	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
21	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
22	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
23	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
24	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
25	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
26	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
27	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
28	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
29	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
30	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
31	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
32	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
33	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
34	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
35	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
36	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
37	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
38	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
39	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
40	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
41	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
42	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
43	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
44	CH(CH3)2	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H
45	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	154-160
46	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H
47	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	***
48	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	147-155
49	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	80-86
	(S)-isomer
50	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H
51	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	207-209
	(S)-isomer
52	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	***
53	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H	77-85
	(S)-isomer
54	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
55	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
56	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
57	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
58	C(CH3)2SOCH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
59	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
60	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
61	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
62	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
63	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
64	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
65	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
66	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
67	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
68	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
69	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
70	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
71	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
72	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
73	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
74	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
75	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
76	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
77	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
78	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
79	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
80	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
81	CH(CH3)2	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	***
82	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	83-87
83	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	***
84	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	104-107
85	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	***
86	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	85-93
	(S)-isomer
87	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	213-215
88	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	193-195
	(S)-isomer
89	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	***
90	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	87-93
	(S)-isomer
91	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	79-83
	(S)-isomer
92	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
93	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	79-91
	(S)-isomer
94	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	C3F7-n	H	***
95	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	H	C3F7-n	H
96	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	C3F7-n	H	***
97	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	C3F7-n	H	***
98	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	H	C3F7-n	H
99	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	C3F7-n	H	***
100	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
101	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
102	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
103	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H	***
104	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
105	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
106	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
107	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H	***
108	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
109	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
110	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
111	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q1	CF3	OCHF2	H
	(S)-isomer
112	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
113	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
114	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
115	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
116	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5	***
	(S)-isomer
117	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
118	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
119	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
120	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
121	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
122	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
123	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q1	H	H	C2F5
	(S)-isomer
124	C(CH3)2CH2SCH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
125	C(CH3)2CH2SOCH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
126	C(CH3)2CH2SO2CH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
127	CH(CH3)CH2SCH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
128	CH(CH3)CH2SCH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H	177-180
	(S)-isomer
129	CH(CH3)CH2SOCH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
130	CH(CH3)CH2SOCH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
131	CH(CH3)CH2SO2CH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
132	CH(CH3)CH2SO2CH3	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H	85-93
	(S)-isomer
133	CH(CH3)CH2SC2H5	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
134	CH(CH3)CH2SOC2H5	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
135	CH(CH3)CH2SO2C2H5	3-OSO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
136	CH(CH3)2	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—
137	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	70-72
138	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	84-90
139	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	88-95
140	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	76-80
141	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	72-81
	(S)-isomer
142	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	186-188
143	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	195-198
	(S)-isomer
144	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	116-118
145	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	95-99
	(S)-isomer
146	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	73-76
	(S)-isomer
147	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	180-183
	(S)-isomer
148	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q2	CF3	CF3	—	66-72
	(S)-isomer
149	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—	***
150	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—	59-64
151	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—	82-87
152	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—
153	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—	***
	(S)-isomer
154	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—
155	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—	175-178
	(S)-isomer
156	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—
157	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—	82-90
	(S)-isomer
158	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
159	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
160	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
161	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
162	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
163	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
164	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
165	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
166	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
167	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
168	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
169	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
170	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
171	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
172	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
173	CH(CH3)2	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—
174	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	77-82
175	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—
176	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	151-155
177	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	167-169
178	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	68-73
	(S)-isomer
179	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—
180	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	***
	(S)-isomer
181	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	90-98
182	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—	99-112
	(S)-isomer
183	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
184	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
185	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
186	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
187	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
188	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
189	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
190	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
191	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
192	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
193	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
194	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
195	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
196	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
197	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
198	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
199	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
200	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
201	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
202	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
203	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
204	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
205	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
206	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
207	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
208	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
209	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
210	CH(CH3)2	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	102-105
211	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	93-97
212	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	92-93
213	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	104-107
214	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	92-95
215	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	81-90
	(S)-isomer
216	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	192-195
217	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	192-199
	(S)-isomer
218	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	99-104
219	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	164-167
	(S)-isomer
220	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	90-94
	(S)-isomer
221	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	201-205
	(S)-isomer
222	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q2	CF3	CF3	—	91-99
	(S)-isomer
223	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
224	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
225	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
226	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—	89-94
227	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—	91-104
	(S)-isomer
228	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
229	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—	190-193
	(S)-isomer
230	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—	99-116
231	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—	126-132
	(S)-isomer
232	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
233	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
234	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
235	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
236	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
237	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2
238	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—	85-88
239	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—	160-161
	(S)-isomer
240	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
241	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
242	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—	***
243	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—	174-178
	(S)-isomer
244	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
245	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
246	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q2	CF3	CHF2	—
	(S)-isomer
247	C(CH3)2CH2SCH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
248	C(CH3)2CH2SOCH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
249	C(CH3)2CH2SO2CH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
250	CH(CH3)CH2SCH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
251	CH(CH3)CH2SCH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—	***
	(S)-isomer
252	CH(CH3)CH2SOCH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
253	CH(CH3)CH2SOCH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
254	CH(CH3)CH2SO2CH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
255	CH(CH3)CH2SO2CH3	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—	207-208
	(S)-isomer
256	CH(CH3)CH2SC2H5	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
257	CH(CH3)CH2SOC2H5	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
258	CH(CH3)CH2SO2C2H5	3-OSO2CH3	2-CH3	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
259	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q3	OCHF2	CHF2	CF3
260	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q3	OCHF2	CHF2	CF3
261	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q3	OCHF2	CHF2	CF3
262	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q3	OCHF2	CHF2	CF3	82-90
263	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q3	OCHF2	CHF2	CF3
264	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q3	OCHF2	CHF2	CF3	88-99
265	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q4	OCHF2	CHF2	CF3
266	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q4	OCHF2	CHF2	CF3
267	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q4	OCHF2	CHF2	CF3
268	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q4	OCHF2	CHF2	CF3	149-151
269	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q4	OCHF2	CHF2	CF3
270	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q4	OCHF2	CHF2	CF3	81-90
271	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q5	CF3	CF3	OH	***
272	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q5	CF3	CF3	OH
273	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q5	CF3	CF3	OH
274	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q5	CF3	CF3	OH
275	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q5	CF3	CF3	OH
276	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q5	CF3	CF3	OH
277	CH(CH3)2	3-I	2-CH3	CH2	1	Q6	Cl	Cl	H	***
278	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q6	H	CF3	CF3
279	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q6	H	CF3	CF3
280	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q6	H	CF3	CF3
281	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q6	H	CF3	CF3	149-158
	(S)-isomer
282	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q6	H	CF3	CF3
283	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q6	H	CF3	CF3
284	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q7	CH2CF3	CF3	—
285	C(CH3)2SOCH3	3-I	2-CH3	CH2	1	Q7	CH2CF3	CF3	—
286	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q7	CH2CF3	CF3	—
287	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q7	CH2CF3	CF3	—
288	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q7	CH2CF3	CF3	—
289	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q7	CH2CF3	CF3	—
290	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q8	CH2CF3	CF3	—
291	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q8	CH2CF3	CF3	—
292	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q8	CH2CF3	CF3	—
293	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q8	CH2CF3	CF3	—
294	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q8	CH2CF3	CF3	—
295	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q8	CH2CF3	CF3	—
296	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
297	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
298	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
299	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—	65-79
	(S)-isomer
300	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
301	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
302	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q10	CF3	CF3	H
303	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q10	CF3	CF3	H
304	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q10	CF3	CF3	H
305	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q10	CF3	CF3	H
306	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q10	CF3	CF3	H
307	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q10	CF3	CF3	H
308	C(CH3)2CH2SCH3	3-I	2-CH3	O	1	Q10	CF3	CF3	H	179-181
309	C(CH3)2CH2SOCH3	3-I	2-CH3	O	1	Q10	CF3	CF3	H
310	C(CH3)2CH2SO2CH3	3-I	2-CH3	O	1	Q10	CF3	CF3	H	148-153
311	CH(CH3)CH2SCH3	3-I	2-CH3	O	1	Q10	CF3	CF3	H
312	CH(CH3)CH2SOCH3	3-I	2-CH3	O	1	Q10	CF3	CF3	H
313	CH(CH3)CH2SO2CH3	3-I	2-CH3	O	1	Q10	CF3	CF3	H
314	C(CH3)2CH2SCH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
315	C(CH3)2CH2SOCH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
316	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
317	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
318	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H	209-210
	(S)-isomer
319	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
320	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
321	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
322	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H	218-219
	(S)-isomer
323	CH(CH3)CH2SC2H5	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
324	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
325	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
326	C(CH3)2CH2SCH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
327	C(CH3)2CH2SOCH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
328	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
329	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
330	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
331	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
332	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
333	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
334	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
335	CH(CH3)CH2SC2H5	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
336	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
337	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
338	C(CH3)2CH2SCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
339	C(CH3)2CH2SOCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
340	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
341	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
342	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
343	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
344	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
345	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
346	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
347	CH(CH3)CH2SC2H5	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
348	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
349	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
350	C(CH3)2CH2SCH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
351	C(CH3)2CH2SOCH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
352	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
353	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
354	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
355	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
356	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
357	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
358	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
359	CH(CH3)CH2SC2H5	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
360	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
361	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
362	C(CH3)2CH2SCH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
363	C(CH3)2CH2SOCH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
364	C(CH3)2CH2SO2CH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
365	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
366	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
367	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
