Pesticidally active 1,2,4-triazole derivatives with sulphur containing substituents

Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides and can be prepared in a manner known per se. ##STR00001##

Claims

1. A compound of formula I ##STR00232## wherein G.sub.1 is nitrogen or CR.sub.2; G.sub.2 is nitrogen or CR.sub.3; G.sub.3 is nitrogen or CR.sub.4; G.sub.4 is nitrogen or CR.sub.5; G.sub.5 is nitrogen or CR.sub.6, with the proviso that not more than 2 nitrogens as G may follow consecutively; R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, hydrogen, halogen, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkyl substituted by one or two hydroxy, C.sub.1-C.sub.4haloalkyl substituted by one or two methoxy, C.sub.1-C.sub.4haloalkyl substituted by one or two cyano; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4haloalkoxy, SF.sub.5, phenylcarbonylthio, cyano, mercapto, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkylcarbonyl or C(O)C.sub.1-C.sub.4haloalkyl; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, C.sub.3-C.sub.6cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or two adjacent R.sub.i, wherein R.sub.i is selected from R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, taken together may form a fragment OCH.sub.2O or OCF.sub.2O, R.sub.8 is hydrogen, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4haloalkyl; R.sub.7 is a radical selected from the group consisting of formula Q1 and Q2 ##STR00233## wherein the arrow denotes the point of attachment to the triazole ring; and wherein A represents CH or N; Q is phenyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl; or Q is a five- to ten-membered monocyclic or fused bicyclic ring system linked via a carbon atom to the ring which contains the group A, said ring system can be aromatic, partially saturated or fully saturated and contains 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, said five-to ten-membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C(O)C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl; or Q is a five- to six-membered, aromatic, partially saturated or fully saturated ring system linked via a nitrogen atom to the ring which contains the group A, said ring system can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C(O)C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl; and said ring system contains 1, 2 or 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where said ring system may not contain more than one oxygen atom and not more than one sulfur atom; or Q is C.sub.3-C.sub.6cycloalkyl, or C.sub.3-C.sub.6cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl and phenyl, wherein said phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl; or Q is C.sub.2-C.sub.6alkenyl, or C.sub.2-C.sub.6alkenyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.3-C.sub.6cycloalkyl and phenyl, wherein said phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4halo-alkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl; or Q is C.sub.2-C.sub.6alkynyl, or C.sub.2-C.sub.6alkynyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, tri(C.sub.1-C.sub.4alkyl)silyl and phenyl, wherein said phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl; or Q is C.sub.1-C.sub.6haloalkylsulfanyl, C.sub.1-C.sub.6haloalkylsulfinyl, C.sub.1-C.sub.6haloalkylsulfonyl, C.sub.1-C.sub.6haloalkoxy, C(O)C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.6alkylsulfanyl, C.sub.1-C.sub.6alkylsulfinyl, or C.sub.1-C.sub.6alkylsulfonyl; X is S, SO or SO.sub.2; and R.sub.1 is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.3-C.sub.6cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl or C.sub.2-C.sub.6alkynyl; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N -oxides of the compounds of formula I.

2. A compound of formula I according to claim 1, wherein Q is selected from the group consisting of the following heterocyclic groups: pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridyl; pyrimidyl; pyrazinyl; pyridazinyl; triazinyl, pyranyl; quinazolinyl; isoquinolinyl; indolizinyl; isobenzofuranylnaphthyridinyl; quinoxalinyl; cinnolinyl; phthalazinyl; benzothiazolyl; benzoxazolyl; benzotriazolyl; indazolyl; indolyl; (1H-pyrrol-1-yl)-; (1H-pyrrol-2-yl)-; (1H-pyrrol-3-yl)-; (1H-pyrazol -1-yl)-; (1H-pyrazol-3-yl)-; (3H-pyrazol-3-yl)-; (1H-pyrazol-4-yl)-; (3-isoxazolyl)-; (5-isoxazolyl)-; (2-furanyl)-; (3-furanyl)-; (2-thienyl)-; (3-thienyl)-; (1H-imidazol-2-yl)-; (1H-imidazol-4-yl)-; (1H-imidazol-5-yl)-; (2-oxazol-2-yl)-; (oxazol-4-yl)-; (oxazol-5-yl)-; (thiazol-2-yl)-; (thiazol-4-yl)-; (thiazol-5-yl)-; (isothiazol-3-yl)-; (isothiazol-5-yl)-; (1H-1,2,3-triazol-1-yl)-; (1H-1,2,4-triazol-3-yl)-; (4H-1,2,4-triazol-4-yl)-; (1H-1,2,4-triazol-1-yl)-; (1,2,3-oxadiazol-2-yl)-; (1,2,4-oxadiazol-3-yl)-; (1,2,4-oxadiazol-4-yl)-; (1,2,4-oxadiazol-5-yl)-; (1,2,3-thiadiazol-2-yl)-; (1,2,4-thiadiazol-3-yl)-; (1,2,4-thiadiazol-4-yl)-; (1,3,4-thiadiazol-5-yl)-; (1H-tetrazol-1-yl)-; (1H-tetrazol-5-yl)-; (2H-tetrazol-5-yl)-; (2-pyridyl)-; (3-pyridyl)-; (4-pyridyl)-; (2-pyrimidinyl)-; (4-pyrimidinyl)-; (5-pyrimidinyl)-; (2-pyrazinyl)-; (3-pyridazinyl)-; (4-pyridazinyl)-; (1,3,5-triazin-2-yl)-; (1,2,4-triazin-5-yl)-; (1,2,4-triazin-6-yl)-; (1,2,4-triazin-3-yl)-; (furazan-3-yl)-; (2-quinolinyl)-; (3-quinolinyl)-; (4-quinolinyl)-; (5-quinolinyl)-; (6-quinolinyl)-; (3-isoquinolnyl)-; (4-isoquinolnyl)-; (2-quinozolinyl)-; (2-quinoxalinyl)-; (5-quinoxalinyl)-; (pyrido[2,3-b]pyrazin-7-yl)-; (benzoxazol-5-yl)-; (benzothiazol-5-yl)-; (benzo[b]thien-2-yl) and (benzo[1,2,5]oxadiazol-5-yl)-; indolinyl and tetrahydroquinolynyl.

3. A compound of formula I according to claim 1, wherein Q is selected from the group consisting of J-0 to J-51: ##STR00234## ##STR00235## ##STR00236## ##STR00237## wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx, wherein each Rx is, independently selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C(O)C.sub.1-C.sub.4alkyl, C.sub.1C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl.

4. A compound of formula I according to claim 1, represented by the compounds of formula I-1 ##STR00238## wherein A, Q, G.sub.1, G.sub.2, G.sub.3, G.sub.4, and G.sub.5 are as defined under formula I in claim 1; X.sub.1 is S, SO or SO.sub.2; R.sub.11 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; and R.sub.8 is as defined under formula I in claim 1.

5. A compound of formula I according to claim 1 represented by the compounds of formula I-2 ##STR00239## wherein A, G.sub.1, G.sub.2, G.sub.3, G.sub.4, and G.sub.5 are as defined under formula I in claim 1; X.sub.2 is S, SO or SO.sub.2; R.sub.12 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; R.sub.8 is as defined above under formula I in claim 1; and Qa.sub.1 is selected from the group consisting of ##STR00240## wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx, wherein each Rx is, independently selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C(O)C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl.

6. A compound of formula I according to claim 1, represented by the compounds of formula I-3 ##STR00241## wherein A is N or CH; R.sub.10 is pyridyl or pyrimidyl mono- or polysubstituted by C.sub.1-C.sub.4haloalkyl; X.sub.3 is S or SO.sub.2; Qa.sub.2 is selected from the group consisting of ##STR00242## wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx, wherein each Rx is, independently selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4alkoxy; R.sub.13 is C.sub.1-C.sub.4alkyl; and R.sub.8 is C.sub.1-C.sub.4alkyl.

