WO1994025440A1

WO1994025440A1 - Arthropodicidal and nematocidal heterocyclic sulphonates

Info

Publication number: WO1994025440A1
Application number: PCT/AU1994/000180
Authority: WO
Inventors: Keith Geoffrey Watson; Andris Juris Liepa; Roland Henry Nearn
Original assignee: Dunlena Pty. Limited
Priority date: 1993-04-26
Filing date: 1994-04-14
Publication date: 1994-11-10

Abstract

Compounds of the formula (I): R1-SO2-O-Q, their isomeric forms and salts thereof, wherein Q is the group (a), G is selected from the group S, S(=O), S(=O)2, C=S and C=O; R1 is selected from the group C¿1?-C3 alkyl and C1-C3 haloalkyl; R?2, R3, R4, R5, R6, R7 and R8¿ are various substituents. Arthropodicidal and nematocidal compositions comprising the compounds of formula (I).

Description

Arthropodicidal And Nematocidal Heterocyclic Sulphonates

This invention relates to new arthropodicidal and nematocidal compounds, to methods o preparing these compounds, to new arthropodicidal or nematocidal compositions containing the compounds and to methods of controlling arthropods and/or nematodes using such compositions.

United States Patent 3,966,754 discloses insecticidal sulfonates that contain a heteroaromatic ring containing three hetero atoms. U. S. Patent 4,791,127 discloses insecticidal thiazole sulfonates, and Jacobsen et al, Pest Sci. 29, 95-100 (1990) discloses insecticidal iso-oxazole sulfonates. Insecticidal and nematocidal activity has also been described for various pyridyl sulfonic acid esters in United States Patents 4,652,574 and 4,987,141. Arthropodicidal 4,5-dihydropyrazole and tetrahydro-pyridazine sulfonates o Formula I have hitherto been unknown.

The present invention is based on the discovery of high levels of arthropodicidal and nematocidal activity for the compounds of Formula I. This invention provides arthropodicidal compounds of Formula I, including all geometric and stereoisomers, and all agriculturally suitable salts thereof.

In another aspect, this invention also provides agricultural compositions comprising compounds of Formula I and their use for the control of arthropods and nematodes in both agronomic and non-agronomic uses. The compounds are -

R'-SO₂-O-Q I

wherein: Q is the group

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

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

R² is selected from the group C,-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl each of which is optionally substituted with one or more members independently selected from R⁹; or

R² is selected from the group C,-C₆ haloalkyl, N(R^l0)R^π, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl, and phenyl optionally substituted with one or more members independently selected from W; R\ R\ R⁵, R⁶, R⁷, and R⁸ are independently selected from the group H, halogen, C,-C₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C,-C₆ alkoxy, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl, C₂-C₆ alkoxycarbonyl, N(R¹⁶)R'⁷, C(O)N(R¹⁶)R¹⁷, cyano, and phenyl optionally substituted with one or more members independently selected from W; R⁹ is selected from the group halogen, CF₃, CC1₃, CN, SCN, NO₂, OR¹², SR¹², SOR¹², SO₂R¹², Si(R¹²)(R^,3)(R¹⁴), C(O)N(R¹²)R¹³, N(R¹²)R¹³ , N⁺(R¹²)(R¹³)(R¹⁴) and phenyl optionally substituted with 1 to 5 members independently selected from R¹⁵; R¹⁰ is selected from the group hydrogen, C,-C₆ alkyl optionally substituted with 1 to 5 members independently selected from R¹⁸, C₃-C₆ alkenyl optionally substituted with 1 to 5 members independently selected from R¹⁸, C₃-C₆ cycloalkyl optionally substituted with one or more members independently selected from R²⁰ and C₄-C₇ cycloalkylalkyl optionally substituted with one or more members independently selected from R²¹; R¹¹ is selected from the group H, CN, C,-C₆ haloalkyl and C,-C₆ alkyl optionally substituted with one or more CN groups; or R¹⁰ and R" taken together form -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -CH₂CH*)-O-CH₂CH₂-; R¹², R¹³ and R¹⁴ are independently selected from the group C*-C₃ alkyl and C*-C₃ haloalkyl;

