AU3058492A

AU3058492A - Arthropodicidal and nematicidal sulfonates

Info

Publication number: AU3058492A
Application number: AU30584/92A
Authority: AU
Inventors: Bruce Lawrence Finkelstein
Original assignee: Dunlena Pty Ltd
Current assignee: Dunlena Pty Ltd
Priority date: 1991-11-19
Filing date: 1992-11-09
Publication date: 1993-06-15
Also published as: CA2123902A1; EP0619811A1; TW226012B; CN1072410A; JPH07507267A; HUT68254A; WO1993010096A1; HU9401300D0

Description

ARTHROPODICIDAL AND NEMATICIDAL SULFONATES

The compounds of this invention are characterized by having a substituted (R¹) (R²)N-C (=X) - or R¹-N=c (YR) - moiety located in a 1,3 relationship to an OSO₂R³ substituent in a heteroaromatic system. U.S. Patent 3,818,102 discloses a certain insecticidal phenyl sulfonate carboxamide. The disclosed carboxamide moiety is unsubstituted and its position is variable relative to the sulfonate moiety.

This invention pertains to compounds of Formulae I and II, 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 uses. The compounds are

wherein :

Q is selected from the group

, ,

,

and ;

X is selected from the group O, S and NR⁶;

Y is selected from the group O and S;

Z is selected from the group H, halogen, CN, NO₂,

C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy and S(O)_nR⁷;

R is selected from C₁-C₃ alkyl;

R¹ is selected from the group C₁-C₆ alkyl, C₁-C₆

haloalkyl, C₁-C₅ alkoxy, C₂-C₅ alkoxyalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₄-C₇

cycloalkylalkyl, N(R⁴)R⁵, phenyl optionally substituted with 1 or 2 substituents selected from the group W; benzyl optionally substituted with 1 or 2 substitutents selected from the group W; and C₁-C₅ alkyl substituted with a group selected from CN, N(R⁴)R⁵ and S(O)_nR⁷;

R² is selected from the group H, C₁-C₂ alkyl, C₁-C₂ haloalkyl, formyl, C₂-C₃ alkylcarbonyl, C₂-C₃ alkoxycarbonyl, C₃ alkenyl and C₃ alkynyl; or R¹ and R² can be taken together to form

-CH₂CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂- or

-CH₂CH₂OCH₂CH₂-; R³ is selected from the group C₁-C₂ alkyl and C₁-C₂ haloalkyl;

R⁴ and R⁵ are independently selected from methyl and ethyl; or

R⁴ and R⁵ can be taken together to form

-CH₂CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂ or

-CH₂CH₂OCH₂CH₂-;

R⁶ is selected from the group H, C₁-C₃ alkyl and C₁-C₃ haloalkoxy;

R⁷ is from the group C₁-C₂ alkyl and C₁-C₂ haloalkyl;

W is selected from the group halogen, C₁-C₂ alkyl,

C₁-C₂ alkoxy, CF₃ and OCF₃; and

n is 0, 1 or 2.

Preferred compounds A are compounds of Formula I wherein:

R¹ is selected from the group C₁-C₄ alkyl, C3-C cycloalkyl, C₄-C₅ cycloalkylalkyl and C₁-C₅ alkyl substituted with CN;

R² is selected from the group H and CH₃;

R³ is CH₃;

X is selected from the group 0 and S; and

Z is selected from the group H and halogen.

Preferred compounds B are compounds of Preferred A wherein Q is selected from the group Q-1 and Q-6.

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

Preferred compounds D are compounds of Preferred B wherein Q is Q-6.

Specifically preferred compounds E for biological activity and ease of synthesis are the compounds of

Preferred C which are:

N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide;

N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarbothioamide; N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide; and

3-chloro-N-(1-methylethyl)-6- [(methylsulfonyl)oxy]-2-pyridinecarboxamide. Most preferred compound F for biological activity is the compound of Preferred E which is:

N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide.

Compounds of the instant invention include racemic and optically active stereoisomers. By "stereoisomers" we mean all of the isomers of the Formula I compounds which include enantiomers, diastereomers, and geometric isomers. One skilled in the art will appreciate that one or the other of said stereoisomer (s) will be the more active. It is also known how to separate such

enantiomers, diastereomers, and geometric isomers.

Accordingly, this invention includes racemic mixtures, each individual stereoisomer and enriched mixtures of stereoisomers.

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, ethoxy, n-propyloxy,

isopropyloxy and the different butoxy or pentoxy isomers.

