WO1993021160A1

WO1993021160A1 - Arthropodicidal pyrazole sulfonates

Info

Publication number: WO1993021160A1
Application number: PCT/US1993/001271
Authority: WO
Inventors: Bruce Lawrence Finkelstein
Original assignee: Dunlena Pty. Ltd.
Priority date: 1992-04-13
Filing date: 1993-02-04
Publication date: 1993-10-28
Also published as: CN1078233A; JPH07508265A; EP0636121A1; TW227984B; AU3618293A

Abstract

Arthropodicidal compounds having the formula R1--SO2--O--Q where R1 and Q are as defined in the text, compositions containing said compounds and use of the compounds to control arthropods.

Description

TITLE

ARTHROPODICIDALPYRAZOLE SULFONATES U.S. Patent 3,966,574 discloses insecticidal sulfonates that contain a heteroaromatic ring having three heteroatoms. U.S. Patent 4,791,127 discloses insecticidal thiazole sulfonates and Jacobsen, et al., Pest. Sci., (1990), 29, 96-100 discloses insecticidal oxazole sulfonates. Arthropodicidal pyrazole sulfonates of Formula I have hitherto been unknown.

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 for the control of arthropods and nematodes in both agronomic and nonagronomic environments. The compounds are

wherein:

Q is selected from the group

, and

G is selected from the group S, S(=O), S(=O)₂, C=S and C=O;

R¹ is selected from the group C₁-C₃ alkyl and C₁-C₃ haloalkyl;

R² is selected from the group C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆- alkenyl and C₂-C₆ alkynyl each of which can be optionally substituted with R⁵; or R² is selected from the group C₁-C₆ haloalkyl, N(R⁷)R⁸, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl and C₄-C₇ cycloalkylalkyl substituted with R⁶;

R³ and R⁴ are independently selected from the group H, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆

hdoalkylthio, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloa-kylalkyl, C₁-C₆ alkylsulfmyl, C₁-C₆ hdoalkykulf-nyl, C₁-C₆alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylcarbonyl, formyl, halogen, OH, NO₂, N(R¹⁴)R¹⁵, C(O)N(R¹⁴)R¹⁵, CN andphenyl optionally substituted with W; C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl; C₂-C₆ alkynyl; wherein each of C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl can be optionally substituted with

R¹³;

R⁵ and R¹³ are independently selected from the group CN, SCN, NO₂, OR⁹, SR⁹, S(O)R⁹, SO₂R⁹, OC(O)R⁹, OSO₂R⁹, Si(R⁹)(R¹⁰)(R ¹¹), CO₂R⁹, C(O)N(R⁹)R¹⁰, C(O)R⁹, N(R⁹)R¹⁰ andphenyl optionally substituted with R¹²;

R⁶ is selected from the group halogen, CN and C₁ -C₂ alkyl; R⁷ is selected from the group C₁-C₆ alkyl optionally substituted with R¹⁶, C₃-C₆ cycloalkyl optionally substituted with R¹⁹, and C₄-C₇ cycloalkylalkyl optionally substituted with R¹⁹;

R⁸ is selected from the group H, CN, C₁-C₆ haloalkyl and C₁-C₆ alkyl optionally substituted with CN;

R⁷ and R⁸ can be taken together to form -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -CH₂CH₂-O-CH₂CH₂-;

R⁹, R¹⁰ and R¹¹ are independently selected from the group C₁-C₃ alkyl and C₁-C₃ haloalkyl;

R¹² and W are independently selected from the group halogen, Cι-C₂ alkyl,

C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C_j-C₂ alkylthio,

C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfinyl, C₁-C₂ hdoakylsulfinyl,

C₁-C₂ alkylsulfonyl, C₁-C₂ haloalkylsulfonyl, NO₂ and CN;

R¹⁴ and R¹⁵ are independently selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkylsulfonyl and C(O)N(R¹⁷)R¹⁸; or

R¹⁴ and R¹⁵ can be taken together to form -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -CH₂CH₂-O-CH₂CH₂-;

R¹⁶ is selected from the group 1 to 5 halogens, CN, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₁-C₂ alkylsulfonyl and C₃-C₆ trialkylsilyl;

R¹⁷ and R¹⁸ are independently selected from the group H and C₁ -C₃ alkyl; and

R¹⁹ is selected from the group 1 to 5 halogens, C₁-C₃ alkyl, CN, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₁-C₂ alkylsulfonyl and C₃-C₆ trialkylsilyl.