7. A compound of formula I according to claim 1, represented by the compounds of formula I-4 ##STR00243## wherein R.sub.10 is pyridyl or pyrimidyl monosubstituted by C.sub.1-C.sub.4haloalkyl; and Qa.sub.4 is selected from the group consisting of ##STR00244## ##STR00245## wherein each Rx is independently selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4alkoxy.

8. A compound of formula I according to claim 1, represented by the compounds of formula I-5 ##STR00246## wherein R.sub.5 is C.sub.1-C.sub.4haloalkyl; and Qa.sub.5 is selected from the group consisting of ##STR00247## ##STR00248## wherein each Rx is, independently selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4alkoxy.

9. A compound of formula I according to claim 1, represented by the compounds of formula I-6 ##STR00249## wherein R.sub.6 is C.sub.1-C.sub.4haloalkyl; and Qa.sub.6 is selected from the group consisting of ##STR00250## wherein each Rx is, independently selected from hydrogen, halogen and cyano.

10. A compound of formula I according to claim 1, represented by the compounds of formula I-1p ##STR00251## wherein A, Q, G.sub.l, G.sub.2, G.sub.3, G.sub.4, and G.sub.5 are as defined under formula I in claim 1; X.sub.1 is S, SO or SO.sub.2; R.sub.11 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; and R.sub.8 is as defined under formula I in claim 1.

11. A compound of formula I according to claim 1 represented by the compounds of formula I-2p ##STR00252## wherein A, Q, G.sub.l, G.sub.2, G.sub.3, G.sub.4, and G.sub.5 are as defined under formula I in claim 1; X.sub.2 is S, SO or SO.sub.2; R.sub.12 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; R.sub.8 is as defined above under formula I in claim 1; and Q is selected from the group consisting of ##STR00253## wherein each group J-0 to J-43 is mono-, di- or trisubstituted with Rx, wherein each Rx is, independently selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C(O)C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl and C(O)C.sub.1-C.sub.4haloalkyl.

12. A pesticidal composition, which comprises at least one compound of formula I according to claim 1 or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.

13. A method for controlling pests, which comprises applying a composition according to claim 12 to the pests or their environment with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

14. A method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 12.

15. A compound of formula (Iab) ##STR00254## wherein G.sub.1 is nitrogen or CR.sub.2; G.sub.2 is nitrogen or CR.sub.3; G.sub.3 is nitrogen or CR.sub.4; G.sub.4 is nitrogen or CR.sub.5; G.sub.5 is nitrogen or CR.sub.6, with the proviso that not more than 2 nitrogens as G may follow consecutively; R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, hydrogen, halogen, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkyl substituted by one or two hydroxy, C.sub.1-C.sub.4haloalkyl substituted by one or two methoxy, C.sub.1-C.sub.4haloalkyl substituted by one or two cyano; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4haloalkoxy, SF.sub.5, phenylcarbonylthio, cyano, mercapto, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkylcarbonyl or C(O)C.sub.1-C.sub.4haloalkyl; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, C.sub.3-C.sub.6cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or two adjacent R.sub.i, wherein R.sub.i is selected from R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, taken together may form a fragment OCH.sub.2O or OCF.sub.2O, R.sub.8 is hydrogen, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4haloalkyl; A represents CH or N; X is S, SO or SO.sub.2; and R.sub.1 is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.3-C.sub.6cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl or C.sub.2-C.sub.6alkynyl.

16. A compounds of formula XVII-Int ##STR00255## wherein G.sub.1 is nitrogen or CR.sub.2; G.sub.2 is nitrogen or CR.sub.3; G.sub.3 is nitrogen or CR.sub.4; G.sub.4 is nitrogen or CR.sub.5; G.sub.5 is nitrogen or CR.sub.6, with the proviso that not more than 2 nitrogens as G may follow consecutively; R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, hydrogen, halogen, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkyl substituted by one or two hydroxy, C.sub.1-C.sub.4haloalkyl substituted by one or two methoxy, C.sub.1-C.sub.4haloalkyl substituted by one or two cyano; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4haloalkoxy, SF.sub.5, phenylcarbonylthio, cyano, mercapto, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkylcarbonyl orC(O)C.sub.1-C.sub.4haloalkyl; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, C.sub.3-C.sub.6cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or two adjacent R.sub.i, wherein R.sub.i is selected from R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, taken together may form a fragment OCH.sub.2O or OCF.sub.2O, R.sub.8 is hydrogen, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4haloalkyl; A represents CH or N; X is S, SO or SO.sub.2; and R.sub.1 is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.3-C.sub.6cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4alkyl; or R.sub.1 is C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl or C.sub.2-C.sub.6alkynyl; Yb.sub.3 is B(OH).sub.2, B(OR.sub.b2).sub.2, in which R.sub.b2 is a C.sub.1-C.sub.6alkyl or Yb.sub.3 is ##STR00256## (a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane group).

Description

PREPARATORY EXAMPLES

(1) Mp means melting point in C. Free radicals represent methyl groups. .sup.1H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Common abbreviations: aq=aqueous, min=minute, h=hour, sat=saturated, R.sub.t=retention time, mCPBA=meta-chloroperoxybenzoic acid, MeOH=methanol, EtOH=ethanol, NaHCO.sub.3=sodium hydrogen carbonate, Na.sub.2CO.sub.3=sodium carbonate, HCl=hydrogen chloride, CH.sub.2Cl.sub.2=dichloromethane, Et.sub.3N=triethylamine, DMF=N,N-dimethylformamide. Either one of the LCMS and/or GCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (Rt, recorded in minutes) and the measured molecular ion (M+H).sup.+.

(2) LCMS and GCMS Methods:

(3) Method 1:

(4) Spectra were recorded on a Mass Spectrometer from Waters (ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 C., Desolvation Temperature: 350 C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 m, 302.1 mm, Temp: 60 C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

(5) Method 2:

(6) Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 C., Desolvation Temperature: 350 C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 m, 302.1 mm, Temp: 60 C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH; gradient: 0 min 0% B, 100% A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

(7) Method 3:

(8) GCMS analyses were performed on a Thermo Electron instrument where a TRACE GC ULTRA gas chromatograph (equipped with a Zebron Phenomenex ZB-5 ms 15 m, diam: 0.25 mm, 0.25 m column; H.sub.2 flow 1.2 mL/min; temp injector: 250 C.; temp detector: 220 C.; method: start at 70 C., then 25 C./min until 320 C., hold 2 min at 320 C.) was linked to a DSQ mass spectrometer characterizing the compounds by electron ionisation (EI).

Example P1

Preparation of 5-(4-chlorophenyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Compound P2)

Step A-1: Preparation of methyl 5-bromo-3-chloro-pyridine-2-carboxylate

(9) ##STR00127##

(10) To a slightly cloudy solution of 5-bromo-3-chloro-pyridine-2-carboxylic acid (60 g, 183.2 mmol) in dichloromethane (700 ml) was added dropwise N,N-dimethylformamide (1 ml) and oxalylchloride (24.9 ml, 286.9 mmol). The cloudy solution was stirred for 3 hours at ambient temperature. The resulting yellow solution was cooled to 10 C. and methanol (30.8 ml, 761.3 mmol) was added dropwise to the mixture, keeping the temperature between 15 and 20 C. The solution was stirred overnight at ambient temperature. After neutralisation with an aqueous saturated solution of sodium hydrogen carbonate, the organic layer was washed with brine, dried over sodium sulfate, filtrated and evaporated to give methyl 5-bromo-3-chloro-pyridine-2-carboxylate (55 g) as a yellow solid, which was used without further purification. LCMS (method 2): 250/252/254 (M+H).sup.+, retention time 1.12 min.

