GB1597909A

GB1597909A - Pesticidal n-substituted sulphonamides

Info

Publication number: GB1597909A
Application number: GB21283/78A
Authority: GB
Original assignee: Upjohn Co
Current assignee: Pharmacia and Upjohn Co
Priority date: 1977-06-09
Filing date: 1978-05-23
Publication date: 1981-09-16
Also published as: AU515729B2; DK227878A; NZ187220A; BE867985A; DE2823355A1; JPS545925A; FR2393792A1; IT7849782A0; NL7805551A; FR2393792B1; ZA782801B; AU3627378A; CA1110656A

Description

(54) NOVEL PESTICIDAL N-SUBSTITUTED SULPHONAMIDES (71) We, THE UPJOHN COMPANY, a corporation organized and existing under the laws of the State of Delaware, United States of America, of 301 Henrietta Street, Kalamazoo, State of Michigan, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to pesticidal novel N [[[arylformimidoyl] methylamino] thio]-N-substituted sulfonamides.

N-Alkyl-N'-aryl formamides are described as pesticides in, for example, Belgian Patent Specifications Nos. 760,141 and 770,825 and German Patent Specifications Nos. 1,172,081 and 2,202,034. N-sulfenylated chlorides of sulfonamides are described in, for example, German Patent Specifications Nos.

1,101,407 and 1,156,403. Arylsulfenylated formamidines and amino sulfenylated formamidines are described as insecticides in, for example, US Patent Specifications Nos. 3,887,619; 3,947,591 and 3,998,969.

The novel compounds of the invention have the formula

wherein R1 is chlorine, bromine or C14 alkyl; R2 is hydrogen, chlorine, bromine or C14 alkyl; R3 is C18 alkyl, C5s cycloalkyl, benzyl, phenethyl, a-methylbenzyl, phenyl or phenyl substituted by one to 3 substituents independently selected from methyl, chlorine, bromine, nitro, trifluoromethyl, methoxy, ethoxy and cyano; and R4 is C14 alkyl, phenyl phenyl having a methyl, chlorine of bromine substituent, or optionally ring-substituted benzyl, phenethyl or -methylbenzyl in which there are up to 3 substituents independently selected from methyl, chlorine, bromine, nitro, trifluoromethyl, methoxy, ethoxy and cyano.

This invention excludes compounds of formula I wherein R1 is methyl; R2 is methyl, chlorine or bromine; R3 is C18 alkyl or C6 cycloalkyl; and R4 is C14 alkyl, phenyl, methylphenyl, chlorophenyl or bromophenyl. These compounds are disclosed and claimed in British Patent Specification No. 1,541,800.

A composition according to the invention, which is suitable for controlling arthropodal pest populations, comprises from 0.001 to 96% by weight of a compound of the invention, in association with a suitable carrier. A method for controlling arthropodal pest populations at a locus, according to the invention comprises applying to the locus a compound or composition of the invention.

The sulfonamidosulfenyl formamidine derivatives of this invention are particularly advantageous commercially as invertibrate pesticides because they can be more stable than for example, aminosulfenylated formamidines both in storage and upon application in the field, thus providing a long lasting residual effectiveness.

In addition to killing invertibrate pests on contact, the compounds of the invention can be absorbed by the vascular system of many plants, for example by cotton plants, and act systemically to kill the pests feeding upon the plant. Thus their period of pesticidal activity can be further extended and nonfeeding arachnids and insects, e.g. insects not harmful to the plant, are not necessarily killed during the whole period of pesticidal activity.

The compounds of the invention can also be ovicidal, and are particularly effective in the control of acarine pest populations by this ovicidal action.

Lepidopterous ova can be particularly susceptible to the compounds of the invention.

The compounds of the invention are also advantageous in that they can exhibit relatively low mammalian toxicity and can be non-phytotoxic at effective concentrations.

When R1 is C14 alkyl, it is preferably methyl. R2 is preferably chlorine, bromine or C14 alkyl; when C14 alkyl, it is preferably methyl.

Preferably, R3 is C14 alkyl, Cos~8 cycloalkyl, benzyl, phenethyl, amethylbenzyl, phenyl or phenyl substituted by one to 3 substituents independently selected from methyl, chlorine and bromine.

It is particularly preferred, for best pesticidal effect and for chemical stability, that R1 and R2 are independently selected from methyl, chlorine and bromine and R3 is as defined in the preceding paragraph.