W, and R¹⁵ are independently selected from the group halogen, C,-C, alkyl,

C,-C₂ haloalkyl, C,-C₂ alkoxy, C,-C₂ haloalkoxy, C,-C₂ alkylthio,

C,-C₂ haloalkylthio, C,-C, alkylsulfinyl, C,-C₂ haloalkylsulfinyl, C,-C₂ alkylsulfonyl, C,-C₂ haloalkylsulfonyl, NO, and CN;

R¹⁶ and R¹⁷ are independently selected from the group H, C,-C₆ alkyl,

C_rC₆ haloalkyl, C,-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C,-C₆ alkylsulfonyl and C(O)N(R¹⁹)R²⁰; or

R¹⁶ and R¹⁷ taken together form -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-, -CH₂CH₂-O-CH₂CH₂- or -CH₂CH₂-NH-CH₂CH₂-;

R¹⁸ is selected from the group halogen, CN, C,-C₂ alkoxy, C,-C, alkylthio, C,-C₂ alkylsulfonyl and C--C, trialkylsilyl;

R^19, and R²⁰ are independently selected from the group H and C,-C₃ alkyl;

R²¹ is selected from the group halogen, C,-C₃ alkyl, CN, C*-C₂ alkoxy, C,-C₂ alkylthio, C--C*, alkylsulfonyl and C₃-C₆ trialkylsilyl; and n is 0 or 1.

Some of the compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereoisomers, and geometric isomers. One skilled in the art will 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 isomers of compounds of Formula I as well as agriculturally suitable salts thereof.

In all of the above, the terms "optionally substituted phenyl" and "optionally substituted benzyl" denotes phenyl or benzyl groups which can be substituted by the groups halogen, nitro, methyl, methoxy, trifluoromethyl, cyano, methylthio.

In all of the above, the term "alkyl" used either alone or in compound words such as "haloalkyl", denotes straight or branched alkyl including methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl or hexyl isomers. Alkoxy denotes methoxy, ethoxy, n-propyloxy, /sø-propyloxy 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 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 CH,CH₂F, CF,CF₃ and CH₂CHFC1. The terms "haloalkenyl" and "haloalkynyl" are defined analogously to the term "haloalkyl".

The term "alkylsulphonyl" denotes CH₃S(O)₂, CH₃CH₂S(O)₂, CH₃CH₂CH₂S(O)₂

(CH₃)₂CHS(O)₂, and the different butylsulphonyl, pentylsulphonyl and hexylsulphonyl isomers. The term "alkylsulphinyl" denotes CH₃SO, and CH₃CH₂SO.

The total number of carbon atoms in a substituent group is indicated by the "C_j-C_j" prefix where i and j are numbers from 1 to 7. For example, C₂ alkylcarbonyl designates C(O)CH₃ and C₃-alkylcarbonyl designates C(O)CH₂CH₃; 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.

Preferred compounds A are those compounds where

G is selected from the group SO₂ or C = O; n is 0 or 1;

R¹ is selected from the group CH₃ and C1CH₂;

R² is selected from the group C,-C₆ alkyl, C,-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, and N(R^I0)R";

R³, R⁴, R⁵, R⁶, R⁷ , and R⁸ are independently selected from H, C,-C,alkyl,

C,-C₂haloalkyl, C,-C,alkoxy, N(R¹⁶)R¹⁷, and phenyl. Preferred compounds B are the compounds of Preferred A wherein n is zero.

Preferred compounds C are the compounds of Preferred A wherein n is 1.

Particularly preferred compounds of the invention are compounds of formula I wherein:

G is SO₂ or C = O; n is 0 or 1; R¹ is CH₃; R² is selected from the group C,-C₆ alkyl and C,-C₆ alkylamino;

R³, R\ R⁵, R⁶, R⁷, and R⁸ are independently selected from H and CH₃.

Examples of compounds within the scope of this invention are given in Tables 1 to 3 which follow. In these tables, the following abbreviations for various alkyl chains and rings have been used:

Me = methyl

Et = ethyl

/-Pr = wo-propyl n-Pr = n-propyl c-Pr = cyclopropyl t-Bu = tert-butyl n-Bu = n-butyl

.s-Bu = sec- butyl

Ph = phenyl.

