WO1989000562A1

WO1989000562A1 - Insecticidal pyrazolines

Info

Publication number: WO1989000562A1
Application number: PCT/US1988/002335
Authority: WO
Inventors: George Philip Lahm
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1987-07-17
Filing date: 1988-07-15
Publication date: 1989-01-26
Also published as: AU1993988A; JPH02504273A; EP0367796A1

Abstract

Pyrazoline derivatives of formula (I), wherein R1, R2 and R3 are independently selected from hydrogen or defined organic or inorganic substituents, R5 is a carboxylic acid, ester or amide substituent, or a sulfonamide group; R6 and R7 are H or alkyl; m, n and p are zero or integers; X is O or S; Y is H or an organic substituent; exhibit activity against a wide spectrum of foliar and soil inhabiting insects, and hence may be used for crop protection.

Description

TITLE INSECTICIDAL PYRAZOLINES CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of the application bearing U.S. Serial No. 74,795 filed on July 17, 1987.

BACKGROUND OF THE INVENTION The described triphenylpyrazolines and agricultural compositions containing them are useful as insecticides.

EPA 21,506 discloses insecticidal compounds of the formula

wherein

R₁ is a phenyl group;

R₂ is a halogenalkoxy, halogenalkenyloxy, halogenalkylthio, halogenalkenylthio, halogenalkylsulfonyl or halogenalkenylsulfonyl group having 1 to 6 carbon atoms; and

X and Y represent hydrogen or halogen.

EPA 65,334 discloses insecticidal compounds of the formula

wherein

R is alkoxycarbonyl;

X and Y are hydrogen or halogen, and n is 2, 3, or 4.

EPA 58,424 discloses insecticidal compounds of the formula

wherein

R¹ is phenyl;

R⁴ is hydrogen or lower alkyl;

X is hydrogen or halogen;

Y and Z are hydrogen, halogen, lower alkyl, lower alkoxy, nitro, trifluoromethyl, lower alkylthio, acyl, nitrile, lower alkyl- sulfonyl, lower alkoxycarbonyl, A-R⁵ or Y and Z form

A is O, S, SO, or SO₂ and R⁵ is halogen- substituted lower alkyl.

EPA 113,213 discloses insecticidal compounds of the formula

wherein

R¹ is hydrogen, alkyl or alkenyl; X is oxygen or sulfur; R² is halogen, alkyl, haloalkyl, cyano, nitro, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyloxy, alkylsulfonyl, alkoxycarbonyl or acyl, or two adjacent R² groups may form a ring; m is 0 to 4; R^c is phenyl, para substituted by R₄;

R⁴ and R⁵ are R⁸SO₂O, hydrogen, halogen, alkyl, haloalkoxy, alkylthio or alkylsulfonyl, wherein R⁸ is alkyl or haloalkyl; at least one of R⁴ and R⁵ is R⁸SO₂O, or R⁴ is haloalkoxy.

EPA 153,127 discloses insecticidal compounds of the formula

wherein

A and B are phenyl or substituted phenyl; U is O or S; V is hydrogen, cycloalkyl, aryl or R⁴-Q; Y is unsubstituted or substituted alkyl, unsubstituted or substituted aryl; and Z is cycloalkyl, unsubstituted or substituted aryl or R⁴-Q provided that Z is not hydrogen and Z is not methyl when Y is methyl; and

R⁴-Q is broadly defined. U.S. Patent 4,156,007 discloses insecticidal compounds of the formula

wherein R₁ is phenyl or substituted phenyl;

R₂ and R₃ are equal or different and have the meanings of an alkyl group, a cycloalkyl group, a pyridyl or thienyl group which may be substituted with halogen, alkyl or nitro, a phenyl group or a phenyl group substituted with 1-2 substituents selected from the group consisting of a halogen atom, an alkyl group possibly Substituted with halogen, a cycloalkyl group, an alkylthio group, an alkoxy group, a mono or dialkylamino group, a nitro group, a phenyl group possibly substituted with halogen, and a cyano group; R₄ is hydrogen or alkyl; and X is oxygen or sulfur.

