INSECTICIDAL BIPHENYLTHIOHYDRAZIDES

Abstract: The present invention provides N-biphenylthiohydrazone derivatives of formula (I) and compositions and methods for the use thereof in the control of insect and acarid pests and for the protection of crops therefrom.

Description: INSECT CIDAL BIPHENYLTHIOHYDRAZIDES BACKGROUND OF THE INVENTION Significant global economic losses in major agronomic crop production are caused by the damage and infestation of insect and acarid pests. Crop reduction due to said pests, for example, in cotton and peanuts, can range as high as 39% and 78%, respectively. Pest infestation can result in lower yields, lower crop quality, reduced consumption, increased perishability, increased risk of disease, higher processing cost, higher transportation cost and increased market prices. Therefore, new and effective insect and acarid control agents and crop protection methods are a continuing global need. It is thus an object of this invention to provide N- biphenylthiohydrazone derivatives which are effective agents for the control of pestiferous insects and especially, acarina. It is another object of this invention to provide a method for the protection of growing and harvested crops from the harmful and deleterious effects caused by insects and especially, acarid pests. It is a further object of this invention to provide insecticidal and acaricidal compositions for use in the methods of the invention. SUMMARY OF THE INVENTION The present invention provides novel N- biphenylhydrazone compounds of formula I ( I ) wherein R is hydrogen, C ] _-C ] _oalkyl optionally substituted with one or more halogen, C3 -Cgcycloalkyl , C ] _-C4alkoxy, Cι-C4haloalko y, (C 1 -C 4 -alkyl)SO x , (C 1 -C4haloalkyl) SOy, phenyl optionally substituted with one to three halogen, Cι-C 4 alkyl, C 1 -C 4 haloalkyl, Cι-C4alko y, C -C4haloalkoxy, (C 1 -C 4 alkyl)S0 x , (C 1 -C4haloalkyl) SOy, NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C1-C4alkyl, Cι-C4haloalkyl, C!-C4alko y, Cι-C4haloal o , (C 1 -C 4 alkyl)SO x , (Cι-C 4 haloalkyl) SO y , NO2 or CN groups; C3-C;j_2cycloalkyl optionally substituted with one or more halogens, Cι-C 6 alkyl, C -C4haloalkyl, Cι-C4alkoxy, Cι-C4haloalkoxy, (Cx-C alkyl ) SO x , (C 1 -C 4 haloalkyl)SO x , phenyl optionally substituted with one to three halogen, C2 . -C4alkyl Ci-C^haloalkyl, Cχ-C4alko y, C ] _-C4haloalkoxy, O2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C ] _-C4alkoxy, C ] _-C4haloalkoxy, NO2 or CN groups ; or phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C;]_-C4haloalkyl , C]_-C4al o , C_-C4haloalko y, NO2 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2; ^ 2 f c l~ c 10 a - γl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, Cτ . -C4alkyl, c l~C4haloalkyl , Cι_-C4haloalko y, NO2 or CN groups, C;j_-C4alko y, C -C4haloalkoxy, ( C -C 4 alkyl)SO x , CONR 8 R 9 , Rl2' C3-Cgcycloalkyl optionally substituted with one to three halogen, C1-C4alkyl, Cι_C4 haloalkyl, Cι-C4alkoxy, Cl~ 4ha1oa1koxy, O2 or CN groups, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι-C4halo lkyl, C -C 4 alkoxy, C ] _-C haloalkox , O2 or CN groups, or pyridyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, c l -C 4haloalkyl, C]_-C4alkoxy, c l~ c 4haloalkoxy, NO2 or CN groups; C2-C]_o a lk nyl optionally substituted with one or more halogen, hydroxy, Cι~C4alko y, C 1 -C 4 alkyl) SO x , CONR 8 R 9 , R11, Rl2' C3-Cgcycloalkyl optionally substituted with one to three halogen, C 1 -C 4 alkyl, C 1 -C 4 halo-alkyl, Cι-C4alkoxy, Cχ-C4haloalkoxy, NO2 or CN groups, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι-C4haloalkyl , c l~ c 4 a lkoxy, Cχ-C4haloalkoxy, O2 or CN groups, or pyridyl optionally substituted with one or more halogen, C1-C4alkyl, Cj.-C4haloalkyl, Cι-C4alkoxy, Cχ-C4haloalkoxy, O2 or CN groups ; C2-Cιo a lky yl optionally substituted with one or more halogen, hydroxy, C]_-C4alko y, (C 1 -C 4 alkyl)SO x , CONR 8 R 9 , Rl2' C3-Cgcycloalkyl optionally substituted with one to three halogen, C 1 -C 4 alkyl, C 1 -C 4 halo-alkyl , C;j_-C4alko y, C ] _-C4haloalkoxy, N0 2 or CN groups, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C]_-C4haloalkyl, Cι-C 4 alkoxy, C]_-C4haloalkoxy, NO2 or CN groups, or pyridyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι -C4-ialoalkyl , C^ -C4alkoxy, Ci-C^haloalkoxy, N0 or CN groups; or c 3" c 12 c ycloalkyl optionally substituted with one or more halogen, hydroxy, C]_-C4alkoxy, (C 1 -C 4 alkyl)SO x , CONR 8 R 9 , R 12 , C3-Cgcycloalkyl optionally substituted with one to three halogen, Cχ-C 4 alkyl, C -C4halo-alkyl, Cχ-C 4 alkoxy, Cχ-C4haloalkoxy, NO2 or CN groups, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι_-C4haloalkyl , C -C alkoxy, Cχ-C4haloalko y, NO2 or CN groups, or pyridyl optionally substituted with one or more halogen, Cι-C alkyl, Cι-C4alkoxy, Cι-C 4 haloalkoxy, NO2 or CN groups; phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C ] _-C4haloalkyl, Cτ . -C4alko y, Cι-C4haloalkoxy, N0 2 or CN groups, or pyridyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cτ.-C4haloalkyl , Cι-C4alko y, Cι-C4haloalkoxy, NO2 or CN groups; R2 is hydrogen or C;j_-C4alk l ; R 3 , R 4 , R5, Rg,and R7 are each independently hydrogen, halogen, CN, N0 2 , C^Cgalkyl, C]_- Cghaloalkyl, C^-Cgalkoxy, C]_-Cghaloalkoxy, or phenyl optionally substituted with one to three halogen, C ] _-C4alkyl, Cη . - C4haloalkyl, C]_-C4alkoxy, C ] _-C4haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SO y , N0 2 or CN groups, with the proviso that at least one of R3 , R4 , R5, Rg or R7 must be phenyl optionally substituted with one to three halogen, C;j_-C4alk l , C ] _- C4haloalkyl, C ] _-C4alkoxy, C ] _-C4haloalkoxy, (C ] _- C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SO x , N0 2 or CN groups ; x and y are each independently 0, 1 or 2 ; m is an integer of 0, 1 or 2 ; R 8 , R 9 and Rχo are each independently hydrogen or C Q _- C4alkyl ; R ll ±S NR 13 R 14' R-13 R-14/ an -d 15 are each independently hydrogen or C]_- C 4 alkyl; X is 0, S or NR15; R 16 is hydrogen, halogen or ^C^ alkyl; r is an integer of 0 or 1; p and q are each independently an integer of 0, 1, 2, or 3 with the proviso that only one of p, q, or r can be 0 and with the further proviso that the sum of p + q + r must be 4 , 5 or 6 ; and x is an integer of 0, 1 or 2 ; or the acid addition salts thereof. Also provided are methods and compositions for the control of insect and acarid pests and for the protection of growing and harvested crops from attack and infestation thereby. DETAILED DESCRIPTION OF THE INVENTION A wide variety of insects and acarina cause great economic loss by damaging or destroying agricultural crops and horticultural and pharmaceutical plants; by aiding in the spread and development of bacteria, fungi and viruses that produce diseases of plants; and by destroying or lowering the value of stored foods, other products and possessions. Insect and acarid attack and infestation cause some of the farmers' greatest problems the world over. The need for alternative and effective insect and acarid control is a global concern. It has now been found that the N-biphenylthio- hydrazone compounds of formula I are highly effective agents for the control of a wide variety of insect and, particularly, acarid pests. As such, these compounds can be used to advantage to combat mites of the species Tetranychus uri ticae (Koch) . Moreover, compounds of the present invention have been found to exhibit good activity against mite species