Preferred compounds A are those compounds of Formula I wherein:

G is selected from the group S(=O)₂ and C=O

R¹ is selected from the group CH₃ and ClCH₂;

R² is selected from the group C₁-C₆ alkyl, Ci -Cg haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl and N(R⁷)R⁸;

R³ and R⁴ are independently selected from the group H, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, N(R¹⁴)R¹⁵ and halogen; and R¹⁴ andR¹⁵ are independently selected from the group H and C₁-C₆ alkyl.

Preferred Compounds B are compounds of Preferred A wherein Q is Q-1. Preferred Compounds C are compounds of Preferred A wherein Q is Q-2.

Preferred Compounds D are compounds of Preferred A wherein Q is Q-3.

Some of the compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art wϋl appreciate that one stereoisomer may be more active than the others and how to separate said stereoisomers.

Accordingly, the present invention comprises mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.

In the above recitations, the term "alkyl" used either alone or in compound word such as "haloalkyl", denotes straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl or hexyl isomers. Alkoxy denotes methoxy and ethoxy. Alkenyl denotes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Cycloalkylalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl attached to a straight or branched C1-C4 alkylene group. The term "trialkylsilyl" denotes silicon with three alkyl substituents. The

term"Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.

The term "alkoxycarbonyl" denotes CH₃OC(=O), CH₃CH₂OC(=O), CH₃CH₂CH₂OC(=O), (CH₃)₂CHOC(=O) and the different butoxy-, pentoxy- or hexyloxycarbonyl isomers. The term "alkylcarbonyl" denotes CH3C(=O), CH₃CH₂C(=O), CH₃CH₂CH₂C(=O), (CH₃)₂CHC(=O) and the different butyl-, pentyl- or hexylcafbonyl isomers.

The term "alkylsulfonyl" denotes CH₃S(O)₂, CH₃CH₂S(O)₂,

CH₃CH₂CH₂S(O)₂, (CH₃)₂CHS(O)₂ and the different butylsulfonyl,

pentylsulfonyl and hexylsulfonyl isomers. The term "alkylsulfϊnyl" denotes CH₃S(O) and CH₃CH₂S(O).

The term "halogen", either alone or in compound words such as

"haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and CH₂CHFCl. The teims "haloalkenyl" and "haloalkynyr' are defined analogously to the term "haloalkyl".

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 7. For example, C₂ alkoxycarbonyl designates C(O)OCH₃ and C₃ alkoxycarbonyl designates

C(O)OCH₂CH₃.

DETAILS OF THE INVENTION

Compounds of Formula I can be prepared by reaction of the corresponding hydroxypyrazole (1) with the appropriate sulfonyl halide and a base such as triethylamine or pyridine in a solvent such as dichloromethane or tetrahydrofuran as shown in Equation 1. It is known to one skilled in the art that the hydroxy compounds (1) may exist as the pyrazolone tautomer. In Equations 1-8 R¹, R², R³, R⁴ and G are as previously defined.