Alkenyl denotes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers.

Alkynyl denotes straight chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers.

Cycloalkyl denotes cyclopropyl, cyclobutyl,

cyclopentyl and cyclohexyl. The term "halogen", either alone or in compound word such as "haloalkyl", denotes 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 CH₂CHFC1. The terms "haloalkenyl" and "haloalkynyl" 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 alkylcarbonyl designates C(O)CH₃ and C₄ alkylcarbonyl includes

C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂; C₂ alkoxycarbonyl

designates C(O)OCH₃ and C₃ alkoxycarbonyl designates C(O)OCH₂CH₃: and as a final example C₃ alkoxyalkyl

designates CH₂OCH₂CH₃, CH₂CH₂OCH₃ and CH(CH₃)OCH₃.

DETAILS OF THE INVENTION

Compounds of Formula I wherein Q is Q-1 and X is O can be prepared by reaction of the corresponding

pyridones (1) with the appropriate sulfonyl halide and a base such as triethylamine or pyridine in a solvent such as dichloromethane as shown in Equation 1. (In Equations 1 to 13, R¹, R², R³, R⁶ and Z are as previously defined.) Equation 1

The pyridones 1 can be prepared from the

corresponding benzyloxy compounds (2) under a variety of conditions depending on the nature of the substituents R¹, R² and Z, such as catalytic hydrogenation, heating with aqueous acid, (e.g., aqueous hydrobromic acid in acetic acid) or treatment with iodotrimethylsilane as shown in Equation 2.

Equation 2

The compounds of Formula 2 can be prepared from the corresponding acids (3) by any one of a number of methods for forming amides known to one skilled in the art. For example treatment of the acids with thionyl chloride or with 1,1' -carbonyldiimidazole (CDI) in a solvent such as tetrahydrofuran followed by treatment with the

appropriate amine as shown in Equation 3.

Equation 3

The acids 4 can be prepared from the corresponding halogen compound (5) by displacement with an alkali metal benzyloxide such as sodium benzyloxide in a solvent such as tetrahydrofuran or N, N-dimethyl-formamide with the addition of an extra equivalent of base, such as sodium hydride, to deprotonate the acid as shown in Equation 4. Equation 4

The acids 4 are compounds known in the art or readily prepared by methods known to one skilled in the art. For example, see Abramovitch, R. ed., The Chemistry of Heterocyclic Compounds, Pyridine and its Derivatives, vol 14 supplement 1, Wiley, New York and earlier volumes in that series. In some instances, they can be prepared by oxidation of the corresponding methyl compounds (5) with an oxidant such as potassium premanganate as shown in Equation 5.

Equation 5

The compounds of Formula I wherein Q is Q-2, Q-3 or Q-4 and X is O can be prepared in similar fashion to those wherein Q is Q-1 and X is 0, from the appropriate starting materials.

The compounds of Formula I, wherein Q is Q-5 and X is 0 can be prepared by reaction of the corresponding hydroxy compound (6) with the appropriate sulfonyl halide and a base such as triethylamine or pyridine in a solvent such as dichloromethane as shown in Equation 6. Equation 6

The hydroxy compounds of Formula 6 can be prepared from the corresponding benzyloxy compounds (7) under a variety of conditions depending on the nature of the substituents R¹, R² and Z, such as catalytic

hydrogenation, heating with aqueous acid, (e.g., aqueous hydrobromic acid in acetic acid) or treatment with iodotrimethylsilane as shown in Equation 7.

Equation 7

The compounds of Formula 7, can be prepared from the corresponding acids (8) by any one of a number of methods for forming amides known to one skilled in the art. For example, treatment of the acids with thionyl chloride or with 1,1'-carbonyldiimidazole in a solvent such as tetrahydrofuran followed by treatment with the

appropriate amine as shown in Equation 8. Equation 8

The acids (8) can be prepared from the corresponding halogen compound (9) by displacement with an alkali metal benzyloxide such as sodium benzyloxide in a solvent such as tetrahydrofuran or N,N-dimethyl-formamide with the addition of an extra equivalent of base, such as sodium hydride, to deprotonate the acid as shown in Equation 9. Equation 9

The compounds of Formula 9 can be prepared from the corresponding bromo- (or iodo-) thiazole (10) by reaction with an alkyllithium, such as n-butyllithium, in a

solvent such as tetrahydrofuran followed by reaction with carbon dioxide as shown in Equation 10.