Step A-2: Preparation of methyl 3-chloro-5-(4-chlorophenyl)pyridine-2-carboxylate

(11) ##STR00128##

(12) A solution of methyl 5-bromo-3-chloro-pyridine-2-carboxylate (17.33 g, 69.2 mmol), 4-chlorophenyl-boronic acid (11.36 g, 72.7 mmol), sodium carbonate (14.7 g, 138.4 mmol) in a mixture of 1,2-dimethoxyethane (500 ml) and water (50 ml) was flushed with argon. Tetrakis(triphenylphosphine) palladium (4.0 g, 3.5 mmol) was added and the mixture was stirred at 90 C. for 7 hours. More catalyst was added (0.5 g, 0.4 mmol) and the mixture was stirred another 2 hours at 90 C. After cooling, the reaction mixture was diluted with water and ethyl acetate. The water phase was separated and washed twice with ethyl acetate. The combined organic phases were dried over magnesium sulfate and evaporated under vacuum. The residue was submitted to flash chromatography to give methyl 3-chloro-5-(4-chlorophenyl)pyridine-2-carboxylate (10.5 g). LCMS (method 2): 282/284 (M+H).sup.+, retention time 1.63 min.

Step A-3: Preparation of 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylic Acid

(13) ##STR00129##

(14) To a solution of methyl 3-chloro-5-(4-chlorophenyl)pyridine-2-carboxylate (2.0 g, 7.1 mmol) in 15 ml N,N-dimethylformamide, sodium ethanethiolate (3.3 g, 35 mmol) was added. The temperature rose to 40 C. and the reaction mixture was stirred 1 hour at room temperature. The solution was diluted with tert-butyl methyl ether and was extracted with ice water. The aqueous phase was separated and neutralized with acetic acid and extracted with tert-butyl methyl ether and ethyl acetate. The combined organic layers were dried over magnesium sulfate and evaporated under vacuum to give 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (2.0 g) which was used without further purification. LCMS (method 2): 294/296 (M+H).sup.+, retention time 1.42 min.

Step A-4: Preparation of methyl 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylate

(15) ##STR00130##

(16) To a solution of 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (220 mg, 0.749 mmol) in methanol (5 ml) was added sulfuric acid (3 drops) and the mixture stirred at reflux overnight. After cooling, the reaction mixture was diluted with iced water and extracted with dichloromethane (5). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was submitted to flash column chromatography on silica (cyclohexane/ethyl acetate 1:1) to afford methyl 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylate (184 mg) as a solid, mp 103-105 C. LCMS (method 2): 308/310 (M+H).sup.+, retention time 1.70 min.

Step A-5: Preparation of 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carbohydrazide

(17) ##STR00131##

(18) To a solution of methyl 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylate (184 mg, 0.598 mmol) in methanol (2 ml) was added hydrazine monohydrate (0.0382 ml, 0.777 mmol) and the mixture stirred at reflux for 3.5 hours. After cooling, the reaction mixture was concentrated under reduced pressure, the residue dissolved in dichloromethane, dried over sodium sulfate and evaporated to dryness to afford 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carbohydrazide (145 mg) as a solid, mp 124-126 C. LCMS (method 1): 308/310 (M+H).sup.+, retention time 0.91 min. This material was used without further purification.

Step B-1: Preparation of N,N-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine

(19) ##STR00132##

(20) To a solution of 4-(trifluoromethyl)pyridine-2-carbonitrile (1.7 g, 9.88 mmol) in methanol (18 ml) was added sodium methoxide (25 wt % in MeOH) (2.1 g, 9.9 mmol, 2.3 ml) and the mixture stirred at room temperature for 3 hours. The reaction mixture was concentrated to dryness, the residue suspended in methylamine (33 wt % in EtOH) (25 ml, 200.9 mmol) to which was added methylamine hydrochloride (6.7 g, 99.2 mmol). The reaction mixture was heated in a closed high pressure vial at 90 C. overnight. After cooling, the mixture was concentrated and the residue treated with dichloromethane, filtered and the filtrate evaporated under reduced pressure. This material was dissolved in diethyl ether, treated with a 2M hydrochloric acid solution in diethyl ether under cooling, stirred at 5-10 C. for 20 minutes, then diluted with water. The layers were separated and the organic phase washed twice with water. The combined aqueous phases were basified to pH 12 by addition of an aqueous 30% sodium hydroxide solution under cooling, and the product thoroughly extracted with diethyl ether (4). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to afford N,N-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine as an oil (0.70 g), which was used without further purification. LCMS (method 1): 218 (M+H).sup.+, retention time 0.28 min. .sup.19F-NMR (MeOD, ppm) 66.4.

Step C-1: Preparation of 5-(4-chlorophenyl)-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Compound P1)

(21) ##STR00133##

(22) A solution of 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carbohydrazide (135 mg, 0.439 mmol) and N,N-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine (95.3 mg, 0.439 mmol) in methanol (3 ml) was heated at reflux temperature overnight. After cooling, the reaction mixture was concentrated under reduced pressure, the residue dissolved in dichloromethane, dried over sodium sulfate and evaporated to dryness. The residue was purified over silica by flash column chromatography (cyclohexane/ethyl acetate 3:1) to afford 5-(4-chlorophenyl)-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (compound P1) as a solid (96 mg), mp 147-149 C. LCMS (method 2): 476/478 (M+H).sup.+, retention time 1.97 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.36 (3H), 3.03 (2H), 4.18 (3H), 7.51 (2H), 7.58 (3H), 7.89 (1H), 8.70 (1H), 8.73 (1H), 8.87 (1H).

Step C-2: Preparation of 5-(4-chlorophenyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Title Compound P2)

(23) ##STR00134##

(24) To a solution of 5-(4-chlorophenyl)-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (65 mg, 0.137 mmol) in dichloromethane (2 ml) at 10 C. was added mCPBA (75 wt % in water) (66 mg, 0.287 mmol, 75%) in one portion and the mixture was stirred at 10 C. for 2 hours. The reaction mixture was diluted with tert-butyl methyl ether, washed successively with sat. aqueous sodium hydrogen carbonate (4), a sat. aqueous sodium sodium bisulfite solution (4) and brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified over silica by flash column chromatography (cyclohexane/ethyl acetate 3:1) to afford 5-(4-chlorophenyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (title compound P2) as a solid (32 mg), mp 234-235 C. LCMS (method 2): 508/510 (M+H).sup.+, retention time 1.81 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.40 (3H), 3.86 (2H), 4.10 (3H), 7.56 (2H), 7.60 (1H), 7.67 (2H), 8.66 (1H), 8.72 (1H), 8.87 (1H), 9.18 (1H).

Example P2

Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (Compound P4)

Step A-1: Preparation of 5-bromo-3-chloro-pyridine-2-carbohydrazide

(25) ##STR00135##

(26) Obtained from methyl 5-bromo-3-chloro-pyridine-2-carboxylate (34 g, 135.7 mmol) and hydrazine hydrate (8.75 ml, 176.5 mmol) in methanol (350 ml) according to procedure Example P1, step A-5. The mixture was stirred at reflux temperature for 4 hours. The solid residue obtained after workup was suspended in diethyl ether, filtered, the solid washed with cold diethyl ether and dried in vacuo to afford 5-bromo-3-chloro-pyridine-2-carbohydrazide (32.1 g) as a solid, mp 146-148 C. LCMS (method 2): 250/252/254 (M+H).sup.+; retention time: 0.47 min. .sup.1H-NMR (DMSO-d.sub.6, ppm) 4.59 (br s, 2H), 8.45 (s, 1H), 8.68 (s, 1H), 9.77 (br s, 1H).