which have developed resistance to existing commercial acaricides . Advantageously, compounds of formula I not only possess acaricidal activity but also exhibit useful activity against insect pests including Spodoptera eridania, southern army worms; Diabrotica virgifera, western corn rootworms; Heliothis virescens , tobacco budworms; Aphis fabae, bean aphids, and Aphis gossypii , cotton aphids. Preferred compounds of the invention are those compounds of formula I wherein R4 and Rg are each independently H or phenyl optionally substituted with one or more halogen, C- L -C ialoalkoxy, or C x -C 4 haloalkyl groups. More preferred compounds of the invention are those formula I compounds wherein R is Cη , -Cgalkyl or C3 - Cgcycloalkyl optionally substituted with one to three halogens; R3 and R7 are each independently H or C]_- Cgalkoxy; and R4 and Rg are each independently H or phenyl optionally substituted with one or more halogen, C x -C 4 haloalkoxy or C x -C 4 haloalkyl groups. The term " halogen" as used herein denotes chlorine, fluorine, bromine or iodine. The term " haloalkyl" notes an alkyl group, C n H2 n+ ι which contains from one halogen atom to 2n+l halogen atoms. Similarly, the term " haloalkoxy" denotes a 0C n H2 n+ χ group which contains from one to 2n+l halogen atoms. The halogen atoms may be the same or different. The term w acid addition salts" denotes those salts formed by acids commonly known in the art such as hydrogen chloride, hydrogen bromide, hydrogen bisulfate, hemi-hydrogen sulfate and the like. In the above definition of formula I, when n is 0, then Y is hydrogen. Those compounds of formula I wherein m is an integer of 1 or 2 may be prepared by the oxidation of the appropriate precursor using standard oxidizing reagents such as m-chloroperbenzoic acid (mcpba) , hydrogen peroxide and acetic acid, KMn0 , and the like in accordance with standard known reaction conditions, for instance, those described in U.S. 5,556,885. Typically this reaction is conducted at room temperature for periods of 1-4 days in a suitable solvent such as methylene chloride. This reaction is shown below flow diagram I . Flow Diagram I These compounds of formula I wherein m is 0 may be prepared by reacting the appropriate hydrazinoyl halide of formula II wherein X^ is halogen with a suitable mercaptan of formula III wherein R x is as hereinbefore defined in the presence of a base as shown below in flow diagram II. Flow Diagram II Alternatively, the appropriate N-biphenylthio- hydrazide of formula IV may be reacted with the appropriate alkyl halide in the presence of a suitable base to give the desired N-biphenylthiohydrazone compounds of formula la. The base utilized can be either organic or inorganic, and typically is sodium or potassium carbonate. Suitable solvents include those such as acetone, and typically the reaction is conducted at reflux temperature thereof for periods of about ^ to 4 hours . This reaction is illustrated below in flow diagram III . Flow Diagram III (IV) (la) Compounds of formula IV may be readily prepared by the reaction of the corresponding biphenyl hydrazide of formula V with Lawesson's Reagent. Typically, this reaction is conducted in a suitable solvent, such as toluene or benzene, at temperatures ranging from about 50 °C to about 80° for a period of about ^ to 4 hours. The reaction scheme is shown in flow diagram IV. Flow Diagram IV Compounds of formula II may be prepared by reacting triphenylphosphine and carbon tetrachloride with the corresponding biphenyl hydrazide of formula V. Alternatively, the formula II compound may be prepared by heating the appropriate formula V biphenyl hydrazide with phosphorus pentachloride, and treating the reaction mixture sequentially with carbon tetrachloride and phenol. These reactions are illustrated below in flow diagram V. Flow Diagram V , phenol (II) Further, formula II compounds may be prepared using conventional literature methods such as those described by Tanaka Kiyoshi, Maeno Seiji, and Mitsuhashi Keiryo in the Journal of Heterocyclic Chemistry, 22 (1985), pp. 565- 568. Similarly, compounds of formula V may be readily prepared by conventional methods such as those described in WO 93/10083. Growing or harvested crops may be protected from attack or infestation by insect or, particularly, acarid pests by applying to the foliage of the crops, or to the soil or water in which they are growing, a pesticidally effective amount of N-biphenylthiohydrazone derivative of formula I . In actual agronomic practice, generally about 10 ppm to 10,000 ppm, and preferably about 100 to 5,000 ppm, of the formula I compound is dispersed in a liquid carrier. When applied to the plants or the soil or water in which they are growing, these amounts are effective to protect the plants from insect and acarina attack and infestation. Applications, such as spray applications, of compositions of the invention are generally effective at rates which provide about 0.125 kg/ha to about 250 kg/ha, preferably about 10 kg/ha to 100 kg/ha of active ingredient . The rate of application may be dependent upon the prevailing environmental circumstances such as population density, degree of infestation, stage of plant growth, soil conditions, weather conditions and the like. Advantageously, the formula I compounds may be used in conjunction with, or in combination with, other biological and chemical control agents including insecticides, nematicides, acaricides, molluscicides, and fungicides. Insecticides may include nuclear polyhedrosis viruses, pyrroles, arylpyrroles, halobenzoylureas, pyrethroids, carbamates, phosphates, and similar conventional insect agents. Typical formulations suitable for the formula I N- biphenylthiohydrazone derivatives are sprays, granular compositions, flowable compositions, wettable powders, dusts, microemulsions, emulsifiable concentrates or any conventional agricultural composition. All compositions which lend themselves to soil, water and foliage application and provide effective plant protection are suitable. Compositions of the invention include the I N- biphenylthiohydrazone derivative of formula I admixed with an agriculturally acceptable solid or liquid carrier. Where compositions of the invention are to be employed in combination treatments with other biological or chemical agents, the composition may be applied as an admixture of the components or may be applied sequentially to the target pest and/or crop. While not required, the combination composition comprising a formula I compound and a co-pesticide may also comprise other components, for example, fertilizers, inert formulation aides such as surfactants, emulsifiers, defoamers, dyes, extenders and the like. In order to aid in the understanding of the invention, specific examples thereof are set forth below. The invention described and claimed herein is not to be limited in scope by these merely illustrative examples. Indeed, various modifications of the invention in addition to those exemplified and described herein will become apparent to those skilled in the art from the following examples and the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. The terms 1 H, 13 C, 19 F NMR designate proton, carbon and fluorine nuclear magnetic resonance spectroscopy, respectively. IR designates infrared spectroscopy. EXAMPLE 1 Preparation of (4-methoxy-3-biphenylyl)hydrazine hydrochloride A suspension of 5-phenyl-o-anisidine (10 g, 50.0 mmol) in water and hydrochloric acid (concentrated, 180 ml) is cooled to 0° C, treated dropwise with a 0° C solution of sodium nitrite (3.45 g, 50.0 mmol) in water, stirred for one hour, treated with a -20° C solution of tin chloride (45.2 g,238 mmol) in concentrated hydrochloric acid (80 ml) , stirred for one hour at 0° C and filtered. The filter cake is mixed with hot water and filtered. The filtrate is cooled and filtered to obtain the title product, as beige crystals, in 64.3% yield, mp 184-186° C. EXAMPLE 2 Preparation of 2 ,2-dimeth.ylpropionate, 2- (4-methoxy-3- biphenylyl) hydrazide A suspension of (4-methoxy-3-biphenylyl) hydrazine, hydrochloride (25.07 g, 100 mmol) in methylene chloride is treated with triethylamine (21.25 g, 210 mmol). A solution of trimethylacetyl chloride (12.06 g,100 mmol) in methylene chloride is added dropwise to the reaction mixture and stirred for four hours at room temperature. After pouring the reaction mixture into water, the mixture is extracted with ethyl acetate, and the extract washed with 15% hydrochloric acid, water, and a saturated aqueous solution of sodium chloride, dried over sodium sulfate and filtered. The filtrate is concentrated in vacuo and the resultant pink residue recrystallized from hexane to afford the title product, as a white solid (21.7 g) , in 75.5% yield, mp 153-156° C. Identity is confirmed by ^ΗNMR, 13 CNMR, and IR. EXAMPLE 3 Preparation of l-eh.loro-2, 2-dimethylpropionaldehvde, 2 - (4-methoxy-3-biphenylyl)hvdrazone A solution of 2 , 2-dimethylpropionate, 2- (4-methoxy- 3 -biphenylyl) hydrazide (5.97 g, 20 mmol) and triphenylphosphine (15.7 g,60 mmol) in acetonitrile is treated with carbon tetrachloride (10.15 g, 66 mmol), stirred for one hour and concentrated in vacuo to afford an orange residue. The residue is dissolved in ether, cooled to -32° C and filtered. The filtrate is concentrated in vacuo to afford the title product, as a white solid (3.53 g) , in 55.7% yield. Identity is ■ confirmed by 1 H MR and 13 CNMR. EXAMPLE 4 Preparation of l-chloro-2 , 2-dimethylpropionaldehvde, 2- (4-methoxy-3 -biphenylyl) hvdrazone A suspension of 2 , 2-dimethylpropionate, 2- (4- methoxy-3 -biphenylyl) hydrazide (7.46 g,25 mmol) and phosphorus pentachloride (5.47 g,26 mmol) in carbon tetrachloride is refluxed for 15 minutes. The reaction mixture is cooled to 0° C, treated with phenol (7.9 g,84 mmol) , warmed to room temperature and concentrated in vacuo give a brown oil. The oil is recrystallized from hexane to afford the title product, as a beige solid (4.66 g) , in 58.9% yield. Identity is confirmed by ^NMR, 13 CNMR, and IR. EXAMPLE 5 Preparation of S-methyl 2 , 2-dimethylthiopropionate, (4- methoxy-3 -biphenylyl) hvdrazone A solution of sodium thiomethoxide (1.12 g, 16 mmol) in methylene chloride (150 ml) is treated with 1- chloro-2, 2-dimethylpropionaldehyde, 2- (4-methoxy-3- biphenylyl) hydrazone (4.6 g, 14.5 mmol) and stirred for several hours at room temperature. The reaction mixture is poured into water extracted with methylene chloride. The extract is washed with dilute aqueous sodium hydroxide solution, water, and aqueous saturated sodium chloride, then dried over magnesium sulfate and filtered. After concentration of the filtrate in vacuo, the resultant yellow residue is dissolved in hexane and filtered. The filtrate is concentrated in vacuo to afford the title product, as a yellow oil (3.7 g) , in 77.7% yield. Identity is confirmed by X HNMR, 13 CNMR, and IR. EXAMPLE 6 Preparation of 2 , 2-dimeth.ylthiopropionate, 2- (5-fluoro-4- methoxy-3 -biphenylyl) ydrazide Lawesson's reagent (4.14 g,103 mmol) is added to a solution of 2 , 2-dimethylthiopropionate, 2- (5-fluoro-4- methoxy-3 -biphenylyl) hydrazide (6.33 g,20 mmol) in toluene and the reaction mixture heated to 80 °C . After approximately three hours at 80° C, the reaction mixture is cooled to room temperature and filtered. The filtrate is concentrated in vacuo to give an oily residue which was purified by silica gel flash chromatography. The title product is obtained, as a white solid (4.1 g) in 61.7% yield, mp 96-97° C. Identity is confirmed by ^N R, 13 CNMR, and IR. PAGE INTENTIONALLY LEFT BLANK EXAMPLE 7 Preparation of S-methyl 2 , 2-dimethylthiopropionate, 2- (5-fluoro-4-methoxy-3 -biphenylyl) ydrazone Methyl iodide (0.78 g, 5.5 mmol) is added slowly to a suspension of 2 , 2 -dimethylthiopropionate- , 2- (5-fluoro- 4 -methoxy-3 -biphenylyl) hydrazide (1.6 g, 5 mmol) and potassium carbonate (0.76 g, 5.5 mmol) in acetone at reflux. After three hours, the reaction mixture is cooled, poured into water, and extracted with ethyl acetate. The extract is washed with water and saturated aqueous sodium chloride solution, dried over sodium sulfate and filtered. The filtrate is concentrated in vacuo to afford the title product as a yellow oil, (1.7 g) in 98.3% yield. Identity is confirmed by X HNMR, 13 CNMR, and IR . EXAMPLES 8-14 Preparation of the N-Biphenylthiohydrazone Compounds Using essentially the same procedures described in Examples 1-7, and substituting the appropriate reagents, the compounds specified in the following Table I are prepared. The compounds obtained are oils, except where indicated, and their identity is confirmed by 1 HNMR, 13 CNMR, IR, mass spectral and elemental analyses. EXAMPLE 15 Preparation of S-methyl 2 , 2-dimethylthiopropionate, 2- (4-methoxy-3 -biphenylyl) hydrazone, S, S-dioxide A solution of S-methyl 2 , 2-dimethylthiopropionate, (4 -methoxy-3 -biphenylyl) hydrazone (1.2 g,3.9 mmol) in methylene chloride is treated dropwise with m-chloroper- benzoic acid (1.3 g, 8.1 mmol) and stirred for 3 days at room temperature. The reaction mixture is then poured into water extracted with methylene chloride and the extract washed with an aqueous solution of potassium carbonate (10%) , water, a saturated aqueous solution of sodium chloride, and then dried over magnesium sulfate and filtered. The filtrate is concentrated in vacuo to afford an oil which is purified via flash chromatography on silica gel. The title product is obtained, as a white solid (0.5 g) in 35.5% yield, mp 134-136° C. Identity is confirmed by 1 HNMR, 13 CNMR, IR and C, H, and N elemental analyses . Examples 16-22 Preparation of N-Biphenylthiohvdrazone, S,S-dioxide Compounds Using essentially the same procedure described in Example 15, and substituting the appropriate reagents, the following compounds specified in Table II are prepared. The compounds obtained are oils, except where indicated, and their identity is confirmed by 1 HNMR, 13 CNMR, IR, mass spectral and elemental analyses. EXAMPLE 23 Preparation of S-methyl 2 , 2 -dimethylthiopropionate, 2- [4 / - (trifluoromethyl) -2-biphenylyl] ydrazone, S-oxide A solution of S-methyl 2 , 2-dimethylthiopropionate 2- [4' (trifluoromethyl) -2 -biphenylyl] hydrazone (1.2 g,3.9 mmol) in methylene chloride is treated with 3- chloroperbenzoic acid (1.3 g, 8.1 mole) and stirred overnight at room temperature. After adding methylene chloride, the reaction mixture is then washed with potassium carbonate (10%) , water, and a saturated aqueous solution of sodium chloride. After drying over magnesium sulfate and filtering, the filtrate is concentrated in vacuo to afford an oil which is purified via silica gel flash chromatography. The title product is obtained, as an orange solid ( 0 . 