Patent Description:
<CIT>, <CIT> and <CIT> disclose that certain spiroheterocyclic pyrrolidine diones have insecticidal activity.

The present invention provides a pesticidal mixture comprising as active ingredient a mixture of component (A) and component (B), wherein component (A) is a compound of formula (I)
<CHM>.

wherein the weight ratio of component (A) to component (B) ranges from <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>.

Depending on the nature of the substituents, compounds of formula (I) may exist in different isomeric forms. When G is hydrogen, for example, compounds of formula (I) may exist in different tautomeric forms:
<CHM>
<CHM>.

This invention covers all isomers and tautomers and mixtures thereof in all proportions. Also, when substituents contain double bonds, cis- and trans-isomers can exist. These isomers, too, are within the scope of the claimed compounds of the formula (I).

The invention relates also to the agriculturally acceptable salts which the compounds of formula (I) are able to form with transition metal, alkali metal and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonium bases.

Among the transition metal, alkali metal and alkaline earth metal salt formers, special mention should be made of the hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium, and preferably the hydroxides, bicarbonates and carbonates of sodium and potassium.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C<NUM>-C<NUM>alkylamines, C<NUM>-C<NUM>hydroxyalkylamines and C<NUM>-C<NUM>alkoxyalkyl-amines, for example methylamine, ethylamine, n-propylamine, i-propylamine, the four butylamine isomers, n-amylamine, i-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-n-amylamine, di-i-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, i-propanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-but-<NUM>-enylamine, n-pent-<NUM>-enylamine, <NUM>,<NUM>-dimethylbut-<NUM>-enylamine, dibut-<NUM>-enylamine, n-hex-<NUM>-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-i-opropylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, i-propylamine and di-i-propylamine.

Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(Ra Rb Rc Rd)]OH, wherein Ra, Rb, Rc and Rd are each independently of the others hydrogen or C<NUM>-C<NUM>alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

Preferred tertiary sulfonium bases suitable for salt formation correspond, for example, to the formula [SReRfRg]OH, wherein Re, Rf and Rg are each independently of the others C<NUM>-C<NUM> alkyl. Trimethylsulfonium hydroxide is especially preferred. Suitable sulfonium bases may be obtained from the reaction of thioethers, in particular dialkylsulfides, with alkylhalides, followed by conversion to a suitable base, for example a hydroxide, by anion exchange reactions.

The compounds of the invention may be made by a variety of methods as described in detail, for example, in <CIT>, <CIT> and <CIT>.

In a preferred compound of the formula (I), Q is (i), m is <NUM>, n is <NUM>, X is methyl, Y is in the ortho position and is methyl, Z is in the para position and is methyl, G is -(C=O)OCH<NUM>CH<NUM>, A is methyl, R is methyl.

In another preferred compound of the formula (I), Q is (i), m is <NUM>, n is <NUM>, X is methyl, Y is in the ortho position and is methyl, Z is in the para position and is chloro, G is - (C=O)OCH<NUM>CH<NUM>, A is methyl, R is methyl.

In another preferred compound of the formula (I), Q is (i), m is <NUM>, n is <NUM>, X is methyl, Y is in the ortho position and is methyl, Z is in the para position and is chloro, G is - (C=O)OCH<NUM>CH<NUM>, A is hydrogen, R is methyl.

The compounds of formula (I) according to the following Tables below can be prepared according to the methods disclosed in the art mentioned above.

Table <NUM>: This table discloses the <NUM> compounds T1. <NUM> to T1. <NUM> of the subformula (Ia) not according to the invention with the exception of T1. <NUM> and T1. <NUM> which are in accordance with the invention:
<CHM>
wherein R is CH<NUM>, A is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined below:.