368	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
369	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
370	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
371	CH(CH3)CH2SC2H5	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
372	CH(CH3)CH2SOC2H5	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
373	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
374	C(CH3)2CH2SCH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
375	C(CH3)2CH2SOCH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
376	C(CH3)2CH2SO2CH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
377	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
378	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
379	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
380	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
381	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
382	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
383	CH(CH3)CH2SC2H5	3-Br	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
384	CH(CH3)CH2SOC2H5	3-Br	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
385	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
386	C(CH3)2CH2SCH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
387	C(CH3)2CH2SOCH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
388	C(CH3)2CH2SO2CH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
389	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
390	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
391	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
392	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
393	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
394	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
395	CH(CH3)CH2SC2H5	3-Br	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
396	CH(CH3)CH2SOC2H5	3-Br	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
397	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
398	C(CH3)2CH2SCH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
399	C(CH3)2CH2SOCH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
400	C(CH3)2CH2SO2CH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
401	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
402	CH(CH3)CH2SCH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
403	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
404	CH(CH3)CH2SOCH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
405	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
406	CH(CH3)CH2SO2CH3	3-Br	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
407	CH(CH3)CH2SC2H5	3-Br	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
408	CH(CH3)CH2SOC2H5	3-Br	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
409	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
410	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H
411	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H
412	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H
413	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H	201
414	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H	192-206
	(S)-isomer
415	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H
416	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
417	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H	***
418	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
419	CH(CH3)CH2SC2H5	3-I	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
420	CH(CH3)CH2SOC2H5	3-I	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
421	CH(CH3)CH2SO2C2H5	3-I	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
422	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	H	C2F5	H	***
423	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
424	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
425	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
426	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
427	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
428	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
428	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
430	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
431	CH(CH3)CH2SC2H5	3-I	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
432	CH(CH3)CH2SOC2H5	3-I	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
433	CH(CH3)CH2SO2C2H5	3-I	2-CH3	—	0	Q1	H	C2F5	H
	(S)-isomer
434	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	C2F5	H	H	***
435	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
436	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
437	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
438	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
439	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
440	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
441	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
442	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
443	CH(CH3)CH2SC2H5	3-I	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
444	CH(CH3)CH2SOC2H5	3-I	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
445	CH(CH3)CH2SO2C2H5	3-I	2-CH3	—	0	Q1	C2F5	H	H
	(S)-isomer
446	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C2F5	155-157
447	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
448	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	H	H	C2F5	162-168
449	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
450	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
451	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
452	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
453	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
454	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
455	CH(CH3)CH2SC2H5	3-I	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
456	CH(CH3)CH2SOC2H5	3-I	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
457	CH(CH3)CH2SO2C2H5	3-I	2-CH3	—	0	Q1	H	H	C2F5
	(S)-isomer
458	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	CH3	CF3	H
459	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	CH3	CF3	H
460	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	CH3	CF3	H
461	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	CH3	CF3	H	178-180
462	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	CH3	CF3	H
463	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	CH3	CF3	H	101-112
464	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	CH3	H
465	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	CH3	H
466	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	CH3	H
467	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	CH3	H	187-192
468	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	CH3	H
469	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	CH3	H	108-116
470	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	C2F5	CF3	H
471	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	C2F5	CF3	H
472	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	C2F5	CF3	H
473	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	C2F5	CF3	H	109-111
474	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	C2F5	CF3	H
475	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	C2F5	CF3	H	103-115
476	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	H	Br
477	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	H	Br
478	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	H	Br
479	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	H	Br	235-237
480	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	H	Br
481	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	H	Br	201-209
482	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	H	H
483	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	H	H
484	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	H	H
485	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q1	CF3	H	H	173-174
486	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q1	CF3	H	H
487	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q1	CF3	H	H	107-109
488	C(CH3)2CH2SCH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
489	C(CH3)2CH2SOCH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
490	C(CH3)2CH2SO2CH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
491	CH(CH3)CH2SCH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
492	CH(CH3)CH2SCH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H	175-177
	(S)-isomer
493	CH(CH3)CH2SOCH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
494	CH(CH3)CH2SOCH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
495	CH(CH3)CH2SO2CH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
496	CH(CH3)CH2SO2CH3	3-OSO2CH3	2-CH3	—	0	Q1	CF3	CF3	H
	(S)-isomer
497	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q5	C2F5	CF3	OH
498	C(CH3)2CH3SOCH3	3-I	2-CH3	—	0	Q5	C2F5	CF3	OH
499	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q5	C2F5	CF3	OH
500	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q5	C2F5	CF3	OH	101-106
501	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q5	C2F5	CF3	OH
502	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q5	C2F5	CF3	OH
503	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q11	CH2CF3	H	CF3
504	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q11	CH2CF3	H	CF3
505	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q11	CH2CF3	H	CF3
506	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q11	CH2CF3	H	CF3	106-118
507	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q11	CH2CF3	H	CF3
508	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q11	CH2CF3	H	CF3	127-139
509	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q11	CHF2	H	CF3
510	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q11	CHF2	H	CF3
511	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q11	CHF2	H	CF3
512	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q11	CHF2	H	CF3	138-144
513	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q11	CHF2	H	CF3
514	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q11	CHF2	H	CF3
515	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q12	CHF2	H	OCHF2
516	C(CH3)2CH2SOCH3	3-I	2-CH3	—	0	Q12	CHF2	H	OCHF2
517	C(CH3)2CH2SO2CH3	3-I	2-CH3	—	0	Q12	CHF2	H	OCHF2
518	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q12	CHF2	H	OCHF2	83-89
519	CH(CH3)CH2SOCH3	3-I	2-CH3	—	0	Q12	CHF2	H	OCHF2
520	CH(CH3)CH2SO2CH3	3-I	2-CH3	—	0	Q12	CHF2	H	OCHF2	91-97
521	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	C2F5	H	***
522	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	C2F5	H	***
523	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	C2F5	H	***
524	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	C2F5	H
525	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	H
526	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	H
527	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	H
528	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	H
529	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	H	***
530	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	H	***
531	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	H
532	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	H	***
	(S)-isomer
533	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	H
534	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	H	***
535	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	H
	(S)-isomer
536	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	H	***
537	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	H	***
538	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	H	***
539	CH(CH3)CH2SCH(CH3)2	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	81-83
	(S)-isomer
540	CH(CH3)CH2SOCH(CH3)2	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
541	CH(CH3)CH2SO2CH(CH3)2	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
542	CH(CH3)CH2SCH(CH3)2	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
543	CH(CH3)CH2SCH3	3-NO2	2-CH3	CH2	1	Q1	CF3	CF3	H	161-171
	(S)-isomer
544	CH(CH3)CH2SOCH3	3-NO2	2-CH3	CH2	1	Q1	CF3	CF3	H	227-229
	(S)-isomer
545	CH(CH3)CH2SO2CH3	3-NO2	2-CH3	CH2	1	Q1	CF3	CF3	H	215-216
	(S)-isomer
546	CH(CH3)CH2SCH3	3-NO2	2-CH3	CH2	1	Q2	CF3	CF3	—	175-179
	(S)-isomer
547	CH(CH3)CH2SOCH3	3-NO2	2-CH3	CH2	1	Q2	CF3	CF3	—	225-228
	(S)-isomer
548	CH(CH3)CH2SO2CH3	3-NO2	2-CH3	CH2	1	Q2	CF3	CF3	—	206-208
	(S)-isomer
549	CH(CH3)CH2SCH3	3-F	2-CH3	CH2	1	Q1	CF3	CF3	H	66-68
	(S)-isomer
550	CH(CH3)2	3-SCH3	2-CH3	CH2	1	Q1	CF3	CF3	H	***
551	CH(CH3)CH2SCH3	3-SCH3	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
552	CH(CH3)CH2SCH3	3-SO2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H	***
	(S)-isomer
553	CH(CH3)CH2SCH3	3-SCH2CH3	2-CH3	CH2	1	Q1	CF3	CF3	H	***
	(S)-isomer
554	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	I	***
	(S)-isomer
555	CH(CH3)CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	H	H
556	CH(CH3)CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	H	H	78-89
	(S)-isomer
557	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	H	H	150-152
	(S)-isomer
558	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	H	H	79-86
559	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	80-91
	(S)-isomer
560	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H
	(S)-isomer
561	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	103-105
	(S)-isomer
562	CH(CH3)CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	84-89
	(S)-isomer
563	CH(CH3)CH2SOCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	177-179
	(S)-isomer
564	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	101-105
	(S)-isomer
565	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	98-106
566	C(CH3)2CH2SOCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	132-136
567	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH(CH3)	1	Q1	CF3	CF3	H	173-174
568	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	CF3	CF3	—	87-92
	(S)-isomer
569	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	CF3	CF3	—	***
	(S)-isomer
570	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH(CH3)	1	Q2	CF3	CF3	—	91-95
	(S)-isomer
571	CH(CH3)CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q2	CF3	CF3	—	98-105
	(S)-isomer
572	CH(CH3)CH2SOCH3	3-I	2-CH3	CH(CH3)	1	Q2	CF3	CF3	—	98-105
	(S)-isomer
573	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH(CH3)	1	Q2	CF3	CF3	—	103-106
	(S)-isomer
574	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	CF3	C2F5	—	***
	(S)-isomer
575	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	CF3	C2F5	—
	(S)-isomer
576	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH(CH3)	1	Q2	CF3	C2F5	—
	(S)-isomer
577	CH(CH3)CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q2	CF3	C2F5	—
	(S)-isomer
578	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	C2F5	CF3	—	83-85
	(S)-isomer
579	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	C2F5	CF3	—	121-124
	(S)-isomer
580	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH(CH3)	1	Q2	C2F5	CF3	—	87-94
	(S)-isomer
581	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q2	C2F5	C2F5	—
	(S)-isomer
582	CH(CH3)CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q2	C2F5	C2F5	—
	(S)-isomer
583	CH(CH3)CH2SCH3	3-Cl	2-CH3	S	1	Q10	CF3	CF3	H
	(S)-isomer
584	CH(CH3)CH2SCH3	3-I	2-CH3	S	1	Q10	CF3	CF3	H
	(S)-isomer
585	CH(CH3)CH2SCH3	3-Cl	2-CH3	S	1	Q10	C2F5	C2F5	H
	(S)-isomer
586	CH(CH3)CH2SCH3	3-I	2-CH3	S	1	Q10	C2F5	C2F5	H
	(S)-isomer
587	CH(CH3)CH2SCH3	3-Cl	2-CH3	S	1	Q13	CF3	CF3	—
	(S)-isomer
588	CH(CH3)CH2SCH3	3-I	2-CH3	S	1	Q13	CF3	CF3	—	223-225
	(S)-isomer
589	CH(CH3)CH2SCH3	3-I	2-CH3	SO2	1	Q13	CF3	CF3	—
	(S)-isomer
590	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q7	CH3	CHF2	—
591	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q7	CH3	CHF2	—
592	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q7	CH3	CHF2	—	99-101
593	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q7	CH3	CHF2	—	83-94
594	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q14	H	COCF3	H	***
	(S)-isomer
595	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q14	I	COCF3	H	***
	(S)-isomer
596	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q14	C2F5	COCF3	H	***
	(S)-isomer
597	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C3F7-n
598	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C4F9-n
599	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C6F13-n
600	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q1	H	H	C8F17-n
601	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C3F7-n
	(S)-isomer
602	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C4F9-n	69-72
	(S)-isomer
603	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C6F13-n
	(S)-isomer
604	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C8F17-n
	(S)-isomer
605	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CH3	H	C3F7-n
606	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CH3	H	C4F9-n
607	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CH3	H	C6F13-n
608	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	CF3	H	74-78
	(S)-isomer
609	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	CF3	H	176-177
	(S)-isomer
610	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	CF3	H	81-87
	(S)-isomer
611	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	CF3	H
	(S)-isomer
612	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	CF3	H
	(S)-isomer
613	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	CF3	H
	(S)-isomer
614	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	CF3	H
	(S)-isomer
615	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	CF3	H
	(S)-isomer
616	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	CF3	H
	(S)-isomer
617	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	CF3	H
	(S)-isomer
618	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	CF3	H
	(S)-isomer
619	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	CF3	H
	(S)-isomer
620	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	H
621	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	H
622	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	H
623	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	C2F5	H
624	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	C2F5	H
625	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	C2F5	H
626	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	H	***
	(S)-isomer
627	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	H
	(S)-isomer
628	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	H
	(S)-isomer
629	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	C2F5	H
	(S)-isomer
630	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	C2F5	H
	(S)-isomer
631	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	C2F5	H
	(S)-isomer
632	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	Cl	***
	(S)-isomer
633	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	Cl	***
	(S)-isomer
634	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	Cl	***
	(S)-isomer
635	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	Br	***
	(S)-isomer
636	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	I	***
	(S)-isomer
637	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C2F5	73-78
	(S)-isomer
638	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C2F5	81-84
	(S)-isomer
639	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C2F5	87-90
	(S)-isomer
640	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C2F5	***
	(S)-isomer
641	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C2F5	164-166
	(S)-isomer
642	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C2F5	75-85
	(S)-isomer
643	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C3F7-n	73-75
	(S)-isomer
644	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C3F7-n	86-88
	(S)-isomer
645	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C4F9-n	79-82
	(S)-isomer
646	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C4F9-n	73-76
	(S)-isomer
647	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C4F9-n	83-88
	(S)-isomer
648	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C4F9-n	88-92
	(S)-isomer
649	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C4F9-n	84-90
	(S)-isomer
650	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C4F9-n	75-78
	(S)-isomer
651	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5	***
	(S)-isomer
652	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5	124-125
	(S)-isomer
653	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5	88-91
	(S)-isomer
654	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5	***
	(S)-isomer
655	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5	87-92
	(S)-isomer
656	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5	100-107
	(S)-isomer
657	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n	64-65
	(S)-isomer
658	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n	***
	(S)-isomer
659	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n	78-81
	(S)-isomer
660	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n	***
	(S)-isomer
661	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n	83-85
	(S)-isomer
662	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n	92-96
	(S)-isomer
663	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n	72-74
	(S)-isomer
664	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n	84-88
	(S)-isomer
665	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5	78-85
	(S)-isomer
666	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5	78-85
	(S)-isomer
667	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n	70-74
	(S)-isomer
668	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n	73-77
	(S)-isomer
669	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n	77-82
	(S)-isomer
670	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n	86-90
	(S)-isomer
671	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n	81-84
	(S)-isomer
672	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n	147-148
	(S)-isomer
673	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	C2F5	CF3
	(S)-isomer
674	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	C2F5	CF3
	(S)-isomer
675	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	C2F5	C2F5	***
	(S)-isomer
676	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	C2F5	C2F5
	(S)-isomer
677	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
678	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
679	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
680	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
681	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—	***
	(S)-isomer
682	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
683	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—	162-164
	(S)-isomer
