EP1406863A1 - Insecticidal biphenylthiohydrazides - Google Patents

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, (C₁-C₄-alkyl)SO_x,

(C₁-C4haloalkyl) SOy, phenyl optionally substituted with one to three halogen, Cι-C₄alkyl, C₁-C₄haloalkyl,

Cι-C4alko y, C -C4haloalkoxy, (C₁-C₄alkyl)S0_x, (C₁-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 , (C₁-C₄alkyl)SO_x, (Cι-C₄haloalkyl) SO_y, NO2 or CN groups; C3-C;j_2cycloalkyl optionally substituted with one or more halogens, Cι-C₆alkyl,

C -C4haloalkyl, Cι-C4alkoxy, Cι-C4haloalkoxy, (Cx-C alkyl ) SO_x, (C₁-C₄haloalkyl)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, C₁-C₄alkyl,

C₁-C₄haloalkyl,

C_]_-C4alkoxy,

C_]_-C4haloalkoxy,

NO2 or CN groups ; or phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, 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 ^cl~^c10^a- γl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, Cτ_.-C4alkyl, ^cl~C4haloalkyl , Cι_-C4haloalko y,

NO2 or CN groups, C;j_-C4alko y, C -C4haloalkoxy, ( C -C₄alkyl)SO_x, CONR₈R₉,

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, C₁-C₄alkyl, Cι-C4halo lkyl, C -C₄alkoxy,

C_]_-C haloalkox , O2 or CN groups, or pyridyl optionally substituted with one or more halogen, C₁-C₄alkyl, ^cl^-C4haloalkyl, C]_-C4alkoxy, ^cl~^c4haloalkoxy, NO2 or CN groups; C2-C]_o^alk nyl optionally substituted with one or more halogen, hydroxy,

Cι~C4alko y, C₁-C₄alkyl) SO_x, CONR₈R₉, R11,

Rl2'

C3-Cgcycloalkyl optionally substituted with one to three halogen,

C₁-C₄alkyl, C₁-C₄halo-alkyl,

Cι-C4alkoxy,

Cχ-C4haloalkoxy,

NO2 or CN groups, phenyl optionally substituted with one or more halogen,

C₁-C₄alkyl,

Cι-C4haloalkyl , ^cl~^c4^alkoxy,

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^alky yl optionally substituted with one or more halogen, hydroxy, C]_-C4alko y, (C₁-C₄alkyl)SO_x, CONR₈R₉,

Rl2'

C3-Cgcycloalkyl optionally substituted with one to three halogen,

C₁-C₄alkyl,

C₁-C₄halo-alkyl ,

C;j_-C4alko y,

C_]_-C4haloalkoxy, N0₂ or CN groups, phenyl optionally substituted with one or more halogen,

C₁-C₄alkyl,

C]_-C4haloalkyl, Cι-C₄alkoxy,

C]_-C4haloalkoxy,

NO2 or CN groups, or pyridyl optionally substituted with one or more halogen, C₁-C₄alkyl,

Cι -C4-ialoalkyl ,

C^ -C4alkoxy,

Ci-C^haloalkoxy, N0 or CN groups; or ^c3"^c12^cycloalkyl optionally substituted with one or more halogen, hydroxy, C]_-C4alkoxy,

(C₁-C₄alkyl)SO_x, CONR₈R₉ ,

R₁₂,

C3-Cgcycloalkyl optionally substituted with one to three halogen,

Cχ-C₄alkyl,

C -C4halo-alkyl, Cχ-C₄alkoxy,

Cχ-C4haloalkoxy,

NO2 or CN groups, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl,

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-C₄haloalkoxy,

NO2 or CN groups; phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, C_]_-C4haloalkyl, Cτ_.-C4alko y, Cι-C4haloalkoxy, N0₂ or CN groups, or pyridyl optionally substituted with one or more halogen, C₁-C₄alkyl, Cτ.-C4haloalkyl , Cι-C4alko y,

Cι-C4haloalkoxy, NO2 or CN groups; R2 is hydrogen or C;j_-C4alk l ;

R₃, R₄, R5, Rg,and R7 are each independently hydrogen, halogen, CN, N0₂ , 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, (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl) SO_y, N0₂ 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_]_-

C₄alkyl)SO_x, (C₁-C₄haloalkyl) SO_x, N0₂ or CN groups ; x and y are each independently 0, 1 or 2 ; m is an integer of 0, 1 or 2 ; R₈ , R₉ and Rχo ^are each independently hydrogen or C_Q_- C4alkyl ;

^Rll ^{±S NR}13 ^R14'

R-13 R-14/ ^an-d 15 are each independently hydrogen or C]_- C₄alkyl; X is 0, S or NR15;

R₁₆ 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-C₄haloalkyl 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-C₄haloalkoxy or C_x-C₄haloalkyl groups.

The term " halogen" as used herein denotes chlorine, fluorine, bromine or iodine. The term " haloalkyl" notes an alkyl group, C_nH2_n+ι which contains from one halogen atom to 2n+l halogen atoms. Similarly, the term " haloalkoxy" denotes a 0C_nH2_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 ¹H, ¹³C, ¹⁹F 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, ¹³CNMR, 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 ¹H MR and ¹³CNMR.