Equation 10

The thiazoles (10) are compounds known in the art and are readily prepared by methods known to one skilled in the art (Metzger, ed., The Chemistry of. Heterocyclic Compounds, General Synthetic Methods for Thiazole and

Thiazolium Salts, Vol 34, Part 1, Wiley, New York, 1979).

Alternatively, the acids (8) can be prepared by reaction of the corresponding thiazole (11) with an alkyllithium, such as n-butyllithium, in a solvent such as tetrahydrofuran followed by reaction with carbon dioxide as shown in Equation 11.

Equation 11

The compounds of Formula I wherein Q is Q-6 and X is 0 can be prepared in similar fashion to those wherein Q is Q-5 and X is O, from the appropriate starting

materials.

The compounds of Formula I, wherein X is S, can be prepared by reaction of the compounds of Formula I

wherein X is 0 with 2,4-bis(methcxyphenyl)-1,3-dithia-2,4-diphosphetane-2,2-disulfide as shown in Equation 12. Equation 12

The compounds of Formula I, wherein X is NR⁶, can be prepared from the compounds of Formula I, wherein X is O, by reaction with phosphorous oxychloride, followed by reaction with an amine as shown in Equation 13.

Equation 13

Compounds of Formula II can be prepared from

compounds of Formula I, wherein X is O or S, by treatment with an alkylating agent such as an alkyl halide or a trialkyloxonium tetrafluorborate or by other methods as described in Sandier et al., Organic Functional Group Preparations, Vol. Ill, Academic Press, New York, 1972.

EXAMPLE 1

Preparation of N-(1-Methylethyl)-6-[(methylsulfonyl)oxy]- 2-pyridinecarboxamide

Intermediate 1

6-(Phenylmethoxy)-2-pyridinecarboxylic acid

To a solution of 36 g (230 mmol) of 6-chloro-2- pyridinecarboxylic acid and 31 mL (300 mmol) of benzyl alcohol cooled in an ice bath in 1700 mL of

tetrahydrofuran (THF) was added 21 g (530 mmol) of 60% sodium hydride in mineral oil. The solution was heated to reflux. An additional 300 mL of THF was added. The reaction was refluxed overnight. It was cooled in an ice bath and 7.1 mL (69 mmol) of benzyl alchol and 2.8 g

(69 mmol) of 60% sodium hydride in mineral oil were added. The reaction mixture was refluxed overnight. The reaction mixture was cooled and was poured into water and washed with ethyl acetate. The aqueous layer was

acidified to pH 2 with concentrated HCl and extracted with dichloromethane. The organic layer was dried

(sodium sulfate) and the solvent was removed with a rotary evaporator to afford 39 g of the title compound as a tan solid.

1H NMR (CDCl₃): δ 5.40 (s, 2), 7.1 (m, 2), 7.4 (m, 5), 7.86 (m, 2).

Intermediate 2

N-(1-Methylethyl)-6-(phenylmethoxy)-2-pyridinecarboxamide

A suspension of 20 g (87 mmol) of 6-(phenylmethoxy)-2-pyridinecarboxylic acid in 300 mL of thionyl chloride was heated to reflux. After a few minutes the reaction mixture became homogeneous and it was refluxed for 2 h. The volatiles were removed with a rotary

evaporator. The residue was disolved in 300 mL of

dichloromethane and added dropwise to 29.8 mL (350 mmol) of 2-aminopropane in 100 mL of dichloromethane cooled in an ice bath. After 30 min. the volatiles were removed with a rotary evaporator. The residue was disolved in ethyl acetate and washed with water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator to give 24.7 g of the title compound as an orange oil.

1H NMR (CDCl₃): δ 1.26 (d, 6), 4.22 (m, 1), 5.38 (s,

2), 6.0 (br, 1), 6.95 (d, 1), 7.43 (m, 4), 7.75 (m, 3).

Intermediate 3

1,6-Dihydro-N-(1-methylethyl)-6-oxo-2-pyridinecarboxamide To a mixture of 24.7 g of N-(1-methylethyl)-6- (phenyl-methoxy)-2-pyridinecarboxamide and 11 g of 10% Pd on carbon was added 500 mL of ethanol. The reaction mixture was vigorously stirred and placed under 1

atmosphere of hydrogen for 4 hours. (Approximately

2100 mL of hydrogen was absorbed.) The reaction mixture was filtered and the catalyst was washed with THF. The solvent was removed from the filtrate with a rotary evaporator to give 13.8 g of the title compound as a yellow solid.