684	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
685	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—	103-106
	(S)-isomer
686	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
687	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
688	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
689	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
690	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
691	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
692	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
693	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
694	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
695	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
696	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
697	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
698	CH(CH3)CH2SC2H5	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
699	CH(CH3)CH2SOC2H5	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
700	CH(CH3)CH2SO2C2H5	3-Br	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
701	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
702	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
703	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
704	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
705	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
706	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
707	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
708	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
709	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
710	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
711	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
712	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
713	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C3F7-n	CF3	—
714	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C3F7-n	CF3	—	***
	(S)-isomer
715	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q2	C3F7-n	CF3	—
	(S)-isomer
716	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C3F7-n	C2F5	—
	(S)-isomer
717	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C3F7-n	C2F5	—
	(S)-isomer
718	C(CH3)2CH2SCH3	3-F	2-CH3	CH2	1	Q1	CF3	CF3	H
719	C(CH3)2CH2SOCH3	3-F	2-CH3	CH2	1	Q1	CF3	CF3	H
720	C(CH3)2CH2SO2CH3	3-F	2-CH3	CH2	1	Q1	CF3	CF3	H
721	CH(CH3)CH2SOCH3	3-F	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
722	CH(CH3)CH2SO2CH3	3-F	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
723	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C4F9-n	63-69
	(S)-isomer
724	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	H	H	C4F9-n	95-97
	(S)-isomer
725	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	H	CF3	C3F7-n	76-81
	(S)-isomer
726	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	H	CF3	C3F7-n	***
	(S)-isomer
727	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	H	CF3	C3F7-n	***
	(S)-isomer
728	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	H	C2F5	C2F5	68-72
	(S)-isomer
729	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	H	C2F5	C2F5	***
	(S)-isomer
730	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CHF2	CHF2	H	***
	(S)-isomer
731	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	CF3
732	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	CF3
	(S)-isomer
733	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	CF2CHF2
734	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	CF2CHF2
	(S)-isomer
735	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C4F9-n
736	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C4F9-n
737	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C6F13-n	78-82
	(S)-isomer
738	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	H	C8F17-n	79-82
	(S)-isomer
739	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	CF3
	(S)-isomer
740	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5
741	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5	***
	(S)-isomer
742	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5	64-67
	(S)-isomer
743	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5	83-89
	(S)-isomer
744	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	CF3
745	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	CF3	75-80
	(S)-isomer
746	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	CF2CHF2
	(S)-isomer
747	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	CF2CHF2
	(S)-isomer
748	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	CF2CHF2
	(S)-isomer
749	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5
750	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5
751	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5
752	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5
753	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5
754	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5
755	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	C2F5	95-100
	(S)-isomer
756	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q1	C2F5	H	C2F5
	(S)-isomer
757	CH(CH3)CH2SOCH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	C2F5	89-94
	(S)-isomer
758	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH(CH3)	1	Q1	C2F5	H	C2F5
	(S)-isomer
759	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	—	0	Q1	C2F5	H	C2F5	195-195
	(S)-isomer
760	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH(CH3)	1	Q1	C2F5	H	C2F5
	(S)-isomer
761	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5	70-74
	(S)-isomer
762	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5	79-84
	(S)-isomer
763	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C2F5	185-188
	(S)-isomer
764	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q1	C2F5	H	C3F7-n
765	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
766	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
767	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
768	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
769	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n
770	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C4F9
771	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n	81-85
	(S)-isomer
772	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n
	(S)-isomer
773	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	F	CF3
774	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	F	CF3
775	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	F	CF3	142-146
	(S)-isomer
776	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	F	CF3
	(S)-isomer
777	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	F	CF3
	(S)-isomer
778	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	CH3	C2F5	***
	(S)-isomer
779	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C2F5	C2F5	C2F5
	(S)-isomer
780	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
781	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
782	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
783	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
784	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5	81-83
	(S)-isomer
785	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5	85-90
	(S)-isomer
786	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH(CH3)	1	Q1	C3F-n	H	C3F7-n
787	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F-n	H	C3F7-n
788	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F-n	H	C3F7-n
789	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F-n	H	C3F7-n
790	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F-n	H	C3F7-n
791	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F-n	H	C3F7-n
792	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F-n	H	C3F7-n
793	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	C3F7-n	H	74-78
	(S)-isomer
794	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	C3F7-n	H	72-76
	(S)-isomer
795	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	C3F7-n	C3F7-n	H	149-150
	(S)-isomer
796	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CHFCF3	CF3	—	66-69
	(S)-isomer
797	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CHFCF3	CF3	—	80-85
	(S)-isomer
798	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CHFCF3	CF3	—	81-86
	(S)-isomer
799	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	CF2CHF2	CF2CHF2	—	***
	(S)-isomer
800	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q2	CF2CHF2	CF2CHF2	—	159-163
	(S)-isomer
801	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q2	CF2CHF2	CF2CHF2	—	77-83
	(S)-isomer
802	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C3F7-n	C3F7-n	—
803	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	C4F9-n	H	—	218-210
	(S)-isomer
804	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q2	SC3F7-n	CF3	—	73-76
	(S)-isomer
805	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q6	CF3	CF3	CF3
	(S)-isomer
806	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q6	CF3	CF3	CF3
	(S)-isomer
807	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q6	CF3	CF3	CF3
	(S)-isomer
808	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
809	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
810	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
811	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
812	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
813	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
814	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
815	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
816	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
817	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
818	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
819	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
820	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
821	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
822	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
823	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
824	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
825	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
826	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
827	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
828	CH(CH3)CH2SC2H5	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
829	CH(CH3)CH2SOC2H5	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
830	CH(CH3)CH2SO2C2H5	3-Cl	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
831	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	C2F5	—
832	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	C2F5	—
833	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C2F5	C2F5	—
	(S)-isomer
834	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C3F7-n	CF3	—
835	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q9	C3F7-n	CF3	—
	(S)-isomer
836	CH(CH3)CH2SCH3	3-Cl	2-CH3	S	1	Q18	CF3	CH3	—
	(S)-isomer
837	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q19	CF3	CH3	—
	(S)-isomer
838	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q17	CF3	H	—
839	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q15	H	C2F5	—
840	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q15	H	C2F5	—	71-75
	(S)-isomer
841	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q20	CF3	—	—
	(S)-isomer
842	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q16	C2F5	—	—
843	CH(CH3)CH2SCH3	3-Cl	2-CH3	—	0	Q16	C3F7-n	—	—
844	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	H	C2F5
845	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	H	C4F9-n
846	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF3	H	C4F9-n
847	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5
848	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C2F5
849	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C2F5
850	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C2F5
851	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C2F5
852	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C2F5
853	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C2F5
854	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n
855	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n
856	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
857	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
858	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
859	CH(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
860	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
861	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
862	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
863	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q9	CF3	CF3	—
864	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q9	CF3	CF3	—
865	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q9	CF3	CF3	—
866	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q9	CF3	CF3	—
867	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q9	CF3	CF3	—
868	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q9	CF3	CF3	—
869	C(CH3)2CH2SCH3	3-Br	2-CH3	CH2	1	Q9	C2F5	CF3	—
870	C(CH3)2CH2SOCH3	3-Br	2-CH3	CH2	1	Q9	C2F5	CF3	—
871	C(CH3)2CH2SO2CH3	3-Br	2-CH3	CH2	1	Q9	C2F5	CF3	—
872	CH(CH3)CH2SCH3	3-Br	2-CH3	CH2	1	Q9	C2F5	CF3	—
873	CH(CH3)CH2SOCH3	3-Br	2-CH3	CH2	1	Q9	C2F5	CF3	—
874	CH(CH3)CH2SO2CH3	3-Br	2-CH3	CH2	1	Q9	C2F5	CF3	—
875	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	H	H	C4F9-n	80-85
	(S)-isomer
876	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	H	H	C4F9-n	160-162
	(S)-isomer
877	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	H	H	C4F9-n	85-89
	(S)-isomer
878	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CHF2	CHF2	H	***
	(S)-isomer
879	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	CF3
880	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	CF2CHF2
881	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	CF2CHF2
	(S)-isomer
882	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C2F5
883	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C2F5
884	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C4F9-n
885	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	H	C4F9-n
886	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	CF3
887	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	CF3
888	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	CF2CHF2	H	C2F5
889	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5
890	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5
	(S)-isomer
891	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5
	(S)-isomer
892	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF2CHF2	H	C2F5
	(S)-isomer
893	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	CF3
894	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	CF2CHF2
	(S)-isomer
895	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	CF2CHF2
	(S)-isomer
896	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	CF2CHF2
	(S)-isomer
897	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q1	C2F5	H	C2F5
898	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
899	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
900	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
901	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
902	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
903	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
904	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
905	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
906	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
907	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
908	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
909	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
910	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C3F7-n
911	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n
912	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n
913	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n	90-96
	(S)-isomer
914	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	H	C4F9-n	92-97
	(S)-isomer
915	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	F	CF3
916	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
917	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
918	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
919	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5
920	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5	89-96
	(S)-isomer
921	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C2F5	92-96
	(S)-isomer
922	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
923	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
924	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
925	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
926	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
927	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C3F7-n	H	C3F7-n
928	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q2	C3F7-n	C3F7-n	—
929	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q6	CF3	CF3	CF3
	(S)-isomer
930	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q6	CF3	CF3	CF3
	(S)-isomer
931	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q6	CF3	CF3	CF3
	(S)-isomer
932	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q9	CF3	CF3	—
933	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
934	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
935	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
936	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
937	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
938	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
939	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
940	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
941	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q9	C2F5	CF3	—
942	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
943	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
944	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
945	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
946	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
947	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
948	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
949	CH(CH3)CH2SOCH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
950	CH(CH3)CH2SO2CH3	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
951	CH(CH3)CH2SC2H5	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
952	CH(CH3)CH2SOC2H5	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
953	CH(CH3)CH2SO2C2H5	3-I	2-CH3	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
954	C(CH3)2CH2SCH3	3-I	2-CH3	CH(CH3)	1	Q9	C2F5	C2F5	—
955	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q9	C2F5	C2F5	—
956	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	C2F5	C2F5	—
957	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	C2F5	C2F5	—
	(S)-isomer
958	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q9	C3F7-n	CF3	—
959	CH(CH3)CH2SCH3	3-I	2-CH3	CH2	1	Q9	C3F7-n	CF3	—
	(S)-isomer
960	C(CH3)2CH2SCH3	3-I	2-CH3	S	1	Q18	CF3	CH3	—
961	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q19	CF3	CH3	—
962	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q17	CF3	H	—
963	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q15	H	C2F5	—
964	C(CH3)2CH2SCH3	3-I	2-CH3	—	0	Q20	CF3	—	—
965	CH(CH3)CH2SCH3	3-I	2-CH3	—	0	Q16	CF3	—	—
966	C(CH3)2CH2SCH3	3-Cl	2-F	CH2	1	Q1	CF3	CF3	H
967	C(CH3)2CH2SOCH3	3-Cl	2-F	CH2	1	Q1	CF3	CF3	H
968	C(CH3)2CH2SO2CH3	3-Cl	2-F	CH2	1	Q1	CF3	CF3	H
969	C(CH3)2CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
970	C(CH3)2CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
971	C(CH3)2CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
972	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
973	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
974	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
975	CH(CH3)CH2SCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
976	CH(CH3)CH2SOCH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
977	CH(CH3)CH2SO2CH3	3-Cl	2-CH3	CH2	1	Q1	CF3	CF3	H
	(S)-isomer
978	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	CF3	H
	(S)-isomer
979	CH(CH3)CH2SOCH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	CF3	H
	(S)-isomer
980	CH(CH3)CH2SO2CH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	CF3	H
	(S)-isomer
981	C(CH3)2CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	CF3	H	C2F5
982	C(CH3)2CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	CF3	H	C3F7-n
983	C(CH3)2CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	CF3	H	C4F9-n
984	C(CH3)2CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	CF3	H	C6F13-n
985	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
986	CH(CH3)CH2SOCH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
987	CH(CH3)CH2SO2CH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
988	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	H	C3F7-n
	(S)-isomer
989	CH(CH3)CH2SOCH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	H	C3F7-n
	(S)-isomer
990	CH(CH3)CH2SO2CH3	3-Cl	2-Cl	CH2	1	Q1	C2F5	H	C3F7-n
	(S)-isomer
991	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
992	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
993	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q9	CF3	CF3	—
	(S)-isomer
994	CH(CH3)CH2SCH3	3-Cl	2-Cl	CH2	1	Q9	C2F5	CF3	—
	(S)-isomer
995	C(CH3)2CH2SCH3	3-I	2-F	CH2	1	Q1	CF3	CF3	H	***
996	C(CH3)2CH2SOCH3	3-I	2-F	CH2	1	Q1	CF3	CF3	H
997	C(CH3)2CH2SO2CH3	3-I	2-F	CH2	1	Q1	CF3	CF3	H	113-115
998	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	157-159
999	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H
1000	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	CF3	CF3	H	129-134
1001	C(CH3)2CH2SCH3	3-I	2-CH3	CH2	1	Q1	C2F5	CF3	H
1002	C(CH3)2CH2SOCH3	3-I	2-CH3	CH2	1	Q1	C2F5	CF3	H
1003	C(CH3)2CH2SO2CH3	3-I	2-CH3	CH2	1	Q1	C2F5	CF3	H
1004	C(CH3)2CH2SCH3	3-I	2-Cl	CH2	1	Q1	C2F5	C2F5	H
1005	C(CH3)2CH2SOCH3	3-I	2-Cl	CH2	1	Q1	C2F5	C2F5	H
1006	C(CH3)2CH2SO2CH3	3-I	2-Cl	CH2	1	Q1	C2F5	C2F5	H
1007	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q1	C2F5	H	C2F5
	(S)-isomer
1008	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q1	C2F5	H	C3F7-n
	(S)-isomer
1009	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q1	C2F5	H	C4F9-n
	(S)-isomer
1010	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q1	C2F5	H	C6F13-n
	(S)-isomer
1011	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q2	CF3	CF3	—
	(S)-isomer
1012	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q2	C2F5	CF3	—
	(S)-isomer
1013	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q2	C2F5	C2F5	—
	(S)-isomer
1014	CH(CH3)CH2SCH3	3-I	2-Cl	CH2	1	Q2	C3F7-n	CF3	—
	(S)-isomer
indicates data missing or illegible when filed