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, ¹³CNMR, 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 ^XHNMR, ¹³CNMR, 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, ¹³CNMR, and IR.

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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 ^XHNMR, ¹³CNMR, 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 ¹HNMR, ¹³CNMR, 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 ¹HNMR, ¹³CNMR, 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 ¹HNMR, ¹³CNMR, 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, ¹³CNMR, 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

33495WHAT IS CLAIMED IS:

1. A compound of formula I

(I)

wherein

R is hydrogen,

C]_-C_]__Qal yl optionally substituted with one or more halogen, C_β-Cgcycloalkyl,

C_-C4alkoxy, Cχ-C4haloalkoxy, (C!-C₄-alkyl) SO_x, (C-L-C₄haloalkyl) SOy, phenyl optionally substituted with one to three halogen,

C₁-C₄alkyl,

C_}_-C4haloalkyl,

C]_-C4alkoxy,

C]_-C4haloalkoxy, (C₁-C₄alkyl) SO_x, (C₁-C₄haloalkyl) SOy,

NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl , C]_ -C4haloalkyl , C₁-C₄alkoxy, C]_-C4haloalkoxy, (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl)SO_y, NO2 or CN groups; C3-Ci2^cY^cl°^alkyl optionally substituted with one or more halogens, Cx-Cgalkyl, C₁-C₄haloalkyl, Cι_-C4alkoxy, C₁-C4haloalkoxy, (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl) SO_x, phenyl optionally substituted with one to three halogen, C₁-C₄alkyl C₁-C₄haloalkyl, Cχ-C4alkoxy, Cχ-C4haloalkoxy, NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl, Cι-C₄haloalkyl, C!-C4alko y, C]_-C4haloalkoxy, N0₂ or CN groups; or phenyl optionally substituted with one or more halogen, C₁ -C₄alkyl , 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 R₁₂; C -Cioalkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, C₁-C4haloalkyl, Cι-C4alko y, Cι-C4haloalko y, NO2 or CN groups, Cχ-C4alko y, C_]_-C4haloalkoxy, (C₁-C₄alkyl)SO_x, CONR₈R₉, Rn, R₁₂, C3-Cgcycloalkyl optionally substituted with one to three halogen, C₁-C₄alkyl, l- 4 haloalkyl, C_-C4alko y, C₁-C4haloalkoxy, O2 or CN groups, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, 91 C₁-C₄haloalkyl,