Equation 1

A general review for the synthesis of hydroxypyrazoles can be found in Wiley, et at., Tfie Chemistry ofHetrocyclic Compounds, Pyrazolones,

Pyrazolidones and Derivatives:, Vol. 20, Wiley, New York, (1964). More specifically, the hydroxy pyrazoles 1 wherein Q is Q-1 can be prepared from the appropriate β-dicarbonyl compound 2 or a synthetic equivalent such as acetylenic ester or α-oxodithioketene acetal and the appropriate hydrazide

(3, wherein G is C=O), thiohydrazide (3, wherein G is C=S), sulfonylhydrazide (3, wherein G is S(=O)₂),sulfinylhydrazide (3, wherein G is S(=O), or

sulfenylhydrazide (3, wherein G is S), in the presence of base as shown in

Equation 2. The synthesis of the compounds 3 is known. Equation 2

The hydroxy pyrazoles 1 wherein Q is Q-2 can be prepared from alkoxy compounds 4 by treatment with iodotrimethylsilane or aqueous acid such as hydrobromic acid in acetic acid as shown in Equation 3.

Equation 3

The compounds of Formula 4 can be prepared by treatment of an alkoxypyrazole 5 with the appropriate acid chloride, sulfonyl chloride, sulfinylchloride or sulfenyl chloride (6) and base as shown in Equation 4. The compounds of Formula 4 wherein G is C=S can be prepared from the compounds of Formula 4 wherein G is C=O by treatment with a thiation reagent such as P₂S₅ or 2,4-bis(4-memoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide. The synthesis of 4-alkoxypyrazoles is known to one skilled in the art. (For instance see: Pluempe, H. and Schegk, E., Arch. Pharm., 300, 704, (1967). Equation 4

The hydroxy pyrazoles 1 wherein Q is Q-3 can be prepared by cyclization of β-oxohydrazides (7) with a base such as sodium ethoxide in a solvent such as ethanol as shown in Equation 5. The compounds of Formula 7 are prepared by known methods.

Equation 5

Alternatively, compounds of Formula I wherein Q is Q-1 or Q-3 can be prepared by reaction of a pyrazole sulfonate 8 with a compound of Formula 6 and base as shown in Equation 6. The ratio of products obtained will depend on the nature of the R³ and R⁴ groups. In some instances, only one product will be obtained.

Equation 6

The compounds of Formula 8 can be prepared by the reaction of a hydroxypyrazole 9 with a sulfonyl halide and base as showffln Equation 7. The synthesis of compounds of Formula 9 is known.

Equation 7

Analogously, compounds of Formula I wherein Q is Q-2 can be prepared from pyrazole sulfonates of Formula 10 which in turn can be prepared from hydroxy pyrazoles of Formula II as shown in Equation 8.

Equation 8

EXAMPLE 1

Preparation of 3-Methyl-1-(propylsulfonyl)- 1H-pyrazol-5-ol Methanesulfonate (Ester)

Intermediate 1

3-Methyl-1-(propylsulfonyl)-1H-pyrazol-5-ol

To a solution of 10 g (72 mmol) of 1-propanesulfonic acid, hydrazide in 150 mL of ethanol was added 9.2 mL (72 mmol) of ethyl acetoacetate and 27 mL (72 mmol) of a 2.68 M solution of sodium ethoxide in ethanol. The reaction mixture was refluxed overnight. After cooling, the solvent was removed with a rotary evaporator. The residue was taken up in water, acidified and extracted with dichloromethane. After drying with sodium sulf ate, the solvent was removed with a rotary evaporator to give the product (11.36 g) as an orange solid. ¹H NMR (CDCl₃): d 0.94 (t, 3), 1.62 (m, 2), 2.10 (s, 3), 3.46 (t, 2), 5.2 (br, 1).

3-Methyl-1-(propylsulfonyl)-1H-pyrazol- 5-ol, Methanesulfonate (Ester)

To a solution of 1 g (4.9 mmol) of 3-methyl-1-(propylsulfonyl)-1H-pyrazol-5-ol in 50 mL of dichloromethane at 0°C was added 0.96 mL (6.9 mmol) of triemyl-imine followed by 0.56. mL (6.9 mmol) of methanesulfonyl chloride. The reaction mixture was allowed to stand at room temperature overnight.