Table <NUM>: This table discloses the <NUM> compounds T2. <NUM> to T2. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T3. <NUM> to T3. <NUM> of the formula (la), wherein R is CH<NUM>, A is n-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T4. <NUM> to T4. <NUM> of the formula (la), wherein R is CH<NUM>, A is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T5. <NUM> to T5. <NUM> of the formula (la), wherein R is CH<NUM>, A is n-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T6. <NUM> to T6. <NUM> of the formula (la), wherein R is CH<NUM>, A is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T7. <NUM> to T7. <NUM> of the formula (la), wherein R is CH<NUM>, A is t-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T8. <NUM> to T8. <NUM> of the formula (la), wherein R is CH<NUM>, A is <NUM>,<NUM>-(CH<NUM>)<NUM>-propyl, G -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T9. <NUM> to T9. <NUM> of the formula (la), wherein R is CH<NUM>, A is allyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T10. <NUM> to T10. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>-CH=C(CH<NUM>)<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T11. <NUM> to T11. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>-CH=C(Cl)<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T12. <NUM> to T12. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T13. <NUM> to T13. <NUM> of the formula (Ia), wherein R is CH<NUM>, A is CH<NUM>OCH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T14. <NUM> to T14. <NUM> of the formula (Ia), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T15. <NUM> to T15. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>OCH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T16. <NUM> to T16. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>OCH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T17. <NUM> to T17. <NUM> of the formula (la), wherein R is CH<NUM>, A is tetrahydrofuran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T18. <NUM> to T18. <NUM> of the formula (la), wherein R is CH<NUM>, A is tetrahydrofuran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T19. <NUM> to T19. <NUM> of the formula (la), wherein R is CH<NUM>, A is tetrahydropyran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T20. <NUM> to T20. <NUM> of the formula (la), wherein R is CH<NUM>, A is tetrahydropyran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T21. <NUM> to T21. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>F, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T22. <NUM> to T22. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>CHF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T23. <NUM> to T23. <NUM> of the formula (la), wherein R is CH<NUM>, A is CH<NUM>CF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T24. <NUM> to T24. <NUM> of the formula (la), wherein R is hydrogen, A is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T25. <NUM> to T25. <NUM> of the formula (Ia), wherein R is hydrogen, A is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T26. <NUM> to T26. <NUM> of the formula (Ia), wherein R is hydrogen, A is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T27. <NUM> to T27. <NUM> of the formula (la), wherein R is hydrogen, A is CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T28. <NUM> to T28. <NUM> of the formula (la), wherein R is hydrogen, A is CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T29. <NUM> to T29. <NUM> of the formula (la), wherein R is hydrogen, A is CH<NUM>OCH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T30. <NUM> to T30. <NUM> of the formula (la), wherein R is hydrogen, A is CH<NUM>CH<NUM>OCH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T31. <NUM> to T31. <NUM> of the formula (la), wherein R is hydrogen, A is CH<NUM>CHF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T32. <NUM> to T32. <NUM> of the formula (Ia), wherein R is hydrogen, A is CH<NUM>CF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T33. <NUM> to T33. <NUM> of the formula (la), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T34. <NUM> to T34. <NUM> of the formula (Ia), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T35. <NUM> to T35. <NUM> of the formula (Ia), wherein R is CH<NUM>CH<NUM>, A is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T36. <NUM> to T36. <NUM> of the formula (Ia), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T37. <NUM> to T37. <NUM> of the formula (la), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T38. <NUM> to T38. <NUM> of the formula (la), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>OCH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T39. <NUM> to T39. <NUM> of the formula (la), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CH<NUM>OCH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T40. <NUM> to T40. <NUM> of the formula (Ia), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CHF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T41. <NUM> to T41. <NUM> of the formula (la), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T42. <NUM> to T42. <NUM> of the formula (la), wherein R is CH<NUM>, A is methoxypropyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T43. <NUM> to T43. <NUM> of the formula (Ia), wherein R is H, A is methoxypropyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

Table <NUM>: This table discloses the <NUM> compounds T44. <NUM> to T44. <NUM> of the formula (la), wherein R is CH<NUM>CH<NUM>, A is methoxypropyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table <NUM>.

The compounds of Tables <NUM> to <NUM> are not in accordance with the invention.

Table 1ii: This table discloses the <NUM> compounds T1ii. <NUM> to T1ii. <NUM> of the subformula (Ib):
<CHM>
wherein R is CH<NUM>, A is hydrogen, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined below:.

Table 2ii: This table discloses the <NUM> compounds T2ii. <NUM> to T2ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 3ii: This table discloses the <NUM> compounds T3ii. <NUM> to T3ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 4ii: This table discloses the <NUM> compounds T4ii. <NUM> to T4ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is n-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 5ii: This table discloses the <NUM> compounds T5ii. <NUM> to T5ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 6ii: This table discloses the <NUM> compounds T6ii. <NUM> to T6ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is n-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 7ii: This table discloses the <NUM> compounds T7ii. <NUM> to T7ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 8ii: This table discloses the <NUM> compounds T8ii. <NUM> to T8ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is t-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 9ii: This table discloses the <NUM> compounds T9ii. <NUM> to T9ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is <NUM>,<NUM>-(CH<NUM>)<NUM>-propyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 10ii: This table discloses the <NUM> compounds T10ii. <NUM> to T10ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is allyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table <NUM> ii: This table discloses the <NUM> compounds T11ii. <NUM> to T11ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>-CH=C(CH<NUM>)<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 12ii: This table discloses the <NUM> compounds T12ii. <NUM> to T12ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>-CH=C(Cl)<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 13ii: This table discloses the <NUM> compounds T13ii. <NUM> to T13ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 14ii: This table discloses the <NUM> compounds T14ii. <NUM> to T14ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>OCH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 15ii: This table discloses the <NUM> compounds T15ii. <NUM> to T15ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 16ii: This table discloses the <NUM> compounds T16ii. <NUM> to T16ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>OCH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 17ii: This table discloses the <NUM> compounds T17ii. <NUM> to T17ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is tetrahydrofuran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 18ii: This table discloses the <NUM> compounds T18ii. <NUM> to T18ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is tetrahydrofuran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 19ii: This table discloses the <NUM> compounds T19ii. <NUM> to T19ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is tetrahydropyran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 20ii: This table discloses the <NUM> compounds T20ii. <NUM> to T20ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is tetrahydropyran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table <NUM> ii: This table discloses the <NUM> compounds T21ii. <NUM> to T21ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>CHF<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 22ii: This table discloses the <NUM> compounds T22ii. <NUM> to T22ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is hydrogen, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 23ii: This table discloses the <NUM> compounds T23ii. <NUM> to T23ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 24ii: This table discloses the <NUM> compounds T24ii. <NUM> to T24ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 25ii: This table discloses the <NUM> compounds T25ii. <NUM> to T25ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 26ii: This table discloses the <NUM> compounds T26ii. <NUM> to T26ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is hydrogen, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 27ii: This table discloses the <NUM> compounds T27ii. <NUM> to T27ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 28ii: This table discloses the <NUM> compounds T28ii. <NUM> to T28ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 29ii: This table discloses the <NUM> compounds T29ii. <NUM> to T29ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 30ii: This table discloses the <NUM> compounds T30ii. <NUM> to T30ii. <NUM> of the formula (Ib), wherein R is CH<NUM>, A is CH<NUM>CH<NUM>CH<NUM>OCH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 31ii: This table discloses the <NUM> compounds T31ii. <NUM> to T31ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 32ii: This table discloses the <NUM> compounds T32ii. <NUM> to T32ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is allyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 33ii: This table discloses the <NUM> compounds T33ii. <NUM> to T33ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is tetrahydrofuran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 34ii: This table discloses the <NUM> compounds T34ii. <NUM> to T34ii. <NUM> of the formula (Ib), wherein R is hydrogen, A is tetrahydropyran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 35ii: This table discloses the <NUM> compounds T35ii. <NUM> to T35ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 36ii: This table discloses the <NUM> compounds T36ii. <NUM> to T36ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is allyl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 37ii: This table discloses the <NUM> compounds T37ii. <NUM> to T37ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is tetrahydrofuran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