TABLE 1

TABLE 1 (Continued)

TABLE 2

TABLE 2 (Continued)

TABLE 3

A further example of a compound within the scope of the invention is Compound 4- 1 wherein in Formula 1 :

R'=Me, G=CO, R²=N(H)/-Pr, R³=R⁴=H, R = CO,Me, R⁷=R⁸=H, n=l

Compound Synthesis

Compounds of Formula I can be prepared by the reaction of the corresponding 3-pyrazolidinone or l,4,5,6,-tetrahydro-3-pyridazinone 1 with the appropriate sulphonyl 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 3-pyrazolidinone tautomer. In Equations 1-5 R\ R²,R³, R\ R⁵,R⁶, R⁷, R⁸, and G are as previously defined.

R¹ -S0₂ - 0 - Q

I

The parent 3-pyrazolidinones 3 can be prepared from the appropriate α, β-unsaturated acid or acid derivative 2 by reaction with hydrazine as shown in Equation 2 (wherein R is H or an Alkyl group):

Equation 2

2 3

Alternatively a β-substituted propionic acid derivative, such as a β-halopropionyl halide 4 may be reacted with hydrazine to give the 3-pyrazolidinones ring system 3 as shown in Equation 3.

Equation 3

Treatment of the 3-pyrazolidinones 3 with the appropriate acid chloride, sulfonyl chloride, sulfenyl chloride or sulfamoyl chloride gives the substituted 3-pyrazolidinones 1A as shown in Equation 4.

Equation 4

H

1A

Similarly, treatment of the parent 3-pyrazolidinones 3 with a suitable isocyanate or isothiocyanate 5 allows isolation of compounds 6 wherein X is O or S and R¹⁰ is as previously defined, as shown in Equation 5. Equation 5

H

l,4,5,6-Tetrahydro-3-pyridazinones 7 are known in the chemical literature (for example Can. J. Chem., 49, 1598 (1971)) and can be prepared by a variety of methods.

Reaction of the tetrahydro-3-pyridazinones 7 with acyl chlorides or isocyanates, etc, by analogy with the reactions described in Equations 4 and 5 for 3-pyrazolidinones, gives the substituted 3-pyridazinones IB.

IB

The compounds of the invention, their preparation and properties are illustrated by the following non-limiting examples.

EXAMPLE 1

Preparation of N-propyl-5,5-dimethyl-3-methanesulfonyloxy-4,5-dihydro- 1 H-pyrazole- 1 -carboxamide (Compound 1-10) (i) 5, 5-Dimethyl- 1 -propylcarbamoyl-pyrazolidin-3-one

5-5-Dimethylpyrazolidin-3-one (1.1 g, 10 mmol) was dissolved in toluene (15 ml) with stirring and gentle warming. Propyl isocyanate (1 ml, 11 mmol) was added to the solution and the mixture was stirred at room temperature for 2 hours. A pale grey solid sloλf ly separated from the solution and the product was collected by filtration (1.5 g) m.p. 73-75°, Η nmr (CDC1₃): δ 0.90 (t, 3H); 1.4 (m, 2H); 1.52 (s, 6H); 2.53 (s, 2H); 3.15 (m, 2H); 5.57 (t, IH).

(ii) N-Propyl-5, 5-dimethyl-3-methanesulfonyloxy-4, 5-dihydro-lH-pyrazole-l- carboxamide

Triethylamine (0.5 ml, 4 mmol) was added to a solution of 5,5-dimethyl-l-propylcarbamoyl-pyrazolidin-3-one (0.70 g, 3.5 mmol) in dichloromethane (40 ml). The solution was cooled to 5 °C and methanesulfonyl chloride (0.3 ml, 4 mmol) was added dropwise with stirring. The reaction mixture was stirred overnight at room temperature and then washed with water, dried (MgSO₄) and the solvent removed under reduced pressure. The oily residue was chromatographed on silica, eluting with chloroform. The title compound was isolated as the main band off the column and was a colourless low-melting solid.

Η nmr (CDC1₃): δ 0.91 (t, 3H); 1.51 (m, 2H); 1.62 (3, 6H); 2.93 (s, 2H); 3.1 (m, 2H); 3.32 (s, 3H); 5.60 (t, IH).