SUMMARY OF THE INVENTION This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as insecticides:

wherein

R₁, R₂ and R₃ are independently selected from R₈, halogen, CN, N₃, SCN, NO₂, OR₈, SRg, S(O)R₈, S(O)₂R₈, OC(O)R₈, OS(O)₂R₈, C(O)OR₈, C(O)R₈, C(O)NR₈R₉, S(O)₂NR₈R₉, NR₈R₉, NR₉C(O)R₈, OC(O)NHR₈, NR₉C(O)NHR₈ and NR₉S(O)₂R₈, or when m, n or p is 2, R₁, R₂ or R₃ can be taken together as OCH₂O, OCH₂CH₂O or CH₂CH₂O, to form a 5 or 6 membered ring, each of which can be substituted with 1 to 4 halogen atoms or 1 to 2 methyl groups;

R₅ is selected from C(O)OR₁₀, C(O)R₁₀,

C(O)NR₁₀R₁₁, C(S)SR₁₀, C(S)NR₁₀R₁₁ and S(O)₂NR₁₀R₁₁;

R₆ is H or C1 to C₄ alkyl;

R₇ is H or CH₃; R₈ and R₁₀ are independently selected from H, C₁ to C₄ alkyl, C₃ to C₄ alkenyl, C₃ to C₄ alkynyl, C₁ to C₄ haloalkyl, C₃ to C₄ haloalkenyl, C₁ to C₄ alkyl substituted with CN, C(O)OCH₃, C(O)OCH₂CH₃, OCH₃, OCH₂CH₃, SCH₃, SCH₂CH₃ and NO₂, and phenyl or benzyl, either optionally substituted with W, or R₈ and R₉ can be taken together as (CH₂)₄,

(CH₂)₅ or CH₂CH₂OCH₂CH₂; R₉ and R₁₁ are independently selected from H, C₁ to C₄ alkyl, C₃ to C₄ alkenyl, C₃ to C₄ alkynyl, and C₁ to C₄ haloalkyl, or R₁₀ and R₁₁ can be taken together as (CH₂)₄, (CH₂)₅ or CH₂CH₂OCH₂CH₂; m and n are independently 0 to 5; p is 0 to 4; W is selected from halogen, CN, NO₂, C₁ to C₂ alkyl, C₁ to C₂ haloalkyl, C₁ to C₂ alkoxy, C₁-C₂ haloalkoxy, C₁ to C₂ alkylthio, C₁ to C₂ haloalkylthio, C₁ to C₂ alkylsulfonyl or C₁ to C₂ haloalkyl- sulfonyl; X is O or S; and

Y is selected from H, C₁ to C₆ alkyl, C₂ to C₆ alkoxyalkyl, CHO, C₂ to C₆ alkylcarbonyl, C₂ to C₆ alkoxycarbonyl, C₂ to C₆ haloalkylcarbonyl, C₁ to C₆ alkylthio, C₁ to C₆ haloalkylthio, phenylthio, and phenylthio substituted with 1 to 3 substituents independently selected from W. Preferred compounds A are those of Formula I wherein: R₆ is H;

R₇ is H; n and p are independently 0 to 2; and m is 1 to 2. Preferred compounds B are preferred compounds A wherein:

R₁, R₂, and R₃ are independently R₈, halogen, CN, NO₂, OR₈, SR₈, S(O)R₈, S(O)₂R₈ or NR₈R₉, or when m, n or p is 2, R₁, R₂ or R₃ can be taken together as OCH₂O, OCH₂CH₂O or CH₂CH₂O, each of which can be substituted with 1 to 4 halogen atoms or 1 to 2 methyl groups; R₈ is C ₁ to C₂ alkyl, C₃ to C₄ alkenyl, C₁ to C₂ haloalkyl, C₃ to C₄ haloalkenyl or phenyl optionally substituted with halogen; R₉ is H or C₁ to C₂ alkyl; and X is O. Preferred compounds C are preferred compounds B wherein:

R₁ is halogen, CN, NO₂, OCF₂H, OCF₃ OCF₂CF₂H, CF₃ or when m is 2 then R₁ may be taken together as CH₂C(CH₃)₂O or CF₂CF₂O to form a 5 membered ring. R₂ is H, halogen, CN, N0₂, OCH₃, OCF₂H,

OCF₃, SCH₃, SCF₂H, SCF₃, CF₃, OCF₂CF₂H or phenoxy; R₃ is halogen;

R₅ is C(O)OR₁₀, C(O)R₁₀, C(O)NR₁₀R₁₁ or S(O)₂NR₁₀R₁₁; R₁₀ is H, C₁ to C₄ alkyl, C₃ to C₄ alkenyl, C₃ to C₄ alkynyl, C₁ to C₄ haloalkyl, C₃ to C₄ haloalkenyl, C ₁ to C₄ alkyl substituted with CN, C(O)OCH₃, C(O)OCH₂CH₃, OCH₃, OCH₂CH₃, SCH₃ , SCH₂CH₃ and NO₂; R₁₁ is H or C₁ to C₂ alkyl; and Y is H, C₁ to C₆ alkyl, CHO, C₂ to C₆ alkylcarbonyl or C₂ to C₆ alkoxycarbonyl.