TABLE 2
No.
1	1H-NMR	(CDCl3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 5.4 (2H, s), 6.2 (1H, s), 6.9 (1H,
		s), 7.3-8.7 (8H, m)
3	1H-NMR	(CDCl3, ppm): 1.5 (6H, s), 2.2 (3H, s), 2.6 (3H, s), 3.7 (2H, s), 5.4 (2H, s), 6.4 (1H, s), 6.9 (1H,
		s), 7.3-8.2 (8H, m)
8	1H-NMR	(CDCl3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 5.4 (2H, s), 6.1 (1H, s), 6.9 (1H,
		s), 7.3-8.4 (7H, m)
11	1H-NMR	(CDCl3, ppm): 1.2 (3H, d), 1.9 (3H, s), 2.3 (3H, s), 2.7 (2H, dd), 4.2 (1H, m), 5.4 (2H, s), 6.4
		(1H, d), 6.9 (1H, s), 7.3-8.4 (7H, m)
15	1H-NMR	(CDCl3, ppm): 1.3 (3H, d), 2.2 (3H, s), 2.8 (3H, s), 3.2 (2H, m), 4.6 (1H, m), 5.4 (2H, s), 6.4
		(1H, d), 6.9-8.4 (8H, m)
47	1H-NMR	(CDCl3, ppm): 1.6 (6H, s), 2.3 (3H, s), 2.5 (3H, s), 3.5 (2H, s), 5.4 (2H, s), 6.6 (1H, s), 6.9 (1H,
		s), 7.3-8.2 (7H, m)
52	1H-NMR	(CDCl3, ppm): 1.4 (3H, d), 2.2 (3H, s), 2.7 (3H, s), 3.2 (2H, m), 4.4 (1H, m), 5.4 (2H, s),
		6.9-8.2 (9H, m)
81	1H-NMR	(CDCl3, ppm): 1.1 (6H, d), 2.2 (3H, s), 4.2 (1H, m), 5.3 (2H, s), 5.9 (1H, d), 6.9-8.2 (8H, m)
83	1H-NMR	(CDCl3, ppm): 1.57 (3H, s), 1.60 (3H, s), 2.20 (3H, s), 2.30 (3H, s), 2.93 (2H, dd), 5.43 (2H, s),
		6.57 (1H, s), 6.90 (1H, s), 7.0-8.2 (7H, m)
85	1H-NMR	(CDCl3, ppm): 1.2 (3H, d), 1.8 (3H, s), 2.2 (3H, s), 2.6 (2H, dd), 4.2 (1H, m), 5.3 (2H, s), 6.5
		(1H, d), 6.9 (1H, s), 7.3-8.4 (7H, m)
89	1H-NMR	(CDCl3, ppm): 1.4 (3H, d), 2.2 (3H, s), 2.7 (3H, s), 3.2 (2H, m), 4.5 (1H, m), 5.3 (2H, s), 6.6
		(1H, d), 6.9-7.9 (8H, m)
94	1H-NMR	(CDCl3, ppm): 1.57 (3H, s), 1.60 (3H, s), 2.20 (3H, s), 2.30 (3H, s), 2.93 (2H, dd), 5.43 (2H, s),
		6.57 (1H, s), 6.90 (1H, s), 7.0-8.2 (7H, m)
96	1H-NMR	(CDCl3, ppm): 1.63 (6H, s), 2.27 (3H, s), 2.50 (3H, s), 3.47 (2H, s), 5.30 (2H, s), 6.23 (1H, s),
		6.57 (1H, s), 7.0-8.1 (8H, m)
97	1H-NMR	(CDCl3, ppm): 1.27 (3H, d), 1.93 (3H, s), 2.30 (3H, s), 2.63 (2H, m), 4.33 (1H, m), 5.37 (2H,
		s), 6.07 (1H, m), 6.60 (1H, s), 6.9-8.2 (8H, m)
99	1H-NMR	(CDCl3, ppm): 1.50 (3H, d), 2.27 (3H, s), 2.70 (3H, s), 3.0-3.5 (2H, m), 4.60 (1H, m), 5.37 (2H,
		s), 6.5-8.0 (10H, m)
103	1H-NMR	(CDCl3, ppm): 1.27 (3H, d), 1.93 (3H, s), 2.30 (3H, s), 2.60 (2H, m), 4.33 (1H, m), 5.20 (2H,
		s), 6.17 (1H, s), 6.47 (1H, t), 7.1-8.3 (8H, m)
107	1H-NMR	(CDCl3, ppm): 1.50 (3H, d), 1.93 (3H, s), 2.30 (3H, s), 2.60 (2H, m), 4.33 (1H, m), 5.20 (2H,
		s), 6.17 (1H, s), 6.47 (1H, t), 6.67 (1H, m), 7.0-8.1 (7H, m)
116	1H-NMR	(CDCl3, ppm): 1.2 (3H, d), 1.9 (3H, s), 2.2 (3H, s), 2.6 (2H, dd), 4.2 (1H, m), 5.2 (2H, s), 6.4
		(1H, d), 7.0-8.3 (9H, m)
149	1H-NMR	(CDCl3, ppm): 1.34 (6H, s), 1.95 (3H, s), 2.33 (3H, s), 2.86 (2H, s), 5.48 (2H, s), 6.11 (1H, s),
		7.56-7.00 (4H, m), 7.84-7.72 (1H, m), 8.23 (1H, d), 8.49 (1H, s)
153	1H-NMR	(CDCl3, ppm): 1.22 (3H, d), 2.05 (3H, s), 2.30 (3H, s), 2.61-2.53 (2H, m), 4.40-4.29 (1H, m),
		5.44 (2H, s), 6.19 (1H, d), 7.17 (2H, t), 7.54-7.48 (2H, m), 7.73 (1H, d), 8.15 (1H, d), 8.44 (1H, s)
180	1H-NMR	(CDCl3, ppm): 1.3 (3H, d), 2.2 (3H, s), 2.3 (3H, s), 2.8 (2H, d), 4.5 (1H, m), 5.4 (2H, s), 7.1-8.3
		(8H, m)
242	1H-NMR	(CDCl3, ppm): 1.4 (3H, d), 2.2 (3H, s), 2.8 (3H, s), 3.2 (2H, m), 4.6 (1H, m), 5.5 (2H, s),
		6.2-8.2 (9H, m)
251	1H-NMR	(CDCl3, ppm): 1.25 (3H, d), 1.95 (3H, s), 2.28 (3H, s), 2.63-2.51 (2H, m), 3.28 (3H, s),
		4.36-4.26 (1H, m), 5.43 (2H, s), 6.38 (1H, d, J = 9.3 Hz), 7.39-7.16 (2H, m), 7.62-7.53 (2H,
		m), 7.81-7.74 (1H, m), 8.38 (1H, s)
271	1H-NMR	(CDCl3, ppm): 1.47 (6H, s), 2.00 (3H, s), 2.30 (3H, s), 2.83 (2H, s), 3.30 (1H, m), 4.2-4.6 (4H,
		m), 6.07 (1H, s), 7.1-8.2 (7H, m)
277	1H-NMR	(CDCl3, ppm): 1.1 (6H, d), 2.2 (3H, s), 4.1 (1H, m), 5.0 (2H, s), 6.0 (1H, d), 7.0-8.4 (8H, m)
417	1H-NMR	(CDCl3, ppm): 1.5 (3H, d), 2.3 (3H, s), 2.8 (3H, s), 3.2 (2H, dd), 4.7 (1H, m), 6.5 (1H, m), 7.0
		(1H, s), 7.3-8.3 (6H, m)
422	1H-NMR	(CDCl3, ppm): 1.47 (6H, s), 2.03 (3H, s), 2.40 (3H, s), 2.87 (2H, s), 6.03 (1H, s), 6.80 (1H, m),
		7.1-8.6 (8H, m)
434	1H-NMR	(CDCl3, ppm): 1.40 (6H, s), 2.03 (3H, s), 2.40 (3H, s), 2.87 (2H, s), 6.07 (1H, s), 6.77 (1H, m),
		7.2-8.5 (8H, m)
521	1H-NMR	(CDCl3, ppm): 1.23 (3H, d), 1.90 (3H, s), 2.26 (3H, s), 2.50-2.67 (2H, m), 4.10-4.50 (1H, m),
		5.37 (2H, s), 6.15 (1H, d), 6.60 (1H, bs), 6.90-7.20 (3H, m), 7.57 (1H, bs), 7.70 (1H, d),
		7.80-8.23 (3H, m)
522	1H-NMR	(CDCl3, ppm): 1.50 (3H, d), 2.30 (3H, s), 2.70 (3H, s), 2.97-3.50 (2H, m), 4.56 (1H, m), 5.43
		(2H, s), 6.60-8.03 (10H, m)
523	1H-NMR	(CDCl3, ppm): 1.40 (6H, s), 1.98 (3H, s), 2.30 (3H, s), 2.73 (2H, s), 5.40 (2H, s), 6.03 (1H, bs),
		6.60-7.20 (4H, m), 7.50-8.20 (5H, m)
529	1H-NMR	(CDCl3, ppm): 1.42 (6H, s), 1.98 (3H, s), 2.30 (3H, s), 2.71 (2H, s), 5.30 (2H, s), 6.03 (1H, bs),
		6.52 (1H, d), 7.03-7.35 (4H, m), 7.73 (1H, d), 7.93 (1H, d), 8.10-8.40 (2H, m)
530	1H-NMR	(CDCl3, ppm): 1.63 (6H, s), 2.30 (3H, s), 2.57 (3H, s), 3.47 (2H, s), 5.30 (2H, s), 6.40 (1H, bs),
		6.57 (1H, d), 7.03-8.17 (8H, m)
532	1H-NMR	(CDCl3, ppm): 1.30 (4H, dd), 1.97 (3H, s), 2.28 (3H, s), 2.73-2.42 (2H, m), 4.37-4.28 (1H, m),
		5.28 (2H, s), 6.42 (1H, d), 6.55 (1H, d), 7.09 (2H, t), 7.42-7.39 (2H, m), 7.51 (1H, d), 7.70 (1H,
		t), 8.02 (1H, d), 8.49 (1H, d)
534	1H-NMR	(CDCl3, ppm): 1.24 (3H, d), 1.93 (3H, s), 2.30 (3H, s), 2.50-2.66 (2H, m), 4.23-4.40 (1H, m),
		5.32 (2H, s), 6.16 (1H, d), 6.54 (1H, d), 7.06 (1H, bs), 7.11 (1H, d), 7.22 (1H, t), 7.40 (1H, d),
		7.78 (1H, d), 7.97 (1H, d), 8.17 (1H, d), 8.30 (1H, bs)
536	1H-NMR	(CDCl3, ppm): 1.50 (3H, d), 2.28 (3H, s), 2.73 (3H, s), 2.97-3.50 (2H, m), 4.60 (1H, m), 5.30
		(2H, s), 6.53 (1H, d), 6.73 (1H, d), 7.00-8.07(8H, m)
537	1H-NMR	(CDCl3, ppm): 1.40(6H, s), 1.98 (3H, s), 2.31 (3H, s), 2.81 (2H, s), 5.32 (2H, s), 6.08 (1H, bs),
		6.54 (1H, d), 7.04 (1H, bs) 7.11 (1H, d), 7.20 (1H, t), 7.38 (1H, d), 7.79 (1H, d), 7.96 (1H, d),
		8.22 (1H, d), 8.38 (1H, bs)
538	1H-NMR	(CDCl3, ppm): 1.66(6H, s), 2.30 (3H, s), 2.60 (3H, s), 3.52 (2H, s), 5.30 (2H, s), 6.47 (1H, bs),
		6.57 (1H, d), 7.03-8.23 (8H, m)
550	1H-NMR	(CDCl3, ppm): 1.48 (6H, d), 2.21 (3H, s), 2.48 (3H, s), 4.13 (1H, m), 5.42 (2H, s), 6.18(1H, d),
		6.91 (1H, s), 7.1-7.6 (6H, m), 8.08 (1H, d)
552	1H-NMR	(CDCl3, ppm): 1.17 (3H, d), 1.89 (3H, s), 2.29 (3H, s), 2.42 (1H, dd), 2.60 (1H, dd), 3.29 (3H,
		s), 4.24 (1H, m), 5.42 (2H, s), 6.41 (1H, d), 6.92 (1H, s), 7.1-7.2 (2H, m). 7.6-8.2 (5H, m)
553	1H-NMR	(CDCl3, ppm): 1.21 (3H, d), 1.32 (3H, t), 1.95 (3H, s), 2.29 (3H, s), 2.51 (1H, dd), 2.60 (1H,
		dd), 3.00 (2H, q), 4.31 (1H, m), 5.41 (2H, s), 6.28 (1H, d), 6.91 (1H, s), 7.1-7.2 (2H, m),
		7.4-7.6 (3H, m), 8.09 (1H, d), 8.34 (1H, s)
554	1H-NMR	(CDCl3, ppm): 1.25 (5H, dd), 1.91 (3H, s), 2.29 (3H, s), 2.60-2.54 (2H, m), 4.32-4.27 (1H, m),
