MXPA98010849A - Pesticidal 3-(substituted phenyl)-5-(thienyl or furyl)-1,2,4-triazoles - Google Patents

Abstract

3-(Substituted phenyl)-5-(thienyl or furyl)-1,2,4-triazole compounds are useful as insecticides and acaricides. New synthetic procedures and intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects and mites using the compounds are also provided.

Description

3-.PHENYL SUBSTITUTED.-5-.TIENIL OR FURID-1.2.4-TRIAZOLES PESTICIDES RELATED REQUESTS This application claims the priority of the U.S. Patent Applications. Series No. 60 / 044,697, filed on April 24, 1997 and Series No. 60 / 066,135, filed on November 19, 1997.

FIELD OF THE INVENTION This invention relates to new compounds that are useful as insecticides and acaricides, novel synthetic and intermediate procedures for preparing the compounds, pesticidal compositions containing the compounds, and methods for the control of insects and mites.

BACKGROUND OF THE INVENTION There is an acute need for new insecticides and acaricides. Insects and mites are developing resistance to current use insecticides. At least 400 species of arthropods are resistant to one or more insecticides. The development of resistance to some of the old insecticides, such as DDT, carbamates and organophosphates, is well known. But resistance has developed to some of the newer pyrethroid insecticides and acaricides. Therefore, there is a need for new insecticides and acaricides, and particularly, for compounds that have new or atypical modes of action. A number of derivatives of 3,5-diphenyl-H-1, 2,4-triazole having acaricidal activity have been described in the literature. E.U.A. 5,482,951; JP 8092224, EP 572142, JP 08283261. However, for the applicants none of these compounds has been converted into a commercial product. The nitro furanyl triazoles have been described by L.E. Benjamín and H.R. Snyder as antimicrobials (J. Heterocyclic Chem. 1976, 13, 1115) and by others as antibacterials (J. Med. Chem. 1973, 16 (4), 312-319; J. Med. Chem. 1974, 17 (7) , 756-758). The present invention provides novel compounds with commercial level activity against mites and insects.

COMPENDIUM OF THE INVENTION This invention provides novel derivatives of substituted thienyl and furanyl triazole useful for the control of insects and mites. More specifically, the invention provides novel insecticidally active compounds of the formula (1): wherein: Ar is substituted phenyl; Y is "S" R2 is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl or alkoxyalkyl; R3 is selected from H, halogen, lower alkyl, straight or branched chain alkyl (C7-C21), hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, lower alkynyl, haloalkenyl, CN, NO2, COR6, CO2R6, CON (R6) 2, cycloalkyl (C3-C6), S (O) mR6, -OSOmR6, SCN, - ( CH2) nR6, -CH = CHR6, -C = CR6, - (CH2) qOR6, - (CH2) qSR6, - (CH2) qNR6R6, -O (CH2) qR6, -S (CH2) qR8, -NR6 (CH2) ) qR6, 0 (CH2) aR6, -S (CH2) gR6, -NR6 (CH2) -R6, - > , OR ° O or N O - R ° A. • NR ° A O.R ° • NRb,?. N (Rb) R ° - R6, or O-S A. R -Si (R7) 3, pyridyl, substituted pyridyl, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, thienyl, substituted thienyl, substituted pyrimidyl, substituted pyrimidyl, pyrazolyl or substituted pyrazolyl; R4 and R5 are independently H, halogen, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON (R6) 2, or S (O) m alkyl, or Si R4 and R5 are bonded to adjacent carbon atoms, they join to form a saturated or unsaturated carbocyclic ring of 5 or 6 members, which can be substituted by 1 or 2 halogen, lower alkyl, lower alkoxy or haloalkyl groups; R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl or substituted phenyl; R7 is lower alkyl; m is 0, 1, or 2; n is 1 or 2; p is an integer from 2 to 6; and q is 0 or 1; or a pharmaceutically acceptable acid addition salt thereof. A preferred group of compounds is that of the formula (1A): < 1A > wherein: R1 and R1 'are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy; And it's O u S; R2 is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl or alkoxyalkyl; R3 is selected from H, halogen, lower alkyl, straight or branched chain alkyl (C7-C21), hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, lower alkynyl, haloalkenyl, CN, NO2, COR6, CO2R6, CON (R6) 2, (C3-C6) cycloalkyl, S (O) mR6, SCN, pyridyl, substituted pyridyl, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, - (CH2) nR6, - CH = CHR6, -C = CR6, -CH2OR6, -CH2SR6, SCH2Rβ, -NR6CH2R6, O O R A ORß -NR ° A * .N (Rß) R4 and R5 are independently H, halogen, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON (R6) 2, or S (O) m alkyl, or R4 and R5 form a saturated or unsaturated carbocyclic ring of 5; or 6 members, which can be substituted by 1 or 2 halogen, lower alkyl, lower alkoxy or haloalkyl groups; R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl or substituted phenyl; m is 0, 1, or 2; and n is 1 or 2; p is an integer from 2 to 6; and or a pharmaceutically acceptable acid addition salt thereof. Preferred compounds of the formula (1A) include the following classes: a) compounds of the formula (1A), wherein R1 is F; b) compounds of the formula (1A), wherein Y is sulfur; c) compounds of the formula (1A), and particularly compounds of the above classes a) and b), wherein R1 and R1 are independently Cl or F; d) compounds of the formula (1A), and particularly compounds of the above classes a) to c), wherein R1 and R1 both are F; e) compounds of the formula (1A), and particularly compounds of the above classes a) to c), wherein R1 and R1 are both Cl; f) compounds of the formula (1A), and particularly compounds of the above classes a) to c), wherein R1 is Cl and R1 is F; g) compounds of the formula (1A), and particularly compounds of one of the above classes a) to f), wherein R2 is methyl; h) compounds of the formula (1A), and particularly compounds of one of the above classes a) to g), wherein R3, R4 and R5 are independently selected from H, halogen, methyl and methoxy; i) compounds of the formula (1A), and particularly compounds of one of the above classes a) to g), wherein R3, R4 and R5 are independently H or halogen; j) compounds of the formula (1A), and particularly compounds of one of the above classes a) to g), wherein R3, R4 and R5 are independently H, Cl or Br; k) compounds of the formula (1A), and particularly compounds of one of the above classes a) to g), wherein R3, R4 and R5 are each halogen; I) compounds of the formula (1A), and particularly compounds of one of the above classes a) to g), wherein R3, R4 and R5 are each chloro. A particularly preferred class of compounds includes those of the formula (1B): wherein: R1 and R1 are independently F or Cl; R2 is lower alkyl, methyl being the most preferred; and R3, R4 and R5 are independently H, Cl, or Br. The invention also provides novel methods and intermediates for preparing compounds of the formula (1) as well as compositions and methods of use, which will be described in detail below.

DETAILED DESCRIPTION OF THE INVENTION Throughout this document, all temperatures are given in degrees Celsius, and all percentages are percentages by weight, unless otherwise indicated. The term "lower alkyl" refers to groups of straight hydrocarbon chains of 1 to 6 carbon atoms and branched and cyclic hydrocarbons of 3 to 6 carbon atoms. The terms "lower alkenyl" and "lower alkynyl" refer to straight hydrocarbon chain groups of 2 to 6 carbon atoms and branched hydrocarbon chains of 3 to 6 carbon atoms containing at least one double or triple bond, respectively. The term "lower alkoxy" refers to O-lower alkyl. The terms "halomethyl" and "haloalkyl" refer to methoxy and lower alkyl groups substituted with one or more halogen atoms.

The terms "halomethoxy" and "haloalkoxy" refer to methyl and lower alkoxy groups substituted with one or more halogen atoms. The term "alkoxyalkyl" refers to a lower alkyl group substituted with a lower alkoxy group. The terms "substituted naphthyl", "substituted thienyl", "substituted pyrimidyl", substituted pyrazolyl ", substituted pyridyl" and substituted isoxazolyl "refer to the ring system substituted with one or more groups independently selected from the group consisting of haloalkyl of 1 to 4 carbon atoms, CN, NO2, alkyl of 1 to 4 carbon atoms, branched alkyl of 3 to 4 carbon atoms, phenyl, alkoxy of 1 to 4 carbon atoms, or haloalkoxy of 1 to 4 carbon atoms. The term "substituted phenyl" refers to a phenyl group substituted with one or more groups independently selected from halogen alkyl of 1 to 10 carbon atoms, branched alkyl of 3 to 6 carbon atoms, haloalkyl of 1 to 7 carbon atoms, hydroxyalkyl of 1 to 7 carbon atoms, alkoxy of 1 to 7 carbon atoms, haloalkoxy of 1 to 7 carbon atoms, phenoxy, phenyl, NO2, OH, CN, alkanoyl of 1 to 4 carbon atoms, benzoyl, alkanoyloxy 1 to 4 carbon atoms, alkoxycarbonyl of 1 to 4 carbon atoms, phenoxycarbonyl or benzoyloxy. The term "substituted benzenesulfonyl" refers to p-chlorobenzenesulfonyl or p-toluenesulfonyl. Unless otherwise stated, when it is established that a group can be substituted with one or more substituents selected from an identified class, it is intended that the substituents can be independently selected from the class.