09 g) , in 15% yield, mp 139-140° C. Identity is confirmed by ^NMR, 13 CNMR, IR and C, H, and N elemental analyses. EXAMPLE 24 Insecticidal Evaluation of N-Biphenylthiohydrazone, S- ethyl esters, and S-oxide, and S,S-dioxide Compounds In these evaluations, test solutions are prepared by dissolving the test compound in a 35% acetone in water mixture to give a concentration of 10,000 ppm (4,000 ppm for cotton aphids) . Subsequent dilutions are made with water as needed. Spodoptera eridania, 3rd instar larvae, southern armyworm (SAW) A Sieva limabean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood. The leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 3rd instar caterpillars. At 5 days, observations are made of mortality, reduced feeding, or any interference with normal molting. Diabrotic virgifera vergifera Leconte, 3rd instar western corn rootworm (WCR) One cc of fine talc is placed in a 30 ml wide- mouth screw-top glass jar. One mL of the appropriate acetone test solution is pipetted onto the talc so as to provide 1.25 mg of active ingredient per jar. The jars are set under a gentle air flow until the acetone is evaporated. The dried talc is loosened, 1 cc of millet seed is added to serve as food for the insects and 25 ml of moist soil is added to each jar. The jar is capped and the contents thoroughly mixed on a Vortex Mixer. Following this, ten 3rd instar root-worms are added to each jar and the jars are loosely capped to allow air exchange for the larvae. The treatments are held for 5 days when mortality counts are made. Missing larvae are presumed dead, since they decompose rapidly and can not be found. The concentrations used in this test correspond approximately to 50 kg/ha. Heliothis virenscens, 3rd instar tobacco budworm (TBW) Cotton cotyledons are dipped in the test solution and allowed to dry in a hood. When dry, each is cut into quarters and ten sections are placed indi- vidually in 30 mL plastic medicine cups containing a 5 to 7 mm long piece of damp dental wick. One 3rd instar caterpillar is added to each cup and a cardboard lid placed on the cup. Treatments are maintained for 3 days before mortality counts and estimates of reduction in feeding damage are made. Tetranychus urticae (OP-resistant strain), 2-spotted spider mite (TSM) Sieva limabean plants with primary leaves expanded to 7-8 cm are selected and cut back to one plant per pot. A small piece is cut back to one plant per pot. A small piece is cut from an infested leaf taken from the main colony and placed on each leaf of the test plants. This is done about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs. The size of the cut, infested leaf is varied to obtain about 100 mites per leaf. At the time of test treatment, the piece of leaf used to transfer the mites is removed and discarded. The newly mite-infested plants are dipped in the test solution for 3 seconds with agitiation and set in the hood to dry. After 2 days, one leaf is removed and mortality counts are made. After 5 days, another leaf is removed and observations are made of mortality of the eggs and/or newly emerged nymphs . Aphis fabae. mixed instar, bean aphid (BA) Pots containing single nasturtium plants (Tropaeolum sp . ) about 5 cm tall are infested with about 100-200 aphids one day before the test. Each pot is sprayed with the test formulation for 2 revolutions of a 4 rpm turntable in a hood, using a #154 DeVilbiss atomizer. The spray tip is held about 15 cm from the plant and the spray directed so as to give complete coverage of the plants and the aphids. The sprayed pots are set on their sides on white enamel trays and held for 2 days, following which mortality estimates are made. Aphis gossypii (cotton aphid) A heavily infested leaf is placed on top of a cotton plant which had been grown to the cotyledon stage. The aphids are allowed to transfer from the leaf section to the host plant overnight. The resultant infested leaves of the intact plant are dipped into the test solution and then allowed to dry. Aphid mortality counts are made after the test plants have been maintained under GRO-LUX ® lights (24 hour photoperiod) at 27-28° C for 5 days. Phytotoxicity to the cotton plant is also recorded at this time. The tests are rated according to the scale shown below and the data obtained are shown in Table III . When more than one test is conducted, the results are averaged . RATING SCALE Rate % Mortality Rate % Mortality 0 no effect 5 56-65 1 10-25 6 66-75 2 26-35 7 76-85 3 36-45 8 86-99 46-55 9 100 not tested Table III Insectic:idal Evaluation Of N-Biphenvlthi .ohvdrazone. S- oxide, and S, , S-dioxide Compounds % Mortality SAW WCR TSM TBW BA Compound 300 (50 (300/50 (300 (10 (100 (Ex.No.) ppm) ppm) ppm) ppm) PPm) ppm) 9/9 7 0 9 9/9 0 0 8 8 7 9 9/8 0 7 8 9 - 0 9/8 0 0 5 10 9 0 0/0 - 0 0 11 0 9 8/- 4 7 8 12 2 0 9/0 0 0 8 13 7 0 9/- - - - 14 0 0 0/0 - - - 15 0 0 9/9 2 0 7 16 0 0 9/ - 0 0 0 17 0 0 8/8 0 8 8 18 6 0 9/ ~ 0 0 7 19 0 0 9/9 2 0 7 20 0 0 0/0 - - 0 23 1 0 0/0 - - 0 EXAMPLE 25 Cotton Aphid (Aphis gossypii) A heavily infested leaf is placed on top of a cotton plant which had been grown to the cotyledon stage. The aphids are allowed to transfer from the leaf section to the host plant overnight. The resultant infested leaves of the intact plant are dipped into the test solution and then allowed to dry. Aphid mortality counts are made after the test plants have been maintained under GRO-LUX lights (24 hour photoperiod) at 27-28°C for 5 days. Phytotoxicity to the cotton plant is also recorded at this time. Two-spotted Spider Mite (Tetranychus urticae - 0P- resistant strain) Sieva limabean plants with primary leaves expanded to 7-8 cm are selected and cut back to one plant per pot . A small piece is cut from an infested leaf taken from the main colony and placed on each leaf of the test plants. This is done about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs. The size of the cut, infested leaf is varied to obtain about 100 mites per leaf. At the time of test treatment, the piece of leaf used to transfer the mites is removed and discarded. The newly mite-infested plants are dipped in the test solution for 3 seconds with agitation and set in the hood to dry. After 2 days, one leaf is removed and mortality counts are made. After 5 days, another leaf is removed and observations are made of mortality of the eggs and/or newly emerged nymphs . Compounds are rated according to the following scale: Rate % Mortality 0 No effect 1 10-25 2 26-35 3 36-45 4 46-55 5 56-65 6 66-75 7 86-99 8 100 Test Compounds Compound A Art Compound B Invention Compound C Art Compound D Invention Table A Comparative Insecticidal Evaluation of Test Compounds Dose Compound (ppm) CA TSM A 300 [ART] 300 B 100 [INVENTION] 10 C 300 [ART] 300 D 100 [INVENTION] 10

