GB2150438A

GB2150438A - Pesticidial compositions

Info

Publication number: GB2150438A
Application number: GB08429928A
Authority: GB
Inventors: Victor Fluck; Alexis Herzog
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1983-12-01
Filing date: 1984-11-27
Publication date: 1985-07-03
Also published as: GB8429928D0; GB2150438B; OA07881A; CH658366A5

Abstract

Novel insecticidal compositions with an excellent immediate action are disclosed, said compositions containing as active component a combination of a) a phenyl carbamate and b) a heterocyclic thiophosphoric acid ester or c) a cyclobutenephosphoric acid ester.

Description

SPECIFICATION Pesticidal compositions The present invention relates to novel insecticidal compositions which contain as active component a combination of a) a phenyl carbamate and b) a heterocylicthiophosphoric acid ester or c) a cyclobutenephosphoric acid ester, to the use of such a combination for controlling harmful insects in crops of useful plants, and to methods of controlling harmful insects with the aid of said combination.

Phenyl carbamates suitable for use in this invention are disclosed in French patent 1 458 172, inter alia, as insecticides and acaricides. Heterocyclic thiophosphoric acid esters suitable for use in this invention are known from French patent 1 063 067, inter alia, as insecticides and acaricides. Cyclobutenephosphoric acid esters suitable for use in this invention are described in French patent 1 545034, inter alia, as insecticides and acaricides. Further, all three cited French patents teach that the compounds described therein can be combined with other pesticides, e.g. insecticides, to broaden the activity spectrum. Although these compounds are extremely effective pesticides, it is sometimes a matter of hours before they are fully effective.

It is the object of this invention to provide an insecticidal composition which exerts an excellent immediate action against sucking insects in particular, i.e. which attains a high degree of activity, for example even within half an hour after application, and at the same time is well tolerated by plants and warm-blooded animals.

Surprisingly, it has now been found that such compositions containing as active component a mixture of a) a phenyl carbamate and b) a heterocyclic thiophosphoric acid ester or c) a cyclobutenephosphoric acid ester or c) a cyclobutenephosphoric acid ester possess the desired properties.

Of the large number of phenyl carbamates disclosed in French patent 1 458712, particularly suitable compounds for this invention are those of the formula

wherein R is a 5-to 7-membered, saturated or unsaturated heterocycle containing two hetero atoms.

particularly advantageous compounds are those of the formula

wherein each of R1 and R2 is hydrogen or methyl and X and Y are sulfur or oxygen. Among these compounds, the compound of the formula

known under the name of Dioxacarb, is most advantageous.

Among the heterocyclic thiophosphoric acid esters known from French patent 1 063 067, particularly suitable compounds for this invention are those of the formula

wherein each of R, P1, P2 and P3 is a C1-C3 alkyl radical and X and Y are sulfur or oxygen. Particularly advantageous compounds are those of the formula

wherein each of R4 and P5 is a C1-C3 alkyl radical. Among these compounds, the compound of the formula

known under the name of Diazinon, is most advantageous.

Among the cyclobutenephosphoric acid esters known from French patent 1 545 034, particularly suitable compounds for this invention are those of the formula

wherein A is a C3-C5 alkenylene radical, R1 is halogen, each of R2 and R3 is a C1 -C4 alkyl radical and X and Y are sulfur or oxygen. Particularly advantageous compounds are those of the formula

wherein R4 is a C1 -C3 alkyl radical. Among these compounds, the compound of the formula

known underthe name of Heptenophos, is most advantageous.

The compositions of this invention contain therefore as active component a combination of a compound of formula I and a compound of formula II or a compound of formula Ill. Particularly advantageous combinations are obtained by mixing a compound of formula la and a compound of formula Ila our a compound of formula Illa. The best results are obtained with a combination of the compound of formula Ib and the compound of formula lib or the compound of formula Illb.

The ratio in which the phenyl carbamate can be mixed with the heterocyclic thiophosphoric acid ester or cyclobutenephosphoric acid ester can vary within wide limits and is usually from 1:15 to 10:1, but preferably from 1:10to2:1.

Compared with the individual components, the combinations of this invention have the advantage of possessing an excellent immediate action and being fully effective within half an hour after application. This property is particularly advantageous, inter alia, because the harmful insects are destroyed in an early stage of development and so are able to cause no more than negligible damage.

Further, by destroying the harmful insects in an early stage of development, the progeny is reduced to a minimum, thus also greatly diminishing the possibility of resistant strains being formed. A further advantage of the early control of harmful insects, in particular sucking insects, by "knock-down" is the prevention of vector transmission, i.e. the control of harmful insects also makes it possible to protect plants, inter alia, from virus infections.