SYNTHESIS The compounds of the formula (1) can be prepared by methods described in the U.S. Patents. Nos. 5,380,944 and 5,284,860 (Production Methods 1, 2 and 3). The additional methods will be described here below. For example, the compounds of the formula (1), wherein R1 is F, can be prepared according to the following Reaction Scheme I: SCHEME I wherein Ar, R2, R3, R4, R5 and Y are as defined in formula (1), and W is a conventional amino protecting group. Examples of conventional amino protecting groups include, but are not limited to, the carbobenzyloxy group, tertiary alkoxycarbonyl groups, amides, phosphinyl and phosphoryl groups, and sulfenyl and suifonyl groups. As illustrated in Scheme I, an N-protected amidrazone (2) was reacted with a compound of the formula (3) in the presence of an acid or base as a catalyst. Intermediates of formulas (2) and (3) can be obtained through the application of well-known procedures. An example of an intermediate of the formula (3) is 3,4,5-trichlorothiophen-2-carboxylic acid chloride. The carboxylic acid can be obtained through the treatment of tetrachlorothiophene with n-butyl lithium and subsequent extinction with carbon chloride as in J. Organometal. 1968, 13, 419-430. The conversion of the carboxylic acid to the acid chloride is carried out by conventional methods, as illustrated hereinafter in Example 2. Scheme II illustrates the preparation of the protected benzamidrazone starting material (2).

SCHEME II (4) (5) (2) The benzimidate derivative (4) was reacted, wherein Z is O or S, and R10 is lower alkyl, with a hydrazine derivative (5), wherein Ar, W, and R2 are as defined above in the Scheme I. An example of an intermediate of formula (5) is N-methyl-Nt-butylcarboxyhydrazine. Its use to make regiospecific 2-alkyltriazoles [1,2,4] is found in Chem. Ber. 1982, 115, 2807-2818. The production of benzimide compounds is well known. An example is described in Synth. Commun. 1983, 13, 753.

Another aspect of the invention is a novel method for preparing compounds of the formula (1A), wherein R1 and R1 are F, as illustrated in Scheme III: SCHEME III In Scheme III, R 11 is lower alkyl, preferably methyl; R 12 is lower alkyl, preferably methyl; and Het is a thienyl or furyl group of the formula (9): wherein Y, R3, R4 and R5 are as defined in formula (1). The process illustrated in Scheme III is also applicable to the preparation of compounds wherein Het is any of a variety of other heterocyclic groups, for example, pyridyl and pyrazolyl. In other aspects, the invention provides novel intermediates of formulas (6) and (7), as defined above. As illustrated in step a of Scheme III, 2,6-difluorobenzonitrile was reacted with triethylamine, sodium sulfide hydrate and hydrochloric acid in pyridine at room temperature to give 2,6-difluorobenzothioamide. In step b of Scheme III, 2,6-difluorobenzothioamide was reacted with lower alkyl iodide, for example, iodomethane, in acetone to provide an S- (lower alkyl) thio-2,6-difluorobenzimidinium iodide of the formula (6). The preferred solvent is acetone, however, other polar aprotic solvents such as DMF or THF can be used. In step c of Scheme III, the S- (lower alkyl) thio-2,6-difiuorobenzimidinium iodide was reacted with an Nt-butoxycarbonyl-N- (lower alkyl) hydrazine) to provide the amidrazone of the formula (7). ). The reaction is carried out in methanol or ethanol, preferably methanol, at a temperature of 0 ° C to the boiling point of the solvent. In step d of Scheme III, the amidrazone of formula (7) was reacted with an acid chloride of thiophene or furan in the non-reactive organic solvent such as benzene, toluene, xylenes, chloroform, dichloromethane or 1,2-dichloroethane, at a temperature on the scale of 0 ° C to the boiling point of the solvent. The procedure in Scheme III uses more moderate conditions than previously published procedures, and, therefore, allows thermally sensitive heterocyclics to be used. Higher productions are also provided. A detailed illustration of steps a-c of Scheme III is presented in Example 1 below. The detailed illustrations for step d are presented in Examples 2-4 below.

EXAMPLE 1 The following steps illustrate the preparation of the amidrazone of Formula (2a): A. 2,6-dufluorobencentioamide. In a 3-liter, 3-necked round bottom flask equipped with a mechanical stirrer, a dry ice condenser, a dropping funnel, and a trap outlet filled with bleach, pyridine (550 ml) was added. , 6-difluorobenzonitrile (208 g, 1.50 mol), triethylamine (202 g, 279 ml, 2.0 mol) and sodium sulfide hydrate (521 g, 2.17 mol, separated into pieces small enough to fit the flask). The temperature of the stirred mixture was reduced to about 5 ° C and concentrated hydrochloric acid (143 g, 288 ml, 3.99 mol) was added dropwise to the slurry. An exotherm was observed and the dilution rate of the hydrochloric acid was such that the temperature of the reaction mixture did not exceed 25 ° C for a total addition time of 75 minutes. The cooling bath was removed and the slurry was allowed to warm to room temperature and stirred overnight. The mixture was poured into water (2 liters) and extracted with ether (3 x 500 ml). The ether layer was washed with dilute sulfuric acid, water, brine, dried (MgSO4), and the solvent was removed in vacuo to give 232 g of the crude product. The starting material was removed from the product via a Kugelrohr distillation to give 197 g (76%) of 2,6-difluorobenzothioamide. This material was used without further purification.

B. S-methylt-2,6-difluorobenzamidinium iodide. In a 3-liter, 3-necked flask equipped with a mechanical stirrer and dropping funnel, acetone (1150 ml) and 2,6-difluorobenzothioamide (197 g, 1.14 mol) were added. The temperature of the stirred solution was reduced to about 5 ° C and iodomethane (161 g, 70.6 ml, 1.14 moles) was added dropwise. The ice bath was removed and the grout allowed to stir overnight. The resulting yellow solids were removed through filtration and washed with ether to obtain 223 grams. A portion of filtrate material was obtained through solvent removal, under vacuum. Ether was added to the residue and the resulting solids were removed through filtration to obtain an additional 57 grams of material. The combined solids gave a total of 280 g (77.9% yield) of S-methylthio-2,6-difluoro-benzimidinium; p.f. 168-169 ° C; 1 H NMR (DMSO-d 6) d 7.7 (m, 1 H), 7.4 (m, 2 H), 2.7 (s, 3 H).

C. N-tert-butoxycarbon i-N-methyl hydrazine. To a 1 liter, 3 neck, round bottom flask equipped with a mechanical stirrer and drip funnel was added methyl hydrazine (42.2 g, 0.916 mol) and THF (100 ml). The temperature of the mixture was cooled to 5 ° C and a solution of di-tert-butyl dicarbonate (100 g, 0.458 mol) dissolved in THF (150 ml) was added dropwise. The cooling bath was stirred and the mixture was stirred at room temperature overnight. The liquid was decanted from a gummy precipitate and the solvent was removed under vacuum to give approximately 70 grams of a clear liquid. The gummy precipitate was divided between methylene chloride and water. The methylene chloride was washed with brine, dried (Na2SO4) and the solvent removed in vacuo. The resulting residue was combined with that from the previous evaporation and distilled at approximately 20 mm Hg (bp 77-78 ° C) to give 40.2 g (60% yield) of N-tert-butoxycarbonyl-N-methylhydrazine: 1H NMR (CDCl 3) d 4.1 (s, b, 2 H), 3.05 (s, 3 H), 1.5 (s, 9 H).

D. Amidrazone of the formula (2a). Into a one liter round bottom flask, equipped with a mechanical stirrer, a dropping funnel, and an outlet to a trap filled with bleach, S-methyl-2,6-difluorobenzimidinium iodide (63.8 g, 0.202 g) was added. moles) and methanol (180 ml). To the stirred solution was added dropwise N-tert-butoxycarbonyl-N-methylhydrazine (29.6 g, 0.202 mole). The solution was allowed to stir overnight and the methanol was removed in vacuo. The residue was titrated with ether and the solids were removed by filtration to give 66.3 g (79.0% yield) of the amidrazone of the formula (2a): m.p. 172-173 ° C (dec); 1 H NMR (DMSO-d 6) d 12.3 (s, b, 1 H), 10.4 (d, b, 2 H), 7.9 (m, 1 H), 7.4 (m, 2 H), 3.1 (s, 3 H), 1.5 (s) , 9H).

EXAMPLE 2 3- (2,6-D? -fluorophenyl) -5- (3-n-hexylthien-2-yl) -1-metip.2.4Urizole (Compound 35) To a mixture of 3-n-hexyl-2-thiophene carboxylic acid (0.5 g, 2.4 mmol) in 25 ml of dry 1,2-dichloroethane was added 2.0 ml of thionyl chloride and one drop of dimethylformamide. The mixture was refluxed for 4 hours. After cooling, the reaction mixture was evaporated in vacuo and the residue was combined with 25 ml of dry toluene and 1.24 g (3.0 mmoles) of the amidrazone of the formula (2a) (Example 1). The mixture was refluxed overnight, cooled, and then partitioned between brine and ether. The organic phase was dried (MgSO4), the solvent was evaporated, and the residue was chromatographed on silica gel using ethyl acetate / hexanes as the eluent; 5:95 to 20:80. The product fractions were collected and evaporated to give 0.66 g (76% yield) of the title product as an oil. H NMR d 7.26-7.46 (m, 2H), 6.97-7.06 (m, 2H), 3.97 (s, 3H), 2.71 (m, 2H), 1.23 (m, 6H), 0.84 (m, 3H); cale, for dgHz.FzNsS: C, 62.14; H, 5.86; N, 11.63; S, 8.87; C, 62.90 was found; H, 5.79; N, 11.70; S, 8.77.