		5.44 (2H, s), 6.40 (1H, d), 7.06 (2H, d, J = 7.5 Hz), 7.19-7.12 (1H, m), 7.71 (1H, d), 7.94-7.91
		(1H, m), 8.08 (1H, d), 8.36 (1H, s)
569	1H-NMR	(CDCl3, ppm): 8.50 (1H, m), 7.95 (1H, m), 7.79-7.49 (4H, m), 7.44-7.38 (1H, m), 7.22 (1H, m),
		5.75 (1H, q), 4.38 (1H, m), 2.79 (2H, m), 2.29 (3H, s), 2.20 (3H, s), 2.00 (3H, d), 1.43-1.18 (3H, d)
574	1H-NMR	(CDCl3, ppm): 1.31 (3H, d), 1.95 (3H, s), 2.30 (3H, s), 2.61-2.57 (2H, m), 4.37-4.27 (1H, m),
		5.79-5.73 (1H, m), 6.48 (1H, d), 7.02 (1H, s), 7.25-7.21 (2H, m), 7.52-7.36 (3H, m), 7.84-7.69
		(2H, m), 8.04 (1H, d), 8.50 (1H, s)
594	1H-NMR	(CDCl3, ppm): 1.22 (3H, d), 1.93 (3H, s), 2.26 (3H, s), 2.61-2.55 (2H, m), 4.36-4.27 (1H, m),
		5.49 (2H, d), 6.07 (1H, d), 6.34-6.30 (1H, m), 6.98 (2H, d), 7.13 (1H, t), 7.27-7.22 (3H, m),
		7.79 (1H, d), 7.97 (1H, dd), 8.08 (1H, d), 8.23 (1H, s)
595	1H-NMR	(CDCl3, ppm): 1.25 (3H, d), 1.94 (3H, s), 2.27 (3H, s), 2.60-2.54 (2H, m), 4.34-4.25 (1H, m),
		5.49 (2H, d), 6.42 (1H, d), 7.04-6.99 (2H, m), 7.21-7.14 (2H, m), 7.35-7.32 (1H, m), 7.72 (1H,
		d), 7.93 (1H, dd), 8.05 (1H, d), 8.36 (1H, s)
596	1H-NMR	(CDCl3, ppm): 1.24 (3H, d), 1.97 (3H, s), 2.33 (3H, s), 2.63-2.54 (2H, m), 4.35-4.30 (1H, m),
		5.52 (2H, s), 6.05 (1H, d), 7.02-7.00 (2H, m), 7.26-7.21 (1H, m), 7.35-7.32 (1H, m), 7.42-7.39
		(1H, m), 7.80 (1H, t), 7.98 (1H, d), 8.18 (1H, t), 8.32 (1H, d)
626	1H-NMR	(CDCl3, ppm): 1.22 (3H, d), 1.92 (3H, s), 2.30 (3H, s), 2.54 (1H, dd), 2.61 (1H, dd), 4.32 (1H,
		m), 5.46 (2H, s), 6.23 (1H, m), 6.94 (1H, s), 7.0-7.1 (2H, m), 7.45 (1H, m), 7.54 (1H, d), 7.72
		(1H, d), 8.07 (1H, d), 8.38 (1H, bs)
632	1H-NMR	(CDCl3, ppm): 1.26 (3H, dd), 1.96 (3H, s), 2.32 (3H, s), 2.61-2.55 (2H, m), 4.34-4.29 (1H, m),
		5.22 (2H, s), 6.22 (1H, d), 7.21-7.13 (3H, m), 7.36 (1H, d), 7.78 (1H, d), 7.97 (1H, dd), 8.16
		(1H, d), 8.35 (1H, s)
633	1H-NMR	(CDCl3, ppm): 1.23 (3H, dd), 1.97 (3H, s), 2.31 (3H, s), 2.61-2.56 (2H, m), 4.37-4.32 (1H, m),
		5.25 (2H, s), 6.13 (1H, d), 7.11 (2H, dd), 7.37 (1H, t), 7.48 (1H, dd), 7.61-7.53 (1H, m), 7.79
		(1H, dt), 8.15 (1H, d), 8.43 (1H, d)
634	1H-NMR	(CDCl3, ppm): 1.25 (4H, dd), 1.98 (3H, s), 2.33 (3H, s), 2.61-2.56 (2H, m), 8.41 (1H, s),
		4.38-4.31 (1H, m), 5.24 (2H, s), 6.17 (1H, d), 7.13-7.11 (2H, m), 7.38 (1H, s), 7.46 (1H, t), 7.56
		(1H, dd), 7.79 (1H, t), 8.14 (1H, d)
635	1H-NMR	(CDCl3, ppm): 1.26 (3H, dd), 1.94 (3H, s), 2.31 (3H, s), 2.61-2.52 (2H, m), 4.33-4.29 (1H, m),
		524 (2H, s), 6.34 (1H, d), 7.21-7.11 (3H, m), 7.39 (1H, d), 7.75 (1H, d), 7.95 (1H, dd), 8.13
		(1H, d,)8.38 (1H, s)
636	1H-NMR	(CDCl3, ppm): 1.25 (3H, dd), 1.93 (2H, s), 2.31 (3H, s), 2.65-2.52 (2H, m), 4.32-4.29 (1H, m),
		5.26 (2H, s), 6.40 (1H, d), 7.21-7.11 (3H, m), 8.39 (1H, s), 7.42 (1H, s), 7.74 (1H, d), 7.94 (1H,
		d), 8.11 (1H, d)
640	1H-NMR	(CDCl3, ppm): 1.29 (3H, dd), 1.95 (3H, s), 2.32 (3H, s), 2.62-2.54 (2H, m), 4.34-4.27 (1H, m),
		5.31 (2H, s), 6.21 (1H, d), 7.96 (1H, d), 8.19 (1H, t), 7.21-7.13 (3H, m), 7.62 (1H, s), 7.78 (1H,
		d), 8.37 (1H, d)
651	1H-NMR	(CDCl3, ppm): 1.24 (3H, dd), 1.96 (3H, s), 2.31 (3H, s), 2.60-2.55 (2H, m), 4.36-4.31 (1H, m),
		5.31 (2H, s), 6.34 (1H, d), 7.16-7.14 (2H, m), 7.43 (1H, t), 7.53 (1H, dd), 7.64 (1H, s), 7.71
		(1H, d), 8.12 (1H, d), 8.50 (1H, s)
654	1H-NMR	(CDCl3, ppm): 1.26 (3H, dd), 1.93 (3H, s), 2.34 (3H, d), 2.62-2.55 (2H, m), 4.34-4.29 (1H, m),
		5.31 (2H, s), 6.23 (1H, d), 7.24-7.14 (3H, m), 7.63 (1H, s), 7.78 (1H, d), 7.97 (1H, dd), 8.20
		(1H, d), 8.37 (1H, s)
658	1H-NMR	(CDCl3, ppm): 1.44-1.38 (3H, m), 2.35-2.30 (6H, m), 2.90-2.77 (2H, m), 4.56-4.48 (1H, m),
		5.32 (2H, s), 7.18-7.14 (3H, m), 7.44-7.37 (1H, m), 7.56-7.52 (1H, m), 7.67-7.64 (2H, m),
		8.10-8.07 (1H, m), 8.44-8.39 (1H, m)
660	1H-NMR	(CDCl3, ppm): 1.25 (4H, dd), 1.90 (3H, s), 2.31 (3H, s), 2.63-2.55 (2H, m), 4.37-4.28 (1H, m),
		5.34 (2H, s), 6.12 (1H, d), 7.22-7.15 (2H, m), 7.63 (1H, d), 7.83 (1H, t), 7.98 (1H, dt), 8.25
		(1H, t), 8.34 (1H, s)
675	1H-NMR	(CDCl3, ppm): 1.23 (3H, d), 1.97 (3H, s), 2.33 (3H, s), 2.63-2.54 (2H, m), 4.38-4.29 (1H, m),
		5.41 (2H, s), 6.21 (1H, d), 7.09 (2H, d), 7.44 (1H, t), 7.54 (1H, d), 7.73 (1H, d), 7.84 (1H, s),
		8.07 (1H, d), 8.38 (1H, s)
681	1H-NMR	(CDCl3, ppm): 1.25 (3H, d), 1.95 (3H, s), 2.32 (3H, s), 2.62-2.54 (2H, m), 4.36-4.32 (1H, m),
		5.52 (2H, s), 6.13 (1H, d), 7.18-7.16 (2H, m), 7.57-7.47 (2H, m), 7.76 (1H, d), 8.17 (1H, d),
		8.41 (1H, s)
714	1H-NMR	(CDCl3, ppm): 1.24 (3H, d), 1.99 (3H, s), 2.30 (3H, s), 2.64-2.52 (2H, m), 4.38-4.29 (1H, m),
		5.49 (2H, s), 6.15 (1H, d), 7.17-7.15 (2H, m), 7.57-7.43 (2H, m), 7.75 (1H, d), 8.17 (1H, d),
		8.41 (1H, s)
726	1H-NMR	(CDCl3, ppm): 1.45-1.37 (3H, m), 2.32-2.30 (6H, m), 2.87-2.83 (2H, m), 4.61-4.46 (1H, m),
		5.44 (2H, s), 6.90-6.88 (1H, m), 7.12-7.09 (2H, m), 7.45-7.42 (1H, m), 7.55-7.52 (1H, m),
		7.68-7.66 (1H, m), 7.79-7.77 (1H, m), 8.06-8.04 (1H, m), 8.32-8.24 (1H, m)
727	1H-NMR	(CDCl3, ppm): 1.44 (3H, d), 2.30 (3H, s), 2.75 (3H, s), 3.24-3.21 (2H, m), 4.62-4.53 (1H, m),
		5.44 (2H, s), 6.87-6.85 (1H, m), 7.08-7.06 (2H, m), 7.42-7.32 (1H, m), 7.50-7.47 (1H, m),
		7.60-7.57 (1H, m), 7.77 (1H, s), 7.91-7.87 (1H, m), 8.17-8.14 (1H, m)
729	1H-NMR	(CDCl3, ppm): 1.45 (3H, d), 2.29 (3H, s), 2.75 (3H, s), 3.34-3.12 (2H, m), 4.59-4.54 (1H, m),
		5.38 (2H, s), 6.86 (1H, d), 7.09-7.06 (2H, m), 7.43-7.33 (1H, m), 7.52-7.46 (1H, m), 7.59 (1H,
		d), 7.84 (1H, s), 7.90 (1H, d), 8.15 (1H, s)
730	1H-NMR	(CDCl3, ppm): 1.23 (3H, d), 1.96 (3H, s), 2.29 (3H, s), 2.5-2.7 (2H, m), 4.31 (1H, m), 5.34
		(2H, s), 6.31 (1H, d), 6.4-7.2 (5H, s), 7.4-7.8 (3H, m), 8.06 (1H, d), 8.41 (1H, bs)
741	1H-NMR	(CDCl3, ppm): 1.26 (3H, d), 1.95 (3H, s), 2.18 (3H, s), 2.30 (3H, s), 2.66-2.48 (2H, m),
		4.39-4.20 (1H, m), 5.31 (2H, s), 6.25 (1H, d), 7.07-7.01 (2H, m), 7.44-7.41 (2H, m), 7.55-7.51
		(2H, m), 7.71 (1H, d), 8.01 (1H, d), 8.32 (1H, s)
778	1H-NMR	(CDCl3, ppm): 1.31 (3H, d), 1.95 (3H, s), 2.33 (3H, t), 2.61-2.56 (2H, m), 4.40-4.29 (1H, m),
		5.28 (2H, s), 6.50-6.11 (2H, m), 7.15-7.12 (2H, m), 7.45-7.42 (1H, m), 7.55-7.52 (1H, m), 7.64
		(1H, s), 7.72 (1H, d), 8.12 (1H, d), 8.50 (1H, s)
799	1H-NMR	(CDCl3, ppm): 1.23 (3H, d), 1.93 (3H, s), 2.32 (3H, s), 2.56 (2H, m), 4.22 (1H, m), 5.52 (2H,
		s), 6.55-6.02 (3H, m), 7.21 (2H, m), 7.57-7.43 (2H, m), 7.76 (1H, d), 8.15 (1H, d), 8.39 (1H, s)
	1H-NMR	(CDCl3, ppm): 1.24 (3H, d), 1.94 (3H, s), 2.28 (3H, s), 2.52 (1H, dd), 2.62 (1H, dd), 4.30 (1H,
		m), 5.38 (2H, s), 6.4-7.2 (7H, m), 7.72 (1H, d), 7.93 (1H, d), 8.06 (1H, d), 8.41 (1H, bs)
	1H-NMR	(CDCl3, ppm): 1.40 (6H, s), 1.93 (3H, s), 2.77 (2H, s), 5.40 (2H, s), 5.93 (1H, bs), 6.87-7.23
		(4H, m), 7.63-7.95 (2H, m), 8.35-8.65 (2H, m)