EXAMPLE 2

Preparation of 3-methanesulfonyloxy-5-phenyl-l-propylsulfonyl-4,5-dihydro-lH- pyrazole Compound No 2-10

(i) 5-Phenyl-l-propylsulfonylpyrazolidin-3-one

5-Phenylpyrazolidin-3-one (0.8 g, 5 mmol) was dissolved in dichloromethane (80 ml), pyridine (0.5 ml, 6 mmol) was added and the solution was stirred and cooled to 5°C. n-propylsulfonyl chloride (0.5 ml, 4.5 mmol) was added slowly to the solution and the reaction mixture was allowed to warm to room temperature and to stand for 18 hours. The mixture was poured onto ice water and the organic layer was separated, dried (MgSO₄) and evaporated to give an orange oil (1.3 g). Purification by chromatography over silica gave the title compound as a white solid (0.9g).

Η nmr (CDC1₃): δ 1.08 (t, 3H); 1.93 (m, 2H); 2.62 (dd, IH); 3.0-3.5 (complex m, 3H); 5.54 (dd, IH); 7.35 (s, 5H).

(ii) 3-Methanesulfonyloxy-5-phenyl-l-propyl-sulfonyl-4, 5-dihydro-lH-pyrazole

To a cooled solution of 5-phenyl-l-propyl-sulfonylpyrazolidin-3-one (0.90 g, 3.3 mmol) in dichloromethane (50 ml) was added triethylamine (0.6 ml, 4 mmol) followed by methanesulfonyl chloride (0.3 ml, 4 mmol). The reaction mixture was allowed to warm to room temperature and to stand for 16 hours.

After washing with cold water the dichloromethane layer was dried (MgSO₄) and evaporated. The oily residue was purified by chromatography on silica (40 g) eluting with chloroform and the product was obtained as an oil (0.45 g) in the second and major band. -H nmr (CDC1₃): δ 1.01 (t, 3H); 1.85 (m, 2H); 3.0-3.2 (m, 3H); 3.46 (s, 3H);

3.58 (dd, IH); 5.47 (dd, IH); 7.35 (s, 5H). EXAMPLE 3

Compounds No 1 -7 to 1-9, 1-1 1 to 1-27, and 1-45 to 1-49 were prepared from the appropriate pyrazolidin-3-one following a similar method to that described in Example 1, parts (i) and (ii). Their Η nmr spectra are recorded in Example 6 below.

EXAMPLE 4

Compounds No 2-1, 2-5, 2-14 to 2-17, 2-21 to 2-24, 2-26 and 2-36 to 2-38 were prepared from the appropriate pyrazolidin-3-one following a similar procedure to that described in Example 2, parts (i) and (ii). Their Η nmr spectra are recorded in Example 6.

EXAMPLE 5

Compounds No 3-3, 3-4, 3-1 1, 3-12, 3-15, and 3-21 to 3-27 were prepared from the appropriate l,4,5,6-tetrahydro-3-pyridazinone following similar procedures to those given above for the related pyrazolidinones. Their melting points are recorded in Example 6.

EXAMPLE 6

Many of the compounds of the invention were obtained as oils and were characterized by and can be identified by their proton magnetic resonance spectra. The magnetic resonance spectroscopic data and/or melting point data are recorded in Table 4 below.

TABLE 4

TABLE 4 (Continued)

TABLE 4 (Continued)

TABLE 4 (Continued)

Formulation

The compounds of this invention will generally be used in a formulation with an agriculturally suitable carrier comprising one or more liquid or solid diluent(s) or organic solvent(s). Useful formulations of the compounds of Formula 1 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 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:

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 somewhat 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 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 US 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. 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, pp 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following.

Typical formulations and methods for their manufacture are given below: FORMULATION A Emulsifiable Concentrate

Compound of the invention 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 ensure the absence of any extraneous undissolved material in the product.

FORMULATION B Wettable Powder

Compound of the invention 30% soldium 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 hammermill, the material is re-blended and sifted through a 50 mesh screen.

FORMULATION C Dust

Wettable powder of Formulation 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. FORMULATION D Granule

Compound of the invention 10% attapulgite granules (low volatile matter, 90% 0.71/0.30 mm; USS No 25-30 sieves)

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 packaged.