EXAMPLE 3 3- (2,6-difluorophenip-5- (4-p-chlorobenzenesulfonyl-3-methylthien-2-yl) -1-methyl, 2,4-triazole (Compound 12) To a solution of 0.9 g (2.2 mmol) of the amidrazone of the formula (2a) (Example 1) and 0.75 g (2.2 mmol) of the thiophene acid chloride, (p-chlorobenzenesulfonyl) -3-methylthiophen-2-chloride -carbonyl, in 100 ml of toluene, 1 equivalent (0.4 g, 2.2 mmoles) of p-toluenesulfonic acid monohydrate was added with stirring. The mixture was refluxed overnight using a Dean-Stark trap to remove the water. The solution was cooled and the solvent was removed in vacuo. The residue was dissolved in 100 ml of dichloromethane and washed with 2N NaOH and then with water. The organic phase was dried (MgSO4) and the solvent was evaporated. The residue was recrystallized from ethyl acetate / hexanes to give 0.6 g of the product as off-white crystals, m.p. 183-185 ° C. Performance 59.4%. 1 H NMR d 8.4 (s, 1 H), 7.8 (d, 2 H), 7.4 (d, 2 H), 7.3 (m, 1 H), 7.0 (m, 2 H), 3.98 (s, 3 H), 2.25 (s, 3 H) ); cale, for C2oH14F2CIN3O2S2; C, 51.55; H, 3.01; N, 9.02; it was found: H, 3.26; N, 8.92.

EXAMPLE 4 3- (2,6-difluorophenyl) -5- (5-p-chlorophenyl) furan-2-D-1-methylM, 2,41-triazole (Compound 13) To a solution of 1.0 g (2.4 mmoles) of the amidrazone of the formula (2a) (Example 1) and 0.61 g (2.4 mmoles) of 5- [p-chlorophenyl] -furan-2-carbonyl chloride in 100 ml of toluene was added 1 equivalent (0.43 g, 2.4 mmoles) of p-toluenesulfonic acid monohydrate with stirring. The mixture was refluxed overnight using a Dean-Stark trap to remove the water. The solution was cooled and the solvent was removed in vacuo. The residue was dissolved in 100 ml of dichloromethane and washed with 2N NaOH and then with water. The organic phase was dried (MgSO4) and the solvent was evaporated. The residue was recrystallized from ethyl acetate / hexanes to give 0.4 g of the product as off-white crystals, m.p. 171-173 ° C. Performance of 44.9%; cale, for C19H12F2CIN3 ?: C, 61.37; H, 3.23; N, 11.30; It was found: C, 61.34; H, 3.19; N, 11.06. The invention also provides a new method for preparing compounds of the formula (1A) as illustrated in Scheme IV: SCHEME IV wherein R1, R1 ', Y, R3, R4 and R5 are as defined in formula (1) and R14 is methanesulfonyl, benzenesulfonyl or substituted benzenesulfonyl. In step a, substituted 2,6-benzoyl chloride was reacted with a hydrazide of the formula (11), (wherein R 14 is methanesulfonyl, benzenesulfonyl or substituted benzenesulfonyl, ie p-CI or p-CH 3 benzenesulfonyl), and triethylamine in THF to give the benzhydrazone of the formula (12). In step b, the substituted benzhydrazone of the formula (12) was first reacted with sodium hydride in N, N-dimethylformamide and then with iodomethane to produce the substituted hydrazine of the formula (13). In step c, the substituted hydrazine of the formula (13) was chlorinated using, for example, PCI5 to produce substituted benzylhydrazonoyl chloride of the formula (14). The reaction was carried out in a non-reactive organic solvent such as dichloroethane. In step d, the substituted benzylhydrazonoyl chloride of the formula (14) was reacted with a mixture of aluminum chloride and cyanothiophene or cyanofuran of the formula (15) in a solvent, for example, o-dichlorobenzene, to produce a 3- (2,6-substituted phenyl) -5- (substituted thienyl) -1-methyl [1,4-] triazole of the formula (16). A detailed illustration of steps a-c of Scheme IV is given in Example 5 below. The detailed illustrations of step d are given in Examples 6-9, 11, 13 and 15 below.

EXAMPLE 5 The following steps show the preparation of the benzhydrazonoyl chloride of the formula (14a): A. 1-Benzenesulfonyl-2- (2,6-dichloro) benzhid reasons To a one-liter 3-necked round bottom flask, equipped with a condenser, mechanical stirrer, thermometer, under a nitrogen atmosphere, it is added THF (500 ml), benzenesulfonyl hydrazide (41.1 g, 0.238 moles) and triethylamine (24.1 g, 33.2 ml, 0.238 moles). The resulting solution was cooled to -5 ° C and 2,6-dichlorobenzoyl chloride (50.0 g, 34.2 ml, 0.238 mol) was added dropwise over a period of 55 minutes and the temperature was not increased above 0 °. C. The reaction mixture was allowed to stir for 1 hour and then the cooling bath was removed and the reaction mixture was then stirred for 21 hours at room temperature with verification through TLC and HPLC. The majority of the solvent was removed in vacuo and the residue was partitioned between methylene chloride (1000 ml) and water (2 x 200 ml). The organic layer was washed with saturated brine (250 ml), dried (Na2SO4), and the solvent was removed in vacuo to give a white solid. The white solids were slurried in ether and removed by filtration and dried in vacuo overnight to give 74.3 g (90.5% yield of 1-benzenesulfonyl-2- (2,6-dichlorobenz) hydrazone: mp 180-181 ° C; mass TLC 345/347/349; 1H NMR (CDCl 3) d 8.05 (m, 2H), 7.9 (m, 1H), 7.5-7.7 (m, 4H), 7.3 (m, 3H).

B. 1- (2,6-Dichloro) benzoyl-2-methyl-2-benzenesulfonyl-hydrazine In a 1-liter 3-necked round bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel under an atmosphere of nitrogen, a suspension of sodium hydride (8.49 g of a 60% dispersion, 0.212 mol) was washed with hexanes (3 portions) and most of the hexane from the final wash was removed by suction. N, N-dimethylformamide (200 ml) was added and the temperature of the slurry was reduced to -5 ° C. A solution of N-benzenesulfonyl-2,6-dichloro-benzhydrazone (73.3 g, 0.212 moles, in 300 ml of N, N-dimethylformamide) was added dropwise over a period of 120 minutes at a rate such that the temperature it did not increase above 3 ° C and the hydrogen evolution speed remained at a manageable speed. As the addition proceeded, the mixture became lemon yellow and thickened, but when the addition was complete, the mixture became clear and stirred easily. The resulting mixture was stirred at 0 ° C for 1 hour and the cooling bath was stirred and stirred for an additional 1 hour (the temperature was increased to 15 ° C). The mixture was then cooled to -5 ° C and iodomethane (30.0 g, 13.2 ml) was added dropwise at a rate such that the temperature did not increase above 0 ° C. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature and stirred for 2 hours. The reaction mixture was diluted with brine (300 ml) and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried (Na2SO4), and the solvent was removed in vacuo to give the crude material contaminated with N, N-dimethylformamide, which was removed through a vacuum pump. The crude mixture was crystallized from hexanes / ethyl acetate, the solids were removed by filtration and dried in vacuo to give 40.2 g. The solvent was removed from the filtrate to obtain an additional 21.4 g for a total of 80.9% yield of 1- (2,6-dichloronenzoyl) -2-methyl-2-benzenesulfonyl hydrazine: mp 177-178 ° C; NMR (CDCl 3) d 8.0 (m, 2H), 7.4-7.8 (m, 4H), 7.2 (m, 3H), 3.4 and 3.05 (two individual bands combined for 3H).

C. N- (Benzenesulfonyl) -N-methyl- (2,6-dichlorobenz) hydrazoloyl chloride To a 1-liter, three-necked round bottom flask equipped with a magnetic stirrer and a condenser under a nitrogen blanket. added N-benzenesulfonyl-N-methyl-2,6-dichlorobenzoyl hydrazine (35.9 g, 0.10 mole), 1,2-dichloroethane (500 ml) and phosphorus pentachloride (31.2 g), 0.15 moles). The temperature of the mixture was increased to the reflux point and allowed to stir for 30 minutes. The solvent was removed in vacuo and the residue was dissolved in methylene chloride and carefully diluted with water. The organic phase was washed with water, brine, dried (Na2SO4) and the solvent was removed in vacuo to give an oil, which was solidified when titrated with a mixture of ethyl acetate / hexanes to give 36.1 g (yield 95.7 %) of N-benzenesulfonyl-N-methyl-2,6-dicyclobenzhydrazonoyl chloride as a white crystalline solid: mp 103-104 ° C; 1 H NMR (CDCl 3) d 7.9 (m, 2 H), 7.4-7.7 (m, 3 H), 7.2-7.4 (m, 3 H), 3.1 (s, 3 H). Using the same procedure, N-benzenesulfonyl-N-methyl-2-chloro-6-fluorobenzhydrazonoyl chloride was also made.

EXAMPLE 6 3- (2-Chloro-6-fluorophenip-5- (3,4,5-trichlorothien-2-yl) -1-methylM .2,41-triazole (Compound 2) To a mixture of N-methyl-N-benzenesulfonyl-2-chloro-6-fluorohydrazonoyl chloride (47.5 g, 0.131 mol) and 2-cyano-3,4,5-trichlorothiophene (26.5 g, 0.125 mol) in o- dichlorobenzene (18 ml) was added aluminum chloride (11.1 g, 0.083 mol). The mixture was lowered into a preheated oil bath maintained at 140-150 ° C. The mixture was allowed to remain in the hot oil bath for 40 minutes and then was removed from the bath and stirred for 2 hours as it gradually cooled. The reaction mixture was poured into 2N sodium hydroxide (300 ml, sufficient to dissolve the aluminum salts) and extracted with methylene chloride (3 x 250 ml). The organic phases were combined, washed with brine, dried (MgSO4), and the solvent removed in vacuo to give the crude product. The residue was placed on silica gel (150 ml) and then chromatographed using ethyl acetate / hexanes as eluent to obtain 39.7 g (55.3% yield) of the title compound: 99.4% pure by GC analysis; p.f. 129-130 ° C; 1 H NMR (CDC) d 7.3 (m, 2 H), 7.1 (m, 1 H), 4.0 (s, 3 H); Anal. For C 13 H 6 Cl 4 F N 3 S; Cale. C, 39.32; H, 1.52; N, 10.58. Found C, 39.08; H, 1.30; N, 10.34.