Step B-1: Preparation of 5-bromo-3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine

(27) ##STR00136##

(28) Obtained from 5-bromo-3-chloro-pyridine-2-carbohydrazide (554 mg, 2.21 mmol) and N,N-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine (480 mg, 2.21 mmol) in methanol (4 ml) according to procedure Example P1, step C-1. The mixture was stirred at reflux overnight. Flash chromatography purification (cyclohexane/ethyl acetate 4:1) afforded 5-bromo-3-chloro-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (560 mg) as a solid, mp 152-154 C. LCMS (method 2): 418/420/422 (M+H).sup.+; retention time: 1.53 min. .sup.1H-NMR (CDCl.sub.3, ppm) 4.10 (s, 3H), 7.60 (d, 1H), 8.13 (d, 1H), 8.70 (s, 1H), 8.75 (d, 1H), 8.87 (d, 1H).

Step B-2: Preparation of 3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine

(29) ##STR00137##

(30) To a solution of 5-bromo-3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (250 mg, 0.597 mmol) and 1H-pyrazole (44.7 mg, 0.657 mmol) in N,N-dimethylformamide (2 ml) under argon was added copper(I) iodide (5.7 mg, 0.030 mmol), N,N-dimethylethylenediamine (5.3 mg, 6.36 l, 0.060 mmol) and potassium carbonate (16.5 mg, 0.119 mmol). The mixture was stirred at 100 C. for 4 hours. After cooling, the reaction mixture was diluted with ethyl acetate and filtered over diatomaceous earth (Hyflo). The filtrate was washed with water (3), dried over sodium sulfate and concentrated in vacuo. The residue was purified over silica by flash column chromatography (cyclohexane/ethyl acetate 4:1) to afford 3-chloro-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine as a solid (123 mg), mp 160-162 C. LCMS (method 2): 406/408 (M+H).sup.+; retention time: 1.43 min. .sup.1H-NMR (CDCl.sub.3, ppm) 4.12 (s, 3H), 6.61 (t, 1H), 7.60 (d, 1H), 7.85 (d, 1H), 8.08 (d, 1H), 8.36 (d, 1H), 8.72 (s, 1H), 8.88 (d, 1H), 9.08 (d, 1H).

Step B-3: Preparation of 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (Compound P3)

(31) ##STR00138##

(32) To a solution of 3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (123 mg, 0.303 mmol) in N,N-dimethylformamide (2.5 ml) at 10 C. was added sodium ethanethiolate (38.6 mg, 0.458 mmol) in one portion. The reaction mixture was stirred at 50 C. overnight, then concentrated to dryness under reduced pressure. The residue was diluted with ethyl acetate and water, the layers separated, the organic phase washed with water (3), dried over sodium sulfate and concentrated in vacuo. The solid residue was stirred in diethyl ether, filtered, washed with cold diethyl ether and dried in vacuo to afford 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (compound P3) as a solid (101 mg), mp 121-123 C. LCMS (method 2): 432 (M+H).sup.+; retention time: 1.54 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.39 (t, 3H), 3.06 (q, 2H), 4.16 (s, 3H), 6.59 (t, 1H), 7.58 (d, 1H), 7.83 (d, 1H), 8.07 (d, 1H), 8.19 (d, 1H), 8.72 (s, 1H), 8.83 (d, 1H), 8.87 (d, 1H).

Step B-4: Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (Compound P4)

(33) ##STR00139##

(34) Obtained from 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (95 mg, 0.220 mmol) and mCPBA (106 mg, 0.462 mmol, 75%) in dichloromethane (2.5 ml) according to procedure Example P1, step C-2. The mixture was stirred at room temperature overnight. Flash chromatography purification (cyclohexane/ethyl acetate 3:1) afforded 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine (title compound P4) as a solid (52 mg), mp 174-176 C. LCMS (method 2): 464 (M+H).sup.+; retention time: 1.43 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.41 (t, 3H), 3.88 (q, 2H), 4.08 (s, 3H), 6.65 (t, 1H), 7.60 (d, 1H), 7.89 (d, 1H), 8.15 (d, 1H), 8.71 (s, 1H), 8.77 (d, 1H), 8.87 (d, 1H), 9.47 (d, 1H).

Example P3

Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-vinyl-pyridine (Compound P12)

Step A-1: Preparation of N-methyl-4-(trifluoromethyl)pyridine-2-carboxamide

(35) ##STR00140##

(36) To a solution of 4-(trifluoromethyl)pyridine-2-carboxylic acid (97%, 10.0 g, 50.76 mmol) in dichloromethane (200 ml) was added dropwise N,N-dimethylformamide (0.1 ml) and oxalyl chloride (5.66 ml, 66.00 mmol). The reaction mixture was stirred at ambient temperature overnight, then concentrated to dryness in vacuo to afford 4-(trifluoromethyl)pyridine-2-carbonyl chloride (10.5 g) as a solid.

(37) To methylamine (2M in tetrahydrofuran) (62.6 ml, 125.2 mmol) in tetrahydrofuran (40 ml) at 0-5 C. was added triethylamine (10.4 ml, 75.03 mmol), followed by a solution of 4-(trifluoromethyl)pyridine-2-carbonyl chloride (10.5 g, 50.11 mmol, preparation above) in tetrahydrofuran (60 ml) dropwise. The mixture was allowed to warm to room temperature, and stirred for 2 hours. The resulting suspension was filtered, the solid residue washed with t-butyl methyl ether (3) and the filtrate evaporated under reduced pressure. The residue was dissolved in t-butyl methyl ether, the organic phase washed with water (3) and brine, dried over sodium sulfate and concentrated in vacuo. The crude material was diluted with t-butyl methyl ether, treated with activated charcoal, the mixture stirred for 15 minutes and filtered. Evaporation of the filtrate in vacuo afforded N-methyl-4-(trifluoromethyl)pyridine-2-carboxamide as a solid (9.2 g), mp 60-62 C. This material was used without further purification. LCMS (method 2): 205 (M+H).sup.+; retention time: 0.86 min. .sup.1H-NMR (CDCl.sub.3, ppm) 3.07 (d, 3H), 7.66 (d, 1H), 8.01 (br s, 1H), 8.45 (s, 1H), 8.74 (d, 1H).

Step A-2: Preparation of N-methyl-4-(trifluoromethyl)pyridine-2-carbothioamide

(38) ##STR00141##

(39) To a solution of N-methyl-4-(trifluoromethyl)pyridine-2-carboxamide (32.5 g, 159.2 mmol) in pyridine (870 ml) was added phosphorus pentasulfide (42.5 g, 95.6 mmol) and the mixture was stirred at reflux temperature for 5 hours. After cooling, the solvent was removed in vacuo, the residue diluted with water and the aqueous phase extracted with diethyl ether (3). The combined organic layers were washed with a water/brine (1:1) solution (4), dried over sodium sulfate and concentrated under reduced pressure to afford N-methyl-4-(trifluoromethyl)pyridine-2-carbothioamide as a solid (30.9 g), mp 69-70 C. This material was used without further purification. LCMS (method 2): 221 (M+H).sup.+; retention time: 1.42 min. .sup.1H-NMR (CDCl.sub.3, ppm) 3.43 (d, 3H), 7.66 (d, 1H), 8.68 (d, 1H), 8.96 (s, 1H), 10.14 (br s, 1H).