FORMULATION E Granule

Wettable powder of Formulation 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 (USS 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.

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

FORMULATION G Solution

Compound of the invention 25%

N-methyl-pyrrolidone 75%

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

FORMULATION H Oil Suspension

Compound of the invention 35% blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6% xylene range solvent 59%

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.

FORMULATION I Bait Granules

Compound of the invention 3% blend of polyethoxylated nonylphenols and sodium dodecylbenzene sulfonates 9% ground up corn cobs 88%

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.

Formulations with other active ingredients

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. Example of other agricultural protectants with which compounds of this invention can be formulated are:

Insecticides:

3-hydτoxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran)

O-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester

(tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, O,O-dimethyl, O- -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-O-(2-isopropyl-4-methyl-6-pyrimidyl)phosphoro-thioate (diazinon) octachlorocamphene (toxaphene)

O-ethyl-O- -nitrophenyl phenylphosphonothioate (EPN) (S)-α-cyano-w-phenoxybenzyl

( 1 R,3 R)-3-(2,2-dibromoviny l)-2,2-dimethylcyclopropanecarboxylate (deltamethrin) methyl-N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-l-thiooxamimidate (oxamyl) cyano(3-phenoxyphenyl)-methyl-4-chloro-α-(methylethyl)-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) α-cyano-3-phenoxybenzyl 1 -(4-ethoxyphenyl)-2,2-dichlorocyclopropane 1 -carboxylate

(cycloprothrin) 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-ylmeth/l]- 1 H- 1 ,2,4-triazole (propiconazole)

2-cyano-N-ethylcarbamyl-2-methoxyiminoacetamide (cymoxanil) 1 -(4-chlorophenoxy)-3,3-dimethyl- 1 -( 1 H- 1 ,2,4-triazol- 1 -yl)-2-butanone (triadimefon) N-(trichloromethylthio)tetrahydrophthalimide (captan) N-(trichloromethylthio)phthalimide (folpet) l-[[[bis(4-fluorophenyl)][methyl]silyl]methyl]-lH-l,2,4-triazole

Nematocides: S-methyl l-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thioformimidate S-methyl 1 -carbamoyl-N-(methylcarbamoyloxy)-thioformimidate N-isopropylphosphoramidic acid O-ethyl O'-[4-(methyl-thio)-/n-tolyl]diester (fenamiphos)

Bactericides: tribasic copper sulfate streptomycin sulfate

Acaricides: senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl)

6-methyl-l ,3-dithiolo[4,5-b]quinoxalin-2-one (oxythioquinox) ethyl 4,4'-dichlorobenzilate (chlorobenzilate)

1 , 1 -bis(p-chlorophenyl)-2,2,2-trichloroethanol (dicofol) bis(pentachloro-2,4-cyclopentadien- 1 -yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3-carboxamide

(hexythiazox) amitraz propargite fenbutatin-oxide Utility

The compounds of this invention exhibit activity against a wide spectrum of foliar and soil inhabiting arthropods 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 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 betle, 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 other 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 mide, 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 (teph tidae), and soil maggots;

adults and immatures of the class nematoda including:

Awl nematode Dolichodorus heterocephatus Banana nematode Pratylenchus musicola Bud and leaf nematode Aphelenchoides spp. Burrowing nematode Radopholus similus Carrot root nematode Heterodera carotae Coffee root-knot nematode Meloidogyne exigua Corn nematode Praylenchus zeae Dagger nematodes Xiphinema spp. Golden nematode Globodera rostochiensis Grass nematode Anguina agrosis Lance nematodes Hoplolaimus spp. Lesion nematodes Pratylenchus spp. Northern Root-knot nematode Meloidogyne hapla Pea root nematode Heterodera gottingiana Peanut root-knot nematode Meloidogyne arenaria Pin nematodes Paratylenchus spp. Potato rot nematode Ditylenchus destructor Reinform nematode Rotylenchulus reinformus Rice nematode Ditylenchus angustus Ring nematodes Criconemoides spp.