Claims: 33495 WHAT IS CLAIMED IS: 1. A compound of formula I (I) wherein R is hydrogen, C]_-C ] _ Q al yl optionally substituted with one or more halogen, C β -Cgcycloalkyl, C_-C4alkoxy, Cχ-C4haloalkoxy, (C!-C 4 -alkyl) SO x , (C-L-C 4 haloalkyl) SOy, phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl, C } _-C4haloalkyl, C]_-C4alkoxy, C]_-C4haloalkoxy, (C 1 -C 4 alkyl) SO x , (C 1 -C 4 haloalkyl) SOy, NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl , C]_ -C4haloalkyl , C 1 -C 4 alkoxy, C]_-C4haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl)SO y , NO2 or CN groups; C3-Ci2 c Y c l° a lkyl optionally substituted with one or more halogens, Cx-Cgalkyl, C 1 -C 4 haloalkyl, Cι_-C4alkoxy, C 1 -C4haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SO x , phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl C 1 -C 4 haloalkyl, Cχ-C4alkoxy, Cχ-C4haloalkoxy, NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, Cι-C 4 haloalkyl, C!-C4alko y, C]_-C4haloalkoxy, N0 2 or CN groups; or phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl , C ] _-C4haloalkyl , C ] _ -C4alkoxy, Cχ-C4haloalkoxy, NO2 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2 ; RQ_ is R 12 ; C -Cioalkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C 1 -C4haloalkyl, Cι-C4alko y, Cι-C4haloalko y, NO2 or CN groups, Cχ-C4alko y, C ] _-C4haloalkoxy, (C 1 -C 4 alkyl)SO x , CONR 8 R 9 , Rn, R 12 , C3-Cgcycloalkyl optionally substituted with one to three halogen, C 1 -C 4 alkyl, l- 4 haloalkyl, C_-C4alko y, C 1 -C4haloalkoxy, O2 or CN groups, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, 91 C 1 -C 4 haloalkyl, 92 C 1 -C 4 alkoxy, 93 C 1 -C 4 haloalkoxy, 94 NO2 or CN groups, or 95 pyridyl optionally substituted with one or more 96 halogen, 97 C 1 -C 4 alkyl, 98 C 1 -C 4 haloalkyl, 99 C 1 -C 4 alkoxy, 100 C; ] _-C4haloalkoxy, 101 NO2 or CN groups ; 102 C2 -C]_o a lkenyl optionally substituted with one or 103 more halogen, 104 hydroxy, 105 C 1 -C 4 alkoxy, 106 (C 1 -C 4 alkyl)SO x , 107 CONR 8 R 9 , 109 R 11# 110 R 12 , 111 C3-Cgcycloalkyl optionally substituted with one 112 to three halogen, 113 C 1 -C 4 alkyl, 114 C 1 -C 4 halo-alkyl, 115 C 1 -C 4 alkoxy, 116 C 1 -C 4 haloalkoxy, 117 NO2 or CN groups, 118 phenyl optionally substituted with one or more 119 halogen, 120 C 1 -C 4 alkyl, 121 C 1 -C4haloalkyl, 122 Cι-C 4 alkoxy, 123 C ] _-C4haloalkoxy, 124 NO2 or CN groups, or 125 pyridyl optionally substituted with one or more 126 halogen, 127 C 1 -C alkyl, 128 Cι-C4haloalkyl, 129 C 1 -C 4 alkoxy, 130 C;ι_-C4haloalkoxy, 131 NO2 or CN groups; 132 C2 -Ci Q alkγnyl optionally substituted with one or 133 more halogen, 134 hydroxy, 135 C 1 -C 4 alkoxy, 136 (C 1 -C 4 alkyl) SO x , 137 CONR 8 R 9 , 139 R 11# 140 R 12 , 141 C3-Cgcycloalkyl optionally substituted with one 142 to three halogen, 143 C 1 -C 4 alkyl, 144 C 1 -C 4 halo-alkyl, 145 Cι-C 4 alkoxy, 146 Cι-C4haloalkoxy, 147 NO2 or CN groups, 148 phenyl optionally substituted with one or more 149 halogen, 150 , C 1 -C 4 alkyl, 151 Cι-C 4 haloalkyl / 152 C 1 -C 4 alkoxy, 153 Cι-C4haloalkoxy, 154 NO2 or CN groups, or 155 pyridyl optionally substituted with one or more 156 halogen, 157 C 1 -C 4 alkyl, 158 C 1 -C 4 haloalkyl, 159 Cι-C 4 alkoxy, 160 C ~C4haloal o y, 161 N0 2 or CN groups; or 162 C3-C12cycloalkyl optionally substituted with one or 163 more halogen, 164 hydroxy, 165 Cι-C4alkoxy, 166 (C 1 -C 4 alkyl)SO x , 167 CONR 8 R 9 , 168 CO 2 R 10 , 169 R n , 170 R 12 , 171 C3-Cgcycloalkyl optionally substituted with one 172 to three halogen, 173 C 1 -C 4 alkyl, 174 C 1 -C4halo-alkyl, 175 C 1 -C 4 alkoxy, 176 Cι-C4haloalko y, 177 NO2 or CN groups, 178 phenyl optionally substituted with one or more 179 halogen, 180 C ] _-C4alkyl, 181 C 1 -C 4 haloalkyl, 182 C ] _-C4alkoxy, 183 Cι-C4haloalkoxy, 184 NO2 or CN groups, or 185 pyridyl optionally substituted with one or more 186 halogen, 187 C 1 -C4alkyl, 188 C 1 -C4haloalkyl, 189 C ] _-C4alkoxy, 190 C 1 -C 4 haloalkoxy, 191 N0 2 or CN groups ; 192 phenyl optionally substituted with one or more 193 halogen, 194 C 1 -C 4 alkyl, 195 C 1 -C 4 haloalkyl, 196 C 1 -C 4 alkoxy, 197 C 1 -C 4 haloalkoxy, 198 N0 2 or CN groups, or 199 pyridyl optionally substituted with one or more 200 halogen, 201 C 1 -C 4 alkyl, 202 C 1 -C 4 haloalkyl, 203 C 1 -C 4 alkoxy, 204 Cι-C 4 haloalkoxy, 205 N0 2 or CN groups; 206 R 2 is hydrogen or C -C4alkyl; 207 R3, R4, R5, Rg,and R7 are each independently hydrogen, 208 halogen, CN, N0 2 , Cx-Cg lkyl, C]_- 209 Cghaloalkyl, C]_-Cgalkoxy, C^-Cghaloalkoxy, 210 or phenyl optionally substituted with one 211 to three halogen, C ] _-C4alkyl, C]_- 212 C4haloalkyl, C;j_-C4alkoxy, C ] _-C4haloalkoxy, 213 (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SO y , N0 2 214 , or CN groups, 215 with the proviso that at least one of R3 , R4 , R5 , Rg or 216 R7 must be phenyl optionally substituted with 217 one to three halogen, C ] _-C4alkyl , C]_- 218 C4haloalkyl, Cι-C4alkoxy, C]_-C4haloalkoxy, (C ] _- 219 C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) S0 X , N0 2 or CN 220 groups; 221 x and y are each independently 0, 1 or 2 ; 222 m is an integer of 0, 1 or 2 ; 223 R 8 , R 9 and R^Q are each independently hydrogen or Ci- 224 C 4 alkyl; 225 R lχ is NR 13 R 14 , 229 230 i3, R-14' an d R-15 are each independently hydrogen or C]_- 231 C 4 alkyl ; 232 R 1S is hydrogen, halogen or C 1 -C 4 alkyl ; 233 X is O, S or NR 15 ; 234 r is an integer of 0 or 1 ; 235 p and q are each independently ail integer of 0, 1, 2, or 236 3 with the proviso that only one of p, q, or r can 237 be 0 and with the further proviso that the sum of p 238 + q + r must be 4 , 5 or 6; and 239 x is an integer of 0, 1 or 2 ; or 240 the acid addition salts thereof. 1 2. The compound according to Claim 1 wherein 2 R3 and R7 are each independently H or C]_-Cgalkoxy; and R4 3 and Rg are each independently H or phenyl optionally 4 substituted with one or more halogen, Cι-C4h loalko y, or 5 C ] _-C4haloalkyl groups. 3. The compound according to Claim 2 wherein R is Cχ-Cgalkyl or C3-Cgcycloalkyl optionally substituted with one to three halogens . 4. The compound according to Claim 2, S-methyl - 2, 2 -dimethylthiopropionate, 2- ( -methoxy-3 -biphenylyl) - hydrazone; the S-oxide thereof; the S,S-dioxide thereof; or the acid addition salt thereof. 5. A method for the control of insect or acarid pests which comprises contacting said pests, their food supply, habitat or breeding grounds with a pesticidally effective amount of a compound of formula I (I) wherein R is hydrogen, C;j_-C;]_o a l yl optionally substituted with one or more halogen, C3 -Cgcycloalkyl , C_-C4alkoxy, C1~ 4 a1oa1koxy, (C 1 -C 4 -alkyl) SO x , (C 1 -C 4 haloalkyl) SO y , phenyl optionally substituted with one to three halogen, Cι-C4alkyl, c l~ c 4h loalkyl , C-L -C4alkoxy, Cι-C4haloal oxy, (C 1 -C 4 alkyl)S0 x , (C 1 -C 4 haloalkyl)S0 y , NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C -C4haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl)SO y , N0 2 or CN groups; C3-Cι 2 cycloalkyl optionally substituted with one or more halogens, C -Cgalkyl, C 1 -C 4 haloalkyl, Cι-C4alkoxy, Cι-C4haloalkoxy, (C 1 -C 4 alkyl) SO x , (Cι -C 4 haloalkyl ) S0 X , phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl C 1 -C 4 haloalkyl, C ] _-C 4 alkoxy, Cι-C 4 haloalkoxy, N0 2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C -C4alkoxy, C ] _-C4haloalkoxy, NO2 or CN groups; or phenyl optionally substituted with one or more halogen, C 1 -C alkyl, C 1 -C 4 haloalkyl, C]_-C4alkoxy, Cι-C4haloalkoxy, NO2 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2; R]_ is R 12 ; C -C ] _o a lkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι-C 4 haloalkyl, Cι-C 4 alkoxy, C 1 -C 4 haloalkoxy, N0 2 or CN groups, Cχ-C4alkoxy, Cι-C4haloalko y, (C 1 -C 4 alkyl)SO x , CONR 8 R 9 , CO 2 R 10 , R llf ι 2 , C3-Cgcycloalkyl optionally substituted with one to three halogen, C 1 -C4alkyl, 85 C1-.C4 haloalkyl, 86 Cι-C 4 alkoxy, 87 C]_-C 4 haloalkoxy, 88 N0 2 or CN groups, 89 phenyl optionally substituted with one or more 90 halogen, 91 C 1 -C 4 alkyl, 92 C 1 -C 4 haloalkyl, 93 Cj_-C4alkoxy, 94 Cχ-C4haloalkoxy, 95 N0 or CN groups, or 96 pyridyl optionally substituted with one or more 97 halogen, 98 C 1 -C 4 alkyl, 99 Cχ-C4haloalkyl , 100 Cχ-C4alkoxy, 101 Cι-C4haloalkoxy, 102 N0 or CN groups; 103 C -Cιo a lkenyl optionally substituted with one or 104 more halogen, 105 hydroxy, 106 C]_-C alkoxy, 