The compounds of this invention can be synthesised by reacting a N-methyl N'-arylformamidine of the formula

wherein R1 and R2 are as defined above, with a N-substituted sulfonamide-Nsulfenyl chloride of the formula Cl-S-NR3-SO2R4 IV wherein R3 and R4 are as defoned above, in an inert solvent and in the presence of an acid acceptor.

The inert solvent should neither enter into reaction with the reaction mixture nor alter the desired course of the reaction in any way. Suitable inert organic solvents are benzene, tetrahydrofuran, ethyl ether. Carbon tetrachloride and, most preferably, methylene chloride.

The proportion of solvent employed is not critical, but advantageously is a sufficient quantity to solubilize the reactant formamidine (III).

During the course of the above illustrated reaction, hydrochloric acid is generated as a by-product. Preferably this acid is removed from the reaction mixture as it forms. This may be accomplished by conventional and known methods, for example by adding an acid acceptor compound to the reaction mixture. Examples of acid acceptor compounds are the tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine and pyridine.

Although the above reaction may be carried out over a broad range of temperature conditions, i.e., from about -30"C. to about reflux temperature for the reaction mixture, it is preferably carried out at about 0 to 200 C.

Progress of the above reaction may be followed by conventional analytical methods, such as for example by nuclear magnetic resonance analysis which will show spectral characteristics of the product compounds (I) or by thin-layer chromatography which will show the appearance of product compounds. Upon completion, the desired compounds (I) are readily separated from the reaction mixture by conventional methods such as by filtration to remove solid residues, distillation to remove solvents, and recrystallization or silica gel chromatography.

Sulfonamide-N-sulfenyl chlorides (IV) are known in the literature and can be prepared by chlorination of an N,N'-dithiobissulfonamide (see German patent Specification No. 1,101,407) or by reaction of an N-substituted sulfonamide with sulfur dichloride in the presence of a tertiary amine (see German Patent Specification No. 1,156,403). N,N'-dithiobissulfonamides can be generated by reacting an N-substituted sulfonamide with sulfur monochloride in the presence of a tertiary amine.

N-Alkyl-N'-aryl formamidines (III) are also known in the literature and may be Prepared by methods described in Belgian Patent Specification No. 770,825 and U.S. Patent Specification Nos. 3,729,565 and 3,887,619.

The following Examples illustrate the invention.

All temperatures are in degrees Centigrade.

Ambient temperature is in the range 20 to 250.

SSB refers to Skellysolve B, an isomeric mixture of hexanes.

NMR refers to nuclear magnetic resonance.

Example 1 N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N benzylmethanesulfonamide.

To a stirred solution cooled to --100 of 0.1 mole of N benzylmethanesulfonamide and 10.1 g (0.1 mole) of triethylamine in 300 ml. of methylene chloride are added dropwise 10.3 g (0.1 mole) sulphur dichloride. The reaction mixture is stirred at ambient temperature for 0.5 hour and cooled to 100. A solution of 18.3 g (0.1 mole) of N-methyl-N'-(4-chloro-o-tolyl)formamidine and 10.1 g (0.1 mole) triethylamine in 100 ml. of methylene chloride is added rapidly with stirring. The reaction mixture is stirred at ambient temperature for 0.5 hours and extracted successively with 300 ml. of water, 300 ml. aqueous citric acid solution containing 10.5 g (0.05 mole) of citric acid, and 300 ml. of water. The organic layer is dried and the solvent removed under reduced pressure. The product is recrystallised once from isopropanol followed by two recrystallisations from ether to obtain 3.2 g. (16% yield) of the title product as white crystals, mp. 9495 .

Analysis: Calc'd for C1 7H2ClN3O2S2 C, 51.31; H, 5.07; N, 10.56; Found: C, 51.34; H, 5.07; N, 10.63; Example 2 N-[ [ [N-(4-chloro-o-tolyl formimidolylimethylamino] thiol-N- pheny methanesulfonamide To 0.04 mole of N,N'-dithiobis[N-phenylmethanesulfonamide] in 200 ml. of benzene are added dropwise 5.4 g (0.04 mole) sulfuryl chloride in 10 ml. of benzene. The reaction mixture is heated at reflux for 1.5 hours until evolution of gas ceases, purged with nitrogen, and cooled to 10 . A solution of 14.6 (0.08 mole) of N-methyl-N'-(4-chloro-o-tolyl)formamide and 8.08 g (0.08 mole of triethylamine in 100 ml. of benzene is added rapidly. The mixture is stirred 15 minutes at ambient temperature and extracted consecutively with 500 ml water, 400 ml. aqueous citric acid solution containing 8 g. citric acid, and 500 ml. water. The organic layer is dried and the solvent removed. The product is recrystallised from isopropanol to obtain 5.0 g (16% yield) of the title product as white crystals, mp. 120121 .