Smooth-headed lesion nematode Pratylenchus brachyurus Southern root-knot nematode Meloidogyne incognita Soybean cyst nematode Heterodera glycines Spiral nematodes Helicotylenchus spp. Stem and bulb nematode Ditylenchus dipsaci Sting nematodes Belonolaimus spp. Stubby-root nematodes Trichodorus spp. Sugar beet nematode Heterodera schachtii Tobacco cyst nematode Heterodera tabacum Tobacco stunt nematode Tylenchorhynchus claytoni Wheat nematode Anguina tritici

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 Hvmenoptera 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 Brachvcera. 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.

Application

Arthropod and nematode 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 and nematode 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, in 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 Formula I.

The rate of application of the compounds of Formula I 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 large-scale 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 about 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. Compounds not mentioned were either not screened or gave mortality levels less than 80%.

TEST A Southern Corn Rootworm

The units, each consisting of a 230 mL plastic cup containing 1 sprouted corn seed, 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 third-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardϊ) 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 gave mortality levels of 80% or higher: 1-7, 1-8, 1-9, 1-10, 1-1 1 , 1-12, 1-14, 1-15, 1-16, 1-21, 1-24, 1-25, 1-26, 1-27, 1-41, 1-42, 1-45, 1-46, 1-47, 2-1, 2-5, 2-16, 2-17, 2-21, 2-22, 2-26, 2-36, 2-37, 3-3, 3-4, 3-5, 3-9, 3-11, 3-12, 3-15, 3-21, 3-22, 3-23, 3-24, 3-25, and 3-26.

TEST B Aster Leafhopper

Test units were prepared from a series of 350 mL cups, each containing oat (Avena sativa) seedlings in a 2.5cm layer of sterilised soil. 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 covered cups. 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 gave mortality levels of 80% or higher: 1-7, 1-8, 1-10, 1-11, 1-12, 1-14, 1-15, 1-16, 1-21, 1-24 1-41, 1-42, 2-5, 2-16, 2-24, 2-37, 3-3 3-9, 3-11, 3-24, 3-25, and 3-26.

TEST C Boll Weevil

Five adult boll weevils (Anthonomus grandis grandis) were placed into each of a series of 260 mL cups. The test procedure employed was then otherwise the same as in Test A. Mortality readings were taken 48 hours after treatment. Of the compounds tested, the following gave mortality levels of 80% or higher: 1-9, 1-15, 1-16, 1-21, 1-24, 1-41, 1-42, 2-37, 3-24, and 3-26.

TEST D Black Bean Aphid

Individual nasturtium leaves were infested with 5 to 10 aphids (all stages of Aphis Fabae) and sprayed with their undersides facing up on a hydraulic sprayer as described in Test A. The leaves were then set in 1-inch diameter vials containing sugar water solution and covered with a clear plastic 1 ounce-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 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1-11, 1-12, 1-16, 1-18, 1-21, 1-24, 1-41 , 1-42, 2-1, 2-16, 3-3, 3-1 1, 3-21, 3-24 and 3-26.

TEST E 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 than 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: 1-7, 1-10, 1-12, 3-3 and 3-23.

TEST F

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 24h in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the brown planthopper (Nilaparvata 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. 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: 1-7, 1-10, 1-11, 3-3, 3-12, and 3-23.

Claims

1. Compounds of Formula I, their isomeric forms and salts thereof:

R'-SO₂-O-Q I wherein: Q is the group

G is selected from the group S, S(=O), S(=O)₂, C=S and C=O; R¹ is selected from the group C,-C₃ alkyl and C,-C₃ haloalkyl; R² is selected from the group C,-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl each of which is optionally substituted with one or more members independently selected from R⁹; or R² is selected from the group C,-C₆ haloalkyl, N(R^I0)R", C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl, and phenyl optionally substituted with one or more members independently selected from W; R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selected from the group H, halogen, C,-C₆ alkyl, C,-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C,-C₆ alkoxy, C₃-C₆ cyclohaloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₄-C₇ cycloalkylalkyl, C₂-C₆ alkoxycarbonyl, N(R^I6)R¹⁷, C(O)N(R¹⁶)R¹⁷, cyano, and phenyl optionally substituted with one or more members independently selected from W; R⁹ is selected from the group halogen, CF₃, CC1₃, CN, SCN, NO₂, OR¹², SR¹², SOR¹², SO₂R¹², Si(R¹²)(R^,3)(R¹⁴), C(O)N(R¹²)R'³, N(R¹²)R¹³ , N⁺(R¹²)(R¹³)(R¹⁴) and phenyl optionally substituted with 1 to 5 members independently selected from R¹⁵;