EXAMPLE 7 3- (2,6-Dichlorophenol) -5- (3.4.5-tr.chlorotien-2-yl) -1-methylM, 2.4. triazole (Compound 45) To a 500 ml round bottom flask, equipped with a mechanical stirrer and a condenser, under a nitrogen atmosphere, was added o-dichlorobenzene (150 ml), 2-cyano-3,4,5-trichlorothiophene (23.6 g) , 111 mmol) and aluminum chloride (14.8 g, 111 mmol). The stirred reaction mixture was immersed in an oil bath at 145-150 ° C. When the internal temperature of the mixture reached 130 ° C, N- (benzenesulfonyl) -N-methyl- (2,6-dichlorobenz) hydrazonoyl chloride (35.0 g, 92.6 mmoles) was added in 5 gram portions over 40 minutes. The temperature increased to 141 ° C. The reaction mixture was allowed to stir from the initial addition of N- (benzenesulfonyl) -N-methyl- (2,6-dichlorobenz) hydrazonoyl chloride 1 hour and 40 minutes with verification through HPLC and GC. The oil bath was dripped from the reactor and the mixture was allowed to cool to about 90 ° C and was added to 2N of stirred caustic soda (350 ml). The mixture was stirred for 5 minutes, checked to ensure that the pH was basic, and diluted with methylene chloride (800 ml). The methylene chloride layer was washed with water (250 ml), brine (250 ml), dried (Na2SO4), the solvent was removed in vacuo and the o-chlorobenzene and benzenesulfonyl chloride were removed by Kugelrohr distillation. The straw colored solids were recrystallized from ethyl acetate to give 31.3 g (81.7% yield) of the title compound; p.f. 146-147 ° C; 1 H NMR (CDCl 3) d 7.2-7.5 (m, 3H), 4.0 (s, 3H).

EXAMPLE 8 3- (2,6-Dichlorophenyl) -5- (thien-3-yl) -1-metip.2.4.tr.azole (Compound 48) N- (benzenesulfonyl) -N-methyl- (2,6-diciorobenz) hydrazonoyl chloride (1.13 g, 3 mmol), 3-cyanothiophene (0.327 g, 6 mmol) and methylene chloride (0.40 g, 3 mmol) were combined. ) and were heated at 135-140 ° C for about 14 hours, and then stirred at room temperature for about 48 hours. The mixture was then diluted with dichloromethane, washed with water, washed with brine, and dried over magnesium sulfate. Chromatography afforded 290 mg of the title product as a clear oil. 1 H NMR (CDCl 3) d 7.27-7.85 (m, 5H), 4.15 (s, 3H).

EXAMPLE 9 3- (2,6-Dichlorophenin-5- (thien-2-in-1-metip.2.4, triazole (Compound 50) N- (benzenesulfonyl) -N-methyl- (2,6-dichlorobenz) hydrazonoyl chloride (0.42 g, 1.1 mmol), 2-cyanothiophene (0.24 g, 2.2 mmol) and aluminum chloride (0.417 g, 1.1 mmol) were combined. ) and heated to 138 ° C for about 8 hours. The mixture was then poured into an ice-bath of 1M NaOH, and stirred one hour, extracted into dichloromethane, washed with brine, dried over magnesium sulfate and concentrated to 230 mg of an oil. Chromatography (SiO2, 10% EtOAc-Hex) provided the product (100 mg) as a white solid. P.f. 161-163 ° C. The invention also provides the process for making compounds of formula (16) shown in Scheme V: SCHEME V wherein R15 is methyl, phenyl, p-chlorophenyl or p-tolyl, R14 is methanesulfonyl, benzenesulfonyl or substituted benzenesulfonyl, and R1, R1, R3, R4 and R5 are as defined above for formula d). In step a of Scheme V, the sulfonyl chloride of formula (17) was reacted with methyl hydrazine in a non-reactive organic solvent such as THF in the presence of triethylamine. The reaction can be carried out at room temperature which is typically completed in four hours. In step b of Scheme V, the sulfonyl hydrazine of the formula (19) was reacted with the substituted 2,6-benzoyl chloride of the formula (10) to provide the intermediate of the formula (13). Steps c and d of Scheme V are the same as steps c and d of Scheme IV.

EXAMPLE 10 This Example shows the preparation of the benzhydrazonoyl chloride of the formula (14b): A. 2-Methyl-2- (4-methylphenyl) sulfonyl hydrazine To a 100 ml three-necked round bottom flask, equipped with a mechanical stirrer, thermometer and dropping funnel under a nitrogen atmosphere, was added THF (25 ml), methyl hydrazine (2.53 g, 2.92, ml, 55 mmol) and triethylamine (4.35 g, 5.99 ml, 55 mmol). The temperature of the mixture was reduced to about 5 ° C and 4-methylbenzenesulfonyl chloride (9.5 g, 50 mmol) dissolved in 25 ml of THF was added dropwise at a rate such that the temperature was not increased above 10 ° C. ° C. The cooling bath was stirred and the mixture was allowed to stir overnight at room temperature. Ether (100 mL) was added to the reaction mixture and the resulting slurry was washed with water (50 mL), brine (50 mL), dried (Na2SO), and the solvent was removed in vacuo to give 9.5 g (95 mL). % yield) of the title product. 1 H NMR (CDCl 3) d 7.7 (d, 2 H), 7.4 (d, 2 H), 3.6 (s, b, 2 H), 2.8 (s, 3 H), 2.4 (s, 3 H).

B. Hydrazine of 1 - (2-f luoro-6-chlorobenzoyl) -2-methyl-2- (4-methylene-phenylsulfonyl) To a 100 ml three-necked round bottom flask equipped with a magnetic stirrer , thermometer, and condenser, under a nitrogen atmosphere, was added 2-methyl-2 - [(4-methylphenyl) sulfonyl] hydrazine (9.5 g, 47.4 mmol), pyridine (3.75 g, 3.83 mL, 47.4 mmol) , 4-dimethylaminopyridine (0.30 g, 2.4 mmol) and acetonitrile (50 ml) The resulting mixture was cooled to 10 ° C and 2-fluoro-6-chlorobenzoyl chloride (8.99 g, 45.2 mmol) was added at such a rate that the temperature did not increase above 10 ° C. The cooling bath was stirred and the mixture was allowed to stir at room temperature The solvent was removed from the reaction mixture in vacuo to give an off white solid and the solid was diluted with methylene chloride and extracted with 1N HCl (20 ml), a saturated sodium chloride solution (20 ml), dried (Na2SO4), and the solvent was removed in vacuo to allow This solid was recrystallized from ethyl acetate to give 5.6 g (34.7% yield) of hydrazine of 1- (2-fluoro-6-chlorobenzoyl) -2-methyl-2 - [(4- methylphenyl) sulfonyl] as a crystalline solid; p.f. 135-136 ° C; 1 H NMR (CDCl 3) d 7.6-7.8 (m, 3 H), 7.0-7.4 (m, 5 H), 2.4 and 3.0 (individual bands combined for 3 H), 2.4 and 2.45 (individual bands combined for 3 H); 13C (CDCl 3) 160.2, 144.7, 133.6, 132.7, 132.6, 132.1, 131.9, 130.2, 129.6, 129.0, 128.7, 125.7, 114.6, 114.3, 37.7, 21.7. Anal. Cale, for C15H14CIFN2O3S; C, 50.49; H, 3.95; N, 7.85; Found: C, 50.55; H, 3.89; N, 7.81.

C. N- (4-Methylbenzenesulfonyl) -N-methyl- (2-fluoro-6-chlorobenz) hydrazonoyl chloride In a 250 ml round neck flask, equipped with a magnetic stirrer and a condenser, under a nitrogen atmosphere, 1- (2-fluoro-6-chlorobenzoyl) -2-methyl-2 - [(4-methylphenyl) sulfonyl]] hydrazine (5.0 g, 14.0 mmol), ethylene dichloride (50 ml) was added thereto. ) and phosphorus pentachloride (3.2 g, 21.6 mmol). The mixture was heated to reflux and maintained at that temperature for about 30 minutes. The progress of the reaction was verified through TLC using 50/50 ethyl acetate / hexane (starting material Rf = 0.55; product Rf = 0.70). The solvent was removed in vacuo and the residue was dissolved in methylene chloride (100 ml) and carefully diluted with water. The organic phase was washed with water, brine, dried (Na2SO) and the solvent was removed in vacuo to give a yellow oil, which solidified after cooling. The solids were formed to a slurry in hexane / ethyl acetate (70/30) and were removed through filtration to give 4.5 g (87% yield) of N- (4-methyIbenzenesulfonyl) -N-methyl- chloride. (2-fluoro-6-chlorobenz) hydrazonoyl. P.f. 98-99 ° C; 1 H NMR (CDCl 3) d 7.8 (d, 2 H), 7.2-7.5 (m, 4 H), 7.1 (m, H), 3.1 (s, 3 H), 2.5 (s, 3 H); 13 C NMR (CDCl 3) 161.6, 158.5, 144.6, 140.7, 133.6, 132.1, 131.9, 131.1, 129.5, 125.6, 125.5, 114.7, 114.4, 38.1, 21.6. Anal. Cale, for C15H13Cl2F2? 2S; C, 48.01; H, 3.49; N, 7.47. Found: C, 48.10; H, 3.49; N, 7.47.

