GB1592229A

GB1592229A - Pesticidal formulations

Info

Publication number: GB1592229A
Application number: GB2426578A
Authority: GB
Original assignee: Wellcome Foundation Ltd
Current assignee: Wellcome Foundation Ltd
Priority date: 1978-05-30
Filing date: 1978-05-30
Publication date: 1981-07-01
Also published as: MY8500282A

Description

(54) PESTICIDAL FORMULATIONS (71) We, THE WELLCOME FOUNDATION LIMITED, of 183-193 -Euston Road, London, N.W.I, a company incorporated in England do hereby declare that the invention for which we pray that a Patent may be granted to us and the method by which it is performed, to be particularly described in and by the following statement:- This invention relates to novel potentiating compositions, their preparation formulations containing them, the preparation of such formulations and to their use for the control of arthropod pests.

Arthropod pests are troublesome to man, animal and plants. They are vectors of disease, and ecomomic losses result from their depredations on plants and animals. Control of such pests over the years has come to depend strongly upon the use of chemical pesticides, and prominent amongst those which have been extensively investigated are pyrethroids-esters of -cyclopropane carboxylic acid derivatives.

Amongst pyrethroids known to be active against a variety of arthropod pests are the compounds of formula (I). These are disclosed in British Patent Specifications Nos. 1413491 and 1448228 and include a number of compounds having considerable potency as insecticides.

It has now been found that the activity against arthropod pests of one compound of formula (I) can be potentiated by another compound of formula (I).

For example, the ixodicidal activities of the compounds 3 - phenoxybenzyl (+) cis, trans - 2,2 - dimethyl - 3 - (2,2 - dichlorovinyl) cyclopropane - 1 - carboxylate (permethrin) and (-) - a - cyano .3 - phenoxybenzyl (+) - cis - 2,2 dimethyl .3 - (2,2 - dibromovinyl) cyclopropane - I - carboxylate (decamethrin) are potentiated by mixtures of these compounds when tested against the cattle tick Boophilus microplus.

In the compounds of formula (I):

R2 represents halo and R3 represents alkyl or halo; R represents a group of the formula:

wherein Z represents 0, S, CH2 or CO, Y represents hydrogen, alkyl, alkenyl or alkynyl, or aryl or furyl which is unsubstituted or substituted in the ring by one or more alkyl, alkenyl, alkoxy or halo radicals, R7 and RB, which may be the same or different, each represent hydrogen, alkyl or alkenyl, R9 represents hydrogen or methyl, R10 and R", which may be the same or different, each represent hydrogen or alkyl, R12 represents an organic radical having carbon-carbon unsaturation in a position a to the CH2 group to which R12 is attached, indicates an aromatic ring or a dihydro or tetrahydro analogue thereof, X', X2, X3 and X4, which may be the same or different, each represent hydrogen, chloro or methyl, Z3 represents -CM2- or -0- or -S- or -CO-, D represents hydrogen, cyano or --CECH, Z' and Z2, which may be the same or different, each represent chloro or methyl, and each n, which may be the same or different, is 0, 1 or 2.

Formula (I) is intended to encompass all the possible geometric and optical isomers. More particularly the acid moiety of the ester may be selected from the (+) - cis - isomer, the (+) trans - isomer, the (I) - cis - isomer, the (j) - trans isomer and the (+) - cis, trans - isomer (the stereochemistry referring to that of the cyclopropane ring), and especially form the dihalo acids such as the dichloro and dibromo acids (in formula (I) R2, R3=CI or Br). The alcohol moiety may especially be chosen from 3 - phenoxybenzyl alcohol and a - cyano - 3 - phenoxybenzyl alcohol. Preferred esters of formula (I) which may be used together include permethrin; decamethrin; (+) - a - cyano - 3 - phenoxybenzyl - (+) - cis, trans 2,2 - dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropane - 1 carboxylate(cypermethrin); and (±) - a - cyano - 3 - phenoxybenzyl - (+) - cis 2,2 - dimethyl - 3 - (2,2 - dibromovinyl)cyclopropane - 1 - carboxylate.

Two or more compounds of formula (I) may therefore be used together to control arthropod pests and especially insects and acarines. Insects and acarines requiring control for agricultural, public health domestic, veterinary and medical purposes include adult and juvenille stages of flies, mites, ticks, cockroaches, mosquitoes, tetse fly, moths including warehouse and clothes moths, fleas, lice and timber and grain infesting insects and dther ectoparasites of mammals and birds.