Synthesis Example 6

Starting material

3-Methyl-4-nitrobenzyl chloride (1.81 g), 3,5-bis(trifluoromethyl)-1H-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 chromatography to obtain 1-(3-methyl-4-nitrobenzyl)-3,5-bis-(trifluoromethyl)-1H-pyrazole (3.3 g).

¹H-NMR (CDCl₃, 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

To a mixture of 1-(3-methyl-4-nitrobenzyl)-3,5-bis(trifluoromethyl)-1H-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 1-(3-methyl-aminobenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole (1.19 g).

¹H-NMR (CDCl₃, 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

1-(3-Methyl-4-nitrobenzyl)-3,5-bis(trifluoromethyl)-1H-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, 1N aqueous solution of sodium hydrate (200 ml) and ethyl acetate (200 ml) were added. The organic layer was separated, washed with water, and then, dried with anhydrous magnesium sulfate. After distilling off the solvent, 1-(3-methyl-4-aminobenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole (13.0 g), which was the same as that obtained in Synthesis Example 7, was obtained.

Synthesis Example 9

Starting Material

3-Fluorophthalic anhydride (4.98 g) and 1-(3-methyl-4-aminobenzyl)-3,5-bis(trifluoromethyl)-1H-pyrazole (9.70 g) were refluxed in acetic acid (43 ml) for 3 hours. After finishing the reaction, the acetic acid was distilled off wader 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)-1H-pyrazol-1-ylmethyl]-2-methylphenyl}-4-fluoroisoindol-1,3-dione (10.80 g). mp. 158-159° C.

Synthesis Example 10

Starting Material

3-Methyl-4-nitrobenzyl chloride (0.56 g), 5-(difluoromethyl)-1,2-dihydro-2-methyl-3H-1,2,4-(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-difluoromethyl-2-methyl-4-(3-methyl-4-nitrobenzyl)-2,4-dihydro-[1,2,4]triazol-3-one (0.45 g).