Dichloromethane was added. The organic layer was washed with water, dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was purified by flash chromatography to give 0.79 g of the title compound as a yellow oil. 1H NMR (CDCl₃): δ 1.08 (t, 3), 1.62 (m, 2), 2.31 (s, 3), 3.33 (s, 3), 3.43 (t, 2), 6.12 (s, 1).

EXAMPLE 2

Preparation of 5-Methyl-1-(propylsulfonyl)- 1H-pyrazol-3-ol Methanesulfonate (Ester)

Intermediate 1

5-Methyl-1H-pyrazol-3-ol Methanesulfonate (Ester) To a solution of 10 g (102 mmol) of 2,4-dihydro-3H-pyrazol-3-one in

250 mL of dichloromethane at 0°C was added 15.6 mL (112 mmol) of

triethylamine followed by 8.7 mL (112 mmol) of methanesulfonyl chloride dropwise. The reaction mixture was stirred overnight at room temperature. It was washed with water, dried (Na₂SO₄) and the solvent was removed with a rotary evaporator. The residue was purified by flash chromatography (45-60% ethyl acetate in hexanes as eluant) to afford 4.98 g of the title compound as a white solid (m.p. 104-106°C) !HNMR (CDCl₃) δ 2.32 (s,3), 3.28 (s,3),

5.94 (s,l) 9.6 (br,1).

5-Methyl-1H (propylsulfonyl)-1H-pyrazol-3-ol Methanesulfonate (Ester) To a solution of 1.70 g (9.6 mmol) of 5-methyl-1H-pyrazol-3-ol, methanesulfonate (ester) in 50 mL of dichloromethane at 0°C was added 1.87 mL (13.4 mmol) of triethylamine followed by 1.5 mL (13.4 mmol) of

propanesulfonyl chloride. The reaction mixture was stirred overnight at room temperature. An additional 0.67 mL of triethylamine was added. The reaction mixture was cooled in an ice bath of 0.54 mL of propanesulfonyl chloride was added. It was stirred at room temperature for 4 h. Water was added. The organic layer was dried (Na₂SO₄) and the solvent was removed with a rotary evaporator. The residue was purified by flash chromatography (30% ethyl acetate in hexanes as eluant) to afford 2.15 g of the title compound as a white solid (m.p. 84-85°C) ¹H NMR (CDCl₃) δ 1.4 (t,3), 1.77 (m,2), 2.54 (s,3) 3.34 (s,3), 3.45 (m,2), 6.10 (s,1).

By applying the procedures of Examples 1 and 2 and Equations 1 through 8, one skilled in the art can prepare the compounds in Tables 1 through 3. In the following Tables, abbreviations for G, various alkyl chains and rings have been used with the following corresponding definitions.

iPr = isopropyl = CH(CH₃)₂

nPr = n-propyl = CH₂CH₂CH₃

cPr = cylopropyl = CH(CH₂)₂

iBu = isobutyl = CH₂CH(CH₃)₂

sBu = 5-butyl = CH(CH₃)CH₂CH₃

tBu = fert-butyl = C(CH₃)₃

nBu = n-butyl = (CH₂)₃CH₃

iAm = isoamyl = CH₂CH₂CH(CH₃)₂

Ph=phenyl = C₆H₅

cPrCH₃ = 2-cyclopropylmethyl = CH(CHCH₃)CH₂

Formulation/Utility

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 include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

Weight Percent

Active

Ingredient Diluent Surfactant

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, Emulsions, 5-50 40-95 0-15 Solutions, (including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

Granules, Baits and Pellets 0.01-99 5-99.99 0-15

High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. 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. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill- Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, W-ishington, D.C., 1988, pp 251-259. 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 Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed.,

McGraw-Hill, New York, (1963), pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE^~3 ,246,493.

For further information regarding the art of formulation, see U.S.