92 C₁-C₄alkoxy,

93 C₁-C₄haloalkoxy,

94 NO2 or CN groups, or

95 pyridyl optionally substituted with one or more

96 halogen,

97 C₁-C₄alkyl,

98 C₁-C₄haloalkyl,

99 C₁-C₄alkoxy,

100 C;_]_-C4haloalkoxy,

101 NO2 or CN groups ;

102 C2 -C]_o^alkenyl optionally substituted with one or

103 more halogen,

104 hydroxy,

105 C₁-C₄alkoxy,

106 (C₁-C₄alkyl)SO_x,

107 CONR₈R₉,

109 R_11#

110 R₁₂,

111 C3-Cgcycloalkyl optionally substituted with one

112 to three halogen,

113 C₁-C₄alkyl,

114 C₁-C₄halo-alkyl,

115 C₁-C₄alkoxy,

116 C₁-C₄haloalkoxy,

117 NO2 or CN groups,

118 phenyl optionally substituted with one or more

119 halogen,

120 C₁-C₄alkyl,

121 C₁-C4haloalkyl,

122 Cι-C₄alkoxy,

123 C_]_-C4haloalkoxy, 124 NO2 or CN groups, or

125 pyridyl optionally substituted with one or more

126 halogen,

127 C₁-C alkyl,

128 Cι-C4haloalkyl, 129 C₁-C₄alkoxy,

130 C;ι_-C4haloalkoxy, 131 NO2 or CN groups;

132 C2 -Ci_Qalkγnyl optionally substituted with one or

133 more halogen,

134 hydroxy,

135 C₁-C₄alkoxy,

136 (C₁-C₄alkyl) SO_x,

137 CONR₈R₉,

139 R_11#

140 R₁₂,

141 C3-Cgcycloalkyl optionally substituted with one

142 to three halogen,

143 C₁-C₄alkyl,

144 C₁-C₄halo-alkyl,

145 Cι-C₄alkoxy,

146 Cι-C4haloalkoxy, 147 NO2 or CN groups,

148 phenyl optionally substituted with one or more 149 halogen,

150 , C₁-C₄alkyl,

151 Cι-C₄haloalkyl_/

152 C₁-C₄alkoxy,

153 Cι-C4haloalkoxy,

154 NO2 or CN groups, or

155 pyridyl optionally substituted with one or more

156 halogen, 157 C₁-C₄alkyl,

158 C₁-C₄haloalkyl,

159 Cι-C₄alkoxy,

160 C ~C4haloal o y,

161 N0₂ or CN groups; or

162 C3-C12cycloalkyl optionally substituted with one or

163 more halogen,

164 hydroxy,

165 Cι-C4alkoxy,

166 (C₁-C₄alkyl)SO_x,

167 CONR₈R₉,

168 CO₂R₁₀,

169 R_n,

170 R₁₂,

171 C3-Cgcycloalkyl optionally substituted with one

172 to three halogen,

173 C₁-C₄alkyl,

174 C₁-C4halo-alkyl,

175 C₁-C₄alkoxy,

176 Cι-C4haloalko y,

177 NO2 or CN groups,

178 phenyl optionally substituted with one or more

179 halogen,

180 C_]_-C4alkyl,

181 C₁-C₄haloalkyl,

182 C_]_-C4alkoxy,

183 Cι-C4haloalkoxy,

184 NO2 or CN groups, or

185 pyridyl optionally substituted with one or more

186 halogen,

187 C₁-C4alkyl,

188 C₁-C4haloalkyl,

189 C_]_-C4alkoxy, 190 C₁ -C₄haloalkoxy,

191 N0₂ or CN groups ;

192 phenyl optionally substituted with one or more

193 halogen,

194 C₁-C₄alkyl,

195 C₁-C₄haloalkyl,

196 C₁-C₄alkoxy,

197 C₁-C₄haloalkoxy,

198 N0₂ or CN groups, or

199 pyridyl optionally substituted with one or more 200 halogen,

201 C₁-C₄alkyl,

202 C₁-C₄haloalkyl,

203 C₁-C₄alkoxy,

204 Cι-C₄haloalkoxy,

205 N0₂ or CN groups;

206 R₂ is hydrogen or C -C4alkyl;

207 R3, R4, R5, Rg,and R7 are each independently hydrogen,

208 halogen, CN, N0₂ , 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 (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl) SO_y, N0₂

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 C₄alkyl)SO_x, (C₁-C₄haloalkyl) S0_X, N0₂ 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 R₈ , R₉ and R^Q are each independently hydrogen or Ci-

224 C₄alkyl;

225 R_lχ is NR₁₃ R₁₄,

229

230 i3, R-14' ^and R-15 ^are each independently hydrogen or C]_-

231 C₄alkyl ;

232 R_1S is hydrogen, halogen or C₁-C₄ alkyl ;

233 X is O, S or NR₁₅ ;

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^al yl optionally substituted with one or more halogen,

C3 -Cgcycloalkyl , C_-C4alkoxy, C1~ 4 a1oa1koxy, (C₁-C₄-alkyl) SO_x, (C₁-C₄haloalkyl) SO_y, phenyl optionally substituted with one to three halogen,

Cι-C4alkyl, ^cl~^c4h loalkyl , C-L -C4alkoxy, Cι-C4haloal oxy, (C₁-C₄alkyl)S0_x, (C₁-C₄haloalkyl)S0_y, NO2 or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C -C4haloalkoxy, (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl)SO_y, N0₂ or CN groups; C3-Cι₂cycloalkyl optionally substituted with one or more halogens, C -Cgalkyl, C₁-C₄haloalkyl, Cι-C4alkoxy, Cι-C4haloalkoxy, (C₁-C₄alkyl) SO_x, (Cι -C₄haloalkyl ) S0_X, phenyl optionally substituted with one to three halogen, C₁-C₄alkyl C₁-C₄haloalkyl, C_]_-C₄alkoxy, Cι-C₄haloalkoxy, N0₂ or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C -C4alkoxy, C_]_-C4haloalkoxy, NO2 or CN groups; or phenyl optionally substituted with one or more halogen, C₁-C alkyl, C₁-C₄haloalkyl, 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 R₁₂; C -C_]_o^alkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, Cι-C₄haloalkyl, Cι-C₄alkoxy, C₁-C₄haloalkoxy, N0₂ or CN groups, Cχ-C4alkoxy, Cι-C4haloalko y, (C₁-C₄alkyl)SO_x, CONR₈R₉, CO₂R₁₀, R_llf ι₂, C3-Cgcycloalkyl optionally substituted with one to three halogen, C₁-C4alkyl, 85 C1-.C4 haloalkyl,