Analysis: Calc'd for C,6H,8CIN302S2 C, 50.06; H, 4.72; N, 10.95.

Found: C, 50.01; H, 4.76; N, 10.64.

Example 3 N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N- isopropylbenzylsulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobis(Nisopropylbenzylsulfonamide) for N,N'-dithiobis(N-phenylmethanesulfonamide), and recrystallisation from ether, 21.4 g (51% yield) of the title product are obtained as white crystals, mp. 117118 .

Analysis: Calc'd for C,9H24ClN302S2 C, 53.57; H, 5.68; N, 9.86.

Found: C, 53.75; H, 5.76; N, 9.79.

Example 4 N-[[(N-2,4-xylylformimidoyl)methylamino]thio]-N-phenymethanesulfonamide Following the procedure of Example 2, but substituting chlorine for sulfuryl chloride and N-methyl-N'-2,4-xylylformamidine for N-methyl-N'-(4-chloro-otolyl)formamidine, and recrystallisation from ethyl acetate, 2.0 g (14 ,; yield) of the title product are obtained as white crystals, mp. 12W121.5 .

Analysis: Calc'd for C'7H2,N302S2 C, 56.17; H. 5.82; N, 11.56.

Found: C, 56.06; H, 5.82; N, 11.40.

Example 5 N[ [(N-2,4-xylylformimidoyl)methylaminoithio] -N-isopropylbenzylsulfonamide Following the procedure of Example 4, but substituting N,N'-dithiobis(N isopropylbenzylsulfonamide) for N,N'-dithiobis(N-phenylmethanesulfonamide), and recrystallisation from SSB, 9.0 g (56% yield) of the title product are obtained as white crystals, mp. 8283.5 .

Analysis: Calc'd for C20H27N3O2S2 C, 59.23; H, 6.71; N, 10.36.

Found: C, 59.34; H, 6.56; M, 10.51.

Example 6 N-[[[N-(4-chloro-o-tolyl)formimidoyllmethylamino]thioi-N-p-chlorophenyl-p- toluenesulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobis[N-pchlorophenyl-p-toluenesulfonamide] for N,N'-dithiobis[Nphenylmethanesulfonamide] and chlorine for sulfuryl chloride, and recrystallisation from a mixture of ether and Skellysolve F followed by two recrystallizations from cyclohexane, 1.0 g. (10% yield) of the title product is obtained as white crystals, mp. 103104 .

Analysis: Calc'd for C22H2,C12N302S2 C, 53.44; H, 4.28; N, 8.50.

Found: C, 53.48; H, 4.22; N, 8.09.

Example 7 N- [[ [N-(4-chloro-o-tolyl)forniimidol1methylamino]thioi-N-benzyl toluenesulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobis[N benzyl-p-toluenesulfonamide] for N,N'-dithiobis [N-phenylmethanesulfonamidel and chlorine for sulfuryl chloride, 8.8 g. (93% yield) of the title product is obtained as an oil.

Analysis: Calc'd for C23H24CIN302S2 C, 58.28; H, 5.10; N, 8.86.

Found: C, 58.05; H, 5.17; N, 8.81.

NMR (CDCl3-tetramethylsilane) 7.85, 7.25, 4.63, 3.1, 2.4, 2.18.

Example 8 N-( [[N-(4-chloro-o-tolyl)formimidoyll methylamino]thio]-N-2,4-dichlorophenyl-p- toluenesulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobis[N-2,4- dichlorophenyl-p-toluenesulfonamide] for N,N'-dithiobis[Nphenylmethanesulfonamide] and chlorine for sulfuryl chloride, trituration with methanol and recrystallisation from a mixture of SSB and isopropanol, 0.6 g. (5.7% yield) of the title product is obtained as white crystals, mp. 9798a.

Analysis: Calc'd for C22H20C13N3O2S2 C, 49.96; H, 3.81; N, 7.96.

Found: C, 50.11; H, 3.73; N, 7.97.