Step A-3: Preparation of ethyl N-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate

(40) ##STR00142##

(41) To a solution of N-methyl-4-(trifluoromethyl)pyridine-2-carbothioamide (10.2 g, 46.32 mmol) in ethanol (200 ml) was added sodium ethoxide (21 wt % in EtOH) (15.2 g, 46.3 mmol, 17.3 ml) and the mixture was stirred at room temperature for 40 minutes. Iodoethane (14.5 g, 92.68 mmol, 7.49 ml) was added and stirring continued at room temperature overnight. The reaction mixture was concentrated in vacuo, diluted with t-butyl methyl ether, the organic phase washed successively with water (3), a sat. aqueous sodium carbonate solution and brine, dried over sodium sulfate and evaporated under reduced pressure to afford ethyl N-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate, as a liquid (10.4 g). This material was used without further purification LCMS (method 2): 249 (M+H).sup.+; retention time: 1.20 min. .sup.1H-NMR (CDCl.sub.3, ppm, major isomer) 1.15 (t, 3H), 2.87 (q, 2H), 3.53 (s, 3H), 7.55 (d, 1H), 7.91 (s, 1H), 8.84 (d, 1H).

Step B-1: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile

(42) ##STR00143##

(43) Under nitrogen atmosphere, a solution of 5-bromo-3-fluoro-pyridine-2-carbonitrile (1.005 g, 5.00 mmol) in dry N,N-dimethylformamide (15 ml) was cooled to 50 C. and to this was added dropwise a freshly prepared solution of sodium ethanethiolate (0.429 g, 5.10 mmol) in dry N,N-dimethylformamide (5 ml). After stirring at 50 C. for 30 minutes, the cooling bath was removed and the mixture was allowed to warm to room temperature. Water and brine were added and the aqueous mixture was extracted with ethyl acetate. After separation, the organic layer was washed twice with brine, dried over sodium sulfate and concentrated. The crude product was purified over silica by flash column chromatography (0 to 40% gradient of ethyl acetate in heptane) to afford the title compound (0.93 g) as a solid. GCMS (method 3): 242/244 (M).sup.+, retention time 6.33 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.41 (3H), 3.06 (2H), 7.82 (1H), 8.49 (1H).

(44) Alternative preparation method: Under nitrogen atmosphere, a solution of 5-bromo-3-nitro-pyridine-2-carbonitrile (45.35 g, 199 mmol) in dry N,N-dimethylformamide (500 ml) was cooled to 50 C. and to this was added dropwise a freshly prepared solution of sodium ethanethiolate (17.4 g, 207 mmol) in dry N,N-dimethylformamide (200 ml) (not a completely clear solution). After complete addition, stirring was continued at 50 C. for 30 minutes. Water and brine were added and the cooling bath was removed. The aqueous mixture was extracted with ethyl acetate. After separation, the water layer was extracted with ethyl acetate once more. The combined the organic layers were washed twice with brine, dried over sodium sulfate and concentrated. The crude product was purified over silica by flash column chromatography (0 to 25% gradient of ethyl acetate in heptane) to afford the title compound (33.9 g) as a solid. LCMS (method 1): 243/245 (M+H).sup.+; retention time: 0.95 min.

Step B-2: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic Acid

(45) ##STR00144##

(46) A solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (43 g, 170 mmol, 1.0 eq.) in 800 ml aqueous hydrogen chloride HCl 32% was heated to 60 C. overnight. Dioxane (100 ml) was added and the mixture was further stirred at 60 C. for 48 h. The reaction mixture was cooled to 0-5 C., treated with an aqueous sodium hydroxide solution (NaOH 30%) until pH11 and washed with 2200 ml tert-butyl methyl ether. The water phase was acidified with HCl 10% back to pH4, the resulting solid was filtrated, washed with water and dried in vacuo. LCMS (method 1): 262, 264 (M+H).sup.+; retention time: 0.77 min. .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.50 (s, 1H); 8.06 (s, 1H); 3.03 (q, 2H); 1.24 (t, 3H).

Step B-3:Preparation of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate

(47) ##STR00145##

(48) To a suspension of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid (15.0 g, 57.23 mmol) in methanol (350 ml) was added sulfuric acid (0.5 ml) and the mixture stirred at reflux overnight. After cooling, the solution was concentrated under reduced pressure. The residue was triturated with diethyl ether (200 ml), the suspension filtered, the solid washed with cold diethyl ether and dried in vacuo to afford methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (13.9 g) as a solid, mp 72-74 C. LCMS (method 1): 276/278 (M+H).sup.+, retention time 0.98 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.42 (3H), 2.94 (2H), 4.00 (3H), 7.78 (1H), 8.46 (1H).

Step B-4: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide

(49) ##STR00146##

(50) To a solution of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (19.8 g, 71.70 mmol) in methanol (300 ml) was added hydrazine monohydrate (4.62 ml, 93.2 mmol) and the mixture stirred at reflux for 4 hours. After cooling, the reaction mixture was concentrated under reduced pressure, the residue suspended in diethyl ether, filtered and the solid washed with cold diethyl ether and dried in vacuo to afford 5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide (17.2 g) as a solid, mp 136-138 C. LCMS (method 1): 276/278 (M+H).sup.+, retention time 0.75 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.42 (3H), 2.91 (2H), 4.02 (2H), 7.75 (1H), 8.28 (1H), 8.82 (1H).

Step C-1: Preparation of 5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine

(51) ##STR00147##

(52) A solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide (556 mg, 2.014 mmol) and ethyl N-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate (500 mg, 2.014 mmol) in ethanol (5 ml) was heated in the microwave at 150 C. for 30 minutes. After cooling, the reaction mixture was concentrated under reduced pressure and the residue purified over silica by flash column chromatography (0-25% ethyl acetate gradient in cyclohexane) to afford 5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine as a solid (700 mg), mp 122-123 C. LCMS (method 1): 444/446 (M+H).sup.+, retention time 1.04 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.36 (3H), 2.97 (2H), 4.14 (3H), 7.58 (1H), 7.86 (1H), 8.55 (1H), 8.70 (1H), 8.87 (1H).

(53) Alternative preparation method: To a solution of ethyl N-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate (3.0 g, estimated 90%, 10.88 mmol) in pyridine (12 ml) which was purged with argon for 10 minutes was added 5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide (3.0 g, 10.88 mmol). The mixture was heated in the microwave at 180 C. for 40 minutes. After cooling, the reaction mixture was poured into ice-water, stirred for 10 minutes, the suspension filtered and the solid washed with cold water. This solid was dissolved in dichloromethane, the solution dried over sodium sulfate and concentrated to dryness under reduced pressure to afford 5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine as a solid (4.3 g), which was used without further purification.

Step C-2: Preparation of 5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine

(54) ##STR00148##

(55) To a solution of 5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (4.0 g, 9.00 mmol) in dichloromethane (50 ml) at 10 C. was added mCPBA (75 wt % in water) (4.25 g, 18.46 mmol, 75%) in four portions and the mixture was stirred at 5 C. for 2 hours, then at room temperature overnight. The reaction mixture was diluted with tert-butyl methyl ether, washed successively with a sat. aqueous sodium sodium bisulfite solution (2), sat. aqueous sodium hydrogen carbonate (4) and brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was triturated with diethyl ether, the suspension filtered, the solid washed with cold diethyl ether and dried in vacuo to afford 5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine as a solid (3.6 g), mp 173-175 C. LCMS (method 1): 476/478 (M+H).sup.+, retention time 1.03 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.39 (3H), 3.85 (2H), 4.07 (3H), 7.59 (1H), 8.66 (1H), 8.69 (1H), 8.87 (1H), 9.06 (1H).