The above-mentioned properties make the combinations of this invention particularly suitable for application in crops of useful plants, in particular in crops of sugar beet, cotton, cocoa and rice.

The principal harmful insects in these crops belong to the following orders: Lepidoptera (e.g. the families Noctuidae and Pyralidae), Homoptera (e.g. the families Alphididae and Cicadellidae) and Heteroptera (e.g.

the families Coreidae and Pyrrhocoridae). The most preferred area of application is the control of sucking insects, in particular of Aphididae and Pyrrhocoridae.

The preparation of the combinations of active ingredients of this invention can be carried out by conventional methods, e.g. by mixing the individual active ingredients and, if appropriate, subsequently formulating and diluting the mixture obtained, or by mixing the formulated active ingredients and, if appropriate, subsequently diluting the mixture obtained. Mixing the active ingredients or active ingredient formulations can be carried out by the manufacturer or a formulation plant and by the end user himself, in which latter case it is preferred to use formulated active ingredients.

The combinations of active ingredients of this invention can be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances.

As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the combination of active ingredients of this invention and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as vegetable oils, epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcium, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acids mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts as well as modified and non-modified phospholipids.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C8-C22 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt or lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acidiformaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acids esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22 alkylradical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide. The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981, Helmut Stache "Tensid Taschenbuch" (Surfactant Handbook) Carl HanserVerlag, MunichiVienna, 1981.

The pesticidal compositions usually contain 0.1 to 99%, in particular 0.1 to 95%, of a combination of active ingredients of this invention, 1 to 99.9 of a solid liquid adjuvant, and 0 to 25%, in particular 0.1 to 25%, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which contain substantially lower concentrations of active ingredients.

The formulations may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

Formulation Examples (percentages are by weight) 1. Emulsifiable concentrates a) b) c) d) a combination of active ingredients 25% 40% 50% 10% calcium dodecylbenzenesulfonate 5% 8% 6% 3% octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) - - 3% castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5% - - 4% tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4% cyclohexanone - 15% 20% 30% xylene mixture 65% 25% 20% 50% Emulsions of any required concentration can be produced from such concentrates by dilution with water.

2. Solutions a) b) c) d) a combination of active ingredients 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - polyethylene glycol MG 400 - 70% N-methyl-2-pyrrolidone - 20% epoxidised coconut oil - - 1% 5% petroleum distillate (boiling range 160-190 ) - - 94% These solutions are suitable for application in the form of micro-drops.

3. Granulates a) b) a combination of active ingredients 5% 10% kaolin 94% highly dispersed silicic acid 1% attapulgite - 90% The combination of active ingredients is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

4. Dusts a) b) c) a combination of active ingredients 2% 5% 8% highly dispersed silicic acid 1% 5% talcum 97% kaolin - 90% 92% Ready-for-use dusts are obtained by intimately mixing the carriers with the combination of active ingredients.

5. Wettablepowders a) b) c) a combination of active ingredients 25% 50% 75% sodium lignosulfonate 5% 5% sodium lauryl sulfate 3% - 5% sodiumdiisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% The combination of active ingredients is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

6. Suspension concentrate a combination of active ingredients 40% ethylene glycol 10% nonylphenol polyethylene glycol (15 moles of ethylene oxide) 6% sodium lignosulfonate 10% carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32% The combination of active ingredients is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Example: Contact action against Dysdercus fasciatus N-3 0.3% acetonicsolutions of the active ingredients and mixtures thereof are prepared. 1 ml (3 mg of active ingredient) of each solution is pipetted into an aluminium dish and the acetone is evaporated off over 15 at room temperature. 10 nymphs of Dysdercus fasciatus in the third shedding stage (N-3) are then placed in each dish. Evaluation is made 30,60 and 120 minutes after placing the test insects in the dishes by making a mortality count. The results are shown in percentages in the following tables.

Active ingredients:

TABLE 1: Active Conc. Mixture Action in % after ingredient mg/dish ratio 30' 60' 120' A 3 0 66 100 B 3 20 67 100 A + B 3 1:1 100 100 100 1:2 95 100 100 2:1 95 100 100 1:10 100 100 100 10:1 20 80 100 TABLE 2: Active Conc. Mixture Action in % after ingredient mgidish ratio 30' 60' 120' A 3 0 66 100 C 3 20 100 100 A + C 3 1:1 100 100 100 1:2 100 100 100 2:1 100 100 100 1:10 100 100 100 10:1 20 100 100

Claims

1. An insecticidal composition which contains as active component a combination of a) a phenyl carbamate and b) a heterocyclic thiophosphoric acid ester or c) a cyclobutene-phosphoric acid ester, together with suitable carriers and/or other adjuvants.