EXAMPLE 11 3- (2-Chloro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-methyl H.2.4. triazole (Compound 2) A N- (4-methyl-benzenesulfonyl) -N-methyl- (2-fluoro-6) chloride was added to a 50 ml round neck flask equipped with a magnetic stirrer and a thermometer under a nitrogen atmosphere. chlorobenz) hydrazonoyl (Example 10) (1.4 g, 3.73 mmol), 2-cyano-3,4,5-trichlorothiophene (0.83 g, 3.92 mmol), aluminum chloride (0.53 g, 4.0 mmol) and o-dichlorobenzene (10 ml). The flask containing the reaction mixture was immersed in a preheated oil bath maintained at 120 ° C. In 8 minutes, the temperature of the reaction mixture was increased to 109 ° C and heating was continued for a further 30 minutes. The flask was removed from the oil bath. When the stirred reaction mixture reached about 80 ° C and was emptied into a solution (10 g of sodium hydroxide with 10 ml of ice) with rapid stirring, it was then added to methylene chloride (50 ml) for extraction. The organic phase was washed with water (25 ml), brine, dried (Na 2 SO 4), and the solvent was removed in vacuo. The o-dichlorobenzene was removed from the residue by Kugelrohr distillation to give a residue, which was dissolved in ether (20 ml), stirred with activated carbon at room temperature, filtered, and the solvent was removed in vacuo. filtered out. The solids were recrystallized from ethyl acetate to give 0.9 g (60.8% yield) of 3- (2-chloro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1 -methyl [1, 2,4] triazole as a crystalline solid: > 97% pure through HPLC analysis; 1 H NMR (CDCl 3) d 7.2-7.4 (m, 2H), 7.0-7.4 (m, 1H), 4.0 (s, 3H).

EXAMPLE 12 This Example shows the preparation of the benzhydrazonoyl chloride of the formula (14c): A. Hydrazine of 2-met? L-2-r (4-chlorophenyl) sulfonyl. To a 100 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer, and dropping funnel under a nitrogen atmosphere was added THF (25 ml), methyl hydrazine (2.53 g, 2.92 ml, 55). mmoles) and triethylamine (4.35 g, 43 mmol). The temperature of the mixture was reduced to about 5 ° C and 4-chlorophenylsulfonyl chloride (10.5 g, 50 mmol, containing 4-chlorophenylsulfonyl acid) dissolved in 25 ml of THF was added dropwise at a rate such that the temperature did not increase above 10 ° C. The cooling bath was removed and the mixture was allowed to warm to stir overnight at room temperature. Ether (100 ml) was added to the reaction mixture and the resulting slurry was washed with water (50 ml), brine (50 ml), dried (Na2SO4), and the solvent was removed under vacuum to give 5.4 g (49 g). % yield) of 2-methyl-2 - [(4-chlorophenyl) sulfonyl] hydrazine]. 1 H NMR (CDCl 3) d 7.8 (d, 2 H), 7.6 (d, 2 H), 3.6 (s, b, 2 H), 2.9 (s, 3 H).

B. 1- (2-Fluoro-6-chlorobenzoyl) -2-methyl-2-f (4-chloropheniDsulfonyl) hydrazine To a 100 ml three-necked round bottom flask equipped with a magnetic stirrer and a condenser, under a nitrogen atmosphere, 2-methyl-2 - [(4-c! orophenol) sulfonyl] hydrazine (5.4 g, 24.5 mmol), pyridine (1.93 g, 1.98 mL, 24.5 mmol), 4-dimethylaminopyridine was added. (0.15 g, 1.2 mmol) and acetonitrile (50 ml) The reaction mixture was cooled to 10 ° C and 2-fluoro-6-chlorobenzoyl chloride (4.65 g, 23.4 mmol) was added dropwise to an speed such that the temperature did not increase above 10 ° C. The mixture was allowed to stir at room temperature overnight The solvent was removed from the reaction mixture in vacuo to give an off-white solid and the solid was diluted with chloride of methylene and extracted with 1N HCl (20 ml), saturated sodium bicarbonate (20 ml), dried (Na2SO4) and the solvent was removed under vacuum to give hydrazine of 1- (2-fluoro-6-cl). Orobenzoyl) -2-methyl-2 - [(4-chlorophenyl) sulfonyl] as a yellow oil, which was used without purification.

C. N- (4-chlorophenylsulfonyl) -N-methyl- (2-fluoro-6-chlorobenzlhydrazonoyl) chloride In a round bottom flask with a 250 ml neck, equipped with a magnetic stirrer and a condenser, under a nitrogen atmosphere, was added 1- (2-fluoro-6-chlorobenzoyl) -2-methyl-2- (4-chlorophenylsulfonyl) hydrazine (7.3 g, 16.8 mmol , 87% pure by HPLC), ethylene dichloride (50 ml) and phosphorus pentachloride (6.03 g, 28.9 mmol). The mixture was heated to reflux and maintained at that temperature for about 30 minutes. The solvent was removed in vacuo and the residue was dissolved in methylene chloride (100 ml) and carefully diluted with water. The organic phase was washed with water, brine, dried (Na2SO4) and the solvent was removed in vacuo to give a yellow oil, which was dissolved in hot ethyl acetate to which hexanes were added at the cloud point and after cooling with rub, solids were formed. The solids were recrystallized from hexane / ethyl acetate (70/30) and seeded to give 2.7 g (40.9% yield) of N- (4-chlorophenylsulfonyl) -N-methyl- (2-fluorophenyl) chloride. 6-chlorobenz) hydrazonoyl. P.f. 100-101 ° C; 1 H NMR (CDCl 3) d 7.8 (d, 2 H), 7.2-7.5 (m, 4 H), 7.1 (m, H), 3.1 (s, 3 H), 2.5 (s, 3 H): Anal. Cale, for C 14 H 10 Cl 3 FN 2 O 2 S: C, 42.50; H, 2.55; N, 7.08. Found: C, 42.56; H, 2.47; N, 6.99.

EXAMPLE 13 3- (2-Chloro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-methyl, 2,41-triazole (Compound 2) To a 50 ml neck flask, equipped with a magnetic stirrer and thermometer, under a nitrogen atmosphere, N- (4-chlorophenylsulfonyl) -N-methyl- (2-fluoro-6-chlorobenz) hydrazonoyl chloride was added. (Preparation 4) (2.7 g, 6.8 mmol), 2-cyano-3,4,5-trichlorothiophene (1.44 g, 6.8 mmol), aluminum chloride (1.18 g, 8.9 mmol) and o-dichlorobenzene (20 ml). The flask containing the reaction mixture was immersed in an oil bath maintained at 120 ° C. After 8 minutes, the temperature of the reaction mixture was increased to 109 ° C and heating was continued for a further 50 minutes. The flask was removed from the oil bath. When the stirred reaction mixture reached about 80 ° C and was emptied into a solution of 20 g of sodium hydroxide with 20 ml of ice, with rapid stirring, it was then added to methylene chloride (100 ml) for extraction. The organic phase was washed with water, brine, dried (Na2SO), and the solvent was removed in vacuo. The o-dichlorobenzene was removed from the residue by Kugelrohr distillation to give a residue, which was dissolved in ether (50 ml), stirred with activated carbon at room temperature, filtered and the solvent removed under vacuum of the filtrate. The resulting whitish solids were recrystallized to give 1.8 g (26.6% yield) of 3- (2-chloro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-methyl [1 , 2,4] triazole as a crystalline solid: > 98% pure through HPLC analysis.

EXAMPLE 14 This Example shows the preparation of the benzhydrazoo chloride of the formula (14d): A. 2-Methyl-2-methanesulfonyl hydrazine To a 250 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel under a nitrogen atmosphere was added THF (100 ml). , methyl hydrazine (5.07 g, 5.85 ml, 110 mmol) and triethylamine (11.1 g, 15.3 ml, 110 mmol). The temperature of the mixture was reduced to about 5 ° C and methanesulfonyl chloride (11.4 g, 7.73 ml, 100 mmol) was added dropwise at a rate such that the temperature did not increase above 10 ° C. The cooling bath was removed and the mixture allowed to warm to room temperature and stirred overnight. Ether was added to the reaction mixture and washed with water (50 ml), brine (50 ml), dried (Na2SO4), and the solvent was removed in vacuo to give 2.4 g (19.3% yield) of hydrazine. 2-methyl-2-methanesulfonyl. 1 H NMR (CDCl 3) d 3.8 (s, b, 2 H), 2.95 (s, 3 H), 2.9 (s, 3 H).

B. 1- (2-Fluoro-6-chlorobenzoyl) -2-methyl-2-methanesulfonyl hydrazine To 50 ml were added 2-methyl-2-methanesulfonyl hydrazine (2.4 g, 19.3 mmol), pyridine (1.5 g) , 1.55 ml, 19.3 mmol) and acetonitrile (20 ml), under a nitrogen atmosphere. The mixture was cooled to about 0 ° C and 2-chloro-6-fluorobenzoyl chloride (3.77 g, 19.3 mmol) was added dropwise. The mixture was allowed to warm to room temperature and was stirred for about 3 hours with TLC verification using 50/50 ethyl acetate / hexanes (Rf = 0.7 for 2-chloro-6-fluorobenzoyl chloride and Rf = 0.44 for the product). The solvent was removed from the reaction mixture in vacuo, the residue was diluted with methylene chloride, and extracted with 1N hydrochloric acid (10 ml), saturated sodium bicarbonate, dried (MgSO4) and the solvent was removed at room temperature. vacuum to give 4.6 g of a semi-solid. This material was recrystallized from ethyl acetate to give 1.8 g (33.3% yield) of 1- (2-fluoro-6-chlorobenzoyl) -2-methyl-2-methanesulfonyl hydrazine as a crystalline solid. P.f. 135-136 ° C; 1 H NMR (CDCl 3) d 7.8 (s, b, 1 H), 7.2-7.4 (m, 3 H), 3.4 (s, 3 H), 3.15 (s, 3 H). Anal. Cale, for CgH.oCIFNzOsS: C, 38.51; H, 3.59; N, 9.98. Found: C, 38.28, H, 3.41; N, 9.48.

