WO1993005024A1

WO1993005024A1 - Arthropodicidal anilides

Info

Publication number: WO1993005024A1
Application number: PCT/US1992/007145
Authority: WO
Inventors: William Eldo Barnette; Charles Richard Harrison; George Philip Lahm; David Walter Piotrowski; Keith Dumont Wing
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1991-08-28
Filing date: 1992-08-28
Publication date: 1993-03-18

Abstract

Arthropodicidal anilides of formula (I) wherein R1 to R5 are as defined in the text; arthropodicidal compositions containing such compounds and a method of using the compounds to control arthropods.

Description

TITLE

ARTHROPODICIDAL ANILIDES

U.S. 4,156,007 and EP-A-58,424 disclose

arthropodicidal substituted anilides which broadly encompass those of the instant invention. However, there is no specific disclosure in either publication of any of the compounds of this invention.

This invention concerns anilides of Formula I, all their geometric and stereoisomers, their agronomically and nonagronomically suitable salts, compositions

containing them, and use of the compounds to control arthropods in both agronomic and nonagronomic

environments. The compounds are:

wherein:

R¹ is selected from the group Br, CF₃, OCF₃, OCF₂H and OSO₂CF₃; R² is selected from the group H, F, Cl, Br, CF₃, OCF₃,

OCF₂H and OCH₂CF₃;

R³ is selected from the group C₁-C₆ alkyl, C₂-C₆

alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ cyclohaloalkyl, C₃-C₆ cycloalkylalkyl, COR¹¹,

CO₂R¹¹, NR⁶R⁷, N=CR⁸R⁹, OR⁶' C₁-C₆ alkyl

substituted by a group selected from halogen, C₁- C₃ alkoxy, C₁-C₃ haloalkoxy, NR¹¹R¹², CN, NO₂, S(O)_nR¹¹, COR¹¹, CO₂R¹¹ and phenyl optionally substituted by a group selected from halogen, CN, C₁-C₂ haloalkyl and C₁-C₂ haloalkoxy;

R⁴ is selected from the group CO₂Me, Ph, 4-F-Ph,

4-Cl-Ph and C₁-C₃ alkyl; R⁴ being other than Ph and 4-F-Ph when R² is OCF₂H; and R⁴ being CO₂Me when R³ is COR¹¹ and CO₂R¹¹;

R⁵ is selected from the group H and CH₃; R⁵ being H when R⁴ is Ph;

R⁶ is selected from the group H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, SO₂NR⁸R⁹ SO₂R¹⁰, COR⁸, CONR⁸R⁹, CO₂R⁸, phenyl optionally substituted with halogen, and benzyl optionally substituted with halogen;

R⁷ is selected from the group H, C₁-C₄ alkyl and

COR⁸;

R⁸ is selected from the group H, C₁-C₄ alkyl, C₁-C₄

haloalkyl and phenyl optionally substituted by a group selected from halogen, CN, NO₂, CF₃ and

OCF₃;

R⁹ is selected from the group H and C₁-C₄ alkyl;

R⁸ and R⁹ can be taken together as -CH₂CH₂CH₂-,

-CH₂CH₂CH₂CH₂- and -CH₂CH₂CH₂CH₂CH₂-; R¹⁰ is selected from the group C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R¹¹ is selected from the group C₁-C₃ alkyl and C₁-C₃ haloalkyl;

R¹² is selected from the group H and C₁-C₃ alkyl; and n is 0, 1 or 2.

Preferred for reasons including ease of synthesis and/or greater arthropodicidal efficacy are:

A) Compounds of Formula I wherein R³ is C₁-C₆ alkyl, NR⁶R⁷ or OR⁶;

B) Compounds of Formula I wherein R⁴ is CO₂Me, Ph, 4-Cl-Ph or 4-F-Ph;

C) Compounds of Formula I wherein R³ is CH₃; and D) Compounds of Formula I wherein R⁶ is H or C₁-C₃ alkyl.

Specifically preferred are these compounds of preferred C:

E) methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate; and

F) methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethoxy)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate. In the above definitions, the term "alkyl", used either alone or in compound words such as "haloalkyl" includes straight chain or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl or the

different hexyl isomers. Alkenyl includes straight chain or branched alkenes such as 1-propenyl, 2-propenyl, 3- propenyl and the different hexenyl isomers. Alkynyl includes straight chain or branched chain alkynyl groups such as 1-pentynyl, 2-pentynyl, 3-pentynyl and the different hexynyl isomers. Alkoxy includes methoxy, ethoxy, n-propyloxy and isopropyloxy. The term

"halogen", either alone or in compound words such as "haloalkyl", means fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl can be partially or fully substituted with halogen atoms, which can be the same or different.

Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and

CH₂CHFCl . The total number of carbon atoms in a

substituent group. is indicated by the C_i-C_j prefix where i and j are numbers from 1 to 6. For example, C₁-C₃ alkoxy would designate methoxy through propoxy. The term "cycloalkyl" alone or in compound words such as

"cyclohaloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups - Cycloalkylalkyl includes cyclopropylmethyl, cyclobutylmethyl,

cyclopentylmethyl and cyclohexylmethyl groups.

DETAILS OF THE INVENTION

Formula I compounds can be prepared by the

N-alkylation of Formula II derivatives. For example, Formula II derivatives are treated with a base such as sodium hydride, potassium hydride, potassium tert- butoxide, lithium diisopropyl amide and the like in an inert solvent such as ether, tetrahydrofuran, dioxane, dimethylformamide and dimethylsulfoxide. Subsequent treatment of the anion with an electrophilic reagent such as alkyl halides, dialkylsulfates, alkenyl halides, alkynyl halides, substituted alkyl halides, optionally substituted benzyl halides, alkylsulfonyl halides and the like will result in the formation of Formula I compounds as illustrated in Scheme 1.

SCHEME 1

Formula I compounds, where R³ is NR⁶R⁷, can be prepared by the N-amination of Formula II derivatives. For example, Formula II derivatives are treated with a base such as sodium hydride, potassium hydride, potassium tert-butoxide, lithium diisopropyl amide and the like in an inert solvent such as ether, tetrahydrofuran, dioxane, dimethylformamide and dimethylsulfoxide. Subsequent treatment of the anion with an electrophilic aminating reagent such as O-diphenylphosphinylhydroxylamine, hydroxylamine-O-sulfonic acid (HOSA) , O-2,4-dinitro- phenylhydroxylamine, O-mesitylsulfonylhydroxylamine (MSH) and the like will result in the formation of Formula I compounds where R³ is NR⁶R⁷, as illustrated in Scheme 2. Methods for the preparation and use of such electrophilic aminating reagents may be found in Synthesis 1977, 1.

SCHEME 2

where R³ is NR⁶R⁷

Alternatively, Formula I compounds can be prepared by coupling of the intermediate pyrazolines of Formula III with compounds of Formula IV in the presence of phosgene or a phosgene equivalent. Typical reaction conditions involve combination of phosgene or phosgene equivalents with the Formula III pyrazoline in a solvent such as tetrahydrofuran or chloroform followed by

addition of compounds of Formula IV. This chemistry is depicted in Scheme 3.

Compounds of Formula I where R³ is NH₂, NHR⁷, or OH can be further derivatized by standard alkylation, acylation, sulfonylation and related reactions by procedures known to those skilled in the art.

Furthermore, compounds of Formula I where R³ is NH₂ can be condensed with aldehydes and ketones to form the corresponding hydrazone derivatives of Formula I. These procedures are also well documented in the art.

The preparation of Formula II and Formula III compounds where R⁴ is carbomethoxy and R⁵ is H or methyl is described in U.S. 4,663,341 which involves alkylation of pyrazoline anilides. The preparation of Formula II and III compounds where R⁴ is C₁-C₃ alkyl or optionally substituted phenyl and R⁵ is H is described in U.S.

4,070,365 which involves the preparation of pyrazoline anilides through conventional Mannich reactions. The following Example serves to illustrate the invention.

EXAMPLE 1

Methyl 3- (4-chlprophenyl) -4 , 5-dihydro-4- mgthyl-1 [ [N-methyl-N- [4- ftrifluorometnyl ) - phenyl]aminolcarbonyl]-1H-pyrazole-4-carboxylate

To a solution of 0.57 g of NaH (60%, 0.014 moles) in 15 mL of DMF at 0°C, was added 2.5 g of methyl 3-(4- chlorophenyl)-4,5-dihydro-4-methyl-1-[[4-(trifluoro- methyl)phenylamino]carbonyl]-1H-pyrazole-4-carboxylate

(0.0057 moles) in 10 mL of DMF dropwise while maintaining the temperature at 5°C. When the addition was complete, the solution was stirred at 0°C for 15 minutes. Then, 1.8 mL of methyl iodide was added and the mixture was warmed to ambient temperature. After stirring at ambient temperature for four hours, the solution was poured into 200 mL of ice cold 0.5N HCl, this was extracted with three by 50 mL of ethyl acetate, and the organic phase washed with two by 50 mL of water and one by 50 mL of saturated aqueous sodium chloride and dried over

magnesium sulfate (MgSO₄). The organic phase was then concentrated under vacuum and purified by column

chromatography on silica gel (eluting with a 4:1 ratio of methylene chloride/acetone), to give 1.1 g of an off- white powder, m.p. 90°-91°C.