2. An insecticidal composition according to claim 1, wherein the active component comprises a combination of a) a phenyl carbamate of the formula

wherein R is a 5-to 7-membered, saturated or unsaturated heterocycle containing two hetero atoms, and b) a heterocyclic thiophosphoric acid ester of the formula

wherein each of R, R1, R2 and P3 is a C1 -C4 alkyl radical and X and Y are sulfur or oxygen, or c) a cyclobutenephosphoric acid ester of the formula

wherein A is a C3-Cs alkenylene radical, R1 is halogen, each of R2 and P3 is a C1 -C4 alkyl radical and X and Y are sulfur or oxygen.

3. An insecticidal composition according to either claim 1 or claim 2, wherein the active component comprises a combination of a) a phenyl carbamate of the formula

wherein each of R1 and R2 is hydrogen or methyl and X and Y are sulfur or oxygen, and b) a heterocyclic thiophosphoric acid ester of the formula

wherein each of R4 and P5 is a C1-C3 alkyl radical, or c) a cyclobutenephosphoric acid ester of the formula

wherein R4 is a C1C3 alkyl radical.

4. An insecticidal composition according to any one of claims 1 to 3, wherein the active component comprises a combination of a) the phenyl carbamate of the formula

and b) the heterocyclic thiophosphoric acid ester of the formula

or c) the cyclobutenephosphoric acid ester of the formula

5. An insecticidal composition according to any one of claims 1 to 4, wherein in the combination of active ingredientstheratioofa:bora:cisfrom 1:15to 10:1.

6. An insecticidal composition according to claim 5, wherein the ratio of a:b or a:c is from 1:10 to 2:1.

7. Use of a combination of a) a phenyl carbamate and b) a heterocyclicthiophosphoric acid ester or c) a cyclobutenephosphoric acid ester for controlling harmful insects in crops of useful plants.

8. Use according to claim 7 of a combination of a) a phenyl carbamate of the formula

wherein each of R, R1, R2 and P3 is a Ca-C4 alkyl radical and X and Y are sulfur or oxygen, or c) a cyclobutenephosphoric acid ester of the formula

wherein A is a C3-C5 alkenylene radical, R1 is halogen, each of R2 and P3 its a C1-C4 alkyl radical and X and Y are sulfur or oxygen.

9. Use according to either claim 7 or claim 8 of a combination of a) a phenyl carbamate of the formula

wherein R4 is a C1-C3 alkyl radical.

10. Use according to any one of claims 7 to 9 of a combination of a) the phenyl carbamate of the formula

and b) the heterocyclic thiophosphoric acid ester of the formula

or c) the cyclobutenephosphoric acid ester of the formula

11. Use according to any one of claims 7 to 10 for controlling Lepidoptera, Homoptera and Heteroptera.

12. Use according to claim 11 for controlling representatives of the families Aphididae and Cicadellidae.

13. Use according to any one of claims 7 to 12 for controlling harmful insects in crops of cotton, cocoa, rice orsugarbeet.

14. A method of controlling harmful insects in crops of useful plants, which method comprises treating the habitat of said insects with a pesticidally effective amount of a combination of a) a phenyl carbamate and b) a heterocyclic thiophosphoric acid ester or c) a cyclobutenephosphoric acid ester.

15. A method according to claim 14, which comprises treating the habitat of the insects with a pesticidally effective amount of a combination of a) a phenyl carbamate of the formula

wherein each of R, R1, R2 and P3 is a C1-C4 alkyl radical and X and Y are sulfur or oxygen, or c) a cyclobutenephosphoric acid ester of the formula

wherein A is a C3-C5 alkenylene radical, R1 is halogen, each of R2 and P3 is a C1 -C4 alkyl radical and X and Y are sulfur or oxygen.

16. A method according to either claim 14 or claim 15, which comprises treating the habitat of the insects with a pesticidally effective amount of a combination of a) a phenyl carbamate of the formula

wherein each of P1 and R2 is hydrogen or methyl and X and Y are sulfur or oxygen, and b) a heterocyclic thiophosphoric acid ester of the formula

wherein R4 is a C1 -C3 alkyl radical.

17. A method according to any one of claims 14 to 16, which comprises treating the habitat of the insects with a pesticidally effective amount of a combination of a) the phenyl carbamate of the formula

and b) the heterocyclic thiophosphoric acid ester of the formula

or c) the cyclobutenephosphoric acid ester of the formula

18. An insecticidal composition according to claim 1 substantially as hereinbefore described with reference to any one of the Formulation Examples.