C. N-me tansulfo nyl-N-methyl- (2-fluoro-6-chlorobenzlhydrazonoyl) chloride To a round bottom flask with a 250 ml neck, equipped with a magnetic stirrer and a condenser, under a nitrogen atmosphere, was added 1- (2-fluro-6-chlorobenzoyl) -2-methyl-2-methanesulfonyl hydrazine (1.6 g, 7.12 mmol), dichloride ethylene (25 ml), and phosphorus pentachloride (2.2 g, 10.7 mmol). The mixture was heated to reflux and maintained at that temperature for about 30 minutes. The progress of the reaction was verified through TLC using 50/50 ethyl acetate / hexanes (starting material Rf = 0.44; product Rf = 0.60). The solvent was removed in vacuo and the residue was dissolved in methylene chloride (50 ml) and carefully diluted with water. The organic phase was washed with water (2 x 50 ml), brine (50 ml), dried (Na 2 SO 4) and the solvent was removed in vacuo to give a colorless oil, which solidified after cooling. The solids were recrystallized from hexanes / ethyl acetate (70/30) to give 1.2 g (56.6% yield) of N-methanesulfonyl-N-methyl- (2-fluoro-6-chlorobenz) hydrazonoyl chloride. P.f. 83-85 ° C; 93% pure through HPLC analysis: 1H NMR (CDCI3) d 7.8 (d, 2H), 7.0-7.4 (m, 3H), 3.45 and 3.55 (individual bands added to 3H), 3.15 and 3.05 (individual bands adding to 3H).

EXAMPLE 15 3- (2-chloro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-metpri, 2.4. triazole (Compound 2) To a 50 ml neck flask, equipped with a magnetic stirrer and a thermometer, under a nitrogen atmosphere, was added N-methanesulfonyl-N-methyl- (2-fluoro-6-chlorobenz) hydrazonoyl chloride (Example 14). ) (1.0 g, 3.3 mmol), 2-cyano-3,4,5-trichlorothiophene (0.78 g, 3.7 mmol), aluminum chloride (0.49 g, 3.7 mmol) and o-dichlorobenzene (10 mL). The flask containing the reaction mixture was immersed in a preheated oil bath maintained at 120 ° C. After 10 minutes, the temperature of the reaction mixture was increased to 111 ° C and heating was continued for 90 minutes. The GC analysis indicated that the conversion of the reaction was approximately 66%. The flask was removed from the oil bath. When the reaction mixture reached about 90 ° C and was emptied into a solution (10 g of sodium hydroxide with 10 ml of ice) with rapid stirring, it was then added to methylene chloride (50 ml) for extraction. The organic phase was washed with water (25 ml), brine, dried (Na2SO4) and the solvent was removed in vacuo. The o-dichlorobenzene was removed from the residue through Kugelrohr distillation to give a residue, which was dissolved in ether (20 ml), stirred with activated carbon at room temperature, filtered and the solvent removed under vacuum of the filtrate. to give 0.4 g of 3- (2-chloro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-methyl [1,2,4] triazole contaminated with 3.4, 5-trichloro-2-cyanothiophene. The compounds of the invention can be modified using conventional methods to provide other compounds of the invention, as illustrated in Examples 16 and 17.

EXAMPLE 16 3- (2,6-Dichlorophenyl) -5- (5-bromo-3,4-dichlorothien-2-yl) -1-methyl-2,41-triazole (Compound 46) N-Butyllithium (2. 5 mmol) was slowly added to a solution of 3- (2,6-dichlorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-methyl [1 , 2,4] triazole (325 mg, 1.0 mmol) in THF at -78 ° C, and the mixture was stirred one hour. Bromide (3.0 mmol) was added and the reaction was stirred for two hours, then diluted with water, extracted with ether, washed with brine, and dried over magnesium sulfate. The product was concentrated to 620 mg of dark oil. This was chromatographed (SiO2, 10% EtOAc-Hex) to give 79 mg of the title product as a pink solid. P.f. 197-199 ° C.

EXAMPLE 17 3- (2,6-Dichlorophenyl) -5- (5-bromothien-2-yl) -1-methyri. 2,41 triazole (Compound 47) 3- (2,6-Dichlorophenyl) -5- (thien-2-yl) -1-methyl [1, 2,4] triazole (75 mg, 0.242 mmol) and bromide (39 mg, 0.242 mmol) were combined in glacial acetic acid (3 ml) and the mixture was stirred overnight at room temperature, then heated at 95 ° C for 5 hours. The reaction mixture was poured into a saturated solution of sodium bicarbonate, extracted with ether and dried over magnesium sulfate. Chromatography (SiO2, 25% Hex-CH2Cl2) provided the title product as a white, waxy solid. P.f. 130-132 ° C. The phytologically acceptable acid addition salts of the compounds of the formula (1) are also within the scope of the invention. For example, boron tetrafluoride, hydrogen chloride, hydrogen iodide, hydrogen sulfate or acid addition salts can be used. The compounds identified in the following Table 1 were prepared and tested.

Table 1 CAf refers to an activity at 50 ppm against cotton aphid, TSSM-f: refers to an activity at 100 ppm against red mite, and WF * refers to an activity at 800 ppm against whitefly. The test procedures are described below. In each case, the classification scale is as follows: Utility Insecticide and Miticide The compounds of the invention are also useful for the control of insects, mites and aphids. Therefore, the present invention is also directed to a method for inhibiting an insect, mite or aphid, which comprises applying to an insect site or mite an inhibiting amount of insects or mites of a compound of the formula (1). The compounds are useful for reducing insect and mite populations and are useful in a method for inhibiting the population of insects or mites, which comprises applying to the site of an insect an insect or mite inhibiting effective amount of a compound of the formula (1). The "site" of insects or mites is a term used in the present to refer to the environment in which insects or mites live or where their eggs are present. Including the air that surrounds them, the food they eat or objects with which they are in contact. For example, insects or mites that ingest plants can be controlled by applying the active compound to the parts of the plant that insects or mites eat, particularly the foliage. It is contemplated that the compounds may also be useful for protecting textiles, paper, stored grain, or seeds by applying an active compound to said substance. The term "inhibiting an insect or mite" refers to a reduction in the number of living insects or mites, or a reduction in the number of viable insect eggs or mite. The degree of reduction achieved through a compound depends, of course, on the speed of application of the compound, the particular compound used, and the species of insect or target acarus. At least one amount of inactivation must be used. The terms "insect inactivating amount" and "mite inactivating amount" are used to describe the quantity, which is sufficient to cause a measurable reduction in the insect or mite tested population, generally, an amount on the scale of approximately 1 to about 1000 ppm of the active compound In a preferred embodiment, the present invention is directed to a method for inhibiting a mite or aphid, comprising applying to an plant an effective mite or aphid inhibiting amount of a compound of the formula 1).

Insecticide Test for Cotton Aphid (Aphis qossypii) To prepare spray solutions, 2 mg of each test compound was dissolved in 2 ml of a 90:10 solvent of acetone: ethanol. These 2 ml of the chemical solution were added to 38 ml of water containing 0.05% of the Tween 20 surfactant to produce a 50 ppm spray solution. Cotyledons of squash were infested with cotton aphids (all stages of life) 16-20 hours before application of the spray solution. The solution was sprayed on the sides of each infested pumpkin cotyledon (0.5 ml x 2 each side) with a sweeping action using a total of 2 ml of spray solution. The plants were allowed to air dry and were kept for 3 days in a controlled room at 26 ° C and a relative humidity of 40%, during which time the test was classified. The classification was through the real account using a dissection microscope and comparison of test accounts for untreated verification. The results are presented in Table 1 as the percentage of control based on the reduction of population against the non-treated.

Insecticide test for red spotted mite Tetranychus urticae) Ovicide method: Ten red mites of two adult female spots were placed on eight 2.2 cm leaf discs. they were left ovidepositar during 24 hours, and later they were removed. The leaf discs were immersed in 100 ppm of test solutions for 3 seconds, after they were allowed to dry with 16 discs left untreated as a negative control. The discs were placed on an agar substrate and kept at 24 ° C and at a relative humidity of 90% for 6 days. The control percentage was based on the number of mature larvae on the treatment discs and the number on the untreated discs, is reported in Table 1.

Evaluation of Test Compounds in Whitefly (Bemisia tabacia) of Sweetpotato under Laboratory Conditions 16 mg of each test compound was dissolved by adding 5 ml of a 90:10 solvent mixture of acetone: ethanol to the flask containing the sample compound . This solution was added to 15 ml of water containing 0.05% of the Tween 20 surfactant to produce 20 ml of an 800 ppm spray solution. 5-week-old cotton plants grown in a greenhouse had all the foliage removed, except for the two most superior true leaves that were larger than 5 cm in diameter. These plants were then placed in a colony of laboratory white flies for 3 days for oviposition by females in the colony. All white flies were then removed from the test plants with pressurized air. The spray solution was then applied to the test plants with a manual syringe equipped with a hollow cone nozzle. A 1 ml spray solution was applied to each upper and lower part of the leaf for a total of 4 ml per plant. Four applications of each test compound used a 16 ml spray solution. The plants were air dried and then placed in a maintenance chamber (26 ° C and 40% relative humidity) for 21 days. The efficacy of the compound was evaluated by counting, under a dissecting microscope, the number of pupa cases passed per leaf. A case of pupa elapsed represents a white fly egg that has undergone complete development to obtain an adult status, indicating the lack of control. The percentage of control based on the reduction of pupal cases elapsed from a test compound compared to the solution alone (without test compound) sprayed on the plants is reported in Table 1.