Preferred compounds D are preferred compounds C wherein: R₅ is C(O)OR₁₀;

R₁₀ is C₁ to C₃ alkyl, C₂ to C₃ haloalkyl, propargyl or allyl; and one of R₃ or R₅ is in the para-position and one of R₁ is in the para-position; and Y is H, CH₃ C(O)CH₃, C(O)OCH₃ or CHO.

Specifically preferred compounds are E to L:

E. A compound of Preferred D which is methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4-

(trifluoromethyl)phenylamino]carbonyl]- 1H-pyrazol-4-yl]benzoate;

F. A compound of Preferred D which is methyl 4-[3-(4-chlorophenyl)-1-[(4-chlorophenyl) aminocarbonyl]-4,5-dihydro-1H-pyrazol-4- yl] benzoate; G. A compound of Preferred D which is methyl

4-[3-(4-fluorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-

1H-pyrazol-4-yl]benzoate; H. A compound of Preferred D which is methyl

4-[1-(4-chlorophenyl)aminocarbonyl]-[3-(4- fluorophenyl)-4,5-dihydro-1H-pyrazol-4-yl] benzoate;

I. A compound of Preferred D which is ethyl 4- [3-(4-chlorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate; J. A compound of Preferred D which is ethyl 4-

[1-[(4-bromophenyl)aminocarbonyl]-3-(4- chlorophenyl)-4,5-dihydro-1H-pyrazol-4-yl] benzoate; K. A compound of Preferred D which is methyl, 4- [3-(4-bromophenyl)-4,5-dihydro-1-[[4-

(trifluoromethyl)phenylamino]carbonyl]- 1H-pyrazol-4-yl]benzoate; and L. A compound of Preferred D which is methyl 4-[3-(4-cyanophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate. Hereafter for the sake of brevity, the compounds of this invention are described and claimed as "triphenyl pyrazoline(s)" or "pyrazoline(s)" or "compound(s)", it being understood that such terms include all geometric and stereoisomers and all agriculturally suitable salts of said compounds.

DETAILS OF THE INVENTION Compounds of Formula I can be prepared from deoxybenzoins of Formula II by a three-step process whereby the Formula II compound is condensed with an aldehyde or ketone, then cyclized with hydrazine and finally reacted with a suitably substituted aryl isocyanate to yield the Formula I compound

(Scheme I). Examples of this procedure, where R₆ and

R₇ are equal to hydrogen, can be found in U.S.

4,070,365.

An alternative procedure, where R₆ and R₇ is other than hydrogen, involves first alkylation of the Formula II compound with an alkyl halide followed by bromination/dehydrobromination to yield the α,β-unsaturated ketone IIA. Subsequent reactions with hydrazine and an aryl isocyanate yield the compounds of Formula I (Scheme IA). Examples of this procedure are described in European Patent Application 4,733. Scheme I

The intermediate deoxybenzoin of Formula II can be prepared by various procedures known in the art. The particular method chosen will depend on the substituents R₂, R₃, and R₅ and their compatibility with the conditions and reagents of that method. For example, compounds of Formula II, where R₅ is alkoxycarbonyl or dialkylsulfamoyl, can be prepared by the alkylation of a trimethylsilyl cyanohydrin of Formula III with a benzyl halide of Formula IV followed by conversion of the alkylated trimethylsilyl cyanohydrin to the corresponding carbonyl. The alkylation is typically run. in a solvent such as ether or tetrahydrofuran at temperatures in the range of -78° to 25°C. Deprotonation of the Formula III compound is accomplished by treatment with a strong base such as lithium diisopropylamide and the Formula IV compound is subsequently added. Once alkylation is complete, the trimethylsilyl cyanohydrin of Formula V is converted to the deoxybenzoin of Formula II by procedures documented in the art. One method involves treatment of the Formula V compound with fluoride resulting in direct formation of the compounds of Formula II. Alternatively, the Formula II compounds can be prepared from the intermediates of Formula V by acid catalyzed cleavage of the trimethylsilyl group followed by base catalyed regeneration of the carbonyl. These procedures are depicted in Scheme II. Scheme II

V

Alternatively, compounds of Formula II are accessible via a Friedel-Crafts acylation as depicted in Scheme III. This procedure is particularly useful for the preparation of a variety of R₅ substituents including C(O)₂R₁₀, C(O)NR₁₀R₁₁ and SO₂NR₁₀R₁₁. Generally, best results are achieved when R₂ is an ortho-para directing group such as alkyl, halogen, alkoxy and the like. Scheme III

VI VII

Compounds of Formula II where R₅ is C(O)R₁₀ can be prepared as outlined in Scheme IV from the corresponding bromo derivative IX by metal-halogen exchange followed by reaction with an electrophilic C(O)R₁₀ reagent. Dialkylamides (e.g., dimethylformamide, dimethylacetamide) are particularly suitable reagents for this transformation. Removal of the carbonyl protecting group affords the Formula II compound.