Step C-3: Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-vinyl-pyridine (Compound P12)

(56) ##STR00149##

(57) Each of two microwave vials were charged with 5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (500 mg, 1.050 mmol), dibutoxy(vinyl)borane (0.477 ml, 2.10 mmol) and an aqueous 2M sodium carbonate solution (1.57 ml, 2.0M, 3.14 mmol) in acetonitrile (12 ml). Each mixture was purged with argon for 5 minutes, then chloro(2-dicyclohexylphosphino-2,4, 6-triisopropyl-1,1-biphenyl)[2-(2-amino-1,1-biphenyl)]palladium(II) (82 mg, 0.105 mmol) was added, the vials were capped and stirred in the microwave at 120 C. for 10 minutes. Both reactions were pooled for workup: after dilution with sat. aqueous sodium hydrogen carbonate, the mixture was extracted twice with dichloromethane, the combined organic layers dried over sodium sulfate and concentrated. The residue was purified over silica by flash column chromatography (0-70% ethyl acetate gradient in cyclohexane) to afford 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-vinyl-pyridine (title compound P12) as a solid (615 mg), mp 67-70 C. LCMS (method 1): 424 (M+H).sup.+, retention time 0.97 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.38 (3H), 3.82 (2H), 4.06 (3H), 5.70 (d, 1H), 6.12 (d, 1H), 6.86 (dd, 1H), 7.59 (1H), 8.50 (1H), 8.70 (1H), 8.86 (1H), 8.97 (1H).

Example P4

Preparation of 5-(6-chloro-2-pyridyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Compound P24)

Step 1: Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (Compound Z9)

(58) ##STR00150##

(59) A mixture of 5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (1.50 g, 3.15 mmol), potassium acetate (0.805 g, 7.87 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (1.06 g, 4.09 mmol) in dioxane (10 ml) was purged with argon for 10 minutes. 1,1-Bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (1:1; PdCl.sub.2(dppf).CH.sub.2Cl.sub.2) (129.9 mg, 0.158 mmol) was then added, and the mixture was stirred in the microwave at 110 C. for 30 minutes. The reaction mixture was diluted with water (50 ml) and extracted with ethyl acetate (5). The combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. The residue was triturated with diethyl ether, the suspension filtered, the solid washed with cold diethyl ether and dried in vacuo to afford 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine as a solid (1.12 g), mp 234-236 C. LCMS (method 1): 442 (M+H).sup.+, retention time 0.83 min [consistent with the corresponding boronic acid of formula C.sub.16H.sub.15BF.sub.3N.sub.5O.sub.4S, MW: 441.19]. .sup.1H-NMR (CDCl.sub.3, ppm) 1.38 (3H), 1.40 (12H), 3.79 (2H), 4.05 (3H), 7.58 (1H), 8.70 (1H), 8.86 (2H), 9.27 (1H).

Step 2 : Preparation of 5-(6-chloro-2-pyridyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Compound P24)

(60) ##STR00151##

(61) A mixture of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (200 mg, 0.382 mmol), 2-bromo-6-chloro-pyridine (184 mg, 0.955 mmol) and an aqueous 2M sodium carbonate solution (0.573 ml, 2.0M, 1.15 mmol) in dioxane (2 ml) was purged with argon for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (22.3 mg, 0.019 mmol) was then added, and the mixture was stirred in the microwave at 85 C. for 40 minutes. The reaction mixture was diluted with tert-butyl methyl ether, filtered over diatomaceous earth (Hyflo), the filtrate dried over sodium sulfate and concentrated to dryness under reduced pressure.

(62) The residue was purified over silica by flash column chromatography (0-30% ethyl acetate gradient in cyclohexane) to afford 5-(6-chloro-2-pyridyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (title compound P24) as a solid (120 mg), mp 172-174 C. LCMS (method 1): 509/511 (M+H).sup.+, retention time 1.10 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.42 (3H), 3.89 (2H), 4.10 (3H), 7.46 (1H), 7.59 (1H), 7.84-7.90 (2H), 8.71 (1H), 8.87 (1H), 9.05 (1H), 9.63 (1H).

Example P5

Preparation of 5-cyclopropyl-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Compound P29)

(63) ##STR00152##

(64) A mixture of 5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (250 mg, 0.525 mmol), cyclopropylboronic acid (162 mg, 1.89 mmol) and tripotassium phosphate (689 mg, 3.15 mmol) in toluene/water (2 ml/2 ml) was purged with argon for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (61.3 mg, 0.053 mmol) was then added, and the mixture was stirred in the microwave at 130 C. for a total of 12 hours. The reaction mixture was concentrated, the residue diluted with tert-butyl methyl ether, the organic phase washed twice with water, dried over sodium sulfate and evaporated to dryness. The residue was purified over silica by flash column chromatography (0-35% ethyl acetate gradient in cyclohexane) to afford 5-cyclopropyl-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (title compound P29) as a solid (90 mg). LCMS (method 2): 438 (M+H).sup.+, retention time 1.53 min. .sup.1H-NMR (CDCl.sub.3, ppm) 0.95 (2H), 1.25 (2H), 1.35 (3H), 2.12 (1H), 3.76 (2H), 4.02 (3H), 7.57 (1H), 8.06 (1H), 8.69 (1H), 8.76 (1H), 8.85 (1H).

Example P6

Preparation of 2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrimidine (Compound P9)

(65) ##STR00153##

(66) A mixture of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (200 mg, 0.382 mmol), 2-bromopyrimidine (151.9 mg, 0.956 mmol) and an aqueous 2M sodium carbonate solution (0.573 ml, 2.0M, 1.15 mmol) in dioxane (2 ml) was purged with argon for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (22.3 mg, 0.019 mmol) was then added, and the mixture was stirred in the microwave at 85 C. for 40 minutes. The reaction mixture was diluted with water and extracted with ethyl acetate (4), the combined organic phases were washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified over silica by flash column chromatography (cyclohexane/ethyl acetate 3:1) to afford 2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrimidine (title compound P9) as a solid (117.6 mg), mp 191-193 C. LCMS (method 2): 476 (M+H).sup.+, retention time 1.38 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.43 (3H), 3.87 (2H), 4.11 (3H), 7.39 (1H), 7.59 (1H), 8.72 (1H), 8.87 (1H), 8.93 (2H), 9.52 (1H), 10.00 (1H).

Example P7

Preparation of 1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile (Compound P14)

Step 1: Preparation of 1-[5-ethylsulfanyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile (Compound P30)

(67) ##STR00154##

(68) To a solution of 5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (300 mg, 0.675 mmol) and 1H-pyrazole-4-carbonitrile (69.15 mg, 0.743 mmol) in N,N-dimethylformamide (3.4 ml) under argon was added copper(I) iodide (6.4 mg, 0.034 mmol), N,N-dimethylethylenediamine (6.0 mg, 7.26 l, 0.068 mmol) and potassium carbonate (18.66 mg, 0.135 mmol). The mixture was stirred at reflux for 4 hours. Same quantities of N,N-dimethylethylenediamine, copper(I) iodide and potassium carbonate were added, and stirring continued at 120 C. overnight. After cooling, the reaction mixture was filtered and concentrated in vacuo. The residue was purified over silica by flash column chromatography (0-80% ethyl acetate gradient in cyclohexane) to afford 1-[5-ethylsulfanyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile (compound P30) as a solid (125 mg). LCMS (method 1): 457 (M+H).sup.+, retention time 1.04 min.

Step 2: Preparation of 1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile (Title Compound P14)

(69) ##STR00155##

(70) To a solution of 1-[5-ethylsulfanyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile (125 mg, 0.274 mmol) in dichloromethane (5 ml) at 0 C. was added mCPBA (70 wt % in water) (162 mg, 0.657 mmol, 70%) in one portion and the mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with dichloromethane, washed successively with a 10% aqueous sodium bisulfite solution (3), a 1M aqueous sodium hydroxide solution and brine, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified over silica by flash column chromatography (0-20% ethyl acetate gradient in cyclohexane) to afford 1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile (title compound P14) as a solid. LCMS (method 1): 489 (M+H).sup.+, retention time 0.97 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.42 (3H), 3.93 (2H), 4.11 (3H), 7.62 (1H), 8.15 (1H), 8.60 (1H), 8.71 (1H), 8.82 (1H), 8.88 (1H), 9.45 (1H).