86 Cι-C₄alkoxy,

87 C]_-C₄haloalkoxy,

88 N0₂ or CN groups,

89 phenyl optionally substituted with one or more

90 halogen,

91 C₁-C₄alkyl,

92 C₁-C₄haloalkyl,

93 Cj_-C4alkoxy,

94 Cχ-C4haloalkoxy,

95 N0 or CN groups, or

96 pyridyl optionally substituted with one or more

97 halogen,

98 C₁-C₄alkyl,

99 Cχ-C4haloalkyl ,

100 Cχ-C4alkoxy,

101 Cι-C4haloalkoxy,

102 N0 or CN groups;

103 C -Cιo^alkenyl optionally substituted with one or

104 more halogen,

105 hydroxy,

106 C]_-C alkoxy,

107 (C₁-C₄alkyl) SO_x,

108 CONR₈R₉,

109 CO₂R₁₀,

110 Rll,

111 Rl2*

112 C3-Cgcycloalkyl optionally substituted with one

113 to three halogen,

114 C_]_-C4alkyl,

115 Cι-C₄halo-alkyl,

116 Cχ-C4alkoxy,

117 Cι-C4haloalkoxy, 118 N0 or CN groups,

119 phenyl optionally substituted with one or more 120 halogen,

121 C₁-C₄alkyl_/

122 C₁-C₄haloalkyl,

123 Cι-C₄alkoxy,

124 Cι-C₄haloalkoxy,

125 N0₂ or CN groups, or

126 pyridyl optionally substituted with one or more

127 halogen,

128 C₁-C₄alkyl,

129 C₁-C₄haloalkyl,

130 C_]_-C₄alkoxy,

131 C_]_-C4haloalkoxy,

132 O2 or CN groups;

133 C₂-Cιo^alkynyl optionally substituted with one or

134 more halogen,

135 hydroxy,

136 C;j_-C4alkoxy,

137 (C₁-C₄alkyl)SO_x,

138 CONR₈R₉,

139 CO₂R₁₀,

140 R_11#

141 R₁₂,

142 C3-Cgcycloalkyl optionally substituted with one

143 to three halogen,

144 C₁-C₄alkyl,

145 C₁-C₄halo-alkyl,

146 C₁-C₄alkoxy,

147 C₁-C₄haloalkoxy,

148 N0₂ or CN groups,

149 phenyl optionally substituted with one or more

150 halogen, 151 C₁-C₄alkyl,

152 C₁-C₄haloalkyl,

153 C₁-C₄alkoxy,

154 C]_-C₄haloalkoxy,

155 N0₂ or CN groups, or

156 pyridyl optionally substituted with one or more

157 halogen,

158 C₁-C₄alkyl,

159 C₁-C₄haloalkyl,

160 C₁-C₄alkoxy,

161 C]_-C₄haloalkoxy,

162 N0₂ or CN groups; or

163 C3-Cι_₂cycloalkyl optionally substituted with one or

164 more halogen,

165 hydroxy,

166 Cι-C₄alkoxy,

167 (C₁-C₄alkyl)SO_x,

168 CONR₈R₉,

169 CO₂R₁₀,

170 R_11#

171 R₁₂,

172 C3-Cgcycloalkyl optionally substituted with one

173 to three halogen,

174 C₁-C₄alkyl,

175 C₁-C₄halo-alkyl,

176 C₁-C₄alkoxy,

177 C₁-C₄haloalkoxy,

178 N0₂ or CN groups,

179 phenyl optionally substituted with one or more

180 halogen,

181 C₁-C₄alkyl,

182 Cι-C haloalkyl,

183 Cι-C₄alkoxy, 184 Cι-C₄haloalkoxy,

185 N0₂ or CN groups, or

186 pyridyl optionally substituted with one or more

187 halogen,

188 C₁-C₄alkyl,

189 C₁-C₄haloalkyl,

190 C₁-C₄alkoxy,

191 C]_-C4haloalkoxy,

192 N0₂ or CN groups;

193 phenyl optionally substituted with one or more

194 halogen,

195 C₁-C₄alkyl,

196 Cι-C4haloalkyl,

197 Cι-C₄alkoxy,

198 Cι-C₄haloalkoxy,

199 N0₂ or CN groups, or

200 pyridyl optionally substituted with one or more

201 halogen,

202 C₁-C₄alkyl,

203 Cι-C₄haloalkyl,

204 Cι-C₄alkoxy,

205 C;_]_-C₄haloalkoxy,

206 N0₂ or CN groups;

207 R₂ is hydrogen or C;ι_-C₄alkyl ;

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-C₄alkyl, C_]_-

213 C4haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy,

214 (C₁-C₄alkyl)SO_x, (C₁-C haloalkyl) S0_y, N0₂

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 C₄haloalkyl, C]_-C4alkoxy, C_]_-C4haloalkoxy, (Cχ~

220 C₄alkyl)SO_x, (C₁-C₄haloalkyl) SO_x, N0₂ 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^alkyl optionally substituted with one or more halogen, C3-Cgcycloalkyl, Cι-C₄alkoxy, Cι-C₄haloalkoxy, (C₁-C₄-alkyl)SO_x, (C₁-C₄haloalkyl) SOy, phenyl optionally substituted with one to three halogen, C₁-C₄alkyl, Cι-C₄haloalkyl, C_]_-C₄alkoxy, C_]_-C₄haloalkoxy, ( C_λ-C₄alkyl)SO_x, (C₁-C₄haloalkyl) SOy, N0₂ or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl, Cι-C₄haloalkyl, C;ι_-C₄alkoxy, Cι-C₄haloalkoxy, (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl)S0_y, N0 or CN groups; C3~C;]_₂cycloalkyl optionally substituted with one or more halogens, Cx-Cgalkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, Cι-C4haloalkoxy, (C₁-C₄alkyl)SO_x, (C -C₄haloalkyl) SO_x, phenyl optionally substituted with one to three halogen, C₁-C₄alkyl C₁-C₄haloalkyl, Cι-C₄alkoxy, Cι-C₄haloalkoxy, N0₂ or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl, C2_-C₄haloalkyl, Cι-C₄alkoxy, C_]_-C4haloalkoxy, N0₂ or CN groups; or phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C;_]_-C₄alkoxy, Cχ-C4haloalkoxy, N0₂ or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2; R_]_ is R₁₂; C]_-C o^alkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C_]_-C₄haloalkoxy, N0₂ or CN groups, Cχ-C₄alkoxy, Cι-C₄haloalkoxy, (C₁-C₄alkyl)SO_x, C0NR₈R₉, CO₂ i₀, Rχι, R₁₂, C3-Cgcycloalkyl optionally substituted with one to three halogen, C₁-C₄alkyl, ^cl- 4 haloalkyl, C_]_-C₄haloalkoxy, N0₂ or CN groups, phenyl optionally substituted with one or more halogen, C!-C₄alkyl, C₁-C₄haloalkyl, Cι-C₄alkoxy, Cι-C₄haloalkoxy, 98 N0₂ or CN groups, or