Table 38ii: This table discloses the <NUM> compounds T38ii. <NUM> to T38ii. <NUM> of the formula (Ib), wherein R is CH<NUM>CH<NUM>, A is tetrahydropyran-<NUM>-yl, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1ii.

The compounds of Tables 1ii to 38ii are not in accordance with the invention.

Table <NUM> iii: This table discloses the <NUM> compounds T1iii. <NUM> to T1iii. <NUM> of the subformula (Ic) not according to the invention, with the exception of T1iii. <NUM> which is in accordance with the invention:
<CHM>
wherein R is CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined below:.

Table 2iii: This table discloses the <NUM> compounds T2iii. <NUM> to T2iii. <NUM> of the formula (Ic), wherein R is CH<NUM>CH<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1iii.

Table 3iii: This table discloses the <NUM> compounds T3iii. <NUM> to T3iii. <NUM> of the formula (Ic), wherein R is n-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1iii.

Table 4iii: This table discloses the <NUM> compounds T4iii. <NUM> to T4iii. <NUM> of the formula (Ic), wherein R is i-C<NUM>H<NUM>, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1iii.

Table 5iii: This table discloses the <NUM> compounds T5iii. <NUM> to T5iii. <NUM> of the formula (Ic), wherein R is hydrogen, G is -(C=O)OCH<NUM>CH<NUM> and Ra, Rb, Rc and Rd are as defined in Table 1iii.

The compounds of Tables 2iii to 38iii are not in accordance with the invention.

The compounds of formula (I), including formula (Ia), (Ib) and (Ic), and their manufacturing processes, formulations and adjuvants are known from <CIT>, <CIT> and <CIT>.

The present invention includes all isomers of compounds of formula (I), salts and N-oxides thereof, including enantiomers, diastereomers and tautomers. Component A may be a mixture of any type of isomer of a compound of formula (I), or may be substantially a single type of isomer.

Many sucking pests are known to be vectors of plant diseases caused by microorganisms like bacteria, viruses or phytoplasms. The combination of the compound according to formula (I) for component A and at least one of these compounds for component B has the added advantage of a knock-down effect on various pests that may act as disease vectors, such as for example whiteflies, scales, psyllids, aphids/plant lices and mites. With "knock-down effect", it is meant that the pest to be controlled is rapidly stopped from feeding, quickly totally immobilized or even speedily killed (e.g. at least <NUM>% mortality after <NUM> hours or <NUM>% mortality after <NUM> hours), thereby also reducing the risk of infection of the plant exposed to the specified diseases (e.g. viruses) spread by such pests. Preferably, the active ingredient is a mixture of component A as described above and component B selected from at least one, preferably only one of, thiamethoxam, lambda cyhalothrin, gamma cyhalothrin, and sulfoxaflor.

Reference to the above components B includes reference to their salts and any usual derivatives, such as ester derivatives and isomers.

It has now been found, surprisingly, that the active ingredient mixture according to the invention not only delivers about the additive enhancement of the spectrum of action with respect to the pest to be controlled but achieves a synergistic effect which can extend the range of action of the component A and of the component B in two ways. Firstly, the rates of application of the component A and of the component B are lowered whilst the action remains equally good. Secondly, the active ingredient mixture still achieves a high degree of pest control, sometimes even where the two individual components have become totally ineffective in such a low application rate range. This allows increased safety in use.

However, besides the actual synergistic action with respect to pest control, the pesticidal compositions according to the invention can have further surprising advantageous properties which can also be described, in a wider sense, as synergistic activity. Examples of such advantageous properties that may be mentioned are: a broadening of the spectrum of pest control to other pests, for example to resistant strains; a reduction in the rate of application of the active ingredients; adequate pest control with the aid of the compositions according to the invention, even at a rate of application at which the individual compounds are totally ineffective; advantageous behaviour during formulation and/or upon application, for example upon grinding, sieving, emulsifying, dissolving or dispensing; increased storage stability; improved stability to light; more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination; or any other advantages familiar to a person skilled in the art.

The combinations according to the invention may also comprise more than one of the active components B, if, for example, a broadening of the spectrum of pest control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components B with any of the compounds of formula (I), or with any preferred member of the group of compounds of formula (I). The mixtures of the invention may also comprise other active ingredients in addition to components A and B.

In other preferred embodiments, the active ingredient is a mixture of only component A and a single active component as component B from the list of a). In other words the pesticidal composition has preferably no more than two pesticidally active components.

Each substituent definition in each preferred group of compounds of formula (I) may be juxtaposed with any substituent definition in any other preferred group of compounds, in any combination.