Scheme IV

3. H₂O, acid cat. II (R₅is C(O)R₁₀)

Trimethylsilyl cyanohydrins of Formula III can be prepared from the corresponding benzaldehyde derivatives by reaction with trimethylsilylnitrile in the presence of a Lewis acid catalyst such as zinc iodide; see Evans et al., J. Chem. Soc. Chem. Comm., 55 (1973).

The following Examples illustrate preparation of the compounds of this invention.

Example 1 Step A

4-Chloro-α-(trimethylsilyloxy)benzeneacetonitrile

To a mixture of 32 g of 4-chlorobenzaldehyde and 0.4 g zinc iodide in 40 ml of methylene chloride was added 25 g of trimethylsilylnitrile dropwise under nitrogen. The addition was initiated at room temperature and added at such a rate that gentle reflux of the methylene chloride was maintained. After 24 hours, the reaction was concentrated and the residual oil distilled at 1.0 mm (bath temperature 150°C) using a Kugelrohr apparatus to afford 50.74 g of the title compound as a yellow oil. 1H NMR (CDCl₃) δ 0.24 (s, 9H);

5.50 (s, 1H); 7.41 (s, 4H).

Step B

Methyl 4-(bromomethyl)benzoate To a solution of 10 g of methyl 4-hydroxymethylbenzoate and 80 g of carbon tetrabromide in 300 ml of diethyl ether was added 63.2 g of triphenylphosphine. The reaction was warmed to room temperature overnight, filtered through Celite^® and concentrated to 87.2 g of a yellow oil. Chromatography on silica gel (95:5, hexane:ethyl acetate) afforded 19.62 g of a white solid, m.p. 52° to 55°C.

¹H NMR (CDCl₃) δ 3.92 (s, 3H);

4.50 (s, 2H); 7.45 (d, 2H); 8.01 (d, 2H)

Step C

Methyl 4- 2- (4-chlorophenyl ) -2-oxoethyl benzoate To a -70°C solution of 2.0 ml of diisopropyl- amine in 20 ml of THF, under nitrogen, was added 5.1 ml of 2 . 5 M n-butyllithium and the mixture was stirred for 5 min. A solution of 3.0 g of 4-chloro- α-(trimethylsilyloxy)benzeneacetonitrile in 5 to 10 ml of THF was then added dropwise such that the reaction was maintained at less than -60°C. Once added the reaction was stirred for 15 min, and then a solution of methyl 4-(bromomethyl) benzoate in 5 to 10 ml of THF was added dropwise and the reaction was then gradually warmed to room temperature. After 24 hours, 40 ml of 5% aqueous sodium bicarbonate was added and the reaction was concentrated. The residue was dissolved in 50 ml of methanol and 4.0 g of potassium fluoride was added. After stirring for 4 hours, the reaction was concentrated and the residue was partitioned between chloroform and water. The chloroform extracts were dried over magnesium sulfate and concentrated to 3.6 g of an orange solid. Trituration with n-butyl chloride afforded 2.5 g of a white solid, m.p. 165° to 167°C. ¹H NMR (CDCI₃) δ 3.90 (s, 3H)

4.32 (s, 2H)

7.32 (d, 2H)

7.44 (d, 2H)

7.97 (d, 2H)

8.01 (d, 2H)

IR (Nujol) 1680, 1710 cm^-1.

Step D

Methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1H- pyrazol-4-yl] benzoate

A mixture of 2.0 g of the title ester of Step C, 3.0 ml of 37% formaldehyde, 0.2 ml of piperidine and 0.2 ml of glacial acetic acid was heated at reflux, under nitrogen, for 2 hours after which time TLC indicated the reaction was complete. The mixture was cooled to room temperature, partitioned between CHCI₃ and 5% aqueous NaHCO₃, dried over magnesium sulfate, filtered and concentrated to afford 2.5 g of a yellow oil. The residual oil was taken up in 10 ml of methanol and 0.35 ml of hydrazine hydrate was added. After heating at reflux for 2 hours, a white solid began to precipitate. The reaction was cooled to room temperature, filtered and dried to afford 0.76 g of a pale yellow powder, m.p. 155° to 159°C. ¹H NMR (CDCI₃) δ 3.58 (dd, 1H);