Example P8

Preparation of 1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P17)

Step 1: Preparation of 2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]acetonitrile (Compound Z10)

(71) ##STR00156##

(72) A solution of 5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (500 mg, 1.05 mmol) in DMF (2.1 ml) was placed in a 5 ml microwave vial. Under argon, trimethylsilyl acetonitrile (0.24 g, 0.29 ml, 2.1 mmol), difluorozinc (0.066 g, 0.63 mmol), XANTPHOS (0.025 g, 0.042 mmol) and Pd.sub.2(dba).sub.3 (0.020 g, 0.021 mmol) were added, the vial was capped, and heated at 140 C. for one hour in the microwave. LC/MS after this time showed reaction completion. The reaction mixture was diluted with ethyl acetate, filtered over diatomaceous earth (Hyflo), the filtrate washed with water and brine. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to give the crude product. Purification over a silica gel cartridge (Rf200; 0-75% ethyl acetate gradient in cyclohexane) gave the title compound as a beige solid (240 mg), mp 216-221 C. LCMS (method 1): 437 (M+H).sup.+, retention time 0.88 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.39 (t, J=7.34 Hz, 3H), 3.86 (q, J=7.34 Hz, 2H), 4.02 (s, 2H), 4.08 (s, 3H), 7.60 (m, 1H), 8.51 (d, J=2.20 Hz, 1H), 8.70 (s, 1H), 8.87 (d, J=5.13 Hz, 1H), 9.03 (d, J=2.20 Hz, 1H).

(73) Similarly, 2-[5-ethylsulfonyl-6-[4-methyl-5-[6-(trifluoromethyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]-3-pyridyl]acetonitrile (compound Z11, solid, mp 203-204 C.) may be obtained from 4-[5-(5-bromo-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine and trimethylsilyl acetonitrile according to the protocol described above. LCMS (method 1): 438 (M+H).sup.+, retention time: 0.85 min. .sup.1H NMR (CDCl.sub.3, ppm) 1.39 (t, J=7.34 Hz, 3H), 3.81 (q, J=7.34 Hz, 2H), 4.03 (s, 2H), 4.12 (s, 3H), 8.51 (d, J=2.20 Hz, 1H), 8.78 (d, J=1.10 Hz, 1H), 9.04 (d, J=2.20 Hz, 1H), 9.47 (m, 1H).

Step 2: Preparation of 1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P17)

(74) ##STR00157##

(75) A solution of 2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]acetonitrile (0.10 g, 0.23 mmol) in acetonitrile (3 ml) was treated with cesium carbonate (0.22 g, 0.69 mmol), and then with 1,2-dibromoethane (0.088 g, 0.04 ml, 0.46 mmol). The brown solution was stirred at 80 C. for 6.5 hours. The reaction mixture was concentrated in vacuo, and the residue was dissolved in ethyl acetate and diluted with water. The organic layer was separated, washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified over a silica gel cartridge (Rf200; 0-50% ethyl acetate gradient in cyclohexane) to give the title product P17 as an off-white solid (50 mg), mp 197-198 C. LCMS (method 1): 463 (M+H).sup.+, retention time 0.94 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.37 (t, J=7.34 Hz, 3H), 1.67 (m, 2H), 2.03 (m, 2H), 3.85 (q, J=7.34 Hz, 2H), 4.07 (s, 3H), 7.60 (d, J=5.13 Hz, 1H), 8.24 (d, J=2.20 Hz, 1H), 8.70 (s, 1H), 8.87 (d, J=5.13 Hz, 1H), 9.07 (d, J=2.20 Hz, 1H).

Example P9

Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine (Compound P32)

Step A-1: Preparation of methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate

(76) ##STR00158##

(77) 3,6-Dichloro-2-pyridinecarboxylic acid methyl ester (commercially available, 20.0 g, 97.073 mmol) was dissolved in tetrahydrofuran (200 ml) and 18-crown-6-ether (some crystals) was added. Sodium ethanethiolate (9.073 g, 97.073 mmol) was then added in 3 portions at room temperature and the reaction was stirred for 1 hour at room temperature. The reaction mixture was poured on an aqueous saturated ammonium chloride solution (100 ml) and extracted twice with ethyl acetate (2100 ml). The combined organic layers were washed with an aqueous saturated ammonium chloride solution (250 ml) and water (3100 ml), dried over sodium sulfate, filtered and evaporated under vacuum. The crude was purified by combi flash chromatography (220 g column; gradient cyclohexane+0-10% ethyl acetate) to give the title compound (14.5 g) as a solid, mp 122-124 C. LCMS (method 1): 232/234 (M+H).sup.+, retention time 0.94 min. .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 1.42 (t, 3H), 2.96 (q, 2H), 4.02 (s, 3H), 7.45 (d, 1H), 7.70 (d, 1H).

Step A-2: Preparation of methyl 3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate

(78) ##STR00159##

(79) A solution of methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate (0.3 g, 1.29 mmol) in 1,4-dioxane (7.5 ml) was treated with [4-(trifluoromethyl)phenyl]boronic acid (0.32 g, 1.68 mmol) and anhydrous potassium carbonate (0.537 g, 3.88 mmol), and the mixture purged with argon for 10 minutes. To this mixture was added tetrakis(triphenylphosphine)palladium(0) (0.149 g, 0.129 mmol) and the solution heated at 95 C. overnight. The reaction mixture was quenched with water at room temperature and ethyl acetate was added. The aqueous layer was extracted 3 times with ethyl acetate. The combined organic layer was washed with an aqueous saturated NaHCO.sub.3 solution and brine, dried over sodium sulfate, filtered and evaporated under vacuum at 45 C. The crude product was dissolved in dichloromethane and adsorbed on TEFLON BULK SORBENTS. The crude was purified by Combi flash chromatography (24 g column; gradient cyclohexane+0-50% ethyl acetate) to give the title compound (280 mg) as a white solid, mp 67-69 C. LCMS (method 1): 342 (M+H).sup.+, retention time 1.21 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.41 (t, J=7.34 Hz, 3H), 2.99 (q, J=7.34 Hz, 2H), 4.03 (s, 3H), 7.72 (d, J=8.07 Hz, 2H), 7.80 (m, 2H), 8.13 (d, J=8.07 Hz, 2H).

Step A-3: Preparation of 3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carbohydrazide

(80) ##STR00160##

(81) Obtained from methyl 3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate (500 mg, 1.44 mmol) and hydrazine hydrate (0.091 ml, 1.87 mmol) in methanol (10 ml) according to procedure Example P1, step A-5. The mixture was stirred at reflux temperature for 11 hours. After cooling, the suspension was diluted with diethyl ether, filtered, the solid washed with cold diethyl ether and dried in vacuo to afford 3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carbohydrazide (380 mg) as a solid, mp 154-155 C. LCMS (method 1): 342 (M+H).sup.+; retention time: 1.02 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.45 (t, J=7.34 Hz, 3H), 2.98 (q, J=7.34 Hz, 2H), 4.08 (br s, 2H), 7.74 (d, J=8.11 Hz, 2H), 7.79 (m, 2H), 8.07 (d, J=8.11 Hz, 2H), 9.00 (br s, 1H).