¹H-NMR (CDCl₃, ppm): 2.5 (3H, s), 3.5 (3H, s), 4.9 (2H, s), 6.4 (1H, t), 72-7.3 (2H, m), 7.8-7.9 (1H, m).

Synthesis Example 11

Starting Material

3-Methyl-nitrobenzyl chloride (0.43 g), 3-heptafluoropropylsulfanyl-5-trifluoromethyl-1H-(1,2,4)-triazole (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-hepta fluoropropylsulfanyl-1-(3-methyl-4-nitrobenzyl)-5-trifluoromethyl-1H-(1,2,4)-triazole (0.30 g).

¹H-NMR (CDCl₃, ppm): 2.64 (3H, s), 5.62 (2H, s), 7.31-7.25 (2H, m), 8.05-7.86 (1H, m)

Synthesis Example 12

Starting Material

To a mixture of 3-heptafluoropropylsulfanyl-1-(3-methyl-4-nitrophenyl)-5-trifluoromethyl-1H-(1,2,4)-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 obtain 4-(3-heptafluoropropylsulfanyl-5-trifluoromethyl-[1,2,4]triazol-1-ylmethyl)-2-methyl-phenylamine (0.28 g)

¹H-NMR (CDCl₃, ppm): 2.17 (3H, s), 4.16 (1H, brs), 5.40 (2H, s), 6.63-6.59 (2H, m), 7.13-6.99 (1H, m).

Synthesis Example 13

Starting Material

An acetonitrile solution (30 ml) of 3-trifluoromethyl-1H-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 the reduced pressure to obtain 4-iodo-3-trifluoromethyl-1H-pyrazole (93 g).

¹H-NMR (CDCl₃, ppm): 7.77 (1H, s).

Synthesis Example 14

Starting Material

3-Methyl-4-nitrobenzyl chloride (0.77 g), 4-iodo-3-trifluoromethyl-1H-pyrazole (0.99 g) and potassium 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 under the reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 4-iodo-1-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-1H-pyrazole (1.0 g).

¹H-NMR (CDCl₃, 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-1-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-1H-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 1-(3-methyl-4-nitrobenzyl)-4-pentafluoroethyl-3-trifluoromethyl-1H-pyrazole (1.39 g)

¹H-NMR (CDCl₃, 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-1H-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-1-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl-1H-pyrazole (4.60 g).

¹H-NMR (CDCl₃, 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-1-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl-1H-pyrazole (1.84 g), (trifluoromethyl)trimethylsilane (1.14 g), copper(I) iodide (1.52 g), potassium fluoride (0.28 g) 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. The 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 column chromatography to obtain 1-(3-methyl-4-nitro-benzyl)-3-pentafluoroethyl-4-trifluoromethyl-1H-pyrazole (0.32 g).

¹H-NMR (CDCl₃, ppm): 2.61 (3H, s), 5.41 (2H, s), 7.31-7.18 (2H, m), 7.78 (1H, s), 8.00 (1H, d).

Synthesis Example 18

Starting Material

4-Iodo-1-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-1H-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 1-(3-methyl-4-nitrobenzyl)-4-pentafluoropropyl-3-trifluoromethyl-1H-pyrazole (0.80 g).

¹H-NMR (CDCl₃, 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-1-(3-methyl-4-nitrobenzyl)-3-trifluoromethyl-1H-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 1-(3-methyl-4-nitrobenzyl)-4-nonafluorobutyl-3-trifluoromethyl-1H-pyrazole (1.50 g).

¹H-NMR (CDCl₃, ppm): 2.62 (3H, s), 5.42 (2H, s), 7.18-7.24 (2H, m), 7.74 (1H, s), 8.00 (1H, d).

Synthesis Example 20

Starting Material

An acetonitrile solution (20 ml) of 3-trifluoromethyl-1H-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-1H-pyrazole (1.6 g).

¹H-NMR (CDCl₃, ppm): 7.73 (1H, s), 12.86 (1H, brs).

Synthesis Example 21

Starting Material

3-Methyl-4-nitrobenzyl chloride (0.77 g), 4-bromo-3-trifluoromethyl-1H-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 1-(3-methyl-4-nitrobenzyl)-4-bromo-3-trifluoromethyl-1H-pyrazole (0.9 g).

¹H-NMR (CDCl₃, 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-1H-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-chloro-3-trifluoromethyl-1H-pyrazole (0.9 g).

¹H-NMR (CDCl₃, ppm): 7.80 (1H, s).

Synthesis Example 23

Starting Material

3-Methyl-4-nitrobenzyl chloride (0.82 g), 4-chloro-3-trifluoromethyl-1H-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 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 1-(3-methyl-4-nitrobenzyl)-4-chloro-3-trifluoromethyl-1H-pyrazole (0.98 g).

¹H-NMR (CDCl₃, ppm): 2.62 (3H, s), 5.33 (2H, s), 7.21-7.19 (2H, m), 7.46 (1H, s), 7.98 (1H, d).

Synthesis Example 24

Starting Material

2-(Trifluoroacetyl)-1H-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 mutes. 3-Methyl-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 1-(3-methyl-4-nitrobenzyl)-2-(trifluoroacetyl)-1H pyrrole (1.53 g).

¹H-NMR (CDCl₃, 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 (1H, m), 7.93 (1H, d).

Synthesis Example 25

Starting Material

An acetonitrile solution (20 ml) of 2-(trifluoroacetyl)-1H pyrrole (0.5 g), dicerium ammonium nitrate (0.84 g) and iodine (0.47 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-iodo-2-(trifluoroacetyl)-1H pyrrole (0.6 g).

¹H-NMR (CDCl₃, ppm): 7.28-7.35 (2H, m), 9.52 (1H, brs).

Synthesis Example 26

Starting Material

3-Methyl-4-nitrobenzyl chloride (0.63 g), 4-iodo-2-(trifluoroacetyl)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-1-(3-methyl-4-nitrobenzyl)-2-trifluoroacetyl-1H-pyrrole (0.45 g).

¹H-NMR (CDCl₃, 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 (1H, d).

Synthesis Example 27

Starting Material

4-Iodo-1-(3-methyl-4-nitrobenzyl)-2-trifluoroacetyl-1H-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 1-(3-methyl-4-nitrophenyl)-4-pentafluoroethyl-1H-pyrrole (1.35 g).

¹H-NMR (CDCl₃, 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-nitro-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 1N 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 4,4,4-trifluoro-2-(3-methyl-4-nitro-benzyl)-3-oxo-butyrate (6.3 g). n_D²⁰ 1.4970

Synthesis Example 29

Starting Material

Ethyl 4,4,4-trifluoro-2-(3-methyl-4-nitro benzyl)-3-oxo-butyrate (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 1N 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).

¹H-NMR (DMSO-d₆, 90 MHz): δ2.2 (3H, s), 3.8 (2H, s), 7.0 (1H, d, J=5.5 Hz), 7.2 (1H, s), 7.8 (1H, d, J=5.5 Hz), 11.2 (1H, brs).

Synthesis Example 30

Starting Material

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-1-difluoromethyl-4-(3-methyl-4-nitro-benzyl)-3-trifluoromethyl-1H-pyrazole (IX-1) (0.5 g) and 3-difluoromethoxy-1-difluoromethyl-4-(3-methyl-4-nitro-benzyl)-5-trifluoromethyl-1H-pyrazole (IX-2) (0.4 g) respectively.

(IX-1): n_D²⁰ 1.4780, (IX-2): n_D²⁰ 1.4855.

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 1-(3-methyl-4-nitrophenyl)-3,5-bis(trifluoromethyl)-1H-pyrazole (5.6 g). n_D²⁰ 1.4890.

Synthesis Example 32

Starting Material

(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 1-(3-methyl-4-nitro-phenyl)-3-pentafluoroethyl-5-trifluoromethyl-1H-pyrazole (IX-3) (3.0 g) and 2-(3-methyl-nitro-phenyl)-5-pentafluoroethyl-3-trifluoromethyl-3,4-dihydro-2H-pyrazol-3-ol (IX-4) (0.5 g), respectively.

(IX-3): n_D²⁰ 1.4690,

(IX-4): ¹H-NMR (CDCl₃, 90 MHz): δ2.6 (3H, s), 3.3 (1H, br d, J=16 Hz), 3.7 (1H, br d, J=16 Hz), 4.1 (1H, s), 7.2 (2H, m), 7.8 (1H, d, J=7.8 Hz).

Synthesis Example 33

Starting Material

To a THF suspension of 1-(3-methyl-4-nitro-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 pressure. The residue was suspended in ethyl acetate and washed with 1N 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-1-(3-methyl-4-nitro-phenyl)-butane-1,3-dione (2.5 g).

¹H NMR (CDCl₃, 90 MHz): δ2.6 (3H, s), 6.5 (1H, s), 7.7-8.1 (3H, m).

Synthesis Example 34

Starting Material

A toluene solution of 4,4,4-trifluoro-1-(3-methyl-4-nitro-phenyl)-butane-1,3-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-methyl-4-nitro-phenyl)-1-(2,2,2-trifluoro-ethyl)-5-trifluoro-methyl-1H-pyrazole (IX-5) (1.1 g) and 5-(3-methyl-4-nitro phenyl)-1-(2,2,2-trifluoro-ethyl)-3-trifluoromethyl-1H-pyrazole (IX-6) (0.5 g), respectively.

(IX-5) mp; 98-104° C., (IX-6) mp; 50-53° C.

Synthesis Example 35

Starting Material

To a dichloromethane solution of 2,2-dimethyl-1,3-dioxane-4,6-dione (10 g) and dimethylaminopyridine (17 g), a dichloromethane solution of 3-methyl-4-nitro-benzoyl 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 1N 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.

Synthesis Example 36

Starting Material

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-nitro-phenyl)-2,4-dihydro-pyrazol-3-one (2.6 g). mp; 218-219° C.

Synthesis Example 37

Starting Material

To a DMF suspension of 5-(3-methyl-4-nitro-phenyl)-2,4-dihydro-1H-pyrazol-3-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-difluoromethoxy-1-difluoromethyl-3-(3-methyl-4-nitro-phenyl)-1H-pyrazole (IX-7) (0.7 g) and 3-difluoromethoxy-1-difluoromethyl-5-(3-methyl-4-nitro-phenyl)-1H-pyrazole (IX-8) (0.5 g), respectively.

(IX-7) rap; 80-82° C., (IX-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 refluxing it, 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.

¹H-NMR (CDCl₃, 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).

Synthesis Example 39

Starting Material

(3-Methyl-4-nitrobenzyl)-hydrazine (1.81 g) and 5-ethoxy-1,1,1,2,2-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 1-(3-methyl-4-nitrobenzyl)-5-pentafluoroethyl-1H-pyrazole (0.96 g) as the first elution portion and 1-(3-methyl-4-nitrobenzyl)-3-pentafluoroethyl-1H-pyrazole (0.50 g) as the second elution portion.

(IX-9): ¹H-NMR (CDCl₃, ppm): 2.61 (3H, s), 5.49 (2H, s), 6.70 (1H, bs), 7.05-7.15 (2H, m), 7.66 (1H, bs), 7.94 (1H, d).