107 (C 1 -C 4 alkyl) SO x , 108 CONR 8 R 9 , 109 CO 2 R 10 , 110 Rll, 111 Rl2* 112 C3-Cgcycloalkyl optionally substituted with one 113 to three halogen, 114 C ] _-C4alkyl, 115 Cι-C 4 halo-alkyl, 116 Cχ-C4alkoxy, 117 Cι-C4haloalkoxy, 118 N0 or CN groups, 119 phenyl optionally substituted with one or more 120 halogen, 121 C 1 -C 4 alkyl / 122 C 1 -C 4 haloalkyl, 123 Cι-C 4 alkoxy, 124 Cι-C 4 haloalkoxy, 125 N0 2 or CN groups, or 126 pyridyl optionally substituted with one or more 127 halogen, 128 C 1 -C 4 alkyl, 129 C 1 -C 4 haloalkyl, 130 C ] _-C 4 alkoxy, 131 C ] _-C4haloalkoxy, 132 O2 or CN groups; 133 C 2 -Cιo a lkynyl optionally substituted with one or 134 more halogen, 135 hydroxy, 136 C;j_-C4alkoxy, 137 (C 1 -C 4 alkyl)SO x , 138 CONR 8 R 9 , 139 CO 2 R 10 , 140 R 11# 141 R 12 , 142 C3-Cgcycloalkyl optionally substituted with one 143 to three halogen, 144 C 1 -C 4 alkyl, 145 C 1 -C 4 halo-alkyl, 146 C 1 -C 4 alkoxy, 147 C 1 -C 4 haloalkoxy, 148 N0 2 or CN groups, 149 phenyl optionally substituted with one or more 150 halogen, 151 C 1 -C 4 alkyl, 152 C 1 -C 4 haloalkyl, 153 C 1 -C 4 alkoxy, 154 C]_-C 4 haloalkoxy, 155 N0 2 or CN groups, or 156 pyridyl optionally substituted with one or more 157 halogen, 158 C 1 -C 4 alkyl, 159 C 1 -C 4 haloalkyl, 160 C 1 -C 4 alkoxy, 161 C]_-C 4 haloalkoxy, 162 N0 2 or CN groups; or 163 C3-Cι_ 2 cycloalkyl optionally substituted with one or 164 more halogen, 165 hydroxy, 166 Cι-C 4 alkoxy, 167 (C 1 -C 4 alkyl)SO x , 168 CONR 8 R 9 , 169 CO 2 R 10 , 170 R 11# 171 R 12 , 172 C3-Cgcycloalkyl optionally substituted with one 173 to three halogen, 174 C 1 -C 4 alkyl, 175 C 1 -C 4 halo-alkyl, 176 C 1 -C 4 alkoxy, 177 C 1 -C 4 haloalkoxy, 178 N0 2 or CN groups, 179 phenyl optionally substituted with one or more 180 halogen, 181 C 1 -C 4 alkyl, 182 Cι-C haloalkyl, 183 Cι-C 4 alkoxy, 184 Cι-C 4 haloalkoxy, 185 N0 2 or CN groups, or 186 pyridyl optionally substituted with one or more 187 halogen, 188 C 1 -C 4 alkyl, 189 C 1 -C 4 haloalkyl, 190 C 1 -C 4 alkoxy, 191 C]_-C4haloalkoxy, 192 N0 2 or CN groups; 193 phenyl optionally substituted with one or more 194 halogen, 195 C 1 -C 4 alkyl, 196 Cι-C4haloalkyl, 197 Cι-C 4 alkoxy, 198 Cι-C 4 haloalkoxy, 199 N0 2 or CN groups, or 200 pyridyl optionally substituted with one or more 201 halogen, 202 C 1 -C 4 alkyl, 203 Cι-C 4 haloalkyl, 204 Cι-C 4 alkoxy, 205 C; ] _-C 4 haloalkoxy, 206 N0 2 or CN groups; 207 R 2 is hydrogen or C;ι_-C 4 alkyl ; 208 R3 , R4, R5, Rg,and R7 are each independently hydrogen, 209 halogen, CN, N0 , Cx-Cgalkyl, C x - 210 Cghaloalkyl, C ] _-Cgalkoxy, C^-Cghaloalkoxy, 211 or phenyl optionally substituted with one 212 to three halogen, Cι-C 4 alkyl, C ] _- 213 C4haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, 214 (C 1 -C 4 alkyl)SO x , (C 1 -C haloalkyl) S0 y , N0 2 215 or CN groups, 216 with the proviso that at lea ' st one of R3 , R4 , R5, Rg or 217 R7 must be phenyl optionally substituted with 218 one to three halogen, C]_-C4alkyl, C ] _- 219 C 4 haloalkyl, C]_-C4alkoxy, C ] _-C4haloalkoxy, (Cχ~ 220 C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SO x , N0 2 or CN 221 groups; 1 6. The method according to Claim 5 wherein 2 said pests are acarid pests. 1 7. The method according to Claim 5 having a 2 formula I compound wherein R3 and R7 are each 3 independently H or C^-Cgalkoxy; and R4 and Rg are each 4 independently H or phenyl optionally substituted with one 5 or more halogen, Cχ-C4haloalkoxy, or Cι_-C4haloalkyl 6 groups . 1 8. The method according to Claim 7 having a 2 formula I compound wherein R is C^-Cgalkyl or C3- 3 Cgcycloalkyl optionally substituted with one to three 4 halogens . 1 9. The method according to Claim 7 having the 2 formula I compound, S-methyl-2 , 2 -dimethylthiopropionate, 3 2- (4 -methoxy-3 -biphenylyl) -hydrazone; the S-oxide 4 thereof; the S,S-dioxide thereof and the acid addition 5 salt thereof. 1 10. A method for the protection of growing or 2 harvested plants from attack or infestation by insect or 3 acarid pests which comprises applying to the foliage of 4 the plants, or to the soil or water in which they are growing, a pesticidally effective amount of a compound of formula I (I) wherein R is hydrogen, C ] _-C ] _o a lkyl optionally substituted with one or more halogen, C3-Cgcycloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, (C 1 -C 4 -alkyl)SO x , (C 1 -C 4 haloalkyl) SOy, phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl, Cι-C 4 haloalkyl, C ] _-C 4 alkoxy, C ] _-C 4 haloalkoxy, ( C λ -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SOy, N0 2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, Cι-C 4 haloalkyl, C;ι_-C 4 alkoxy, Cι-C 4 haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl)S0 y , N0 or CN groups; C3~C;]_ 2 cycloalkyl optionally substituted with one or more halogens, Cx-Cgalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, Cι-C4haloalkoxy, (C 1 -C 4 alkyl)SO x , (C -C 4 haloalkyl) SO x , phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl C 1 -C 4 haloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, N0 2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, C2_-C 4 haloalkyl, Cι-C 4 alkoxy, C ] _-C4haloalkoxy, N0 2 or CN groups; or phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C; ] _-C 4 alkoxy, Cχ-C4haloalkoxy, N0 2 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2; R ] _ is R 12 ; C]_-C o a lkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C ] _-C 4 haloalkoxy, N0 2 or CN groups, Cχ-C 4 alkoxy, Cι-C 4 haloalkoxy, (C 1 -C 4 alkyl)SO x , C0NR 8 R 9 , CO 2 i 0 , Rχι, R 12 , C3-Cgcycloalkyl optionally substituted with one to three halogen, C 1 -C 4 alkyl, c l- 4 haloalkyl, C ] _-C 4 haloalkoxy, N0 2 or CN groups, phenyl optionally substituted with one or more halogen, C!-C 4 alkyl, C 1 -C 4 haloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, 98 N0 2 or CN groups, or 99 pyridyl optionally substituted with one or more 100 halogen, 101 C 1 -C 4 alkyl, 102 C 1 -C 4 haloalkyl, 103 C 1 -C 4 alkoxy, 104 C 1 -C 4 haloalkoxy, 105 N0 2 or CN groups; 106 C 2 -C ] _o a lkenyl optionally substituted with one or 107 more halogen, 108 hydroxy, 109 C 1 -C 4 alkoxy, 110 (C 1 -C 4 alkyl)SO x , 111 CONR 8 R 9 , 112 CO 2 R 10 , 113 Rii, 114 R 12 , 115 C3-Cgcycloalkyl optionally substituted with one 116 to three halogen, 117 C 1 -C 4 alkyl, 118 C 1 -C 4 halo-alkyl, 119 C 1 -C 4 alkoxy, 120 C -C 4 haloalkoxy, 121 N0 2 or CN groups, 122 phenyl optionally substituted with one or more 123 halogen, 124 C 1 -C 4 alkyl, 125 C 1 -C 4 haloalkyl, 126 C 1 -C 4 alkoxy, 127 Cι-C 4 haloalkoxy, 128 N0 2 or CN groups, or 129 pyridyl optionally substituted with one or more 130 halogen, 131 C 1 -C 4 alkyl, 132 Cι-C 4 haloalkyl, 133 C 1 -C 4 alkoxy, 134 C]_-C haloalkoxy, 135 N0 2 or CN groups; 136 C2-Cχo a lkynyl optionally substituted with one or 137 more halogen, 138 hydroxy, 139 C 1 -C 4 alkoxy, 140 (C 1 -C alkyl)SO x , 141 CONR 8 R 9 , 143 R ll7 144 R 12 , 145 C3-Cgcycloalkyl optionally substituted with one 146 to three halogen, 147 C 1 -C 4 alkyl, 148 C 1 -C 4 halo-alkyl, 149 C 1 -C 4 alkoxy, 150 C ] _-C4haloalkoxy, 151 NO2 or CN groups, 152 phenyl optionally substituted with one or more 153 halogen, 154 C 1 -C 4 alkyl, 155 C 1 -C 4 haloalkyl, 156 Cι-C4alkoxy, 157 Cι-C4haloalkoxy, 158 NO2 or CN groups, or 159 pyridyl optionally substituted with one or more 160 halogen, 161 C 1 -C 4 alkyl, 162 Cι-C 4 haloalkyl, 163 Cι-C 4 alkoxy, 164 Cι-C4haloalkoxy, 165 NO2 or CN groups; or 166 C3-C12cycloalkyl optionally