The weight ratio of A to B is <NUM>:<NUM> and <NUM>:<NUM>, more preferably <NUM>:<NUM> and <NUM>:<NUM>. In other embodiments that weight ratio of A to B may be between <NUM>:<NUM> to <NUM>:<NUM>, for example between <NUM>:<NUM> to <NUM>:<NUM>, for example between <NUM>:<NUM> to <NUM>:<NUM>, for example between <NUM>:<NUM> to <NUM>:<NUM>, for example between <NUM>:<NUM> to <NUM>:<NUM> etc. Such weight ratios lead to synergistic mixtures.

The invention also provides pesticidal mixtures comprising a combination of components A and B as mentioned above in a synergistically effective amount, together with an agriculturally acceptable carrier, and optionally a surfactant.

The following mixtures are particularly favoured for treating Myzus persicae (Green peach aphid) :.

The present invention also relates to a method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a combination of components A and B; seeds comprising a mixture of components A and B; and a method comprising coating a seed with a mixture of components A and B.

Components A and B may be provided and/or used in amounts such that they are capable of synergistic pest control. For example, the present invention includes pesticidal mixtures comprising a component A and a component B in a synergistically effective amount; agricultural compositions comprising a mixture of component A and B in a synergistically effective amount; the use of a mixture of component A and B in a synergistically effective amount for combating animal pests; a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a mixture of component A and B in a synergistically effective amount; a method for protecting crops from attack or infestation by animal pests which comprises contacting a crop with a mixture of component A and B in a synergistically effective amount; a method for the protection of seeds from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pre-germination with a mixture of component A and B in a synergistically effective amount; seeds comprising, e.g. coated with, a mixture of component A and B in a synergistically effective amount; a method comprising coating a seed with a mixture of component A and B in a synergistically effective amount; a method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a combination of components A and B in a synergistically effective amount. Mixtures of A and B will normally be applied in an insecticidally, acaricidally, nematicidally or molluscicidally effective amount. In application components A and B may be applied simultaneously or separately.

The mixtures of the present invention can be used to control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are herein collectively referred to as pests. The pests which may be controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fiber products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies). The mixtures of the invention are particularly effective against insects, acarines and/or nematodes. More particularly, the mixtures are effective against hemipterans, acarines and nematodes.

According to the invention "useful plants" with which the mixture according to the invention can be applied, typically comprise the following species of plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not represent any limitation.

The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ACCase inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (<NUM>-enol-pyrovyl-shikimate-<NUM>-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9c, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp. , such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as <NUM>-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, <CIT>). An example for a truncated toxin is a truncated Cry1Ab, which is expressed in the Bt11 maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see <CIT>).

Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from <CIT>, <CIT>, <CIT> and <CIT>.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9c toxin); Herculex I® (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCOT® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard® and Protecta®.

Further examples of such transgenic crops are:.

Transgenic crops of insect-resistant plants are also described in BATS (<NPL>).

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. <CIT>). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from <CIT>, <CIT>, and <CIT>. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. <CIT>); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. <CIT>) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in <CIT>).

Useful plants of elevated interest in connection with present invention are cereals; soybean; corn; cotton; rice; oil seed rape; sunflowers; sugarcane; pome fruits; stone fruits; citrus fruits; peanuts, potatoes; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, cucurbits and lettuce.

The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term "plant propagation material" is understood to denote generative parts of a plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds. Insecticides that are of particular interest for treating seeds include thiamethoxam, imidacloprid and clothianidin.

A further aspect of the instant invention is a method of protecting natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms against attack of pests, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components A and B in a synergistically effective amount.

According to the instant invention, the term "natural substances of plant origin, which have been taken from the natural life cycle" denotes plants or parts thereof which have been harvested from the natural life cycle and which are in the freshly harvested form. Examples of such natural substances of plant origin are stalks, leafs, tubers, seeds, fruits or grains. According to the instant invention, the term "processed form of a natural substance of plant origin" is understood to denote a form of a natural substance of plant origin that is the result of a modification process. Such modification processes can be used to transform the natural substance of plant origin in a more storable form of such a substance (a storage good). Examples of such modification processes are pre-drying, moistening, crushing, comminuting, grounding, compressing or roasting. Also falling under the definition of a processed form of a natural substance of plant origin is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.

According to the instant invention, the term "natural substances of animal origin, which have been taken from the natural life cycle and/or their processed forms" is understood to denote material of animal origin such as skin, hides, leather, furs, hairs and the like.

A preferred embodiment is a method of protecting natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms against attack of pests, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components A and B in a synergistically effective amount.

A further preferred embodiment is a method of protecting fruits, preferably pomes, stone fruits, soft fruits and citrus fruits, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said fruits and/or their processed forms a combination of components A and B in a synergistically effective amount.

The combinations according to the present invention are furthermore particularly effective against the following pests: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta_migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp. ), the Kalotermitidae (for example Neotermes spp. ), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulfureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans_(vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug), Diaphorina (psyllids), Cacopsylla, Paratrioza, and Brevipalpus (Leprosis mite).

In another embodiment, the combinations according to the present invention are also particularly effective against the following pests:.

The active ingredients according to the invention can be used for controlling, i. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.

The mixtures of the invention may be used for pest control on various plants, including soybean, alfalfa, brassicas (e.g. broccoli, cabbage, cauliflower), or oil crops, such as oilseed rape, mustard, canola, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts, or potatoes (including sweet potatoes), almonds, fruiting vegetables (e.g. tomatoes, pepper, chili,eggplant, etc.), leafy vegetables (lettuce, spinach), bulb vegetables (e.g. onion, leek etc.), grapes, fruit, for instance pomaceous fruit, stone fruit or soft fruit (e.g. apples, pears, plums, peaches, nectarines, almonds, cherries etc.) or berries, for example strawberries, raspberries or blackberries.