3,235,361, Col.6, line 16 through Col.7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S.2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, (1961), pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all

formulations are worked up in conventional ways. Compound numbers refer to compounds in Index Table A.

Example A

Wettable Powder

Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example B

Granule

Compound 1 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No.

25-50 sieves) 90.0%.

Example C

Extruded Pellet

Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example D

Emulsifiable Concentrate

Compound 1 20.0% blend of oil soluble sulfonates

and polyoxyethylene ethers 10.0% isophorone 70.0%.

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropod" includes insects, mites and nematodes) 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. Those skilled in the art will appreciate that not all compounds are equally effective against all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the

Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, junveniles and adults of the Phylum Nemata. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Phthiraptera, Siphonoptera, Blattaria, Thysanaura and Pscoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. The compounds are particularly active against southern corn rootworm (Diabrotica undecimpunctata howardϊ), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptnis oryzophilus), rice leaf beetle (Oulema oryzae), wbitebacked planthopper (Sogatellafurcifera), green leafhopper

(Nephotettixcincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (Scotinophara luridά), rice stink bug (Lagynotomus elongatus), rice bug (Leptocorisa chinensis), slender rice bug (Cletus punttger), and southern green stink bug (Nezara viridula). See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos,

methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, tefbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanatemethyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasϊc copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as Bacillus thuringiensis and baculovirus.

In certain instances, combinations with other arthropodicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

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. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, systemic uptake, baits, eartags, boluses, foggers, fumigants, 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.

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, 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, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.

The rate of application 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, and the like. Under normal

circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as

0.001 kg/hectare may be sufficient 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 may be sufficient or as much as 150 mg/square meter may be required. The following Tests demonstrate the control efficacy of compounds of this invention on specific pests. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A and B for compound descriptions.

TEST A

Fall Armvworm

Test units, each consisting of a H.I.S. (high impact sytrene) tray with 16 cells were prepared. In 12 of the cells is placed wet filter paper and

approximately 8 cm² of lima leaf, in the other 4 cells is a 0.5 cm layer of wheat germ diet. Fifteen to twenty third instar larvae of fall armyworm (Spodoptera frugiperda) were placed in a 8 ounce (230 mL) plastic cup. Solutions of each of the test compounds in 75/25 acetone/distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup, 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 psi (207 kPa). The insects were transferred into the tray (one insect per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 h after which time readings were taken on the 12 cells with lima leaves. The 4 remaining cells were read at 7 days for a delayed toxicity reading. Of the compounds tested, the following gave mortality levels of 80% or higher: 24.

TESTB

Southern Corn Rootworm

Units consisting of an 8-ounce (230 mL) plastic cup containing 1 one-inch square of a soybean-wheatgerm diet were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern com rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were then covered and held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 17*, 21*, 22, 24, 25, 26, 29* 30*, 31*, 32, 33, 36, 37, 38*, 39, 40, 41, 42, 43*, 44, 45*.

* Compound sprayed at a rate of 0.13 kg/ha.

TEST C

Boll Weevil

Five adult boll weevils (Anthonomus grandis) were placed into each of a series of 9-ounce (260 mL) cups. The test units were sprayed as described in TEST A with individual solutions of the below-listed compounds. Each cup was then covered with a vented lid and held at 27°C. and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 11, 13, 22, 24, 25, 32, 36, 38, 41, 43*, 45*.

* Compound sprayed at a rate of 0.13 kg/ha. TEST D

Aster Leafhopper

Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat (Avena sativa) seedlings in a 1-inch (2.5 cm) layer of sterilized soil and a 1/2 inch layer of sand. The test units were sprayed as described in TEST A with individual solutions of the compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the cups covered and vented lids. The cups were held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 2, 3, 4, 7, 10, 21*, 22, 24, 25, 29*, 30, 31*, 32, 33, 36, 37, 38*, 40, 42, 43*, 44, 45*.