Seed Treatment against Pumpkin Cotton Aphid 10.16 cm containers were filled to two thirds with a screened earth mixture (70 sand / 30 ground pulverized). The compound was applied as a suspension to the center in a volume of 4 ml. The pumpkin seed placed in the area of chemical applied was covered with the soil mixture to a depth of 1 cm. The containers were irrigated and kept in the greenhouse for 10 days, at which time each plant presented a fully expanded leaf available for infestation. The plants were then infested with aphids. Four days later, aphid accounts were made. The results are summarized in the following tables: Cotton aphid counts in pumpkin cotyledons Compound Average Regimen SD% Mg Control / vessel Compound 2 12.8 7.0 6.2 93.3 3.2 7.3 4.0 93.1 0.8 48.0 42.1 54.4 Compound 45 12.8 80.0 37.7 24.0 3.2 50.3 14.8 52.3 0.8 165.5 8.6 0 Imidaclopride 0.8 0 0 100 (control) 0.2 0 0 100 • 0.05 2.5 3.5 97.6 Verification 0 105.3 45.8 0 Cotton aphid beads in pumpkin - 1st true leaf Compound Regimen Mean SD% Mg Control / container Compound 2 12.8 3.3 2.6 96.1 3.2 3.5 2.4 95.9 0.8 12.0 14.2 85.8 Compound 45 12.8 8.3 5.1 90.2 3.2 18.8 12.5 77.8 0.8 40.8 18.9 51.7 Imidaclopride 0.8 0.0 0.0 100.0 (control) 0.2 9.8 6.5 88.4 0.05 35.0 21.2 58.5 Verification 0 84.4 53.2 0 In addition to being effective against mites, aphids and insects, when applied to foliage, the compounds of formula (1) have exhibited systemic activity. Accordingly, another aspect of the invention is a method for protecting an insect plant, which comprises treating the seed of the plant before planting it, treating the soil where the seed of the plant is to be planted, or treating the soil. in the roots of a plant after planting, with an effective amount of a compound of the formula (1).

COMPOSITIONS The compounds of this invention are applied in the form of compositions, which are important embodiments of the invention and which comprise a compound of this invention and an inert, phytologically acceptable carrier. The compositions are either in concentrated formulations, which are dispersed in water for application, or are powder or granulated formulations, which are applied without further treatment. The compositions are prepared according to methods and formulas that are conventional in the agricultural chemistry art, but which are novel and important due to the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to ensure that agricultural chemists can easily prepare any desired composition. The dispersions in which the compounds are applied in general are aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Said water soluble formulations, which are suspended with water or emulsifiable are either solid, usually as wettable powders, or liquid, commonly known as emulsifiable concentrates or aqueous suspensions. The wettable powders, which can be compacted to form water-dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is generally from about 10% to about 90% by weight. The inert vehicle is usually selected from among attapulgite clays, montmorillonite clays, diatomaceous earths, or purified silicates. Effective surfactants comprising from about 0.5% to about 10% of the wettable powder are among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalene sulphonates, the alkyl benzene sulphonates, the alkyl sulfates and the nonionic surfactants, such as oxide adducts. of ethylene of alkyl phenols. The emulsifiable concentrates of the compound comprise a convenient concentration of a compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier, which is either a solvent miscible in water or a mixture of an organic solvent not miscible in water and emulsifiers. Suitable organic solvents include aromatics, especially xylenes, and petrolatum fractions, especially the high boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents can also be used, such as terpene solvents including rosin derivatives, aliphatic ketones such as cyclohexanone and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are selected from conventional nonionic surfactants, such as those discussed above. Aqueous suspensions comprise suspensions of water insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range of about 5% to about 50% by weight. The suspensions are prepared by finely grinding the compound, and mixing it vigorously in a vehicle comprising water and surfactants selected from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, can also be added to increase the density and viscosity of the aqueous vehicle. It is generally more effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston type homogenizer. The compounds can also be applied as granular compositions, which are particularly useful for earth applications. The granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier, which consists completely or largely of clay or a similar inexpensive substance. Said compositions are usually prepared by dissolving the compound in a suitable solvent and applying them to a granular carrier, which has been pre-formed to the appropriate particle size, on the scale of about 0.5 to 3 mm.

Said compositions can also be formulated by making a dough or paste from the vehicle and grinding or drying to obtain the desired granulated particle size. The powders containing the compounds are prepared simply by intimately mixing the compound in powder form with a suitable powdered agricultural vehicle, such as kaolin clay, ground volcanic rock, and the like. The powders can conveniently contain from about 1% to about 10% of the compound. It is equally practical, when desired for some reason, to apply the compound in the form of a solution in an appropriate organic solvent, usually a soft petroleum oil, such as the spray oils, which are widely used in agricultural chemistry. Insecticides and acaricides are generally applied in the form of a dispersion of the active ingredient in a liquid vehicle. It is conventional to refer to the application rates in terms of the concentration of the active ingredient in the vehicle. The most widely used vehicle is water. The compounds of the invention can also be applied in the form of an aerosol composition. In said compositions, the active compound is dissolved or dispersed in an inert carrier, which is a mixture of pressure generating propellant. The aerosol composition is packaged in a container from which the mixture is dispensed through a spray valve. The propulsion mixtures comprise either low boiling hydrocarbons, which can be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons. The actual amount of the compound that will be applied to the sites of insects, mites and aphids is not critical and can be easily determined by those skilled in the art in view of the above examples. In general, concentrations of 10 ppm to 5000 ppm of the compounds are expected to provide good control. With the many compounds, concentrations of 100 ppm to 1500 ppm will be sufficient. For field crops, such as soybean and cotton, a suitable application rate for the compounds is from about 0.227 to 0.681 kg / A, typically applied at 18.92 to 75.68 liters / A of spray formulation containing from 1200 to 3600 ppm of the compound . For citrus crops, a suitable application rate is approximately 378.4 to 5676 liters / A of spray formulation, which is a rate of 100 to 1000 ppm. The site to which a compound is applied can be any site inhabited by an insect or arachnid, for example, vegetable crops, fruit and nut trees, grapes, and ornamental plants. Since many mite species are specific to a particular host, the above list of mite species provides an illustration of the wide variety of conditions in which the compounds of the present invention can be used.

Due to the unique ability of the mite eggs to resist the toxic action, repeated applications may be desirable to control newly emerged larvae, just as it is true in other acaricides. The following formulations of compounds of the invention are typical of compositions useful in the practice of the present invention.

A. 0.75 Emulsifiable Concentrate Compound of the formula (1) 9.38% "TOXIMUL D" (mixture of nonionic / anionic surfactant) 2.50% "TOXIMUL H" (mixture of nonionic / anionic surfactant) 2.50% "EXXON 200" (naphthalene solvent) 85.62% B. 1.5 Emulsifiable Concentrate Compound of formula (1) 18.50% "TOXIMUL D" 2.50% "TOXIMUL H" 2.50% "EXXON 200" 76.50% C. 1.0 Emulsifiable Concentrate Compound of the formula (1) 12.5% N-methylpyrrolidone 25.00% "TOXIMUL D" 2.50% "TOXIMUL H" 2.50% "EXXON 200" 57.50% D. 1.0 Aqueous Suspension Compound of the formula (1) 12.00% "PLURONIC'P-103" (block copolymer of propylene oxide and ethylene oxide, surfactant) 1.50% "PROXEL GXL" (biocide / preservative) .05% "AF-100" (foaming agent based on silicon) .20% "REAX 88B" (lignosulfonate dispersing agent) 1.00% Propylene glycol 10.00% "Vegum" .75% Xantano .25% Water 74.25% E. 1.0 Aqueous Suspension Compound of the formula (1) 12.50% "MAKON 10" (10 moles of ethylene oxide-nonylphenol surfactant) 1.00% "ZEOSYL 200" (silica) 1.00% "AF-100" 0.20% "AGRIWET FR" (surfactant) 3.00% 2% xanthan hydrate 10.00% Water 72.30% F. 1.0 Aqueous Suspension Compound of the formula (1) 12.50% "MAKON 10" 1.50% "ZEOSYL 200" (silica) 1.00% "AF-100" 0.20% "POLYFON H" (lignosulfonate dispersing agent) 0.20% 2% xanthan hydrate 10.00% Water 74.60% G. Wettable Powder Compound of the formula (1) 25.80% "POLYFON H" 3.50% "SELLOGEN HR" 5.00% "STEPANOL ME DRY" 1.00% Gum arabic 0.50% "HISIL 233" 2.50% Clay of Barden 61.70% H. 1.0 Aqueous Suspension Compound of the formula (1) 12.40% "TERGITOL 158-7" 5.00% "ZEOSYL 200" 1.00% "AF-100" 0.20% "POLYFON H" 0.50% 2% xanthan solution 10.00% Running water 70.90% 1. 1.0 of Emulsifiable Concentrate Compound of the formula (1) 12.40% "TOXIMUL D" 2.50% "TOXIMUL H" 2.50% "EXXON 200" 82.60% J. Wettable Powder Compound of the formula (1) 25.80% "SELLOGEN HR" 5.00% "POLYFON H" 4.00% "STEPANOL ME DRY" 2.00% "HISTIL 233" 3.00% Clay Barden 60.20% K. 0.5 Emulsifiable Concentrate Compound of the formula (1) 6.19% "TOXIMUL H" 3.69% "TOXIMUL D" 0.40% "EXXON 200" 89.81% L. Emulsifiable Concentrate Compound of the formula (1) 5 to 48 Surfactant or surfactant mixture 2 to 20% Aromatic solvent or mixture 55 to 75%