¹ H NMR (CDCl₃, 200 MHz) 5 7.46 (AB, J_AB=8.2Hz, 4H), 7.06 (AB, J_AB=8.7Hz, 4H), 4.20 (AB, J_AB=11.4Hz, 2H), 3.72 (s, 3H), 3.45 (s, 3H), 1.52 (s, 3H).

By the general procedures described herein, the compounds of Tables 1 through 4 can be prepared.

Formulation and Use

The compounds of this invention will generally be used in formulation with an agriculturally suitable 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, baits, 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 from less than 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 effective amounts of these ingredients in the following approximate proportions:

Percent by Weight

Active

ingredient Diluent (s) Surfactant (3) 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, Baits 0.01-95 5-99 0-15 and Pellets

High Strength Compositions 90-99 0-10 0-2 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. 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", Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood,

"Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and

recommended uses. All formulations can contain minor amounts of additives to reduce foam, 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, U.S. 3,060,084). Granules and pellets can 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, pages 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following. Example A

Emulsifiable Concentrate

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 20%

blend of oil soluble sulfonates

and polyoxyethylene ethers 10% isophorone 70%

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 B

Wettable Powder

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 30%

sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 63% The active ingredient is mixed with the inert materials in a blender. After grinding in a hammer-mill, the material is re-blended and sifted through a 50 mesh screen.

Example C

Wettable powder of Example B 10% pyrophyllite (powder) 90% The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust.

Granule

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 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 volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packagee.

Example E

Granule

Wettable powder of Example B 15% gypsum 69% potassium sulfate 16%

The ingredients are blended in a rotating mixer and water 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 4.5% active ingredient.

Example F

Solution

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 25%

N-methyl-pyrrolidone 75% The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.

Example G

Aqueous Suspension

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 40 %

polyacrylic acid thickener 0 .3 % dodecyclophenol polyethylene glycol

ether 0 .5% disodium phosphate 1 . 0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles substantially all under 5 microns in size.

Example H

Oil Suspension

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 35.0% blend of polyalcohol carboxylic 6.0% esters and oil soluble petroleum

sulfonates

xylene range solvent 59.0%

The ingredients are combined and ground together in a sand mill to produce particles substantially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Example I

Bait Granules

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-1- [[N-methyl-N-[4-(trifluoromethyl)phenyl]amino]- carbonyl]-1H-pyrazole-4-carboxylate 3.0% blend of polyethoxylated nonyl- 9.0% phenols and sodium dodecylbenzene

sulfonates

ground up corn cobs 88.0% The active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground corn cobs. The granules are then dried 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 this invention can be formulated are:

Insecticides:

3-hydroxy-N-methylcrotonamide (dimethylphosphate) ester

(monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-

7-benzofuranol (carbofuran)

0-[2,4,5-trichloro-α-(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 α-naphthol (carbaryl) methyl O-(methylcarbamoyl)thiolacetohydroxamate

(methomyl)

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

(chlordimeform)

O,O-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl- phosphorothioate (diazinon) octachlorocamphene (toxaphene)

O-ethyl-O-p-nitrophenyl phenylphosphonothioate (EPN) (S)-α-cyano-m-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl)- 2,2-dimethylcyclopropanecarboxylate (deltamethrin) Methyl-N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-1-thioox amimidate (oxamyl)

cyano (3-phenoxyphenyl)-methyl-4-chloro-a-(1-methyl- ethyl) benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl (±)-cis,trans-3-(2,2-dichloro ethenyl)-2,2-dimethylcyclopropanecarboxylate

(permethrin)

α-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,

azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotphos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, 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-yl- methyl]-1H-1,2,4-triazole (propiconazole)

2-cyano-N-ethylcarbamoy1-2-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

Nematocjdes:

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-methyl-1,3-cithiolo[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-oxo- thiazolidine-3-carboxamide (hexythiazox)

amitraz

propargite

fenbutatin-oxide

Biological

Bacillus thuringiensis

Avermectin B.