99 pyridyl optionally substituted with one or more

100 halogen,

101 C₁-C₄alkyl,

102 C₁-C₄haloalkyl,

103 C₁-C₄alkoxy,

104 C₁-C₄haloalkoxy,

105 N0₂ or CN groups;

106 C₂-C_]_o^alkenyl optionally substituted with one or

107 more halogen,

108 hydroxy,

109 C₁-C₄alkoxy,

110 (C₁-C₄alkyl)SO_x,

111 CONR₈R₉,

112 CO₂R₁₀,

113 Rii,

114 R₁₂,

115 C3-Cgcycloalkyl optionally substituted with one

116 to three halogen,

117 C₁-C₄alkyl,

118 C₁-C₄halo-alkyl,

119 C₁-C₄alkoxy,

120 C -C₄haloalkoxy,

121 N0₂ or CN groups,

122 phenyl optionally substituted with one or more

123 halogen,

124 C₁-C₄alkyl,

125 C₁-C₄haloalkyl,

126 C₁-C₄alkoxy,

127 Cι-C₄haloalkoxy,

128 N0₂ or CN groups, or

129 pyridyl optionally substituted with one or more

130 halogen, 131 C₁-C₄alkyl,

132 Cι-C₄haloalkyl,

133 C₁-C₄alkoxy,

134 C]_-C haloalkoxy, 135 N0₂ or CN groups;

136 C2-Cχo^alkynyl optionally substituted with one or

137 more halogen,

138 hydroxy,

139 C₁-C₄alkoxy,

140 (C₁-C alkyl)SO_x,

141 CONR₈R₉,

143 R_ll7

144 R₁₂,

145 C3-Cgcycloalkyl optionally substituted with one

146 to three halogen,

147 C₁-C₄alkyl,

148 C₁-C₄halo-alkyl,

149 C₁-C₄alkoxy,

150 C_]_-C4haloalkoxy,

151 NO2 or CN groups,

152 phenyl optionally substituted with one or more

153 halogen,

154 C₁-C₄alkyl,

155 C₁-C₄haloalkyl,

156 Cι-C4alkoxy,

157 Cι-C4haloalkoxy,

158 NO2 or CN groups, or

159 pyridyl optionally substituted with one or more

160 halogen,

161 C₁-C₄alkyl,

162 Cι-C₄haloalkyl,

163 Cι-C₄alkoxy, 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_]_ -C₄alkyl) SO_x,

171 CONR₈R₉,

173 R_xl,

174 R₁₂,

175 C3-Cgcycloalkyl optionally substituted with one

176 to three halogen,

177 C₁-C₄alkyl,

178 Cι-C₄halo-alkyl,

179 Cι-C₄alkoxy,

180 C_]_-C4haloalkoxy,

181 N0₂ or CN groups,

182 phenyl optionally substituted with one or more

183 halogen,

184 C₁-C₄alkyl,

185 C₁-C₄haloalkyl,

186 Cχ-C4alkoxy,

187 C₁-C haloalkoxy,

188 NO2 or CN groups, or

189 pyridyl optionally substituted with one or more

190 halogen,

191 C₁-C alkyl,

192 C₁-C₄haloalkyl,

193 C₁-C₄alkoxy,

194 C₁-C₄haloalkoxy,

195 N0₂ or CN groups; 196 phenyl optionally substituted with one or more

197 halogen,

198 C₁-C₄alkyl,

199 C₁-C₄haloalkyl, 200 C₁-C₄alkoxy,

201 C₁-C₄haloalkoxy,

202 N0₂ or CN groups, or

203 pyridyl optionally substituted with one or more

204 halogen,

205 C₁-C₄alkyl,

206 C₁-C₄haloalkyl,

207 C₁-C₄alkoxy,

208 C₁-C₄haloalkoxy,

209 N0₂ or CN groups;

210 R₂ is hydrogen or C_]_-C₄alkyl ;

211 R3 , R₄ , R5, Rg,and R7 are each independently hydrogen,

212 halogen, CN, N0₂ , 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 C₄haloalkyl, Cι_-C₄alkoxy, C -C haloalkoxy,

217 (C!-C₄alkyl)SO_x, (C₁-C₄haloalkyl) S0_γ, N0₂

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-C₄alkyl, C_]_-

222 C₄haloalkyl, Cι-C₄alkoxy, Cι-C₄haloalkoxy, (C_]_-

223 C₄alkyl)SO_χ/ (C₁-C₄haloalkyl) SO_x, N0₂ 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__Qalkyl optionally substituted with one or more halogen,