* Compound sprayed at a rate of 0.13 kg/ha.

TEST E

Black Bean Aphid

Individual nasturtium leaves were infested with 10 to 15 aphids (all stages of Aphis fabae) and sprayed with their undersides facing up as described in TEST A. The leaves were then^et in 3/8-inch (0.94 cm) diameter vials containing 4 mL of sugar water solution and covered with a clear plastic 1 -ounce (29 mL) portion cup to prevent escape of aphids that drop from the leaves. The test units were held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality at 1000 ppm: 22, 25, 32, 33, 36, 38, 41, 42, 45*.

* Compound sprayed at a rate of 0.13 kg/ha.

TEST F

Two-Spotted Spider Mite

Onejnch squares (2.54 cm) of kidney bean leaves that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae) were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound (acetone/distilled water 75/25 solvent). Spraying was accomplished by passing the leaves, on a conveyer 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 psi (207 kPa). The leaf squares were then placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites cannot escape onto the untreated leaf surface. The test units were held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 4, 22, 24, 25, 36, 38*, 41, 43*.

* Compound sprayed at a rate of 0.13 kg/ha

TEST G

Contact Activity Against Green Leafhopper Nymphs

Three rice (Oryza sativa) seedlings, 1.5 leaf stage and about 10 cm tall, are transplanted into a 1/2 oz. (14 mL) plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water is then added to the cup. The test chemical is prepared by first dissolving the chemical in acetone and then adding water to produce a final test concentration of 75:25 (acetone:water). Four plastic cups, each cup serving as a replicate, are then placed on a spray chamber turntable. The cups are sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of 2.0 kg/cm² with air atomizing spray nozzles. The turntable completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 h. After drying, the cups are placed into conical shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the green leafhopper {Nephotettix cincticeps) are transferred into the test units using an aspirator. The test units are held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 2, 3, 4, 5, 7, 9, 11, 12, 13, 17, 21, 22, 24, 25.

TEST H

Contact Activity Against Brown Planthopper Nymphs

Three rice {Oryza sativά) seedlings, 1.5 leaf stage and about 10 cm tall are transplanted into a 1/2 oz. (14 mL) plastic cup containing Kumiai Brown artificial soil- Seven milliliters of distilled water is then added to the cup. The test chemical is prepared by first dissolving the chemical in acetone and then adding water to produce a final test concentration of 75:25 (acetone:water). Four plastic cups, each cup serving as a replicate, are then placed on a spray chamber turntable. The cups are sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of 2.0 kg/cm² with air atomizing spray nozzles. The turntable completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 h. After drying, the cups are placed into conical shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the brown planthopper (Nilaparvata lugens) are transferred into the test units using an aspirator. The test units are held at 27°C and 65% relative humidity, counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 2, 3, 4, 5, 7, 8, 11, 12, 13, 17, 21, 22, 23, 24, 25, 26.

TEST I

Solution Systemic Activity Against Green Leafhopper Nvmphs

The test chemical is added directly into 10 mL of distilled water and dissolved completely. This chemical solution is poured into a conical shaped test unit. Three rice seedlings are then positioned in the unit by a notched sponge disk. The sponge disk allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The sponge also prevents the test nymphs from accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of the sponge disk, prevents accidental chemical contamination of the sponge. The rice seedlings are allowed to absorb the chemical from the solution for 24 h in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) are transferred into the test units using an aspirator. The infested units are held under the same temperature and humidity conditions described above. Counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Inspects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 2, 3, 5, 7, 11, 12, 13, 17, 21. TEST J

Solution Systemic Activity Against Brown Planthopper Nymphs

The test chemical is added directly into 10 mL of distilled water and dissolved completely. This chemical solution is poured into a conical shaped test unit. Three rice seedlings are then positioned in the unit by a notched sponge disk. The sponge disk allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The sponge also prevents the test nymphs from, accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of the sponge disk, prevents accidental chemical contamination of the sponge. The rice seedlings are allowed to absorb the chemical from the solution for 24 h in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the brown planthopper (Nϊlaparvata lugens) are transferred into the test units using an aspirator. The infested units are held under the same temperature and humidity conditions described above. Counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Inspects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 2, 3, 5, 7, 11, 12, 13, 21.