1H NMR (CD₃SOCD₃) : 5 1.17 (d, 6), 4.0 (m, 1), 6.67 (d, 1) and 7.2 (br, 1), 7.75 (dd, 1), 8.15 (br, 1), 11.5 (br, 1).

N-(1-Methylethyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide

To a solution of 0.50 g (2.8 mmol) of 1,6-dihydro-N- (1-methylethyl)-6-oxo-2-pyridinecarboxamide in 40 mL of dichloromethane was added 0.46 mL (3.3 mmol) of

triethylamine. The reaction mixture was cooled in an ice bath and 0.26 mL (3.3 mmol) of methanesulfonyl chloride was added. The reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with dichloromethane, washed with water and dried (sodium sulfate). The solvent was removed with a rotary

evaporator and the residue was purified by flash

chromatography on silica gel with 25% ethyl acetate in hexanes as eluant to give 0.49 g of the title compound as a white solid, mp 78-79°C.

1H NMR (CDCl₃) : δ 1.29 (d, 1), 3.40 (s, 3), 4.23 (m,

1), 7.30 (d, 1), 7.40 (br, 1), 8.00 (d, 1), 8.19 (d, 1).

EXAMPLE 2

Preparation of N-(1-Methylethyl)-6-[(methylsulfonyl)oxy]- 2-pyridinecarbothioamide

To a solution of 0.50 g (1.9 mmol) of N-(1-methylethyl)-6-methylsulfonyloxy)-2-pyridinecarboxamide in

25 mL of toluene was added 0.59 g of 2,4-bis(methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,2-disulfide. The reaction mixture was refluxed for 2.5 hours. The solvent was removed with a rotary evaporator. The residue was purified by flash chromatography on silica gel with a gradient of 10-20% ethyl acetate in hexanes as eluant to give 0.47 g of a yellow solid. ¹H NMR indicated this to be the title compound with a small impurity. The solid was recrystallized from a mixture of ether/petroleum ether to give yellow needles, mp 110-112°C.

1H NMR (CDCI₃): 51.18 (d, 6), 3.37 (s, 3), 4.87 (m, 1), 7.28 (d, 1), 7.97 (dd, 1), 8.63 (d, 1).

By applying the procedures of Examples 1 and 2 and Equations 1 through 13, one skilled in the art can

prepare the compounds in Tables 1 through 7. In the following Tables, abbreviations for various alkyl chains and rings have been used with the following corresponding definitions.

iPr = isopropyl = CH(CH₃)₂

nPr = n-propyl = CH₂CH₂CH₃

cPr = cyclopropyl = CH(CH₂)₂

tBu = tert-butyl = C(CH₃)₃

nBu = n-butyl -= (CH₂)₃CH₃

sBu = sec-butyl = CH (CH₃)CH₂CH₃

iBu = iso-butyl = CH₂CH(CH₃)₂

Formulation/Utility

Compounds of this invention will generally be used formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Use 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, 5-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

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

Pellets

High Strength 90-99 0-10 0-2

Compositions

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 Emulsif iers 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 be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations,

Washington, 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 Chemi cal 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 includes 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. 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 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, terbufos, 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, thiophanate-methyl, 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 tribasic 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, baculovirus and avermectin B.

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-C for compound descriptions.

TEST A

Fall Armyworm

Test units, each consisting of a H.I.S. (high impact styrene) with 16 cells. In 12 of the cells is a 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 an 8 ounce (230 ml) plastic cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup, 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 p.s.i. (207 kPa). The insects were transferred into the tray (one insect per cell). The trays were then covered and held at 27°C and 50% relative humidity for 48 hours, 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 resulted in

greater than or equal to 80% mortality: 4*.

*Tested at 0.13 kg/ha

TEST B

Southern Corn Rootworm

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

prepared. Sets of three 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 third-instar larvae of the southern corn rootworm

(Diabrotica undecimpunctata howardi) were placed into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were 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 greate than or equal to 80% mortality: 1, 2, 3*, 4*, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14**, 15, 16, 17, 18, 19, 20, 21, 22,

24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 38 *

* Trested at 0.13 kg/ha. The listed compounds 14-38 were tested under an analogous protocol where the cups contained a soybean-wheatgerm diet, and second-instar larvae were used. TE ST C

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 (2.54 cm) layer of sterilized soil and a 1/2 inch (1.27 cm) layer of sand. The test units were 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 each of the cups covered with vented lids. The cups were 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, 2 , 7, 15, 16, 21, 22, 25, 26, 38*.

*Tested at 0.13 kg/ha

TEST D

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. Eac cup was then covered with a vented lid and 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, 15, 21, 29, 32.