C3~Cgcycloalkyl, C^-C4alko y, C_]_-C₄haloalkoxy, ( C -C₄-alkyl)S0_X, (C₁-C₄haloalkyl) SO_y, phenyl optionally substituted with one to three halogen, Cι-C₄alkyl, C₁ -C₄haloalkyl , C₁-C4alkoxy, C_]_-C₄haloalkoxy, (C₁-C₄alkyl ) SO_x, (C₁-C₄haloalkyl)SOy, N0₂ or CN groups, or phenoxy optionally substituted with one to - three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C;_]_-C₄alkoxy, C_-C₄haloalkoxy, (C!-C4alkyl)SO_x, (Cι-C₄haloalkyl ) SOy, N0₂ or CN groups ; C3-C_]_₂cycloalkyl optionally substituted with one or more halogens, Cx-Cgalkyl, C₁-C₄haloalkyl, C!-C₄alkoxy, C_]_-C₄haloalkoxy, (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl) S0_X, phenyl optionally substituted with one to three halogen, C₁-C₄alkyl C;_]_-C haloalkyl, C₁-C₄alkoxy, C2_-C₄haloalkoxy, N0₂ or CN groups, or phenoxy optionally substituted with one to three halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, Cι-C₄haloalkoxy, N0₂ or CN groups; or phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, Cι-C haloalkyl, Cι-C₄alkoxy, C;]_-C₄haloalkoxy, N0 or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2; Ri is R₁₂ ; C -C]_o^alkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, N0₂ or CN groups, Cχ-C₄alkoxy, C;]_-C₄haloalkoxy, (Cx-C₄alkyl) SO_x, CONR₈R₉, CO₂R₁₀, Rii, R₁₂, C3-Cgcycloalkyl optionally substituted with one to three halogen, 86 C₁-C₄alkyl,