Example 9 N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N- phenyl-p-toluenesulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobis[N phenyl-p-toluenesulfonamide] for N,N'-dithiobis[N-phenylmethanesulfonamide] and chlorine for sulfuryl chloride, 3.2 g. (40% yield) of the title product are obtained as white crystals, mp. 9596o.

Analysis: Calc'd for C22H22ClN3O2S2 C, 57.44; H, 4.82; N, 9.13.

Found: C, 57.79; H, 4.79; N, 9.17.

Example 10 N- [ [(N-2,4-dichloroformimidoyl)methylamino] thio] -N-isopropyl p-toluenesulfonamide To a stirred solution cooled to --200, of 10.6 g (0.05 mole) of N-isopropyl-ptoluenesulfonamide and 5.05 g (0.05 mole) of triethylamine in 150 ml of methylene chloride, are added, dropwise, 3.4 g. (0.025 mole) of sulfur monochloride. The reaction mixture is stirred at ambient temperature for one hour. A solution of 1.77 g. (0.025 mole) of chlorine in 50 ml. carbon tetrachloride is added rapidly and the reaction mixture stirred for 0.5 hour. The reaction mixture is cooled to 100 and a solution of (0.05 mole) of N-methyl-N'-2,4-dichlorophenyl formamidine and 5.05 g (0.05 mole) of triethylamine in 75 ml. methylene chloride is added. The mixture is stirred at ambient temperature for 30 minutes and extracted with a solution of 10 g.

citric acid in 200 ml. of water. The organic layer is dried and the solvent removed.

The product is recrystallised from methanol to give 11.0 g (49% yield) of the title product as white crystals, mp. 7981 .

Analysis: Calc'd for C,8H2tC12N302S2 C, 48.43; H, 4.74; N, 9.41.

Found: C, 48.63; H, 4.80; N, 9.55.

Example 11 N-[ [ [N-(2-chloro-p-tolyl)-formimidoyl] methylamino]thioi-N- isopropyl-p-toluenesulfonamide Following the procedure of Example 10, but substituting N-methyl-N'-(2 chloro-p-tolyl)formamidine for N-methyl-N'-2,Sdichlorophenylformamidine, and recrystallisation from methanol, 8.0 g (47% yield) of the title product are obtained as white crystals, mp. 101103 .

Analysis: Calc'd for C,9H24ClN302S2 C, 53.57; H, 5.68; N, 9.86.

Found: C, 53.60; H, 5.71; N, 9.94.

The compounds of formula I can be particularly advantageous commercially as arthropodal pesticides. For example, they can be relatively stable both in storage and upon application in the field thus providing long-lasting residual effectiveness.

In addition to killing arthropod pests on contact, the compounds of the invention may be absorbed by the vascular system of many plants, for example by cotton plants, and may act systemically to kill the pests feeding upon the plant.

Thus, their period of pesticidal activity is further extended and non-feeding arthropods, e.g., insects not harmful to the plant, are not unnecessarily killed during the whole period of pesticidal activity.

Compounds of the invention may also be ovicidal, and can be particularly effective in the control of acarine pest populations by this ovicidal action.

The compounds of the Formula I are also advantageous in that they can exhibit relatively low mammalian toxicity and are non-phytotoxic at effective concentrations.

The invention also comprises compositions for arthopod control which comprise an acceptable carrier and an effective amount of a compound of the invention. The compositions are useful in the method of the invention which is a process for controlling invertebrate pests, which comprises applying to a situs, effective amounts of the compounds of the invention.

By the term "situs" is meant plants such as ornamentals, food crops, fruit trees, textile producing plants, berry bushes, and lumber forests; animals, particularly domestic animals; farm yards; animal shelters; buildings; sanitary land tlll areas; ponds and standing water; and like sites which are infected with or are potential infestation sites for invertebrate pests controllable with the compounds of the invention.

The novel compounds of the invention are useful in controlling invertebrate pest populations, e.g., in killing adults, larvae, and ova of invertebrate pests or animals of the Phylum Arthropoda, for example those of Class Insecta such as those of the order Coleoptera as illustrated by the cotton boll weevil (Anthonomus grandis Boheman); those of the order Lepidoptera as illustrated by the southern army worm (Spodoptera eridania Cramer); those of Class Arachnida such as those of the order Acerina as illustrated by the two-spotted spider mite (Tetranvchus telarius Linnaeus or Tetranychus urticae Koch).

In addition to controlling pest populations through their lethal effect, the compounds are also useful in control through their effect as behavioral modifiers.