The compounds may be used to combat arthropod infestations either as a mixture of the raw chemicals (hereafter called the 'compositions') or as a formulation with an inert carrier or diluent. The formulations may be prepared by customary methods as dusts or granular solids, wettable powders, baits, solutions, laquers, creams, pastes, gels, foams, greases, shampoos, ointments, emulsifiable concentrates, sprays, aerosols and other liquid preparations after the addition of appropriate solvents, synergists, diluents and surface active agents. The formulations may contain up to 99 /" by weight of a mixture of compounds of formula (I) and may be diluted prior to use.

Such formulations may be applied directly to arthropod pests or to their environment by dusting, spraying, pouring, fogging, vaporisation, painting, dipping' and other methods customarily used in arthropod control. The amount and concentration of a mixture of compounds of formula (I) which should be applied will vary with the nature of the compounds and formulation, the pests to be controlled, and the habitat and method of application but in general the total concentration should be in the range of 0.0001 to l.0V w/v. In a composition, the compounds of formula (I) should be present in potentiating amounts from 50/1 to 1/50, especially 10/1 to 1/10, parts by weight of the respective compounds.

The following Examples are provided by way of an illustration of the present invention and should not be construed as in any way constituting a limitation thereof.

EXAMPLE 1 Engorged female ticks of the Biarra strain of Boophilus microplus are immersed, in groups of 20 ticks per concentration, in a range of dilutions of (-) a - cyano - 3 - phenoxybenzyl - (+)- cis - 2,2 - dimethyl - 3 - (2,2 dibromovinyl)cyclopropane - 1 - carboxylate (hereafter referred to as decamethrin) in combination with 3 - phenoxybenzyl(+)- cis, trans - 2,2 dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropane - 1 - carboxylate (hereinafter referred to as permethrin) at a ratio of 1/1 w/w of decamethrin and permethrin.

The composite wash is prepared by mixing the two constituents at a ratio of 1:1 and then diluting the mixture with water to give the desired range of concentration for the test. The constituents were in the form of miscible oil concentrates.

The ticks are removed from the wash after 10 minutes, dried, and stuck dorsal side down on double-sided adhesive tape. They remain in this position for 14 days when the numbers laying viable eggs are determined. From this data a regression line is plotted (concentration against V0 inhibition of egg-production) and the IR99 values determined (Table I).

IR99=concentration at which 99Vo inhibition of egg-production occurs.

The values so obtained for the composite wash are compared with similar values obtained for the constituents of the composite wash when alone. By reference to the equation for the harmonic mean, the factor of potentiation is determined (Table I).

The equation for the harmonic mean is: Proportion of A + Proportion of B X=.

Proportion of A Proportion of B ~ + IR99A IR99B X IR99 mixture of A and B YxPronortinn of A Factor of Potentiation (FOP)= Proportion of A+Proportion of B TABLE I B. microplus Biarra Strain Factor of Chemical IR99 ( /n) Potentiation Permethrin 0.13 Decamethrin 0.0039 Permethrin/Decamethrin (1:1) 0.00032 11.9 Example 2 Wettable Powders Parts by Weight (a) (b) Permethrin 2.5 15.0 Decamethrin 2.5 15.0 Fine silica 5.0 20.0 Kaolin 84.5 44.5 Sodium alkyl naphthalene sulphonate 0.5 0.5 Sodium salt of condensed naphthalene sulphonic acid 5.0 5.0 100.0 100.0 Example 3 Miscible Oils Parts by Weight Permethrin 2.5 12.5 Decamethrin 2.5 12.5 Solvent 200 82.5 57.5 Cyclohexanone - 5.0 Ethylan KEO 8.5 7.5 Tergitol XD 0.7 1.5 Arylan CA 3.3 3.5 100.0 100.0 'Solvent 200' is a liquid comprising 95V aromatic hydrocarbons. 'Ethylan KEO' (Registered Trade Mark) is an emulsifying agent of a nonyl phenol ethoxylate condensate with ethylene oxide having arl average chain length of 9.5 mols. 'Tergitol XD' (Registered Trade Mark) is a non-ionic liquid emulsifier of a polyalkylene glycol ether. 'Arylan CA' is an emulsifier of calcium dodecyl benzene sulphonate.

Example 4 Dusts Parts by Weight Permethrin 0.01 1.0 Decamethrin 0.01 1.0 Talc 99.98 98.0 100.00 100.0 WHAT WE CLAIM IS: 1. A method of controlling arthropod ectoparasites of birds or mammals (other than man) comprising the simultaneous application to the animal or the ectoparasite of two or more esters of formula (I) as hereinbefore defined.