87 ^cl-^c4 haloalkyl, 88 C;L-C₄alkoxy,

89 Cι-C₄haloalkoxy,

90 N0 or CN groups,

91 phenyl optionally substituted with one or more

92 halogen,

93 C₁-C₄alkyl,

94 C₁-C₄haloalkyl,

95 C;_]_-C₄alkoxy,

96 C3_-C₄haloalkoxy,

97 N0₂ or CN groups, or

98 pyridyl optionally substituted with one or more

99 halogen,

100 C₁-C₄alkyl,

101 C₁-C₄haloalkyl,

102 Cι-C4alko y,

103 Cι~C4haloalkoxy,

104 N0₂ or CN groups;

105 C₂-C^o lkenyl optionally substituted with one or

106 more halogen,

107 hydroxy,

108 C_]_-C₄alkoxy,

109 (C₁-C₄alkyl)SO_x,

110 CONR₈R₉,

111 CO₂R₁₀,

112 R_n,

113 R₁₂,

114 C3-Cgcycloalkyl optionally substituted with one

115 to three halogen,

116 C₁-C₄alkyl,

117 Cι-C₄halo-alkyl,

118 Cι-C₄alkoxy, 119 C_]_-C₄haloalkoxy,

120 N0₂ or CN groups,

121 phenyl optionally substituted with one or more

122 halogen,

123 C₁-C₄alkyl,

124 C₁-C₄haloalkyl,

125 C₁-C₄alkoxy,

126 C_]_-C4haloalkoxy,

127 N0₂ or CN groups, or

128 pyridyl optionally substituted with one or more

129 halogen,

130 C₁-C₄alkyl,

131 C₁-C₄haloalkyl,

132 C₁-C₄alkoxy,

133 Cι-C4haloalkoxy,

134 N0₂ or CN groups;

135 C₂-C_]__Q ^alkynyl optionally substituted with one or

136 more halogen, 137 hydroxy,

138 C₁-C₄alkoxy,

139 (C₁-C₄alkyl)SO_x,

140 CONR₈R₉,

141 CO₂R₁₀,

142 R_llf

143 R₁₂,

144 C3-Cgcycloalkyl optionally substituted with one

145 to three halogen,

146 Cι~C4alkyl,

147 C -C₄halo-alkyl,

148 Cι-C4alko y,

149 C₁-C₄haloalkoxy,

150 N0₂ or CN groups,

151 phenyl optionally substituted with one or more 152 halogen,

153 C₁-C₄alkyl,

154 Cι-C4haloalkyl,

155 C_]_-C4alkoxy,

156 Cι-C4 aloalko y,

157 N0₂ or CN groups, or

158 pyridyl optionally substituted with one or more

159 halogen,

160 C₁-C₄alkyl,

161 C₁-C₄haloalkyl,

162 Cχ-C4alkoxy,

163 Cι-C4haloalko y,

164 N0₂ or CN groups; or

165 C3-Cι₂cycloalkyl optionally substituted with one or

166 more halogen,

167 hydroxy,

168 Cχ-C4alkoxy,

169 (C₁-C₄alkyl) SO_x,

170 CONR₈R₉,

171 CO₂R₁₀,

172 R_llf

173 R₁₂,

174 C3-Cgcycloalkyl optionally substituted with one

175 to three halogen,

176 C₁-C₄alkyl,

177 C₁-C₄halo-alkyl, .

178 C₁-C₄alkoxy,

179 Cι-C₄haloalkoxy,

180 N0₂ or CN groups,

181 phenyl optionally substituted with one or more

182 halogen,

183 C₁-C₄alkyl,

184 C₁-C₄haloalkyl, 185 C;ι_-C4al oxy,

186 Cι-C4haloalkoxy,

187 N0₂ or CN groups, or

188 pyridyl optionally substituted with one or more

189 halogen,

190 C₁-C₄alkyl,

191 C₁-C₄haloalkyl,

192 C₁-C₄alkoxy,

193 C;L-C4haloal oxy,

194 N0₂ or CN groups;

195 phenyl optionally substituted with one or more

196 halogen,

197 C₁ -C₄alkyl ,

198 C;L-C4haloalkyl ,

199 Cι -C4alkoxy,

200 Cι -C4haloalkoxy,

201 N0₂ or CN groups, or

202 pyridyl optionally substituted with one or more

203 halogen,

204 C₁-C₄alkyl,

205 C₁-C₄haloalkyl,

206 C_]_-C4alkoxy,

207 Cι-C4haloalkoxy,

208 N0₂ or CN groups; 209 R₂ is hydrogen or C^-C4alkyl;

210 R3 , R4 , R5, Rg,and R₇ are each independently hydrogen,

211 halogen, CN, N0₂ , Cx-Cgalkyl, C₁ -

212 Cghaloalkyl, C^-Cgalkoxy, Cχ-Cghaloalkoxy,

213 or phenyl optionally substituted with one

214 to three halogen, Cχ-C4alkyl, C_]_-

215 C4haloalkyl, Cι-C₄alkoxy, Cι-C₄haloalkoxy,

216 (C₁-C alkyl) SO_x, (C₁-C₄haloalkyl) SO_y, N0₂

217 or CN groups, 218 with the proviso that at least one of R3 , R4 , R5 , Rg or

219 R₇ must be phenyl optionally substituted with

220 one to three halogen, C]_-C4alkyl, Cχ~

221 C4haloalkyl, Cι-C₄alkoxy, C₁-C₄haloalkoxy, (C_j^-

222 C₄alkyl)SO_x, (C₁-C haloalkyl) SO_x, N0₂ or CN

223 groups;

1 15. The composition according to Claim 14 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, 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^alkyl optionally substituted with one or more halogen,

C3-Cgcycloalkyl,

C]_-C₄alkoxy,

C]_-C₄haloalkoxy,

(C₁-C₄-alkyl) SO_x,

(C₁-C₄haloalkyl) SOy, phenyl optionally substituted with one to three halogen,

C_.-C₄alkyl,

Cι-C₄haloalkyl,

Cι-C₄alkoxy,

Cι-C₄haloalkoxy,

(C₁-C₄alkyl)SO_x,

(Cι-C₄haloalkyl) SOy,

N0₂ or CN groups, or phenoxy optionally substituted with one to three halogen,

C!-C₄alkyl,

Cι-C₄haloalkyl ,

Cχ-C₄alkoxy,

C]_-C₄haloalkoxy,

(C₁-C₄alkyl)SO_x,

(C₁-C₄haloalkyl) SO_y,

N0₂ or CN groups ; c₃- -Cι₂cycloalkyl optionally substituted with one or more halogens,

Cx-Cgalkyl,

Cx-C.jhaloalkyl,

Cι-C₄alkoxy,

Cι-C₄haloalkoxy,

(C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl)SO_x, phenyl optionally substituted with one to three halogen, C₁-C₄alkyl C₁-C₄haloalkyl, C;ι_-C₄alkoxy, Cι-C₄haloalkoxy, N0₂ or CN groups, or phenoxy optionally substituted with one to three halogen, Ci-C^^alkyl, C₁ -C₄haloalkyl , Cι -C₄alkoxy, C_]_ -C₄haloalkoxy, N0₂ or CN groups; or phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, Cι-C₄haloalkyl, C₁-C₄alkoxy, C]_-C4haloalkoxy, N0₂ or CN groups; with the proviso that when R is phenyl, then m must be 1 or 2 ; R_j_ is R₁₂ ; C_]_ -Cιo^alkyl optionally substituted with one or more halogen, hydroxy, phenyl optionally substituted with one or more halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, Cι-C₄alkoxy, 71 Cι-C₄haloalkoxy,