For example, young lepidopteran larvae, aphids, ticks, and mites are repelled by the chemicals or by treated foliage or animals, resulting in a marked reduction in population density. Adult moths are affected and ovipost less on treated plant parts. In addition to being repelled, mites exhibit spindown and walkdown activity from treated foliage.

The compounds of this invention may be employed in their pure forms to control invertebrate pest populations. However, it is preferred that they be applied to a situs in the form of a composition, comprising the compound and an acceptable diluent or carrier. The concentration of the active compound can range from about 0.001% to about 96% w/w depending on the type of composition, the solubility of the compound, the pest to be controlled, etc. Acceptable carriers or diluents are well known in the art. For example, those compounds which are solids at ambient temperatures may be formulated as Granulars, dusts, wettable powders, emulsifiable concentrates, aqueous dispersions, solutions, and flowable creams for application to insects, mites, ticks, objects, or other situs. Those compounds which are liquids at ambient temperatures may be formulated as emulsifiable concentrates, aqueous dispersions, suspensions, solutions, aerosols, dusts, granulars and the like.

The compounds (I) of the invention may also be admixed with other known pesticides to form compositions of the invention. For example, they may be mixed with malathion, azinphosmethyl, carbaryl, methoxychlor, and like pesticidal compounds.

Illustratively, dust are readily formulated by grinding a mixture of the solid compounds (I) and a pulverulent carrier in the presence of each other. Grinding is conveniently accomplished in a ball mlll, a hammer mill, or by alr-blast micronization. A preferred ultimate particle size is less than 60 microns. Preferably, 95% of the particles are less than 50 microns, and about 75% are 5 to 20 microns.

Dusts of that degree of comminution are conveniently free flowing and can be applied to inanimate matter, fruit trees, crop plants, animals, and soil so as to effect thorough distribution and coverage. Dusts are particularly adapted for effectively controlling invertebrate pests such as insects and mites over wide areas when applied by airplane. They are also indicated for application to the undersides of plant foliage.

Representative pulverulent diluent carriers which are acceptable are the natural clays such as attapulgite, kaolin (e.g., China and Barden), and montmorillonite (e.g., bentonite); minerals in their natural forms as they are obtained from the earth such as talc, pyrophillite, quartz, diatomaceous earth, fuller's earth, chalk, rock phosphates and sulfates, sulfur, silica and silicates; chemically modified minerals such as washed bentonite, precipitated calcium silicate, synthetic magnesium silicate, and colloidal silica; and organic flours such as wood, walnut shell, soybean, cottonseed, and tobacco flours, and free-flowing hydrophobic starches.

Dusts may also be prepared by dissolving a compound (I) in a volatile solvent such as methylene chloride, mixing the solution with a pulverulent diluent carrier and evaporating the solvent.

The proportions of pulverulent carrier and compound (I) may be varied over a wide range depending upon the pests to be controlled and the conditions of treatment. In general, dust formulations contain up to about 50% (on a weight basis) of the compound (I) as the active ingredient. Dusts having as little as 0.001% of the active ingredient may be used, but a generally preferred proportion is from about 1% to about 10% of the compound.

Wettable powder formulations are prepared by incorporating a surfactant in a dust composition prepared as described above. By incorporating from 0.1% to about 12% of a surfactant in a dust, a wettable powder is obtained which is particularly adapted for further admixture with water for spraying on inanimate matter and products, fruit trees, field crops, animals, and soil. Such wettable powders may be admixed with water to obtain any desired concentration of compound (I) and the mixture may be applied in amounts sufficient to obtain predetermined rates of application and uniform distribution. Preferably wettable powders contain from about 10 percent to about 80 percent by weight of compound (I) as the active ingredient.

The surfactants employed may be characterized as capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1% or less.

Representative surfactants conventionally employed for preparing wettable powder formulations include alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfate, polyoxyethylensorbitan monolaurate, alkyl-aryl polyether sulfates, alkylaryl polyether alcohols, alkyl naphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fatty acids and esters, sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids, and the like. The preferred class of surfactants for preparing compositions of this invention are blends of sulfonated oils and polyalcohol carboxylic acid esters such as the commercially available Emcol H-77, blends of polyoxyethylene ethers and oil-soluble sulfonates such as commercially available Emcol H-400, blends of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols such as the commercially available Tritons (registered Trade Mark) X-151, X-161, and X-171, e.g. about equal parts of sodium dodecylbenzenesulfonate and isooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups, and blends of calcium alkyl-aryl sulfonates and polyethoxylated vegetable oils such as commercially available Agrimul N4S. The sulfate and sulfonate surfactants discussed above are preferably used in the form of their soluble salts, for example, their sodium salts.