Other suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; leguminous crops, such as beans, lentils, peas, peanuts or soya; cucurbits, such as pumpkins, cucumbers, squash or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts (e.g. pecan nuts, walnut), coffee, , sugarcane, tea, pepper, grapevines, tropical fruits (e.g. papaya, mango), hops, the plantain family, latex plants and ornamentals. The mixtures of the invention can also be applied on turf, lawn and pastures.

The mixtures of the invention may be used on soybean to control, for example, Elasmopalpus lignosellus, Diloboderus abderus, Diabrotica speciosa, Sternechus subsignatus, Formicidae, Agrotis ypsilon, Julus sspp. , Anticarsia gemmatalis, Megascelis ssp. , Procornitermes ssp. , Gryllotalpidae, Nezara viridula, Piezodorus spp. , Acrosternum spp. , Neomegalotomus spp. , Cerotoma trifurcata, Popillia japonica, Edessa spp. , Liogenys fuscus, Euchistus heros, stalk borer, Scaptocoris castanea, phyllophaga spp. , Pseudoplusia includens, Spodoptera spp. , Bemisia tabaci, Agriotes spp. Aphis sp (e.g. Aphis glycines). The mixtures of the invention are preferably used on soybean to control Diloboderus abderus, Diabrotica speciosa, Nezara viridula, Piezodorus spp. , Acrosternum spp. , Cerotoma trifurcata, Popillia japonica, Euchistus heros, phyllophaga spp. , Agriotes sp, Aphis sp (e.g. Aphis glycines).

The mixtures of the invention may be used on corn to control, for example, Euchistus heros, Dichelops furcatus, Diloboderus abderus, Elasmopalpus lignosellus, Spodoptera frugiperda, Nezara viridula, Cerotoma trifurcata, Popillia japonica, Agrotis ypsilon, Diabrotica speciosa, Heteroptera, Procornitermes ssp. , Scaptocoris castanea, Formicidae, Julus ssp. , Dalbulus maidis, Diabrotica virgifera, Mocis latipes, Bemisia tabaci, heliothis spp. , Tetranychus spp. , thrips spp. , phyllophaga spp. , scaptocoris spp. , Liogenys fuscus, Spodoptera spp. , Ostrinia spp. , Sesamia spp. Agriotes spp. , Aphis sp. The mixtures of the invention are preferably used on corn to control Euchistus heros, Dichelops furcatus, Diloboderus abderus, Nezara viridula, Cerotoma trifurcata, Popillia japonica, Diabrotica speciosa, Diabrotica virgifera, Tetranychus spp. , thrips spp. , phyllophaga spp. , scaptocoris spp. , Agriotes spp. , Aphis sp.

The mixtures of the invention may be used on sugar cane to control, for example, Sphenophorus spp. , termites, Mahanarva spp. The mixtures of the invention are preferably used on sugar cane to control termites, Mahanarva spp.

The mixtures of the invention may be used on alfalfa to control, for example, Hypera brunneipennis, Hypera postica, Colias eurytheme, Collops spp. , Empoasca solana, Epitrix, Geocoris spp. , Lygus hesperus, Lygus lineolaris, Spissistilus spp. , Spodoptera spp. , Trichoplusia ni. The mixtures of the invention are preferably used on alfalfa to control Hypera brunneipennis, Hypera postica, Empoasca solana, Epitrix, Lygus hesperus, Lygus lineolaris, Trichoplusia ni.

The mixtures of the invention may be used on brassicas to control, for example, Plutella xylostella, Pieris spp. , Mamestra spp. , Plusia spp. , Trichoplusia ni, Phyllotreta spp. , Spodoptera spp. , Empoasca solana, thrips spp. , Spodoptera spp. , Delia spp. Brevicoryne sp,, Macrosiphum sp. The mixtures of the invention are preferably used on brassicas to control Plutella xylostella Pieris spp. , Plusia spp. , Trichoplusia ni, Phyllotreta spp. , thrips sp.

The mixtures of the invention may be used on oil seed rape, e.g. canola, to control, for example, Meligethes spp. , Ceutorhynchus napi, Psylloides spp.

The mixtures of the invention may be used on potatoes, including sweet potatoes, to control, for example, Empoasca spp. , Leptinotarsa spp. , Diabrotica speciosa, Phthorimaea spp. , Paratrioza spp. , Maladera matrida, Agriotes spp. , Bemisia sp, Myzus sp. , Macrosiphum sp. Aphis sp, Aulacorthum sp. Rhopalosiphum sp. The mixtures of the invention are preferably used on potatoes, including sweet potatoes, to control Empoasca spp. , Leptinotarsa spp. , Diabrotica speciosa, Phthorimaea spp. , Paratrioza spp. , Agriotes spp, Bemisia sp, Myzus sp. , Macrosiphum sp. Aphis sp, Aulacorthum sp. Rhopalosiphum sp.

The mixtures of the invention may be used on cotton to control, for example, Aphis gossypii, Anthonomus grandis, Pectinophora spp. , heliothis spp. , Spodoptera spp. , Tetranychus spp. , Empoasca spp. , thrips spp. , Bemisia tabaci, Lygus spp. , phyllophaga spp. , Scaptocoris spp. The mixtures of the invention are preferably used on cotton to control Aphis gossypii, Anthonomus grandis, Tetranychus spp. , Empoasca spp. , thrips spp. , Lygus spp. , phyllophaga spp. , Scaptocoris spp.