2. A method as claimed in claim 1 wherein two esters of formula (I) are applied.

3. A method as claimed in claim 1 or 2 wherein the esters are applied as a mixture.

4. A method as claimed in claims 2 or 3 wherein the esters are applied in the ratio of 1 to 50 to 50 to 1 parts by weight.

5. A method as claimed in claims 2 or 3 wherein the esters are applied in the ratio of 1 to 10 to 10 to 1 parts by weight.

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

Claims

**WARNING** start of CLMS field may overlap end of DESC **. TABLE I B. microplus Biarra Strain Factor of Chemical IR99 ( /n) Potentiation Permethrin 0.13 Decamethrin 0.0039 Permethrin/Decamethrin (1:1) 0.00032 11.9 Example 2 Wettable Powders Parts by Weight (a) (b) Permethrin 2.5 15.0 Decamethrin 2.5 15.0 Fine silica 5.0 20.0 Kaolin 84.5 44.5 Sodium alkyl naphthalene sulphonate 0.5 0.5 Sodium salt of condensed naphthalene sulphonic acid 5.0 5.0 100.0 100.0 Example 3 Miscible Oils Parts by Weight Permethrin 2.5 12.5 Decamethrin 2.5 12.5 Solvent 200 82.5 57.5 Cyclohexanone - 5.0 Ethylan KEO 8.5 7.5 Tergitol XD 0.7 1.5 Arylan CA 3.3 3.5 100.0 100.0 'Solvent 200' is a liquid comprising 95V aromatic hydrocarbons. 'Ethylan KEO' (Registered Trade Mark) is an emulsifying agent of a nonyl phenol ethoxylate condensate with ethylene oxide having arl average chain length of 9.5 mols. 'Tergitol XD' (Registered Trade Mark) is a non-ionic liquid emulsifier of a polyalkylene glycol ether. 'Arylan CA' is an emulsifier of calcium dodecyl benzene sulphonate. Example 4 Dusts Parts by Weight Permethrin 0.01 1.0 Decamethrin 0.01 1.0 Talc 99.98 98.0 100.00 100.0 WHAT WE CLAIM IS:

1. A method of controlling arthropod ectoparasites of birds or mammals (other than man) comprising the simultaneous application to the animal or the ectoparasite of two or more esters of formula (I) as hereinbefore defined.

6. A method as claimed in any foregoing claims wherein in the esters of

formula (I), R2 and R3 are both halo.

7. A method as claimed in claim 6 wherein R2 and R3 are the same and each is selected from chloro and bromo.

8. A method as claimed in any foregoing claim wherein R is selected from 3phenoxybenzyl and a - cyano - 3 - phenoxybenzyl.

9. A method as claimed in any foregoing claim where the esters are selected from: 3 - phenoxybenzyl (+) - cis, trans - 2,2 - dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropane - 1 - carboxylate; (-) - a - cyano - 3 - phenoxybenzyl-(+) - cis - 2,2 - dimethyl - 3 - (2,2 - dibromovinyl)cyclopropane - - carboxylate, (±) - a - cyano - 3 - phenoxybenzyl - (j) - cis, trans - 2,2 - dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropane - 1 - carboxylate; and (+) - a cyano - 3 - phenoxybenzyl - -(+) - cis - 2,2 - dimethyl - 3 - (2,2 dibromovinyl)cyclopropane - 1 - carboxylate.

10. A method as claimed in any of claims I to 9 wherein permethrin and decamethrin are applied.

11. A method as claimed in claim 10 wherein the esters are applied in the ratio of 1 part each by weight.

12. A method as claimed in any foregoing claim wherein the ectoparasites are acarine ectoparasites.

13. A method as claimed in claim 12 wherein the acarine ectoparasites are ticks.

14. A method as claimed in any foregoing claim wherein the esters are applied as a formulation including an inert carrier or diluent.

15. A method as claimed in claim 14 wherein the formulation applied is an aqueous suspension of a wettable powder or an aqueous emulsion of an emulsifiable concentrate.

16. A method as claimed in any foregoing claim wherein the esters are applied by dipping or spraying.

17. A method as claimed in any foregoing claim wherein the esters are applied at a concentration of 0.0001 to 1%.

18. A method for the control of ectoparasites of animals (other than man) substantially as hereinbefore described.