Utility

The compounds of this invention exhibit activity against a wide spectrum of foliar- and soil-inhabiting arthropods which are pests of growing and stored

agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Some of the compounds of this invention are characterized by

favorable metabolic and soil residual properties. Those skilled in the art will recognize that not all compounds are equally effective against all pests but the compounds of this invention display activity against economically important agronomic, forestry, greenhouse, ornamental food and fiber product, stored product, domestic

structure, and nursery pests, such as: larvae of the order Lepidoptera including fall and beet armyworm and other Spodoptera spp., tobacco budworm, corn earworm and other

Heliothis spp., European corn borer, navel orangeworm, stalk/stem borers and other

pyralids, cabbage and soybean loopers and other loopers, codling moth, grape berry moth and other tortricids, black cutworm, spotted cutworm, other cutworms and other noctuids, diamondback moth, green cloverworm, velvetbean caterpillar, green cloverworm, pink bollworm, gypsy moth, and spruce budworm; foliar feeding larvae and adults of the order

Coleoptera including Colorado potato beetle, Mexican bean beetle, flea beetle, Japanese beetles, and other leaf beetles, boll weevil, rice water weevil, granary weevil, rice weevil and other weevil pests, and soil inhabiting insects such as Western corn rootworm and other Diabrotica spp., Japanese beetle, European chafer and other coleopteran grubs, and

wireworms; adults and larvae of the orders Hemiptera and Homoptera including tarnished plant bug and other plant bugs (miridae), aster leafhopper and other leafhoppers (cicadellidae), rice

planthopper, brown planthopper, and other planthoppers (fulgoroidea), psylids, whiteflies (aleurodidae), aphids (aphidae), scales

(coccidae and diaspididae), lace bugs (tingidae), stink bugs (pentatomidae), cinch bugs and other seed bugs (lygaeidae), cicadas (cicadidae), spittlebugs (cercopids), squash bugs (coreidae), red bugs and cotton stainers (pyrrhocoridae); adults and larvae of the order acari (mites) including European red mite, two spotted spider mite, rust mites, McDaniel mite, and foliar feeding mites; adults and immatures of the order Orthoptera including grasshoppers; adults and immatures of the order Diptera

including leafminers, midges, fruit flies

(tephritidae), and soil maggots; adults and immatures of the order Thysanoptera including onion thrips and other foliar feeding thrips. The compounds are also active against economically important livestock, household, public and animal health pests such as: insect pests of the order Hymenoptera including carpenter ants, bees, hornets, and wasps; insect pests of the order Diptera including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other Brachycera, mosquitoes, black flies, biting midges, sand flies, sciarids, and other Nematocera; insect pests of the order Orthoptera including cockroaches and crickets; insect pests of the order Isoptera including the Eastern subterranean termite and other termites; insect pests of the order Mallophaga and Anoplura including the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the cat flea, dog flea and other fleas.

The specific species for which control is

exemplified are: fall armyworm, Spodoptera fruigiperda; tobacco budworm, Heliothis virescens; boll weevil,

Anthonomus grandis; aster leafhopper, Macrosteles

fascifrons; black bean aphid, (Aphis Fabae); southern corn rootworm, Diabrotica undecimpunctata. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species. The compounds of this invention may also be utilized as rodenticides. Application

Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod pest species, many different methods of application are employed. A preferred method of application is by spraying with equipment that distributes the compound in the

environment of the pests, on the foliage, animal, person, or premise, in the soil or animal, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these toxicant compounds can be applied to or incorporated into the soil. Other methods of application can also be employed including direct and residual sprays, aerial sprays, baits, eartags, boluses, foggers, aerosols, and many others. The compounds can be incorporated into baits that are consumed by the

arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compounds.

The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with

suitable carriers (including diluents and surfactants) and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, and synergists such as

piperonyl butoxide often enhance the efficacy of the compounds of this invention.

The rate of application of the compounds required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, etc. In general,

application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide effective control of pests in agronomic ecosystems under normal

circumstances, but as little as 0.001 kg/hectare or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter or as much as 150 mg/square meter may be required.

The following Tests demonstrate the control efficacy of compounds of Formula I on specific pests. See the Index Table for compound descriptions.

TEST A

Fall Armyworm

Test units, each consisting of an 8-ounce (230 mL) plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared. Ten third- instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cup. Spraying was accomplished by passing the cup, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.25 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. (207 kPa). The cup was then covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality:1.