The mixtures of the invention may be used on rice to control, for example, Nilaparvata lugens, Leptocorisa spp. , Cnaphalocrosis spp. , Chilo spp. , Scirpophaga spp. , Lissorhoptrus spp. , Oebalus pugnax. The mixtures of the invention are preferably used on rice to control Nilaparvata lugens, Leptocorisa spp. , Lissorhoptrus spp. , Oebalus pugnax.

The mixtures of the invention may be used on coffee to control, for example, Brevipalpus sp, Hypothenemus Hampei, Perileucoptera Coffeella, Tetranychus spp. The mixtures of the invention are preferably used on coffee to control Hypothenemus Hampei, Perileucoptera Coffeella, Brevipalpus sp,The mixtures of the invention may be used on citrus to control, for example, Panonychus citri, Phyllocoptruta oleivora, Brevipalpus spp. , Diaphorina citri, Scirtothrips spp. , thrips spp. , Unaspis spp. , Ceratitis capitata, Phyllocnistis spp. , Brevipalpus sp. Aonidiella sp, Parlatoria sp, Ceroplastes sp, Planococcus sp, Pseudococcus sp. , Tetranychus sp. The mixtures of the invention are preferably used on citrus to control Panonychus citri, Phyllocoptruta oleivora, Brevipalpus spp. , Diaphorina citri, Scirtothrips spp. , thrips spp. , Phyllocnistis spp, Brevipalpus sp. Aonidiella sp, Parlatoria sp, Ceroplastes sp, Planococcus sp, Pseudococcus sp. , Tetranychus sp. , Aphis sp.

The mixtures of the invention may be used on almonds to control, for example, Amyelois transitella, Tetranychus spp.

The mixtures of the invention may be used on fruiting vegetable, including tomatoes, pepper, chili, eggplant, cucumber, squash etc, to control Myzus sp, Aphis sp, thrips spp. , Tetranychus spp. , Polyphagotarsonemus spp. , Aculops spp. , Empoasca spp. , Spodoptera spp. , heliothis spp. , Tuta absoluta, Liriomyza spp. , Bemisia tabaci, Trialeurodes spp. , Paratrioza spp. , Frankliniella occidentalis, Frankliniella spp. , Anthonomus spp. , Phyllotreta spp. , Amrasca spp. , Epilachna spp. , Halyomorpha spp. , Scirtothrips spp. , Leucinodes spp. , Neoleucinodes spp. The mixtures of the invention are preferably used on fruiting vegetable, including tomatoes, pepper, chili, eggplant, cucumber, squash etc, to control, for example, Myzus sp, Aphis sp , thrips spp. , Tetranychus spp. , Polyphagotarsonemus spp. , Aculops spp. , Empoasca spp. , Spodoptera spp. , heliothis spp. , Tuta absoluta, Liriomyza spp. , Paratrioza spp. , Frankliniella occidentalis, Frankliniella spp. , Amrasca spp. , Scirtothrips spp. , Leucinodes spp. , Neoleucinodes spp.

The mixtures of the invention may be used on tea to control, for example, Pseudaulacaspis spp. , Empoasca spp. , Scirtothrips spp. , Caloptilia theivora. The mixtures of the invention are prefrerably used on tea to control Empoasca spp. , Scirtothrips spp.

The mixtures of the invention may be used on bulb vegetables, including onion, leek etc to control, for example, thrips spp. , Spodoptera spp. , heliothis spp. The mixtures of the invention are preferably used on bulb vegetables, including onion, leek etc to control thrips spp.

The mixtures of the invention may be used on grapes to control, for example, Empoasca spp. , Lobesia spp. , Frankliniella spp. , thrips spp. , Tetranychus spp. , Rhipiphorothrips Cruentatus, Eotetranychus Willamettei, Erythroneura Elegantula, Scaphoides spp, Pseudococcus sp, Planococcus sp The mixtures of the invention are preferably used on grapes to control Frankliniella spp. , thrips spp. , Tetranychus spp. , Rhipiphorothrips Cruentatus, Scaphoides spp, Pseudococcus sp, Planococcus sp.

The mixtures of the invention may be used on pome fruit, including apples, pairs etc, to control, for example, Cacopsylla spp. , Psylla spp. , Panonychus ulmi, Cydia pomonella, Quadraspidiotus sp, Lepidosaphes sp, Aphis sp, Dysaphis sp, Eriosoma sp. The mixtures of the invention are preferably used on pome fruit, including apples, pairs etc, to control Cacopsylla spp. , Psylla spp. , Panonychus ulmi Quadraspidiotus sp, Lepidosaphes sp, Aphis sp, Dysaphis sp, Eriosoma sp.

The mixtures of the invention may be used on stone fruit to control, for example, Grapholita molesta, Scirtothrips spp. , thrips spp. , Frankliniella spp. , Tetranychus spp. , Myzus sp. The mixtures of the invention are preferably used on stone fruit to control Scirtothrips spp. , thrips spp. , Frankliniella spp. , Tetranychus spp. , Myzus sp.

The amount of a combination of the invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of pest to be controlled or the application time.

The invention also provides mixtures suitable for resistance management. In particular, the mixtures according to the invention are suitable for controlling insects, for example from the Hemiptera order such as aphids (e.g. Myzus spp), which are resistant to neonicotinoid insecticides. The method comprises applying to said neonicotinoid resistant insects a mixture according to the invention.