72 N0₂ or CN groups,

74 C₁-C₄haloalkoxy,

75 (C₁-C₄alkyl)SO_x,

76 CONR₈R₉,

78 R_11#

79 R₁₂,

80 C3-Cgcycloalkyl optionally substituted with one

81 to three halogen,

82 C₁-C₄alkyl,

83 ^cl-^c4 haloalkyl,

84 Cι-C₄alkoxy,

85 Cι-C4haloalkoxy,

86 N0₂ or CN groups,

87 phenyl optionally substituted with one or more

88 halogen,

89 C₁-C alkyl,

90 C₁-C₄haloalkyl,

91 C -C₄alkoxy,

92 C_]_-C₄haloalkoxy,

93 N0 or CN groups, or

94 pyridyl optionally substituted with one or more

95 halogen,

96 Cι-C₄alkyl,

97 Cχ-C₄haloalkyl,

98 Cι-C₄alkoxy,

99 C]_-C4haloalkoxy,

100 N0 or CN groups;

101 C₂-Cιo^alkenyl optionally substituted with one or

102 more halogen,

103 hydroxy, 104 C₁-C₄alkoxy,

105 (C₁-C₄alkyl)SO_x,

106 CONR₈R₉,

107 CO₂R₁₀,

108 R_{l l r}

109 R₁₂,

110 C3-Cgcycloalkyl optionally substituted with one

111 to three halogen,

112 C₁-C₄alkyl,

113 Cι-C₄halo-alkyl,

114 C₁-C₄alkoxy,

115 C]_-C4haloalkoxy,

116 N0 or CN groups,

117 phenyl optionally substituted with one or more

118 halogen,

119 C₁-C₄alkyl,

120 C₁-C₄haloalkyl,

121 C₁-C₄alkoxy,

122 Cχ-C₄haloalkoxy,

123 N0₂ or CN groups, or

124 pyridyl optionally substituted with one or more

125 halogen,

126 C₁-C₄alkyl,

127 C₁-C₄haloalkyl,

128 C₁-C₄alkoxy,

129 C₁-C₄haloalkoxy, 130 N0 or CN groups;

131 C₂-C]_oalkynyl optionally substituted with one or

132 more halogen,

133 hydroxy,

134 C₁-C₄alkoxy,

135 (C₁-C₄alkyl)S0_χ,

136 CONR₈R₉, 137 CO₂R₁₀,

138 R_11;

139 R₁₂,

140 C3-Cgcycloalkyl optionally substituted with one

141 to three halogen,

142 C₁-C₄alkyl,

143 C₁-C₄halo-alkyl,

144 C₁-C4alkoxy,

145 Cχ-C haloalkoxy, 146 N0 or CN groups,

147 phenyl optionally substituted with one or more

148 halogen,

149 C₁-C₄alkyl,

150 C!-C₄haloalkyl,

151 Cι-C₄alkoxy,

152 C_]_-C₄haloalkoxy,

153 N0₂ or CN groups, or

154 pyridyl optionally substituted with one or more

155 halogen,

156 C₁-C₄alkyl,

157 Cι-C₄haloalkyl,

158 Cι-C₄alkoxy,

159 C2_.-C₄haloalkoxy,

160 N0₂ or CN groups; or

161 C3-C12cycloalkyl optionally substituted with one or

162 more halogen,

163 hydroxy,

164 Cι-C₄alkoxy,

165 (Cx-C₄alkyl) SO_χ,

166 CONR₈R₉,

167 CO₂Ri₀,

168 R11,

169 R12, 170 C3-Cgcycloalkyl optionally substituted with one

171 to three halogen,

172 C₁-C₄alkyl,

173 C₁-C₄halo-alkyl,

174 C₁-C₄alkoxy,

175 C]_-C₄haloalkoxy,

176 N0₂ or CN groups,

177 phenyl optionally substituted with one or more

178 halogen,

179 C₁-C₄alkyl,

180 C₁-C₄haloalkyl,

181 C;_]_-C alkoxy,

182 C;_]_-C₄haloalkoxy,

183 O2 or CN groups, or

184 pyridyl optionally substituted with one or more

185 halogen,

186 C₁-C₄alkyl,

187 C₁-C₄haloalkyl,

188 C₁-C₄alkoxy,

189 Ci- _jhaloalkoxy,

190 N0₂ or CN groups;

191 phenyl optionally substituted with one or more

192 halogen,

193 C₁-C₄alkyl,

194 C₁-C₄haloalkyl,

195 Cι-C₄alkoxy,

196 Cι-C₄haloalkoxy,

197 NO2 or CN groups, or

198 pyridyl optionally substituted with one or more

199 halogen,

200 C₁-C₄alkyl,

201 C;_]_-C₄haloalkyl,

202 Cι-C₄alkoxy, 203 Cι-C₄haloalkoxy,

204 N0₂ 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, N0₂ , Cx-Cgalkyl, C^.-

208 Cghaloalkyl, C]_-Cgalkoxy, C^-Cghaloalkoxy,

209 or phenyl optionally substituted with one

210 to three halogen, C^-C₄alkyl, Cι~

211 C₄haloalkyl, C_]_-C₄ lkoxy, C₁-C₄haloalkoxy,

212 (C₁-C₄alkyl)SO_x, (C₁-C₄haloalkyl) S0_y, N0₂

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-C₄alkyl, Cι~

217 C₄haloalkyl, C_]_-C₄alkoxy, C_]_-C₄haloalkoxy, (C^-

218 C₄alkyl)SO_x, (Cι-C₄haloalkyl) S0_X, N0₂ 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 R₈, R₉ and R^Q are each independently hydrogen or C_]_-

223 C₄alkyl;

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 C₁-C₄alkyl;

231 R₁₆ is hydrogen, halogen or C₁-C₄ alkyl;

232 X is O, S or NR₁₅;

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 X¹ is halogen and R, R₂, R₃, R₄, R₅, R₆, and R₇ 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.