substituted with one or 167 more halogen, 168 hydroxy, 169 Cι-C4alko y, 170 (C ] _ -C 4 alkyl) SO x , 171 CONR 8 R 9 , 173 R xl , 174 R 12 , 175 C3-Cgcycloalkyl optionally substituted with one 176 to three halogen, 177 C 1 -C 4 alkyl, 178 Cι-C 4 halo-alkyl, 179 Cι-C 4 alkoxy, 180 C ] _-C4haloalkoxy, 181 N0 2 or CN groups, 182 phenyl optionally substituted with one or more 183 halogen, 184 C 1 -C 4 alkyl, 185 C 1 -C 4 haloalkyl, 186 Cχ-C4alkoxy, 187 C 1 -C haloalkoxy, 188 NO2 or CN groups, or 189 pyridyl optionally substituted with one or more 190 halogen, 191 C 1 -C alkyl, 192 C 1 -C 4 haloalkyl, 193 C 1 -C 4 alkoxy, 194 C 1 -C 4 haloalkoxy, 195 N0 2 or CN groups; 196 phenyl optionally substituted with one or more 197 halogen, 198 C 1 -C 4 alkyl, 199 C 1 -C 4 haloalkyl, 200 C 1 -C 4 alkoxy, 201 C 1 -C 4 haloalkoxy, 202 N0 2 or CN groups, or 203 pyridyl optionally substituted with one or more 204 halogen, 205 C 1 -C 4 alkyl, 206 C 1 -C 4 haloalkyl, 207 C 1 -C 4 alkoxy, 208 C 1 -C 4 haloalkoxy, 209 N0 2 or CN groups; 210 R 2 is hydrogen or C ] _-C 4 alkyl ; 211 R3 , R 4 , R5, Rg,and R7 are each independently hydrogen, 212 halogen, CN, N0 2 , C^Cgalkyl, C ] _- 213 Cghaloalkyl, C ] _-Cgalkoxy, C]_-Cghaloalkoxy, 214 or phenyl optionally substituted with one 215 to three halogen, C ] _-C alkyl, C^- 216 C 4 haloalkyl, Cι_-C 4 alkoxy, C -C haloalkoxy, 217 (C!-C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) S0 γ , N0 2 218 or CN groups, 219 with the proviso that at least one of R3 , R4 , R5, Rg or 220 R7 must be phenyl optionally substituted with 221 one to three halogen, Cι-C 4 alkyl, C ] _- 222 C 4 haloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, (C ] _- 223 C 4 alkyl)SO χ/ (C 1 -C 4 haloalkyl) SO x , N0 2 or CN 224 groups; 1 11. The method according to claim 10 wherein 2 said pests are acarid pests. 12. The method according to Claim 10 wherein the compound of formula I is applied in a concentration of about 10 ppm to 10,000 ppm. 13. The method according to Claim 10 wherein the compound of formula I is applied in a concentration in about 100 ppm to 5,000 ppm. 14. A composition for controlling insect or acarid pests which comprises an agriculturally acceptable carrier and a pesticidally effective amount of a compound of formula I (I) wherein R is hydrogen, C ] _-C_ Q alkyl optionally substituted with one or more halogen, C3~Cgcycloalkyl, C^-C4alko y, C ] _-C 4 haloalkoxy, ( C -C 4 -alkyl)S0 X , (C 1 -C 4 haloalkyl) SO y , phenyl optionally substituted with one to three halogen, Cι-C 4 alkyl, C 1 -C 4 haloalkyl , C 1 -C4alkoxy, C ] _-C 4 haloalkoxy, (C 1 -C 4 alkyl ) SO x , (C 1 -C 4 haloalkyl)SOy, N0 2 or CN groups, or phenoxy optionally substituted with one to - three halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C; ] _-C 4 alkoxy, C_-C 4 haloalkoxy, (C!-C4alkyl)SO x , (Cι-C 4 haloalkyl ) SOy, N0 2 or CN groups ; C3-C ] _ 2 cycloalkyl optionally substituted with one or more halogens, Cx-Cgalkyl, C 1 -C 4 haloalkyl, C!-C 4 alkoxy, C ] _-C 4 haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) S0 X , phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl C; ] _-C haloalkyl, C 1 -C 4 alkoxy, C2_-C 4 haloalkoxy, N0 2 or CN groups, or phenoxy optionally substituted with one to three halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, Cι-C 4 haloalkoxy, N0 2 or CN groups; or phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι-C haloalkyl, Cι-C 4 alkoxy, C;]_-C 4 haloalkoxy, N0 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2; Ri is R 12 ; C -C]_o a lkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, N0 2 or CN groups, Cχ-C 4 alkoxy, C;]_-C 4 haloalkoxy, (Cx-C 4 alkyl) SO x , CONR 8 R 9 , CO 2 R 10 , Rii, R 12 , C3-Cgcycloalkyl optionally substituted with one to three halogen, 86 C 1 -C 4 alkyl, 87 c l- c 4 haloalkyl, 88 C;L-C 4 alkoxy, 89 Cι-C 4 haloalkoxy, 90 N0 or CN groups, 91 phenyl optionally substituted with one or more 92 halogen, 93 C 1 -C 4 alkyl, 94 C 1 -C 4 haloalkyl, 95 C; ] _-C 4 alkoxy, 96 C3_-C 4 haloalkoxy, 97 N0 2 or CN groups, or 98 pyridyl optionally substituted with one or more 99 halogen, 100 C 1 -C 4 alkyl, 101 C 1 -C 4 haloalkyl, 102 Cι-C4alko y, 103 Cι~C4haloalkoxy, 104 N0 2 or CN groups; 105 C 2 -C^o lkenyl optionally substituted with one or 106 more halogen, 107 hydroxy, 108 C ] _-C 4 alkoxy, 109 (C 1 -C 4 alkyl)SO x , 110 CONR 8 R 9 , 111 CO 2 R 10 , 112 R n , 113 R 12 , 114 C3-Cgcycloalkyl optionally substituted with one 115 to three halogen, 116 C 1 -C 4 alkyl, 117 Cι-C 4 halo-alkyl, 118 Cι-C 4 alkoxy, 119 C ] _-C 4 haloalkoxy, 120 N0 2 or CN groups, 121 phenyl optionally substituted with one or more 122 halogen, 123 C 1 -C 4 alkyl, 124 C 1 -C 4 haloalkyl, 125 C 1 -C 4 alkoxy, 126 C ] _-C4haloalkoxy, 127 N0 2 or CN groups, or 128 pyridyl optionally substituted with one or more 129 halogen, 130 C 1 -C 4 alkyl, 131 C 1 -C 4 haloalkyl, 132 C 1 -C 4 alkoxy, 133 Cι-C4haloalkoxy, 134 N0 2 or CN groups; 135 C 2 -C ] _ Q a lkynyl optionally substituted with one or 136 more halogen, 137 hydroxy, 138 C 1 -C 4 alkoxy, 139 (C 1 -C 4 alkyl)SO x , 140 CONR 8 R 9 , 141 CO 2 R 10 , 142 R llf 143 R 12 , 144 C3-Cgcycloalkyl optionally substituted with one 145 to three halogen, 146 Cι~C4alkyl, 147 C -C 4 halo-alkyl, 148 Cι-C4alko y, 149 C 1 -C 4 haloalkoxy, 150 N0 2 or CN groups, 151 phenyl optionally substituted with one or more 152 halogen, 153 C 1 -C 4 alkyl, 154 Cι-C4haloalkyl, 155 C ] _-C4alkoxy, 156 Cι-C4 aloalko y, 157 N0 2 or CN groups, or 158 pyridyl optionally substituted with one or more 159 halogen, 160 C 1 -C 4 alkyl, 161 C 1 -C 4 haloalkyl, 162 Cχ-C4alkoxy, 163 Cι-C4haloalko y, 164 N0 2 or CN groups; or 165 C3-Cι 2 cycloalkyl optionally substituted with one or 166 more halogen, 167 hydroxy, 168 Cχ-C4alkoxy, 169 (C 1 -C 4 alkyl) SO x , 170 CONR 8 R 9 , 171 CO 2 R 10 , 172 R llf 173 R 12 , 174 C3-Cgcycloalkyl optionally substituted with one 175 to three halogen, 176 C 1 -C 4 alkyl, 177 C 1 -C 4 halo-alkyl, . 178 C 1 -C 4 alkoxy, 179 Cι-C 4 haloalkoxy, 180 N0 2 or CN groups, 181 phenyl optionally substituted with one or more 182 halogen, 183 C 1 -C 4 alkyl, 184 C 1 -C 4 haloalkyl, 185 C;ι_-C4al oxy, 186 Cι-C4haloalkoxy, 187 N0 2 or CN groups, or 188 pyridyl optionally substituted with one or more 189 halogen, 190 C 1 -C 4 alkyl, 191 C 1 -C 4 haloalkyl, 192 C 1 -C 4 alkoxy, 193 C;L-C4haloal oxy, 194 N0 2 or CN groups; 195 phenyl optionally substituted with one or more 196 halogen, 197 C 1 -C 4 alkyl , 198 C;L-C4haloalkyl , 199 Cι -C4alkoxy, 200 Cι -C4haloalkoxy, 201 N0 2 or CN groups, or 202 pyridyl optionally substituted with one or more 203 halogen, 204 C 1 -C 4 alkyl, 205 C 1 -C 4 haloalkyl, 206 C ] _-C4alkoxy, 207 Cι-C4haloalkoxy, 208 N0 2 or CN groups; 209 R 2 is hydrogen or C^-C4alkyl; 210 R3 , R4 , R5, Rg,and R 7 are each independently hydrogen, 211 halogen, CN, N0 2 , Cx-Cgalkyl, C 1 - 212 Cghaloalkyl, C^-Cgalkoxy, Cχ-Cghaloalkoxy, 213 or phenyl optionally substituted with one 214 to three halogen, Cχ-C4alkyl, C ] _- 215 C4haloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, 216 (C 1 -C alkyl) SO x , (C 1 -C 4 haloalkyl) SO y , N0 2 217 or CN groups, 218 with the proviso that at least one of R3 , R4 , R5 , Rg or 219 R 7 must be phenyl optionally substituted with 220 one to three halogen, C]_-C4alkyl, Cχ~ 221 C4haloalkyl, Cι-C 4 alkoxy, C 1 -C 4 haloalkoxy, (C j^ - 222 C 4 alkyl)SO x , (C 1 -C haloalkyl) SO x , N0 2 or CN 223 groups; 1 15. The composition according to Claim 14 wherein 2 R 3 and R7 are each independently H or C ] _-Cgalkoxy; and R 4 3 and Rg are each independently H or phenyl optionally 4 substituted with one or more halogen, Cχ-C4haloalkoxy, or 5 C ] _-C4haloalkyl groups. 