3.89 (s, 3H); 4.02 (dd, 1H);

4.55 (dd, 1H); 7.1-7.3 (m, 4H); 7.47 (d, 2H); 7.97 (d, 2H). Step E

Methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1- [14- (trifluoromethyl)-phenylamino]carbonyl-

1H-pyrazol-4-yl]benzoate

A mixture of 0.31 g of the title ester of Step D and 0.19 g of 4-trifluoromethylphenylisocyanate in 8 ml of 1:1 ether-THF was stirred 24 hours at room temperature and then concentrated. Trituration of the residue with ether/hexane afforded 0.28 g of the title compound as a yellow solid, m.p. 168° to 171°C. ¹H NMR (CDCl₃) δ 3.90 (s, 3H);

4.10 (dd, 1H); 4.45 (t, 1H);

4.82 (dd, 1H); 7.2-8.1 (m, 12H); 8.1 (bs, 1H). By the general procedures described therein, or obvious modifications thereof, the compounds of Tables 1 to 3 can be prepared.

General Structure for Tables 1 to 3

The following numbering system describes the compounds of Tables 1 to 3.

1. R₁ or R₂ substitutents designated as disubstituted with two open termini are bound to phenyl to form a bicyclic ring such that the first numerical designation defines the position of the first listed terminus and the second numerical designation defines the position of the other terminus.

Formulation and Use

The compounds of this invention will generally be used in formulation with a carrier comprising a liquid or solid diluent or an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

Percent by Weight

Active Ingredient Diluent(s) Surfactant (s)

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, 5-50 40-95 0-15

Emulsions, Solutions, (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 1-95 5-99 0-15 High Strength 90-99 0-10 0-2

Compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound.

Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing. Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual:, MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering. December 4, 1967, pp. 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following. Examples of useful formulations of compounds of the present invention are as follows:

Example 2 Emulsifiable Concentrate

N,3-bis[4-(trifluoromethyl)phenyl]-4-[4-(dimethylamino)-sulfonyl]phenyl1-4 ,5-dihydro-1H-pyrazole- 1-carboxamide 10% blend of oil soluble sulfonates and polyoxyethylene ethers 4% isophorone 86%

The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.

Example 3 Wettable Powder methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 3% The active ingredient is blended with the inert materials in a blender. After grinding in a hammermili, the material is reblended and sifted through a U.S.S. 50 mesh screen and packaged.

Example 4 Dust wettable powder of Example 2 5% pyrophyllite (powder) 95%

The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust.

Example 5 Granule methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate 10% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No.

25-50 sieves) 90%

The active ingredient is dissolved in a suitable solvent and sprayed onto dedusted attapulgite granules in a double cone blender. The granules are warmed to drive off solvent, cooled and packaged.

Example 6 Granule wettable powder of Example 2 15% gypsum 69% potassium sulfate 16%

The ingredients are blended in a rotating mixer and water is sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 12% active ingredient.

Example 7 Solution methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate 15%

4-butyrolactone 85%

The ingredients are combined and stirred to produce a solution suitable for direct, low volume application. Example 8

Oil Suspension methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70% The ingredients are ground together in a sand mill until the solid particles have been reduced to under 5 microns. The resulting thick suspension may be applied directly, but preferable after being extended with oils or emulsified in water.

Example 9 Wettable Powder methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4- (trifluoromethyl)phenylamino]carbonyl]-1H- pyrazol-4-yl]benzoate 20% sodium alkylnaphthalenesulfonate 4% sodium lignosulfonate 4% low viscosity methyl cellulose 3% attapulgite 69% The active ingredient is blended with the inert materials in a blender. After griding in a hammermill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. 50 mesh screen and packaged.

Compounds of Formula I can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, or other biologically active compounds to form a multi- component pesticide giving an even broader spectrum of effective agricultural protection. Examples of other agricultural protectants with which compounds of the present invention can be mixed or formulated are:

Insecticides:

3-hydroxy-N-methylcrotonamide(dimethylphosphate) ester (monocrotophos) methylcarbamic acid, ester with 2, 3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran) O-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (carbaryl) methyl O-(methylcarbamoyl) thiolacetohydroxamate (methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine

(chlordimeform) O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate (diazinon) octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) (S)-a-cyano-m-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin) Methyl N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-1-thiooxamimidate (oxamyl) cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(1-methylethyl)benzeneacetate (fenvalerate) (3-phenoxyphenyl)methyl(±)-cis,trans-3-(2,2-dichloroethenyl) -2 , 2-dimethylcyclopropanecarboxylate (permethrin) a-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylate (cypermethrin) O-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate

(profenofos) phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)- phenyl]-S-n-propyl ester (sulprofos).