(IX-10): ¹H-NMR (CDCl₃, ppm): 2.64 (3H, s), 5.40 (2H, s), 6.63 (1H, d), 7.07-7.20 (2H, m), 7.52 (1H, d), 7.95 (1H, d).

Synthesis Example 40

Starting Material

A mixture of 5-fluoro-2-nitrotoluene (2.33 g), 4-iodo-1H-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-1-(3-methyl-4-nitrophenyl)-1H-pyrazole (4.60 g) was obtained.

¹H-NMR (CDCl₃, ppm): 2.70 (3H, s), 7.50-7.70 (3H, m), 7.95-8.15 (2H, m).

Synthesis Example 41

Starting Material

4-Iodo-1-(3-methyl-4-nitrophenyl)-1H-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 acetate. 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 1-(3-methyl-4-nitrophenyl)-4-pentafluoroethyl-1H-pyrazole (0.72 g).

¹H-NMR (CDCl₃, 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 1-(3-methyl-4-nitrophenyl)-ethanol (23.33 g) was obtained.

¹H-NMR (CDCl₃, 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

Into a THF solution (35 ml) of 1-(3-methyl-4-nitrophenyl)-ethanol (5.44 g) and triethylamine (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 1-(3-methyl-4-nitrophenyl)-ethyl methanesulfonate (5.80 g) was obtained.

¹H-NMR (CDCl₃, 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).

Synthesis Example 44

Starting Material

1-(3-Methyl-4-nitrophenyl)-ethyl methanesulfonate (2.59 g), 3-trifluoromethyl-1H-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 1-[1-(3-methyl-4-nitrophenyl)-ethyl]-3-trifluoromethyl-1H-pyrazole (1.60 g).

¹H-NMR (CDCl₃, 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 (1H, bs), 8.00 (1H, d).

Synthesis Example 45

Starting Material

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-1H-(1,2,4)-triazole (7.9 g).

Synthesis Example 46

Starting Material

1-(3-Methyl-4-nitrophenyl)-ethyl methanesulfonate (2.5 g), 3-pentafluoroethyl-5-trifluoromethyl-1H-(1,2,4)-triazole (2.2 g), potassium carbonate (1.6 g) and 18-crown-6 (0.26 g) were refluxed in acetonitrile (100 mil) 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 solvent of n-hexane and ethyl acetate) to obtain (IX-11) 1-([1-(3-methyl-4-nitro phenyl)-ethyl]-5-pentafluoroethyl-3-trifluoromethyl-1H-(1,2,4)-triazole (0.95 g) as the first elution portion and (IX-12) 1-([1-(3-methyl-4-nitro-phenyl)-ethyl]-3-pentafluoroethyl-5-trifluoromethyl-1H-(1,2,4)-triazole (1.35 g) as the second elution portion.

(IX-11)

¹H-NMR (CDCl₃) δ: 8.03-7.97 (1H, m), 7.37 (2H, t, J=5.4 Hz), 5.86 (1H, q, J=7.0 Hz), 2.62 (3H, s), 2.00 (3H, d, J=7.0 Hz).

(IX-12)

¹H-NMR (CDCl₃) δ: 7.98 (1H, d; J=8.2 Hz), 7.34 (2H, t, J=7.1 Hz), 5.81 (1H, q, J=7.0 Hz), 2.63 (3H, s), 2.01 (3H, d, J=7.0 Hz).

Synthesis Example 47

Starting Material

Sodium hydride (0.10 g) was added to a DMF solution (12 ml) of 4-methyl-5-pentafluoroethyl-4H-[1,2,4]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-4-nitrophenyl sulfanyl)-5-pentafluoroethyl-4H-(1,2,4)-triazole (0.55 g).

¹H-NMR (CDCl₃, ppm): 2.70 (3H, s), 3.80 (3H, s), 8.10-8.30 (3H, m).

Synthesis Example 48

Starting Material

A mixture of 2-methylmelcapto-4.6-bistrifluoromethyl-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-bistrifluoromethyl-pyrimidine (7.5 g).

¹H-NMR (CDCl₃, ppm): 3.48 (3H, s), 8.19 (1H, s).

Synthesis Example 49

Starting Material

4-Nitro-m-cresol (0.77 g), 2-methanesulfonyl-4,6-bistrifluoromethyl-pyrimidine (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).

¹H-NMR (CDCl₃, ppm): 2.60 (3H, s), 7.1-7.3 (2H, m), 7.67 (1H, s), 8.10 (1H, d).

Synthesis Example 50

Starting Material

(3-Methyl-4-nitrophenyl)-acetonitrile (3.52 g) 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).

¹H-NMR (CDCl₃, ppm): 2.60 (3H, s), 4.06 (2H, s), 6.40-8.00 (5H, m)

Synthesis Example 51

Starting Material

2-(3-Methyl-4-nitrophenyl)-thioacetamide (1.00 g), 1-bromo-3,3,4,4,4-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 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 2-(3-Methyl-4-nitro-phenyl)-thioacetimidic acid 3,3,4,4,4-pentafluoro-2-oxo-butyl ester (1.30 g).

¹H-NMR (CDCl₃, ppm): 2.55 (3H, s), 3.57 (2H, dd), 3.90 (2H, d), 7.24-7.22 (2H, m), 7.91-7.89 (1H, m)

Synthesis Example 52

Starting Material

Trifluoroacetic anhydride (1.47 g) was added to 2-(3-Methyl-4-nitro-phenyl)-thioacetimidic acid 3,3,4,4,4-pentafluoro ester (130 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-methyl-4-nitro-benzyl)-4-perfluoroethyl-thiazole (0.70 g).

¹H-NMR (CDCl₃, 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

Starting Material

An acetonitrile solution (20 ml) of 3-pentafluoroethyl-1H-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 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-3-pentafluoroethyl-1H-pyrazole (32 g).

¹H-NMR (CDCl₃, ppm): 7.77 (1H, s), 11.11 (1H, m)

Synthesis Example 54

Starting Material

4-Iodo-3-pentafluoroethyl-1H-pyrazole (6.24 g), copper powder (3.81 g), Iodo-1,1,2,2-tetrafluoroethane (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 with 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-(1,1,2,2-tetrafluoroethyl)-1H-pyrazole (0.60 g), bp. 125-135° C./20 mbar.

¹H-NMR (CDCl₃, ppm): 5.98 (1H, tt), 7.96 (1H, s), 12.22 (1H, m)

Synthesis Example 55

Starting Material

4-Iodo-3-pentafluoroethyl-1H-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 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 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-1H-pyrazole (1.20 g), bp. 110-115° C./20 mbar.

¹H-NMR (CDCl₃, ppm): 7.99 (1H, s), 12.31 (1H, m).

Synthesis Example 56

Starting Material

An acetonitrile solution (20 ml) of 4-methyl-1H-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-1H-pyrazole (1.2 g).

¹H-NMR (CDCl₃, ppm): 2.03 (3H, s), 6.96 (1H, br s)

Synthesis Example 57

Starting Material

5-Trifluoromethyl-1H-(1,2,4)-triazole-3-thiol (1.0 g), 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; the 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-heptafluoropropylsulfanyl-5-trifluoromethyl-1H-(1,2,4)-triazole (0.70 g).

USE 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 of Spodoptera 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 Cnaphalocrocis medinalis Guenee

Test Method:

Paddy rice (variety: Tamanishiki) planted in a pot was treated by spraying 50 ml 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 Cnaphalocrocis 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 ⅓ 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 Biological Test Examples 1 and 2, as specific examples, the compounds of the 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, 262, 264, 268, 270, 281, 299, 308, 310, 318, 322, 413, 414, 417, 422, 434, 446, 448, 473, 475, 492, 506, 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 Myzus 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

Granule

To a mixture of 10 parts of the compound of the present invention (No. 8), 30 parts of bentonite (montmorillonite), 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.

Formulation Example 3

Emulsifiable Concentrate

30 Parts of the compound of the present invention (No. 12), 55 parts of xylene, 8 parts of polyoxyethylene alkyl 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-formalin-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, 15 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.

Claims

1-3. (canceled)

4. A process for the preparation of a compound of formula (I),

wherein

X represents hydrogen, halogen, nitro, C1-6alkylsulfonyloxy, C1-6alkylsulfinyl, C1-6alkylsulfenyl or C1-6alkylsulfonyl,

R1 represents C1-6alkyl, C1-6alkylthio-C1-6alkyl, C1-6alkylsulfinyl-C1-6alkyl or C1-6alkylsulfonyl-C1-6alkyl,

Y represents halogen or C1-6alkyl,

m represents 0 or 1,

A represents O, S, SO, SO2, CH2 or CH(CH3), and

Q represents a 5-membered 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;

comprising (a) reacting a compound of formula (II)

wherein R1 and X have the same definition as above, with a compound of formula (III)

wherein Y, A, m and Q have the same definition as above, in the presence of an inert solvent, and optionally in the presence of an acid catalyst, or (b) reacting a compound of formula (IV)

wherein X, Y, A, m and Q have the same definitions as above with a compound of formula (V) H2N—R1  (V) wherein R1 has the same definition as above, in the presence of an inert solvent, and optionally in the presence of an acid catalyst, or (c) reacting a compound of formula (VI)

wherein X and R1 have the same definitions as above, with a compound of formula (III),

wherein Y, A, m and Q have the same definition as above, in the presence of an inert solvent, and optionally in the presence of an acid catalyst, or (d) reacting a compound of formula (VII)

wherein X, Y, A, m and Q have the same definitions as above, with a compound of formula (V), H2N—R1  (V) wherein R1 has the same definitions as above, in the presence of an inert solvent, and optionally in the presence of an acid catalyst, or (e) reacting a compound of formula (VIII)

wherein X, Y, A, m and Q have the same definitions as above, with a compound of formula (V), H2N—R1  (V) wherein R1 has the same definitions as above, in the presence of an inert solvent, and optionally in the presence of an acid catalyst, or (f) in case where R1 represents C1-6alkylsulfinyl-C1-6alkyl or C1-6alkylsulfonyl-C1-6alkyl in formula (I): reacting a compound of formula (If)

wherein RIf represents C1-6alkylthio-C1-6alkyl, and X, Y, A, m and Q have the same definitions as above, with an oxidizing agent in the presence of an inert solvent.

5-9. (canceled)

10. A compound of formula (VII)

wherein

X represents hydrogen, halogen, nitro, C1-6alkylsulfonyloxy, C1-6alkylsulfinyl, C1-6alkylsulfenyl or C1-6alkylsulfonyl,

Y represents halogen or C1-6alkyl,

A represents O, S, SO, SO2, CH2 or CH(CH3),

m represents 0 or 1, and

Q represents a 5-membered 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.

11. (canceled)

12. A compound of formula (IX)

wherein

X represents hydrogen, halogen, nitro, C1-6alkylsulfonyloxy, C1-6alkylsulfinyl, C1-6alkylsulfenyl or C1-6alkylsulfonyl,

Y represents halogen or C1-6alkyl,

A represents O, S, SO, SO2, CH2 or CH(CH3),

m represents 0 or 1, and

Q represents a 5-membered 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.