If desired, dispersants such as methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, and the like may be included in'the wettable powder compositions of this invention. Adhesive or sticking agents such as vegetable oils, naturally occurring gums, casein, and others may also be included. If unlined storage or shipping drums are to be used a corrosion inhibitor may be added. Likewise, antifoaming agents such as stearic acid may be added.

Granular compositions of this invention are convenient for application to soil when persistence is desired. Such compositions are readily applied by broadcast or by localized, e.g., in-the-row applications. The individual granules may be any desired size from 30 to 60 mesh up to 20 to 40 mesh, or even larger. Granulates are prepared by dissolving the active compound in a solvent such as methylene chloride, xylene, or acetone and applying the solution to a quantity of a granulated absorbent carrier. Representative granulated absorbent carriers are ground corn cobs, ground walnut shells, ground peanut hulls, and the like. When desired, the impregnated granulated absorbent carrier may be coated with a coating that will preserve the integrity of the granular until it is applied to an object or situs favourable for release of the active ingredient. Such coatings are well known in the art.

The compounds (I) of the invention may be applied to the pests themselves or to a situs in aqueous sprays without a solid carrier. Such aqueous sprays are advantageous for certain types of spray equipment and conditions of application as is well known in the art. They are also advantageous when uniform dispersions, homogeneous solutions, or other easily mixed aqueous sprays are desired.

Aqueous sprays without a solid carrier are prepared from concentrated solutions of the compounds (I) of the invention in an inert organic solvent carrier.

The inert organic solvent carrier may be one that is miscible or immiscible with water. The compounds (I) that are somewhat soluble in water may be dissolved in a water miscible solvent carrier, e.g., ethanol, and mixed with water to give homogeneous solutions. The compounds (I) that are less soluble in water may be dissolved in a solvent carrier that is immiscible with water and the solution dispersed in water to give a uniform dispersion, e.g., an emulsion.

In an oil-in-water emulsion, the solvent phase is dispersed in the water phase and the dispersed phase contains the compound (I). In this way, uniform distribution of a water insoluble compound (I) is achieved in an aqueous spray. A solvent carrier in which the compounds (I) are highly soluble is desirable so that relatively high concentrations of the compound (I) canbe obtained. One or more solvent carriers with or without a co-solvent may be used in order to obtain concentrated solutions of the compounds (I), the main consideration being to employ a water-immiscible solvent for the compound (I) that will hold the compound in solutions over the range of concentrations useful for applying to invertebrate pests or a situs.

The emulsifiable concentrate compositions of the invention are preferred compositions prepared by dissolving the compound (I) as the active ingredient and a surfactant such as one of those previously described, in a substantially waterimmiscible solvent carrier (i.e., a solvent carrier which is soluble in water to the extent of less than 2.5% by volume at temperatures of the order of 20"C. to 300 C.), for example: summer oils (a paraffinic, intermediate distillation fraction having a viscosity range from 40 to 85 seconds Saybolt and an unsulfonatable residue over 90 percent); ethylene dichloride; aromatic hydrocarbons such as benzene, toluene, and xylene; and high-boiling petroleum hydrocarbons such as kerosene, diesel oil or a high flash ( > 380C.) xylene-range solvent, e.g., Tenneco (registered Trade Mark) 500100. When desired, a co-solvent such as methyl ethyl ketone, acetone, isopropanol, and the like may be i amounts of the compounds (I) for pesticidal activity is obtained when the compounds (I) are applied at concentrations of about 30 to about 6000 ppm, preferably at concentrations of about 100 to about 4000 ppm.

The following Examples illustrate compositions of the invention. All parts and percentages are by weight.

Example 12 A wettable powder formulation is obtained by blending and milling 327 Ibs. of Georgia Clay, 4.5 Ibs. of isooctylphenoxy ethanol (Triton X-100) as a wetting agent, 9 Ibs. of a polymerized sodium salt of substituted benzoid long-chain sulfonic acid (Daxad 27-"Daxad" is a registered Trade Mark) as a dispersing agent, and 113 Ibs. of the compound of Example 1. The resulting formulation has the following percentage composition: N-[ [ [N-(4-chloro-o-tolyl)-formimidoyl]methyl- amino]thio-N-benzylmethanesulfonamide 25% Isooctylphenoxy polyethoxy ethanol 1% Polymerized sodium salt of substituted benzoid long-chain sulfonic acid 2% Georgia Clay 72% This formulation, when dispersed in water at the rate of 10 Ibs. per 100 gals., gives a spray formulation containing about 0.3% (3000 ppm) active ingredient which can be applied to invertebrate pests, plants, or other invertebrate pest habitats or invertebrate pest foods to kill such pests or control them through behavior modification.