Additional insecticides are listed Hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphos-methyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, profenofos, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone, Fungicides: methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb) 1, 4-dichloro-2, 5-dimethoxybenzene (chloroneb) methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl) 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2- ylmethyl]-1H-1,2,4-triazole (propiconazole) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-

1-yl)-2-butanone (triadimefon) N-(trichloromethylthio) tetrahydrophthalimide (captan) N-(trichloromethylthio)phthalimide (folpet) 1-[[[bis(4-fluorophenyl)][methyl]silyl]methyl]-1H- 1,2,4-triazole. Nematocides:

S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)- thioformimidate S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate N-isopropylphosphoramidic acid, O-ethyl O'-[4-(methyl- thio)-m-tolyl]diester (fenamiphos). Bactericides: tribasic copper sulfate streptomycin sulfate. Acaricides: senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl) 6-methy1-1,3-dithiolo[4,5-β]quinoxalin-2-one (oxythioquinox) ethyl 4,4'-dichlorobenzilate (chlorobenzilate) 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3-carboxamide (hexythiazox) amitraz propargite fenbutatin-oxide bisclofentezin. Biological

Bacillus thuringiensis Avermectin B.

Ut i l ity

The compounds of the present invention exhibit activity against a wide spectrum of foliar and soil inhabiting insects. Those skilled in the art will recognize that not all compounds will be equally effective against all insects, but compounds of this invention display control of many of the economically important pest species of the insect orders

Lepidoptera, Homoptera, and Coleoptera among many others. The specific species for which control is exemplified below are: fall armyworm, Spodoptera frugjperda; boll weevil, Anthonomus grandis; European corn borer, Ostrinia nubilalis; southern corn rootworm, Diabrotica undecimpunctata howardi; aster leafhopper, Macrosteles fascifrons. The pest control afforded by the compounds of the present invention is not limited, however, to these species.

Application

Insects are controlled and agricultural crops are protected by applying one or more of the Formula I compounds of this invention, in an effective amount, to the locus of infestation, to the area to be protected (the environment of the pests), or directly on the pests to be controlled. A preferred method of application is by spraying with spray equipment that distributes the compound on the foliage, in the soil, or to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these compounds can be applied to soil or foliage or, optionally, incorporated into the soil. Either aerial or ground application can be used. The pyrazoline compound(s) of this invention can be applied in its (their) pure state, but most often application will be of a formulation comprising one or more compounds of this invention, in an agriculturally suitable carrier or diluent. A most preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. The rate of application of the Formula I compounds required for effective control wi ll depend on such factors as the insect species population size, the pest's life stage, insect size, its location, the host crop, the host stage, time of year of application, placement of the insecticide, temperature conditions, and others. In general, application rates of 0.05 to 2 kg of active ingredient per hectare are sufficient to provide effective control in large scale field operations under normal circumstances, but as little as 0.01 kg/hectare may be sufficient or as much as 8 kg/hectare may be required, depending upon the factors listed above.

Examples 10 to 15 demonstrate the control efficacy of compounds of Formula I on specific insect pests. Compounds 1 through 115 in these tests are described in Table 4. In each of Compounds 1 to 115, R₆, R₇ and Y are hydrogen and X is oxygen with the following exceptions: in compound 81, Y is methyl and in compounds 104 to 106, R₆ is methyl.

c

. Ω

Example 10 Fall Armvworm A test unit consisted of an 8-ounce plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick infested with ten third-instar larvae of fall armyworm (Spodoptera frugiperda). Solutions of each of the above-listed test compounds were made by combining the compound in an acetone/distilled water 75/25 solvent and then sprayed onto the cups; a single solution per cup replicated three times. Spraying was accomplished by passing the cups, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. The cups were then covered and held at 27°C and 50% relative humidity for 72 hours, after which time mortality readings were taken. Tested compounds which killed 80% or more of the larvae are listed below:

Example 11 Tobacco Budworm The test procedure of Example 10 was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. Tested compounds which killed 80% or more of the larvae are listed below:

Example 12 European Corn Borer A test unit consisted of an 8-ounce plastic cup containing a one-inch square of wheat germ/soyflour diet infested with five third-instar larvae of the European corn borer (Ostrinia nubilalis). Test units were sprayed as described in Example 10. The cups were then covered and held at 27°C and 50% relative himidity for 48 hours, after which time mortality readings were taken. Tested compounds which killed 80% or more of the larvae are listed below:

1 21

2 22

3 26

4 30

11 33

12 50

13 52

14

15

Example 13 Southern Corn Rootworm A test unit consisted of an 8-ounce plastic cup containing 1 sprouted corn seed. The test units were sprayed as described in Example 10. After the treated cup had dried it was infested with five third-instar larvae of the Southern corn rootworm (Diabrotica undecimpunctata howardi) and replicated three times. A moistened dental wick was inserted into each cup to prevent drying and the cups were covered. The cups were then held at 27°C and 50% humidity for 48 hours, after which time mortality readings were taken. Tested compounds which killed 80% or more of the larvae are listed below: 8

10 28

55 56 58 91 93

Example 14 Boll Weevil The test unit consisted of five adult boll weevils (Anthonomus grandis) in a 9-ounce cup. The test procedure employed was the same as in Example 10. Mortality readings were taken 48 hours after treatment. Tested compounds which killed 80% or more of the adults are listed below: 1 15

2 21

3 22

4 26 12 30 13 33

14 52

Example 15 Aster Leafhopper A test unit was a 12-ounce cup containing oat (Avena sativa) seedlings in a 1-inch layer of sterilized soil. Test units were sprayed as described in Example 10. After the treated oats had dried between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, and evaluated for mortality. Tested compounds which killed 80% or more of the insects are 22, 49, 50, 58 and 91.

Claims

CLAIMSWhat is claimed is

1. A compound of the formula

wherein

R₁, R₂ and R₃ are independently selected from R₈, halogen, CN, N₃, SCN, NO₂, OR₈,

SR₈, S(O)R₈, S(O)₂R₈, OC(0)Rg, OS(0)₂Rg,

C(O)OR₈, C(O)R₈, C(O)NR₈R₉, S(O)₂NR₈R₉, NR₈R₉, NR₉C(O)R₈, OC(O)NHR₈, NR₉C(O)NHR₈ and NR₉S(O)₂R₈, or when m, n or p is 2, R₁, R₂ or R₃ can be taken together as OCH₂O, OCH₂CH₂O or CH₂CH₂O, to form a 5 or 6 membered ring, each of which can be substituted with 1 to 4 halogen atoms or 1 to 2 methyl groups; R₅ is selected from C(O)OR₁₀, c(O)R_10'

C(O)NR₁₀R₁₁, C(S)SR₁₀, C(S)NR₁₀R₁₁ and S(O)₂NR₁₀R_11;

R₆ is H or C₁ to C₄ alkyl; R₇ is H or CH₃;

R₈ and R₁₀ are independently selected from H, C₁ to C₄ alkyl, C₃ to C₄ alkenyl, C₃ to C₄ alkynyl, C₁ to C₄ haloalkyl, C₃ to C₄ haloalkenyl, C₁ to C₄ alkyl substituted with CN, C(O)OCH₃, C(O)OCH₂CH₃, OCH₃, OCH₂CH₃, SCH₃,SCH₂CH₃ and NO₂, and phenyl or benzyl, either optionally substituted with W, or R₈ and R₉ can be taken together as (CH₂)₄,

(CH₂)₅ or CH₂CH₂OCH₂CH₂; R₉ and R₁₁ are independently selected from H, C₁ to C₄ alkyl, C₃ to C₄ alkenyl, C₃ to C₄ alkynyl, and C ₁ to C₄ haloalkyl, or R₁₀ and R₁₁ can be taken together as (CH₂)₄, (CH₂)₅ or CH₂CH₂OCH₂CH₂; m and n are independently 0 to 5; p is 0 to 4;

W is selected from halogen, CN, NO₂, C₁ to C₂ alkyl, C₁ to C₂ haloalkyl, C₁ to C₂ alkoxy, C₁-C₂ haloalkoxy, C₁ to C₂ alkylthio, C₁ to C₂ haloalkylthio, C₁ to C₂ alkylsulfonyl and C₁ to C₂ haloalkyl- sulfonyl; X is O or S; and

Y is selected from H, C₁ to C₆ alkyl, C₂ to C₆ alkoxyalkyl, CHO, C₂ to C₆ alkylcarbonyl, C₂ to C₆ alkoxycarbonyl, C₂ to C₆ haloalkylcarbonyl, C₁ to C₆ alkylthio, C₁ to C₆ haloalkylthio, phenylthio, and phenylthio substituted with 1 to 3 substituents independently selected from W.