The mixtures of the invention are particularly applicable to the control of neonicotinoid resistant insects (and neonicotinoid resistance in insects) of the order Hemiptera, such as: Acyrthosiphum pisum, Aphis citricola, Aphis craccivora, Aphis fabae, Aphis frangulae, Aphis glycines, Aphis gossypii, Aphis nasturtii, Aphis pomi, Aphis spiraecola, Aulacorthum solani, Brachycaudus helichrysi, Brevicoryne brassicae, Diuraphis noxia, Dysaphis devecta, Dysaphis plantaginea, Eriosoma lanigerum, Hyalopterus pruni, Lipaphis erysimi, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphum rosae, Myzus cerasi F. , Myzus nicotianae, Myzus persicae, Nasonovia ribisnigri, Pemphigus bursarius, Phorodon humuli, Rhopalosiphum insertum Wa, Rhopalosiphum maidis Fitch, Rhopalosiphum padi L. , Schizaphis graminum Rond. , Sitobion avenae, Toxoptera aurantii, Toxoptera citricola, Phylloxera vitifoliae, Acyrthosiphon dirhodum, Acyrthosiphon solani, Aphis forbesi, Aphis grossulariae, Aphis idaei, Aphis illinoisensis, Aphis maidiradicis, Aphis ruborum, Aphis schneideri, Brachycaudus persicaecola, Cavariella aegopodii Scop. , Cryptomyzus galeopsidis, Cryptomyzus ribis, Hyadaphis pseudobrassicae, Hyalopterus amygdali, Hyperomyzus pallidus, Macrosiphoniella sanborni, Metopolophium dirhodum, Myzus malisuctus, Myzus varians, Neotoxoptera sp, Nippolachnus piri Mats. , Oregma lanigera Zehnter, Rhopalosiphum fitchii Sand. , Rhopalosiphum nymphaeae, Rhopalosiphum sacchari Ze, Sappaphis piricola Okam. + T, Schizaphis piricola, Toxoptera theobromae Sch, and Phylloxera coccinea,.

Preferably, the neonicotinoid resistant insects are one or more of as an example Acyrthosiphum pisum, Aphis citricola, Aphis craccivora, Aphis fabae, Aphis frangulae, Aphis glycines, Aphis gossypii, Aphis nasturtii, Aphis pomi, Aphis spiraecola, Aulacorthum solani, Brachycaudus helichrysi, Brevicoryne brassicae, Diuraphis noxia, Dysaphis devecta, Dysaphis plantaginea, Eriosoma lanigerum, Hyalopterus pruni, Lipaphis erysimi, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphum rosae, Myzus cerasi F. , Myzus nicotianae, Myzus persicae, Nasonovia ribisnigri, Pemphigus bursarius, Phorodon humuli, Rhopalosiphum insertum Wa, Rhopalosiphum maidis Fitch, Rhopalosiphum padi L. , Schizaphis graminum Rond. , Sitobion avenae, Toxoptera aurantii, Toxoptera citricola, Phylloxera vitifoliae, Bemisia tabaci, Myzus persicae, Nilaparvata lugens, Aphis gossypii, Trialeurodes vaporariorum, Bactericera cockerelli.

More preferably, the neonicotinoid resistant insects are one or more of as an example Bemisia tabaci, Myzus persicae, Nilaparvata lugens, Aphis gossypii, Trialeurodes vaporariorum, Bactericera cockerelli.

The mixtures comprising a compound of formula (I), e.g. those selected from the tables above, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) e.g. those selected from the tables above and the active ingredients as described above is not essential for working the present invention.

The synergistic activity of the combination is apparent from the fact that the pesticidal activity of the composition of A + B is greater than the sum of the pesticidal activities of A and B.

The method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a synergistically effective aggregate amount of a component A and a component B.

Some of said combinations according to the invention have a systemic action and can be used as foliar, soil and seed treatment pesticides. The invention also covers a a method comprising coating a seed with a mixture of components A and B as defined above.

With the combinations according to the invention it is possible to inhibit or destroy the pests which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by pests.

The combinations of the present invention are of particular interest for controlling pests in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.

The combinations according to the invention are applied by treating the pests, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by pests, attack with a combination of components A and B in a synergistically effective amount.

The combinations according to the invention may be applied before or after infection or contamination of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the pests.

The combinations according to the invention can be used for controlling, i. containing or destroying, pests of the abovementioned type which occur on useful plants in agriculture, in horticulture and in forests, or on organs of useful plants, such as fruits, flowers, foliage, stalks, tubers or roots, and in some cases even on organs of useful plants which are formed at a later point in time remain protected against these pests.

When applied to the useful plants the compound of formula (I) is generally applied at a rate of <NUM> to <NUM> a. /ha in association with <NUM> to <NUM> a. /ha, of a compound of component B, depending on the class of chemical employed as component B.

Generally for plant propagation material, such as seed treatment, application rates can vary from <NUM> to <NUM> / kg of seeds of active ingredients. When the combinations of the present invention are used for treating seed, rates of <NUM> to <NUM> of a compound of formula (I) per kg of seed, preferably from <NUM> to <NUM> per kg of seed, and <NUM> to <NUM> of a compound of component B, per kg of seed, preferably from <NUM> to <NUM> per kg of seed, are generally sufficient.

Spodoptera preferably means Spodoptera littoralis. Heliothis preferably means Heliothis virescens. Tetranychus preferably means Tetranychus urticae.