Claims

CLAIMS:

1. A compound of the formula

wherein:

Q is selected from the group

, and

;

G is selected from the group S, S(=O), S(=O)₂, C=S and C=O;

R¹ is selected from the group C₁-C₃ alkyl and C₁-C₃ haloalkyl;

R² is selected from the group C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆

alkenyl and C₂-C₆ alkynyl each of which can be optionally substituted with R⁵; or R² is selected from the group C₁-C₆ haloalkyl, N(R⁷)R⁸, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl and C₄-C₇ cycloalkylalkyl substituted with R⁶; R³ andR⁴ are independently selected from the group H, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆

haloalkylthio, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl, C₁-C₆alkylsi-lfinyl, C₁-C₆ hdoalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylcarbonyl, formyl, halogen, OH, NO₂, N(R¹⁴)R¹⁵, C(O)N(R¹⁴)R¹⁵, CN and phenyl optionally substituted with W; C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl; C₂-C₆ alkynyl; wherein each of C₁-C₆ alkyl, C₃-Cg cycloalkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl can be optionally substituted with

R¹³;

R⁵ and R¹³ are independently selected from the group CN, SCN, NO₂, OR⁹, SR⁹, S(O)R⁹, SO₂R⁹, OC(O)R⁹, QSO₂R⁹, Si(R⁹)(R¹⁰)(R¹¹), CO₂R⁹, C(O)N(R⁹)R¹⁰, C(O)R⁹, N(R⁹)R¹⁰ andphenyl optionally substituted with R¹²;

R⁶ is selected from the group halogen, CN and C₁-C₂ alkyl;

R⁷ is selected from the group C₁-C₆ alkyl optionally substituted with R¹⁶, C₃-C₆ cycloalkyl optionally substituted with R¹⁹, and C₄-C₇ cycloalkylalkyl optionally substituted with R¹⁹;

R¹² and W are independently selected from the group halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloall-ylthio, C₁-C₂ alkylsulfinyl, C₁-C₂haloakylsulfinyl,

C₁-C₂ alkylsulfonyl, C₁-C₂ haloalkylsulfonyl, NO₂ and CN;

R¹⁴ and R¹⁵ are independently selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkylsulfonyl and C(O)N(R ¹⁷)R¹⁸; or

R¹⁴ and R¹⁵ can be taken together to form -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -CH₂CH₂-O-CH₂CH₂-; R¹⁶ is selected from the group 1 to 5 halogens, CN, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₁-C₂ alkylsulfonyl and C₃-C₆ trialkylsilyl;

R¹⁷ and R¹⁸ are independendy selected from the group H and C₁-C₃ alkyl; and

2. A compound according to Claim 1

wherein:

G is selected from the group S(=O)₂ and C=O

R¹ is selected from the group CH₃ and ClCH₂;

R² is selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl,

C₂-C₆ haloalkenyl and N(R⁷)R⁸;

R³ and R⁴ are independendy selected from the group H, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, N(R¹⁴)R¹⁵ and halogen; and

R¹⁴ and R¹⁵ are independendy selected from the group H and C₁-C₆ alkyl.

3. A compound according to Claim 2

wherein Q is Q-1.

4. A compound according to Claim 2

wherein Q is Q-2.

5. A compound according to Claim 2

wherein Q is Q-3.

6. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to any one of Claims 1 to 5 and a carrier therefor.

7. A method for controlling arthropods comprising applying to them or to their environment an arthropodicidally effective amount of a compound according to any one of Claims 1 to 5.