2. A compound according to Claim 1 wherein: R₆ is H;

R₇ is H; n and p are independently 0 to 2; and m is 1 to 2.

3. A compound according to Claim 2 wherein: R₁, R₂, and R₃ are independently R₈, halogen, CN, NO₂ , OR₈, SR₈, S(O)R₈,

S(O)₂R₈ or NR₈R₉, or when m, n or p is 2, R₁, R₂ or R₃ can be taken together as OCH₂O, OCH₂CH₂O or CH₂CH₂O, each of which can be substituted with 1 to 4 halogen atoms or 1 to 2 methyl groups;

R₈ is C₁ to C₂ alkyl, C₃ to C₄ alkenyl, C₁ to C₂ haloalkyl, C₃ to C₄ haloalkenyl or phenyl optionally substituted with halogen; R₉ is H or C₁ to C₂ alkyl; and

X is O.

4. A compound according to Claim 3 wherein: R₁ is halogen, CN, NO₂, OCF₂H, OCF₃ OCF₂CF₂H, CF₃ or when m is 2 then

R₁ may be taken together as CH₂C(CH₃)₂O or CF₂CF₂O to form a 5 membered ring. R₂ is H, halogen, CN, NO₂, OCH₃ , OCF₂H, OCF₃, SCH₃, SCF₂H, SCF₃, CF₃, OCF₂CF₂H or phenoxy;

R₃ is halogen; R₅ is C(O)OR₁₀, C(O)R₁₀, C(O)NR₁₀R₁₁ or S(O)₂NR₁₀R₁₁; R₁₀ is H, C₁ to C₄ alkyl, C₃ to C₄ alkenyl,

C₃ to C₄ alkynyl, C₁ to C₄ haloalkyl, C₃ to C₄ haloalkenyl, C₁ to C₄ alkyl substituted with CN, C(O)OCH₃, C(O)OCH₂CH₃, OCH₃, OCH₂CH₃, SCH₃, SCH₂CH₃ and NO₂;

R₁₁ is H or C₁ to C₂ alkyl; and

Y is H, C₁ to C₆ alkyl, CHO, C₂ to C₆ alkylcarbonyl or C₂ to C₆ alkoxycarbonyl.

5. A compound according to Claim 4 wherein:

R₅ is C(O)OR₁₀;

R₁₀ is C₁ to C₃ alkyl, C₂ to C₃ haloalkyl, propargyl or allyl; and one of R₃ or R₅ is in the para-position and one of R₁ is in the para-position; and

Y is H, CH₃ C(O)CH₃, C(O)OCH₃ or CHO.

6. A compound according to Claim 5 which is: methyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4-(trifluoromethyl)phenylamino]carbonyl]-1H-pyrazol-4-yl]benzoate.

7. A compound according to Claim 5 which is: methyl 4-[3-(4-chlorophenyl)-1- [(4-chlorophenyl)aminocarbonyl]-4,5- dihydro-1H-pyrazol-4-yl]benzoate.

8. A compound according to Claim 5 which is: methyl 4-[3-(4-fluorophenyl)-4,5-di- hydro-1-[[4-(trifluoromethyl)phenylamino]carbonyl]-1H-pyrazol-4-yl]benzoate.

9. A compound according to Claim 5 which is: methyl 4-[1-(4-chlorophenyl)aminocarbonyl]-[3-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-4-yl]benzoate.

10. A compound according to Claim 5 which is: ethyl 4-[3-(4-chlorophenyl)-4,5-dihydro-1-[[4-(trifluoromethyl)phenylamino]carbonyl]-1H-pyrazol-4-yl ] benzoate .

11. A compound according to Claim 5 which is: ethyl 4-[1-[(4-bromophenyl)aminocarbonyl]-3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol-4-yl]benzoate.

12. A compound according to Claim 5 which is: methyl, 4-[3-(4-bromophenyl)-4,5-dihydro-1-[[4-(trifluoromethyl)phenylamino]carbonyl]-1H-pyrazol-4-yl]benzoate.

13. A compound according to Claim 5 which is: methyl 4-[3-(4-cyanophenyl)-4,5-dihydro-1-[[4-(trifluoromethyl)phenylamino]carbonyl]-1H-pyrazol-4-yl]benzoate.

14. A composition comprising an insecticidally effective amount of a compound according to any one of Claims 1 to 13 together with a carrier therefor.

15. A method for controlling insects comprising applying to the insect or its environment an insecticidally effective amount of a compound according to any one of Claims 1 to 13.