Claims (25)

1. CLAIMS 1. - A compound of the formula (1): R¿A - xp R (1) wherein: Ar is substituted phenyl; And it's O u S; R 2 is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl or alkoxyalkyl; R3 is selected from H, halogen, lower alkyl, straight or branched chain alkyl (C7-C21), hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, lower alkynyl, haloalkenyl, CN, NO2, COR6, CO2R6, CON (R6) 2, cycloalkyl (C3-C6), S (O) mR6, -OSOmR6, SCN, - (CH2) nR6, -CH = CHR6, -C = CR6, - (CH2) qOR6, - ( CH2) qSR6, - (CH2) qNRßR6, -O (CH2) qR6, -S (CH2) qR6, -NR6 (CH2) qR6, 0 (CH2) qR6, -S (CH2) gR6, -NR6 (CH2) qR6, -N (CH2) p -NO,, OR ° OO or NO -NR "A. -NRβ 0Rβ AN (R6) R ° - - OO? R °. Si (R7) 3, pyridyl, substituted pyridyl, isoxazolyl, substituted-substituted-soxazolyl, naphthyl, substituted-naphthyl, phenyl, substituted phenyl, thienyl, substituted thienyl, substituted pyrimidyl, substituted pyrimidyl, pyrazolyl or substituted pyrazolyl; R4 and R5 are independently H, halogen, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON (R6) 2, or S (O) m alkyl, or Si R4 and R5 are bonded to adjacent carbon atoms, they join to form a saturated or unsaturated carbocyclic ring of 5 or 6 members, which can be substituted by 1 or 2 halogen, lower alkyl, lower alkoxy or haloalkyl groups; Rβ is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl or substituted phenyl; R7 is lower alkyl; m is 0, 1, or 2; n is 1 or 2; p is an integer from 2 to 6; and q is 0 or 1; or a pharmaceutically acceptable acid addition salt thereof.
2. 2. A compound of the formula (1A): wherein: R1 and R1 are independently H, Cl, F, methyl, halomethyl, methoxy, or haloomethoxy; And it's O u S; R 2 is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl or alkoxyalkyl; R3 is selected from H, halogen, lower alkyl, straight or branched chain alkyl (C7-C2.), Hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, lower alkynyl, haloalkenyl, CN, NO2, COR6 , CO2R6, CON (R6) 2, cycloalkyl (C3-C6), S (0) mR6, SCN, pyridyl, substituted pyridyl, isoxazolyn, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, - (CH2) nR6, -CH = CHR6, -C = CR6, -CH2OR6, -CH2SR6, SCH2R6, -NR6CH2R6, O O O -N (CH,). -NR A -NR A OR ° -NR ° A N (R6), ^ OR "NOOO Re ^ H -O ^ Rfi, O -s-'X6 R4 and R5 are independently H, halogen, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON (R6) 2, or S ( O) m alkyl, or R4 and R5 form a saturated or unsaturated carbocyclic ring of 5 or 6 members, which can be substituted by 1 or 2 halogen, lower alkyl, lower alkoxy or haloalkyl groups; R6 is * H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl or substituted phenyl, m is 0, 1, or 2, and n is 1 or 2, p is an integer from 2 to 6, and or a pharmaceutically acceptable acid addition salt thereof. - A compound according to claim 2, wherein Y is sulfur 4. A compound according to claim 2, wherein the group: is a 2-thienyl group of the formula: 5. - A compound according to claim 2, wherein R is chloro and R is chloro or fluoro. 6. A compound according to claim 2, wherein R2 is methyl. 7. A compound according to claim 2, wherein R3, R4 and R5 are each halogen. 8.- UYi composed of the formula (1B): wherein: R and R1 are independently F or Cl; R2 is lower alkyl, methyl being the most preferred; and R3, R4 and R5 are independently H, Cl, or Br. 9. A compound according to claim 8, wherein R1 is F or Cl and R1 'is F. 10. The compound according to claim 9, which is 3- (2-cioro-6-fluorophenyl) -5- (3,4,5-trichlorothien-2-yl) -1-methyl [1, 2,4] triazole. 11. A compound according to claim 8, wherein R1 and R1 'are Cl. 12. The compound according to claim 12, which is 3 - ((2,6-dichlorophenyl) -5- ( 3,4,5-trichlorothien-2-yl) -1-methyl [1,2,4] triazole. 13. - A composition for controlling insects or mites, comprising a compound of claim 1 in combination with a phytologically acceptable vehicle. 14. A method for controlling insects or mites, comprising applying to a Site ert where control is desired, an inactivating amount of insects or mites of a compound of claim 1. 15. A method for controlling whitefly, the which comprises applying to a site where control is desired, a white fly inactivating amount of a compound of claim 1. 16. A method for controlling mites, which comprises applying to a site where control is desired, an inactivating amount of a compound of claim 1. 17. A method for controlling aphids, which comprises applying to a site where control is desired, an aphid-inactivating amount of a compound of claim 1. 18.- A method to protect a plant from aphids, mites, or insects, which involves treating the plant seed before planting it, treating the soil where the plant seed is going to be planted, or treating the soil at the roots of a plant after it has been planted, with an effective amount of a compound of claim 1. 19. A compound of the formula (6): wherein R 11 is lower alkyl. 20. A compound of the formula (2b): wherein R 12 is lower alkyl, and R 13 is a conventional amino protecting group. 21. A process for preparing a compound of claim 1, wherein R1 and R1 are F, which comprises reacting a compound of the formula (2b): wherein R12 is lower alkyl, and R13 is a conventional amino protecting group, with a compound of the formula (3): wherein R3, R4 and R5 are independently selected from H, halogen, and lower alkyl. 22. A process for preparing a compound of claim 1, wherein R1 and R1 'are F, which comprises the steps of: (a) reacting a compound of the formula (6): wherein R1 is lower alkyl, with a compound of the formula: R .1'2 H, N-N, 13 to produce a compound of the formula (2b): wherein R 12 is lower alkyl, and R 13 is a conventional amino protecting group; and (b) reacting the compound of the formula (2b) with a compound of the formula (3): wherein R3, R4 and R5 are independently selected from H, halogen, and lower alkyl. 23. A process for preparing a compound of claim 1, wherein R2 is CH3, which comprises: reacting the compound of the formula (14): wherein R1 and R1 are as defined in claim 1, R4 is methanesulfonyl, benzenesulfonyl or substituted benzenesulfonyl, with a compound of the formula (15): wherein: R3 is selected from H, halogen, lower alkyl, straight or branched chain alkyl (C7-C21), hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, lower alkynyl, haloalkenyl, CN, NO2 , COR6, CO2R6, CON (R6) 2, (C3-C6) cycloalkyl, S (O) mR6, -OSOmR6, SCN, pyridyl, substituted pyridyl, "isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, - (CH2) nR6, -CH = CHR6, -C = CR6, - (CH2) qOR6, - (CH2) qSR6, - (CH2) qNR6R6, -O (CH2) qR6, -S (CH2) qR6, -NR6 (CH2) qR6, 0 (CH2) qR6, -S (CH2) qR6, -NR6 (CH2) qR6, N (CH2 'p - N O, \ , ORD or o or N O - R6Xe - NR6XR6 - N 6 N (R6) 2 R6. - O A '"^ .R6 / o R4 and R5 are independently H, halogen, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON (R6) 2, or S (O) m alkyl, or Si R4 and R5 are bonded to adjacent carbon atoms, they join to form a saturated or unsaturated carbocyclic ring of 5 or 6 members, which can be substituted by 1 or 2 halogen, lower alkyl, lower alkoxy or haloalkyl groups; R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl or substituted phenyl; m is 0, 1, or 2; n is 1 or 2; and p is an integer from 2 to 6. 24.- The process for preparing a compound of claim 1, wherein R2 is CH3, which comprises the steps of: (a) reacting a compound of the formula (10): wherein R and R1 are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy, with a compound of the formula (11): H I .N. H, N (11) wherein R 4 is methanesulfonyl, benzenesulfonyl or substituted benzenesulfonyl, to produce a compound of the formula (12): (b) methylating the compound of the formula (12) to produce a compound of the formula (13): (c) chlorinating the compound of the formula (13) to produce a compound of the formula (14): (d) reacting the compound of the formula (14) with a compound of the formula (15): S) wherein: R3 is selected from H, halogen, lower alkyl, straight or branched chain alkyl (C7-C21), hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, lower alkynyl, haloalkenyl, CN , NO2, COR6, CO2R6, CON (R6) 2, (C3-C6) cycloalkyl, S (0) mR6, -OSOmR6, SCN, pyridyl, substituted pyridyl, "isoxazolyl, substituted-substituted-sodium, naphthyl, substituted-naphthyl, phenyl, substituted phenyl, - (CH2) nR6, -CH = CHR6, -C_CR6, - (CH2) qOR6, - (CH2) qSR6, - (CH2) qNR6R6, -O (CH2) qR6, -S (CH2) qR6, - NR6 (CH2) qR6, 0 (CH2 - R ° O - S ^ R6 R4 and R5 are independently H, halogen, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON (R6) 2, or S (O) m alkyl, or R4 and R5 form a saturated or unsaturated carbocyclic ring of 5 or 6 members, which can be substituted by 1 or 2 halogen, lower alkyl, lower alkoxy or haloalkyl groups; R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl or substituted phenyl; m is 0, 1, or 2; and n is 1 or 2; and p is an integer from 2 to 6. 25.- A compound of the formula (14): wherein R1 and R1 'are independently H, Cl, F, methyl, halomethyl, methoxy or halomethoxy, and R14 is methanesulfonyl, benzenesulfonyl or substituted benzenesulfonyl.