The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

The compositions according to the invention can preferably additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive used in the composition according to the invention is generally from <NUM> to <NUM> %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil such as ADIGOR® and MERO®, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhône-Poulenc Canada Inc. ), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially <NUM> % by weight alkyl esters of fish oils and <NUM> % by weight methylated rapeseed oil, and also <NUM> % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C<NUM>-C<NUM> fatty acids, especially the methyl derivatives of C<NUM>-C<NUM> fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important. Those esters are known as methyl laurate (CAS-<NUM>-<NUM>-<NUM>), methyl palmitate (CAS-<NUM>-<NUM>-<NUM>) and methyl oleate (CAS-<NUM>-<NUM>-<NUM>). A preferred fatty acid methyl ester derivative is Emery® <NUM> and <NUM> (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, <NUM>. Also, alkoxylated fatty acids can be used as additives in the inventive compositions as well as polymethylsiloxane based additives, which have been described in <CIT>.

The application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages <NUM> and <NUM> of <CIT>. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C<NUM>-C<NUM> fatty alcohols having a degree of ethoxylation of from <NUM> to <NUM>. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as Silwet L-<NUM>®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from <NUM> to <NUM> % by weight. Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP Oil UK Limited, GB).

The said surface-active substances may also be used in the formulations alone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from <NUM> to <NUM> % by weight of the total weight. Such oil additives, which may be in admixture with solvents, are described, for example, in <CIT>. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada.

In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-<NUM>-p-menthene (e.g. Bond®, Courier® or Emerald®) can also be used. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be mixed into the spray mixture as activity-enhancing agents.

A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. A typical a tank-mix formulation for seed treatment application comprises <NUM> to <NUM>%, especially <NUM> to <NUM> %, of the desired ingredients, and <NUM> to <NUM> %, especially <NUM> to <NUM> %, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of <NUM> to <NUM> %, especially <NUM> to <NUM> %, based on the tank-mix formulation. A typical pre-mix formulation for seed treatment application comprises <NUM> to <NUM> %, especially <NUM> to <NUM> %, of the desired ingredients, and <NUM> to <NUM> %, especially <NUM> to <NUM> %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of <NUM> to <NUM> %, especially <NUM> to <NUM> %, based on the pre-mix formulation.

In general, the formulations include from <NUM> to <NUM>% by weight of active agent, from <NUM> to <NUM>% agriculturally acceptable surfactant and <NUM> to <NUM>% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) together with a compound of component B, and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about <NUM> and <NUM>%, preferably between about <NUM> and <NUM>% by weight of active agent. Application forms of formulation may for example contain from <NUM> to <NUM>% by weight, preferably from <NUM> to <NUM>% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.

The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (<NPL>):.

According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is <MAT>.

If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms the synergism factor SF corresponds to O/E. In the agricultural practice an SF of ≥ <NUM> indicates significant improvement over the purely complementary addition of activities (expected activity), while an SF of ≤ <NUM> in the practical application routine signals a loss of activity compared to the expected activity.

Tables <NUM> to <NUM> show mixtures and compositions including components A as T1. <NUM> and T1iii. <NUM> of the present invention demonstrating control on a wide range of pests. As the percent of mortality cannot exceed <NUM> percent, the unexpected increase in insecticidal activity can be greatest only when the separate active ingredient components alone are at application rates providing considerably less than <NUM> percent control. Synergy may not be evident at low application rates where the individual active ingredient components alone have little activity. However, in some instances high activity was observed for combinations wherein individual active ingredient alone at the same application rate had essentially no activity.

Myzus persicae (Green peach aphid):
feeding/residual contact activity, preventive.

Sunflower leaf discs are placed on agar in a <NUM>-well microtiter plate and sprayed with the DMSO test solutions. After drying, the leaf discs are infested with an aphid population of mixed ages. After an incubation period of <NUM> DAT (days after treatment), samples are checked for mortality. (<NUM> PPM = <NUM> I-<NUM>).

Tetranychus urticae (Two-spotted spider mite):
feeding/contact activity, preventive.

Bean leaf discs on agar in <NUM>-well microtiter plates are sprayed with the DMSO test solutions. After drying, the leaf discs are infested with mite populations of mixed ages. <NUM> days later, discs are checked for mortality against mobile stages. (<NUM> PPM = <NUM> I-<NUM>).

Claim 1:
A pesticidal mixture comprising as active ingredient a mixture of component (A) and component (B), wherein component (A) is a compound of formula (I)
<CHM>
in which Q is (i)
<CHM>
wherein
m is <NUM>, n is <NUM>, X is methyl, Y is in the ortho position and is methyl, Z is in the para position and is chloro, G is -(C=O)OCH<NUM>CH<NUM>, A is hydrogen and R is methyl (compound T1iii.<NUM>); or
m is <NUM>, n is <NUM>, X is methyl, Y is in the ortho position and is methyl, Z is in the para position and is chloro, G is -(C=O)OCH<NUM>CH<NUM>, A is methyl and R is methyl (compound T1.<NUM>); or
m is <NUM>, n is <NUM>, X is methyl, Y is in the ortho position and is methyl, Z is in the para position and is methyl, G is -(C=O)OCH<NUM>CH<NUM>, A is methyl and R is methyl (compound T1.<NUM>);
or an agrochemically acceptable salt or an N-oxide thereof; and
component (B) is abamectin,
wherein the weight ratio of component (A) to component (B) ranges from <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>.