TEST E

Black Bean Aphid

Individual nasturium 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 set in 3/8 inch (0.94 cm) diameter vial containing 4 ml of sugar water solution and covered with a clear plastice 1 ounce (28 ml) portion cup to prevent escape of the aphids that drop from the leaves. The test units were 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: 19, 20, 33.

TEST F

Green Leafhopper

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 75:25 mixture of acetone:water. The

concentration of the test chemical in the solvent mixture is 100 ppm. 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 an air atomizing spray nozzel. 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 hours. After drying, the cups are placed into concial shaped test units and the surface of the soil is 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 hours 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 hours post-infestation: 1, 15, 25, 28, 29, 30, 31, 32. TEST G

Brown Planthopper

Same method as described in Test F, using the brown planthopper (Nilaparvata l ugens) as the test species. Of the compounds tested, the following gave mortality of 80% or higher at 48 hours post-infestation: 1, 4, 9, 14, 15, 19, 21, 22, 24, 25, 26, 28, 29, 30, 31, 32, 33.

TEST H

Solution Systemic Activity Against Green Leafhopper 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 concentration of the test chemical in the chemical solution is 100 ppm. The rice seedlings are allowed to absorb the chemical from the solution for 24 hours 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 hours 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 hours post-infestation: 1, 15, 16, 21, 22, 28, 29. TEST I

Solution Systemic Activity Against Brown Planthopper Nymphs

Same methods as used for Solution Systemic Activity against green leafhopper nymphs, except that the brown planthopper (Nilaparvata lugens) is the test species. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 hours post-infestation: 1, 9, 15,

16, 21, 22, 26, 28, 29.

Claims

A compound having the formulae:

wherein :

Q is selected from the group

X is selected from the group O, S and NR⁶;

Y is selected from the group O and S;

Z is selected from the group H, halogen, CN, NO₂,

C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy and S(O)_nR⁷; R is selected from C₁-C₃ alkyl;

R¹ is selected from the group C-_L-C₆ alkyl, C₁-C₆

haloalkyl, C₁-C₅ alkoxy, C₂-C₅ alkoxyalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₄-C₇

cycloalkylalkyl, N(R⁴)R⁵, phenyl optionally substituted with 1 or 2 substituents selected from the group W; benzyl optionally substituted with 1 or 2 substitutents selected from the group W; and C₁-C₅ alkyl substituted with a group selected from CN, N(R⁴)R⁵ and S(O)_nR⁷;

R² is selected from the group H, C₁-C₂ alkyl, C₁-C₂ haloalkyl, formyl, C₂-C₃ alkylcarbonyl, C₂-C₃ alkoxycarbonyl, C₃ alkenyl and C₃ alkynyl; or R¹ and R² can be taken together to form

-CH₂CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂- or

-CH₂CH₂OCH₂CH₂-;

R³ is selected from the group C₁-C₂ alkyl and C₁-C₂ haloalkyl;

R⁴ and R⁵ are independently selected from methyl and ethyl; or

R⁴ and R⁵ can be taken together to form

-CH₂CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂- or

-CH₂CH₂OCH₂CH₂-;

R⁶ is selected from the group H, C₁-C₃ alkyl and C₁-C₃ haloalkoxy;

R⁷ is from the group C₁-C₂ alkyl and C₁-C₂ haloalkyl; W is selected from the group halogen, C₁-C₂ alkyl,

C₁-C₂ alkoxy, CF₃ and OCF₃; and

n is 0, 1 or 2.
2. A compound according to Claim 1 wherein:

R¹ is selected from the group C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₄-C₅ cycloalkylalkyl and C₁-C₅ alkyl substituted with CN; R² is selected from the group H and CH₃;

R³ is CH₃;

X is selected. from the group O and S; and

Z is selected from the group H and halogen.
3. A compound according to Claim 2 wherein Q is selected from the group Q-1 and Q-6.
4. A compound according to Claim 3 wherein Q is Q-1.
5. A compound according to Claim 3 wherein Q is Q-6.
6. A compound according to Claim 4 selected from the group:

N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide;

N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarbothioamide;

N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide; and

3-chloro-N-(1-methylethyl)-6- [(methylsulfonyl)oxy]-2-pyridinecarboxamide.
7. A compound according to Claim 6 which is:

N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2- pyridinecarboxamide.
8. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound

according to any one of Claims 1 to 7 and a carrier therefor.
9. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound

according to any one of Claims 1 to 7.