TEST B

Tobacco Budworm

The test procedure of Test 1 was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens). Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1.

TEST C

Southern Corn Rootworm

Test units, each consisting of an 8-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were

prepared. The test unit was sprayed as described in Test A with individual solutions of the test compounds. After the spray on the cup had dried, five third-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into the cup. A moistened dental wick was inserted into the cup to prevent drying and the cup was then covered. The cup was then held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality:1.

TEST D

Aster Leafhopper

Test units were prepared from a 12-ounce (350 mL) cup containing oat (Avena sativa) seedlings in a 1-inch (2.54 cm) layer of sterilized soil. The test unit was sprayed as described in Test A with individual solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster

leafhoppers (Mascrosteles fascifrons) were aspirated into the covered cup. The cup was held at 27°C and 50% relative humidity for 48 hours, after which time

mortality readings wre taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1.

TEST E

Boll Weevil

Five adult boll weevils (Anthonomus grandis grandis) were placed into a 9 ounce (260 mL) cup. The test

procedure employed was then otherwise the same as in Test A with one cup per treatment. Mortality readings were taken 48 hours after treatment. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1.

Claims

CLAIMS What is claimed is:

1. A compound of the formula

wherein:

R¹ is selected from the group Br, CF₃, OCF₃, OCF₂H and OSO₂CF₃;

R² is selected from the group H, F, Cl, Br, CF₃, OCF₃,

OCF₂H and OCH₂CF₃;

R³ is selected from the group C₁-C₆ alkyl, C₂-C₆

alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ cyclohaloalkyl, C₃-C₆ cycloalkylalkyl, COR¹¹, CO₂R¹¹, NR⁶R⁷, N=CR⁸R⁹, OR⁶' C₁-C₄ alkyl

substituted by a group selected from halogen, C₁- C₃ alkoxy, C₁-C₃ haloalkoxy, NR¹¹R¹², CN, NO₂, S(O)_nR¹¹, COR¹¹, CO₂R¹¹ and phenyl optionally substituted by a group selected from halogen, CN, C₁-C₂ haloalkyl and C₁-C₂ haloalkoxy; R⁴ is selected from the group CO₂Me, Ph, 4-F-Ph,

4-Cl-Ph and C₁-C₃ alkyl; R⁴ being other than Ph and 4-F-Ph when R² is OCF₂H; and R⁴ being CO₂Me when R³ is COR¹¹ and CO₂R^1:L;

R⁵ is selected from the group H and CH₃; R⁵ being H when R⁴ is Ph;

R⁷ is selected from the group H, C₁-C₄ alkyl and COR⁸; R⁸ is selected from the group H, C₁-C₄ alkyl, C₁-C₄ haloalkyl and phenyl optionally substituted by a group selected from halogen, CN, NO₂, CF₃ and

OCF₃;

R⁹ is selected from the group H and C₁-C₄ alkyl;

R⁸ and R⁹ can be taken together as -CH₂CH₂CH₂-,

-CH₂CH₂CH₂CH₂- and -CH₂CH₂CH₂CH₂CH₂-;

R¹⁰ is selected from the group C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R¹¹ is selected from the group C₁-C₃ alkyl and C₁-C₃ haloalkyl;

R¹² is selected from the group H and C₁-C₃ alkyl; and n is 0, 1 or 2.

2. A compound according to Claim 1 wherein R³ is C₁-C₆ alkyl, NR⁶R⁷ or OR⁶.

3. A compound according to Claim 1 wherein R⁴ is CO₂Me, Ph, 4-Cl-Ph or 4-F-Ph.

4. A compound according to Claim 1 wherein R³ is

CH₃ .

5. A compound according to Claim 1 wherein R⁶ is H or C₁-C₃ alkyl.

6. A compound according to Claim 4:

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl-

1-[[N-methyl-N-]4-(trifluoromethyl)phenyl]- amino]-carbonyl]-1H-pyrazole-4-carboxylate.

7. A compound according to Claim 4:

methyl 3-(4-chlorophenyl)-4,5-dihydro-4-methyl- 1-[[N-methyl-N-[4-(trifluoromethoxy)- phenyl]amino]-carbonyl]-1H-pyrazole-4- carboxylate.

8. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound

according to Claim 1 and a carrier therefor.

9. A method for controlling arthropods comprising applying to them or to their environment an effective amount of a compound according to Claim 1.