The arylformamidine sulfonamide used in the above Example may be replaced by an equal proportion of any of the compounds of the formula (I) as prepared in Examples 2 to 6 and 8 to 11.

Example 13 An emulsifiable concentrate having the following percentage composition: N-[ [ [N-4-chloro-o-tolyl)-formimidoyl]methyl- amino]thio]-N-benzylmethanesulfonamide (Example 1) 15.0% High-flash ( > 38 C.) xylene-range solvent (Tenneco 50Q 100) 80.0% Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) 5.0% is obtained by mixing 15.0 pounds of N-[[[N-(4-chloro-o tolyl)formimidoyl]methylamino]thio]-N-benzylmethanesulfonamide (Example 1), 80 pounds of Tenneco 500--100, and 5.0 pounds of Triton X-151.

6.67 Lbs. of the concentrate mixed with 10 gals. of water gives a spray emulsion containing about 11,000 ppm. of active ingredient which can be applied to invertebrate pests, plants, or other invertebrate pest habitats or invertebrate pest foods to kill such pests or control them through behaviour modification.

The arylformamidine sulfonamide used in the above Example may be replaced by an equal proportion of any of the compounds prepared in Examples 2 to 11.

British Patent No. 1,541,800 claims compounds of formula I wherein R1 is methyl; R2 is methyl, chlorine or bromine; R3 is C18 alkyl or C56cycloalkyl; and R4 is C14 alkyl, phenyl, methylphenyl, chlorophenyl or bromophenyl. We make no claim to such compounds herein, to compositions containing them or methods for their use.

Subject to the foregoing disclaimer, WHAT WE CLAIM IS: 1. A compound of the formula

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

amounts of the compounds (I) for pesticidal activity is obtained when the compounds (I) are applied at concentrations of about 30 to about 6000 ppm, preferably at concentrations of about 100 to about 4000 ppm.

The following Examples illustrate compositions of the invention. All parts and percentages are by weight.

Example 12 A wettable powder formulation is obtained by blending and milling 327 Ibs. of Georgia Clay, 4.5 Ibs. of isooctylphenoxy ethanol (Triton X-100) as a wetting agent, 9 Ibs. of a polymerized sodium salt of substituted benzoid long-chain sulfonic acid (Daxad 27-"Daxad" is a registered Trade Mark) as a dispersing agent, and 113 Ibs. of the compound of Example 1. The resulting formulation has the following percentage composition: N-[ [ [N-(4-chloro-o-tolyl)-formimidoyl]methyl- amino]thio-N-benzylmethanesulfonamide 25% Isooctylphenoxy polyethoxy ethanol 1% Polymerized sodium salt of substituted benzoid long-chain sulfonic acid 2% Georgia Clay 72% This formulation, when dispersed in water at the rate of 10 Ibs. per 100 gals., gives a spray formulation containing about 0.3% (3000 ppm) active ingredient which can be applied to invertebrate pests, plants, or other invertebrate pest habitats or invertebrate pest foods to kill such pests or control them through behavior modification.

The arylformamidine sulfonamide used in the above Example may be replaced by an equal proportion of any of the compounds of the formula (I) as prepared in Examples 2 to 6 and 8 to 11.

Example 13 An emulsifiable concentrate having the following percentage composition: N-[ [ [N-4-chloro-o-tolyl)-formimidoyl]methyl- amino]thio]-N-benzylmethanesulfonamide (Example 1) 15.0% High-flash ( > 38 C.) xylene-range solvent (Tenneco 50Q

100) 80.0% Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) 5.0% is obtained by mixing 15.0 pounds of N-[[[N-(4-chloro-o tolyl)formimidoyl]methylamino]thio]-N-benzylmethanesulfonamide (Example 1), 80 pounds of Tenneco 500--100, and 5.0 pounds of Triton X-151.

6.67 Lbs. of the concentrate mixed with 10 gals. of water gives a spray emulsion containing about 11,000 ppm. of active ingredient which can be applied to invertebrate pests, plants, or other invertebrate pest habitats or invertebrate pest foods to kill such pests or control them through behaviour modification.