R¹⁰ is selected from the group hydrogen, C,-C₆ alkyl optionally substituted with 1 to 5 members independently selected from R¹⁸, C₃-C₆ alkenyl optionally substituted with 1 to 5 members independently selected from R¹⁸, C₃-C₆ cycloalkyl optionally substituted with one or more members independently selected from R²⁰ and C₄-C₇ cycloalkylalkyl optionally substituted with one or more members independently selected from R²';

R^π is selected from the group H, CN, C,-C₆ haloalkyl and C,-C₆ alkyl optionally substituted with one or more CN groups; or

R¹⁰ and Rⁿ taken together form -(CH₂),-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or

-CH,CH₂-O-CH₂CH,-;

R¹², R¹³ and R'⁴ are independently selected from the group C,-C₃ alkyl and C,-C₃ haloalkyl; W, and R¹⁵ are independently selected from the group halogen, C--C, alkyl,

C,-C₂ haloalkyl, C,-C₂ alkoxy, C,-C₂ haloalkoxy, C,-C₂ alkylthio,

C,-C₂ haloalkylthio, C,-C₂ alkylsulfinyl, C,-C, haloalkylsulfinyl, C_rC, alkylsulfonyl, C,-C₂ haloalkylsulfonyl, NO₂ and CN;

R¹⁶ and R¹⁷ are independently selected from the group H, C*-C₆ alkyl, C,-C₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C,-C₆ alkylsulfonyl and C(O)N(R¹⁹)R²⁰; or

R¹⁶ and R¹⁷ taken together form -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-,

-CH₂CH₂-O-CH₂CH₂- or -CH,CH₂-NH-CH₂CH₂-;

R¹⁸ is selected from the group halogen, CN, C,-C, alkoxy, C,-C, alkylthio, C,-C₂ alkylsulfonyl and C.-C, trialkylsilyl;

R¹⁹, and R²⁰ are independently selected from the group H and C,-C₃ alkyl;

R²¹ is selected from the group halogen, C,-C₃ alkyl, CN, C,-C, alkoxy, C,-C₂ alkylthio, C,-C, alkylsulfonyl and C₃-C₆ trialkylsilyl; and n is 0 or 1.

2. Compounds as claimed in Claim 1, characterised in that G is selected from the group SO, or C = O; n is 0 or 1; R¹ is is selected from the group CH₃ and C1CH₂;

R² is selected from the group C,-C₆ alkyl and C,-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, and N(R¹⁰)R^π; R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selected from H and C,-C₂alkyl, C_rC₂haloalkyl, C,-C₂alkoxy, N(R¹⁶)R¹⁷, and phenyl.

V

3. Compounds as claimed in Claim 2, characterised in that n is zero. 5

4. Compounds as claimed in claim 2, characterised in that n is 1.

5. Compounds as claimed in Claim 1, characterised in that

G is SO₂ or C = O; 10 n is 0 or 1;

R¹ is CH₃;

R² is selected from the group C-.-C₆ alkyl and C--C₆ alkylamino; R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selected from H and CH₃.

15 6. An agricultural composition, characterised in that it comprises as an active ingredient a compound of the formula (I) in admixture with a diluent or carrier.

7. An agricultural composition, characterised in that it comprises as an active ingredient a compound as claimed in any one of Claims 2 to 5.

20

8. A composition as claimed in Claim 6 or Claim 7, characterised in that it includes at least one other active ingredient which is an insecticide, fungicide, bactericide, acaricide or other biologically active compound.

25 9. A method of combating arthropods or nematodes, characterised in that a compound of the formula (I) alone or in the form of a composition as claimed in any one of Claims 6 to 8, is applied to the arthropods or nematodes or to a habitat thereof.

10. The use of a compound of formula (I) in the preparation of an arthropodicidal 30 or nematocidal composition.