1 16. The composition according to Claim 14 wherein R 2 is C -Cgalkyl or C3-Cgcycloalkyl optionally substituted 3 with one to three halogens . 1 17. The composition according to Claim 15 wherein 2 the compound of formula I is 5-methyl -2 , 2- 3 dimethylthiopro-pionate (4-methoxy-3 -biphenylyl) hydrazone; 4 the S-oxide thereof; the S,S-dioxide thereof; or the acid 5 addition salt thereof. 1 18. A process for the preparation of a compound of 2 formula I 3 (I) 4 wherein hydrogen, Ci- -Cιo a lkyl optionally substituted with one or more halogen, C3-Cgcycloalkyl, C]_-C 4 alkoxy, C]_-C 4 haloalkoxy, (C 1 -C 4 -alkyl) SO x , (C 1 -C 4 haloalkyl) SOy, phenyl optionally substituted with one to three halogen, C_.-C 4 alkyl, Cι-C 4 haloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, (C 1 -C 4 alkyl)SO x , (Cι-C 4 haloalkyl) SOy, N0 2 or CN groups, or phenoxy optionally substituted with one to three halogen, C!-C 4 alkyl, Cι-C 4 haloalkyl , Cχ-C 4 alkoxy, C]_-C 4 haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) SO y , N0 2 or CN groups ; c 3 - -Cι 2 cycloalkyl optionally substituted with one or more halogens, Cx-Cgalkyl, Cx-C.jhaloalkyl, Cι-C 4 alkoxy, Cι-C 4 haloalkoxy, (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl)SO x , phenyl optionally substituted with one to three halogen, C 1 -C 4 alkyl C 1 -C 4 haloalkyl, C;ι_-C 4 alkoxy, Cι-C 4 haloalkoxy, N0 2 or CN groups, or phenoxy optionally substituted with one to three halogen, Ci-C^^alkyl, C 1 -C 4 haloalkyl , Cι -C 4 alkoxy, C ] _ -C 4 haloalkoxy, N0 2 or CN groups; or phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, Cι-C 4 haloalkyl, C 1 -C 4 alkoxy, C]_-C4haloalkoxy, N0 2 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2 ; R j _ is R 12 ; C ] _ -Cιo a lkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, Cι-C 4 alkoxy, 71 Cι-C 4 haloalkoxy, 72 N0 2 or CN groups, 74 C 1 -C 4 haloalkoxy, 75 (C 1 -C 4 alkyl)SO x , 76 CONR 8 R 9 , 78 R 11# 79 R 12 , 80 C3-Cgcycloalkyl optionally substituted with one 81 to three halogen, 82 C 1 -C 4 alkyl, 83 c l- c 4 haloalkyl, 84 Cι-C 4 alkoxy, 85 Cι-C4haloalkoxy, 86 N0 2 or CN groups, 87 phenyl optionally substituted with one or more 88 halogen, 89 C 1 -C alkyl, 90 C 1 -C 4 haloalkyl, 91 C -C 4 alkoxy, 92 C ] _-C 4 haloalkoxy, 93 N0 or CN groups, or 94 pyridyl optionally substituted with one or more 95 halogen, 96 Cι-C 4 alkyl, 97 Cχ-C 4 haloalkyl, 98 Cι-C 4 alkoxy, 99 C]_-C4haloalkoxy, 100 N0 or CN groups; 101 C 2 -Cιo a lkenyl optionally substituted with one or 102 more halogen, 103 hydroxy, 104 C 1 -C 4 alkoxy, 105 (C 1 -C 4 alkyl)SO x , 106 CONR 8 R 9 , 107 CO 2 R 10 , 108 R l l r 109 R 12 , 110 C3-Cgcycloalkyl optionally substituted with one 111 to three halogen, 112 C 1 -C 4 alkyl, 113 Cι-C 4 halo-alkyl, 114 C 1 -C 4 alkoxy, 115 C]_-C4haloalkoxy, 116 N0 or CN groups, 117 phenyl optionally substituted with one or more 118 halogen, 119 C 1 -C 4 alkyl, 120 C 1 -C 4 haloalkyl, 121 C 1 -C 4 alkoxy, 122 Cχ-C 4 haloalkoxy, 123 N0 2 or CN groups, or 124 pyridyl optionally substituted with one or more 125 halogen, 126 C 1 -C 4 alkyl, 127 C 1 -C 4 haloalkyl, 128 C 1 -C 4 alkoxy, 129 C 1 -C 4 haloalkoxy, 130 N0 or CN groups; 131 C 2 -C]_oalkynyl optionally substituted with one or 132 more halogen, 133 hydroxy, 134 C 1 -C 4 alkoxy, 135 (C 1 -C 4 alkyl)S0 χ , 136 CONR 8 R 9 , 137 CO 2 R 10 , 138 R 11; 139 R 12 , 140 C3-Cgcycloalkyl optionally substituted with one 141 to three halogen, 142 C 1 -C 4 alkyl, 143 C 1 -C 4 halo-alkyl, 144 C 1 -C4alkoxy, 145 Cχ-C haloalkoxy, 146 N0 or CN groups, 147 phenyl optionally substituted with one or more 148 halogen, 149 C 1 -C 4 alkyl, 150 C!-C 4 haloalkyl, 151 Cι-C 4 alkoxy, 152 C ] _-C 4 haloalkoxy, 153 N0 2 or CN groups, or 154 pyridyl optionally substituted with one or more 155 halogen, 156 C 1 -C 4 alkyl, 157 Cι-C 4 haloalkyl, 158 Cι-C 4 alkoxy, 159 C2 . -C 4 haloalkoxy, 160 N0 2 or CN groups; or 161 C3-C12cycloalkyl optionally substituted with one or 162 more halogen, 163 hydroxy, 164 Cι-C 4 alkoxy, 165 (Cx-C 4 alkyl) SO χ , 166 CONR 8 R 9 , 167 CO 2 Ri 0 , 168 R11, 169 R12, 170 C3-Cgcycloalkyl optionally substituted with one 171 to three halogen, 172 C 1 -C 4 alkyl, 173 C 1 -C 4 halo-alkyl, 174 C 1 -C 4 alkoxy, 175 C]_-C 4 haloalkoxy, 176 N0 2 or CN groups, 177 phenyl optionally substituted with one or more 178 halogen, 179 C 1 -C 4 alkyl, 180 C 1 -C 4 haloalkyl, 181 C; ] _-C alkoxy, 182 C; ] _-C 4 haloalkoxy, 183 O2 or CN groups, or 184 pyridyl optionally substituted with one or more 185 halogen, 186 C 1 -C 4 alkyl, 187 C 1 -C 4 haloalkyl, 188 C 1 -C 4 alkoxy, 189 Ci- j haloalkoxy, 190 N0 2 or CN groups; 191 phenyl optionally substituted with one or more 192 halogen, 193 C 1 -C 4 alkyl, 194 C 1 -C 4 haloalkyl, 195 Cι-C 4 alkoxy, 196 Cι-C 4 haloalkoxy, 197 NO2 or CN groups, or 198 pyridyl optionally substituted with one or more 199 halogen, 200 C 1 -C 4 alkyl, 201 C; ] _-C 4 haloalkyl, 202 Cι-C 4 alkoxy, 203 Cι-C 4 haloalkoxy, 204 N0 2 or CN groups; 205 R2 is hydrogen or C ] _-C alkyl ; 206 R3, R4 , R5, Rg,and R7 are each independently hydrogen, 207 halogen, CN, N0 2 , Cx-Cgalkyl, C^.- 208 Cghaloalkyl, C]_-Cgalkoxy, C^-Cghaloalkoxy, 209 or phenyl optionally substituted with one 210 to three halogen, C^-C 4 alkyl, Cι~ 211 C 4 haloalkyl, C ] _-C 4 lkoxy, C 1 -C 4 haloalkoxy, 212 (C 1 -C 4 alkyl)SO x , (C 1 -C 4 haloalkyl) S0 y , N0 2 213 or CN groups, 214 with the proviso that at least one of R3 , R4 , R5, Rg or 215 R7 must be phenyl optionally substituted with 216 one to three halogen, Cι-C 4 alkyl, Cι~ 217 C 4 haloalkyl, C ] _-C 4 alkoxy, C ] _-C 4 haloalkoxy, (C^- 218 C 4 alkyl)SO x , (Cι-C 4 haloalkyl) S0 X , N0 2 or CN 219 groups; 220 x and y are each independently 0, 1 or 2 ,- 221 m is an integer of 0 , 1 or 2 ,- 222 R 8 , R 9 and R^Q are each independently hydrogen or C ] _- 223 C 4 alkyl; 224 R K 1.1, i IsS NINRK. 1.,3„ R1„4 228 229 Rχ3 R-14 / and R15 and are each independently hydrogen or 230 C 1 -C 4 alkyl; 231 R 16 is hydrogen, halogen or C 1 -C 4 alkyl; 232 X is O, S or NR 15 ; 233 r is an integer of 0 or 1; 234 p and q are each independently an integer of 0, 1, 2, or 235 3 with the proviso that only one of p, q, or r can 236 be 0 and with the further proviso that the sum of p 237 + q + r must be 4 , 5 or 6 ; and 238 x is an integer of 0 , 1 or 2 ; 239 which process comprises reacting a compound of formula II 240 241 ( ID 242 243 wherein X 1 is halogen and R, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are 244 as hereinbefore defined, with at least one molar 245 equivalent of a mercaptan of formula III 246 247 HS-Ri 248 (III) 249 250 wherein R x is as hereinbefore defined, 251 in the presence of a base, optionally in the presence of a 252 solvent, to form the compound of formula I wherein m is 0, 253 optionally reacting the compound of formula I wherein m is 0 254 with one or more molar equivalents of an oxidizing reagent 255 to form a compound of formula I wherein m is 1 or 2.

Inventors: DIEHL ROBERT E, HUNT DAVID ALLEN, TROTTO SUSAN HENSEN, DIEHL, ROBERT, E., HUNT, DAVID, ALLEN, TROTTO, SUSAN, HENSEN
Applicants: BASF AG, DIEHL ROBERT E, HUNT DAVID ALLEN, TROTTO SUSAN HENSEN, BASF AKTIENGESELLSCHAFT, DIEHL, ROBERT, E., HUNT, DAVID, ALLEN, TROTTO, SUSAN, HENSEN
Application year: 2001
Main classification: C07C241
IPC codes: A01N37, A01N41, C07C327