The arylformamidine sulfonamide used in the above Example may be replaced by an equal proportion of any of the compounds prepared in Examples 2 to 11.

British Patent No. 1,541,800 claims compounds of formula I wherein R1 is methyl; R2 is methyl, chlorine or bromine; R3 is C18 alkyl or C56cycloalkyl; and R4 is C14 alkyl, phenyl, methylphenyl, chlorophenyl or bromophenyl. We make no claim to such compounds herein, to compositions containing them or methods for their use.

Subject to the foregoing disclaimer, WHAT WE CLAIM IS: 1. A compound of the formula

wherein R1 is chlorine, bromine or C14 alkyl; R2 is hydrogen, chlorine, bromine or C14 alkyl; R3 is C18 alkyl, C58 cycloalkyl, benzyl, phenethyl, I-phenylethyl, phenyl or phenyl substituted by one to 3 substituents independently selected from methyl, chlorine, bromine, nitro, trifluoromethyl, methoxy, ethoxy and cyano; and R4 is C14 alkyl, phenyl, methylphenyl, chlorophenyl, bromophenyl or optionally ring-substituted benzyl, phenethyl, or l-phenylethyl in which there are up to 3 substituents independently selected from methyl, chlorine, bromine, nitro, trifluoromethyl, methoxy ethoxy and cyano.
2. A compound as claimed in claim I wherein R1 is C14 alkyl.
3. A compound as claimed in claim 2 wherein R, is methyl.
4. A compound as claimed in claim 1 wherein R1 is chlorine or bromine.
5. A compound as claimed in any preceding claim wherein R2 is C14 alkyl.
6. A compound as claimed in claim 5 wherein R2 is methyl.
7. A compound as claimed in any of claims 1 to 4 wherein R2 is chlorine or bromine.
8. A compound as claimed in claim 3 or claim 4 wherein R2 is methyl, chlorine or bromine and R3 is C14 alkyl, C58 cycloalkyl, benzyl, phenethyl, I-phenylethyl, phenyl or phenyl substituted by one to 3 substituents independently selected from methyl, chlorine and bromine.
9. N - [[[N - (4 - Chloro - o - tolyl)formimidoyllmethylaminolthiol - N benzylmethanesulfonamide.
10. N - [[[N - (4 - Chloro - o - tolyl)formimidoyllmethylaminolthiol - N phenylmethanesulfonamide.
I 1. N - [[[N - (4 - Chloro - o - tolyl)formimidoyl]methylaminolthio] - N isopropylbenzylsulfonamide.
12. N- [[[N - 2,4 - Xylylformimidoyl]methylaminolthiol - N phenylmethanesulfonamide.
13. N - [[[N - 2,4 - Xylylformimidoyl]methylaminolthiol - N isopropylbenzylsulfonamide.
14. N- [[[N - 2,4 - Xylylformimidoyl]methylamino]thio] - N - p - chlorophenyl - p - toluenesulfonamide.
15. N - [[[N - (4 - Chloro - o - tolyl)formimidoylimethylaminoithio] - N p - chlorophenyl - p - toluenesulfonamide.
16. N - [L[N - (4 - Chloro - o - tolyl)formimidoyl]methylaminolthiol - N benzyl - p - toluenesulfonamide.
17. N - 1[[N - (4 - Chloro - o - tolyl)formimidoyl]methylamino]thiol - N 2,4 - dichlorophenyl - p - toluenesulfonamide.
18. N - [[[N - (4 - Chloro - o - tolyl)formimidoyl]methylamino]thio] - N phenyl - p - toluenesulfonamide.
19. N - [[(N - 2,4 - dichlorophenylformimidoyl)methylamino]thio] - N - isopropyl - p - toluenesulfonamide.
20. N - [[[N - (2 - Chloro - p - tolyl)formimidoyllmethylaminolthio] - N isopropyl - p - toluenesulfonamide.
21. A compound as claimed in claim 1 substantially as described in any of Examples I to 11.
22. A composition for controlling arthropodal pest populations, which comprises from 0.001 to 96% by weight of a compound as claimed in any preceding claim, in association with a suitable excipient.
23. A composition according to claim 22 substantially as described in Example 12 or Example 13.
24. A method for controlling arthropodal pest population at a locus, which comprises applying to the locus a compound as claimed in any of claims 1 to 21 or a composition according to claim 22 or claim 23.