Step B-1: Preparation of 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine (Compound P31)

(82) ##STR00161##

(83) Obtained from 3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carbohydrazide (371 mg, 1.09 mmol) and ethyl N-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate (270 mg, 1.09 mmol) in pyridine (2 ml) according to procedure Example P3, step C-1. The mixture was heated in the microwave at 180 C. for 40 minutes. After cooling, the reaction mixture was concentrated in vacuo. Flash chromatography purification (gradient 0-30% ethyl acetate in cyclohexane) afforded 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]-pyridine (compound P31) as a solid (260 mg), mp 174-175 C. LCMS (method 1): 510 (M+H).sup.+; retention time: 1.25 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.37 (t, J=7.34 Hz, 3H), 3.02 (d, J=7.34 Hz, 2H), 4.22 (s, 3H), 7.59 (dd, J=5.10, 1.10 Hz, 1H), 7.73 (d, J=8.07 Hz, 2H), 7.87 (m, 2H), 8.16 (d, J=8.07 Hz, 2H), 8.73 (m, 1H), 8.88 (d, J=5.10 Hz, 1H).

Step B-2: Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine (Compound P32)

(84) ##STR00162##

(85) Obtained from 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine (190 mg, 0.373 mmol) and mCPBA (172 mg, 0.750 mmol, 75%) in dichloromethane (10 ml) according to procedure Example P1, step C-2. The mixture was stirred at room temperature overnight. Flash chromatography purification (gradient 0-25% ethyl acetate in cyclohexane) afforded 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine (title compound P32) as a solid (130 mg). LCMS (method 1): 542 (M+H).sup.+; retention time: 1.17 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.40 (t, J=7.34 Hz, 3H), 3.85 (q, J=7.34 Hz, 2H), 4.12 (s, 3H), 7.60 (dd, J=5.10, 1.28 Hz, 1H), 7.79 (d, J=8.44 Hz, 2H), 8.13 (d, J=8.44 Hz, 1H), 8.24 (d, J=8.44 Hz, 2H), 8.61 (d, J=8.44 Hz, 1H), 8.73 (m, 1H), 8.88 (d, J=5.10 Hz, 1H).

Example P10

Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine (Compound P34)

Step 1: Preparation of 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine (Compound P33)

(86) ##STR00163##

(87) A 20 ml microwave vial was charged with a solution of 5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (1.0 g, 2.251 mmol) and (bpy)CuSCF.sub.3 (2.328 g, 7.257 mmol; CAS 1413732-47-4) in acetonitrile (15 ml). The mixture was flushed with argon for 10 minutes, the vial was capped, and heated at 100 C. for 20 hours. After cooling, the reaction mixture was diluted with t-butyl methyl ether and filtered over diatomaceous earth (Hyflo), the filtrate dried over sodium sulfate and concentrated in vacuo. The residue was purified over silica by flash column chromatography (cyclohexane/ethyl acetate, gradient 3:1 to 1:1) to afford 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine (compound P33) as a solid (489 mg), mp 94-95 C. LCMS (method 1): 466 (M+H).sup.+; retention time: 1.17 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.37 (t, J=7.34 Hz, 3H), 3.01 (q, J=7.34 Hz, 2H), 4.21 (s, 3H), 7.59 (d, J=5.14 Hz, 1H), 7.99 (m, 1H), 8.67 (m, 1H), 8.71 (s, 1H), 8.88 (d, J=5.14 Hz, 1H).

Step 2: Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine (Compound P34)

(88) ##STR00164##

(89) Obtained from 3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine (460 mg, 0.988 mmol) and mCPBA (451 mg, 1.987 mmol, 75%) in dichloromethane (5 ml) according to procedure Example P1, step C-2. The mixture was stirred at room temperature overnight. Flash chromatography purification (cyclohexane/ethyl acetate 2:1) afforded 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)-pyridine (compound P34) as a solid (420 mg), mp 183-184 C. LCMS (method 1): 498 (M+H).sup.+; retention time: 1.10 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.40 (t, J=7.34 Hz, 3H), 3.90 (q, J=7.34 Hz, 2H), 4.12 (s, 3H), 7.61 (d, J=5.14 Hz, 1H), 8.70 (s, 1H), 8.79 (d, J=1.83 Hz, 1H), 8.88 (d, J=5.14 Hz, 1H), 9.18 (d, J=1.83 Hz, 1H).

Example P11

Preparation of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfonyl)pyridine (Compound P35) and 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfinyl)pyridine (Compound P36)

(90) ##STR00165##

(91) To a solution of 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine (200 mg, 0.402 mmol) in dichloromethane (5 ml) at 0 C. was added mCPBA (75 wt % in water) (190 mg, 0.824 mmol, 75%) in one portion and the mixture was stirred at 0 C. for 15 minutes, room temperature for 4 hours, then at 30 C. for 24 hours. Another portion of mCPBA (18.5 mg, 0.080 mmol, 75%) was added and stirring continued at 30 C. for 24 hours. The reaction mixture was diluted with dichloromethane, washed successively with a 10% aqueous sodium bisulfite solution (2), a saturated aqueous sodium bicarbonate solution (4) and brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified over silica by flash column chromatography (cyclohexane/ethyl acetate, gradient 3:1 to 1:1) to afford 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfonyl)pyridine (compound P35) as a solid (24 mg). LCMS (method 2): 530 (M+H).sup.+; retention time: 1.78 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.44 (t, J=7.34 Hz, 3H), 4.03 (q, J=7.34 Hz, 2H), 4.20 (s, 3H), 7.64 (d, J=5.13 Hz, 1H), 8.71 (s, 1H), 8.91 (d, J=5.13 Hz, 1H), 9.11 (d, J=1.91 Hz, 1H), 9.51 (d, J=1.91 Hz, 1H).

(92) Further elution then gave 3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfinyl)pyridine (compound P36) as a solid (18 mg). LCMS (method 2): 514 (M+H).sup.+; retention time: 1.60 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.41 (t, J=7.35 Hz, 3H), 3.95 (q, J=7.35 Hz, 2H), 4.15 (s, 3H), 7.63 (d, J=5.14 Hz, 1H), 8.71 (s, 1H), 8.91 (m, 2H), 9.32 (d, J=1.83 Hz, 1H).

Example P12

Preparation of 4-[5-[6-(3-chloro-1,2,4-triazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine (Compound P48)

Step A-1: Preparation of N-methyl-6-(trifluoromethyl)pyrimidine-4-carboxamide

(93) ##STR00166##

(94) To a solution of 6-(trifluoromethyl)pyrimidine-4-carboxylic acid (24.2 g, 126.0 mmol) in dichloromethane (300 ml) at 5-10 C. was added dropwise N,N-dimethylformamide (0.1 ml) and oxalyl chloride (13.6 ml, 151.2 mmol). The reaction mixture was stirred at ambient temperature overnight, then concentrated to dryness in vacuo to afford 6-(trifluoromethyl)pyrimidine-4-carbonyl chloride (25.3 g) as a solid.

(95) The title compound N-methyl-6-(trifluoromethyl)pyrimidine-4-carboxamide was obtained from 6-(tri-fluoromethyl)pyrimidine-4-carbonyl chloride (24 g, 114.0 mmol), methylamine (2M in tetrahydrofuran) (142.5 ml, 285.0 mmol) and triethylamine (171.0 mmol) in tetrahydrofuran (total 300 ml) according to procedure Example P3, step A-1. The mixture was stirred at 0-5 C. for one hour. The crude material obtained after aqueous workup was used without further purification (19.9 g as a solid). LCMS (method 1): 206 (M+H).sup.+; retention time: 0.70 min. .sup.1H-NMR (CDCl.sub.3, ppm) 3.10 (d, 3H), 7.97 (br s, 1H), 8.48 (s, 1H), 9.39 (s, 1H).

Step A-2: Preparation of N-methyl-6-(trifluoromethyl)pyrimidine-4-carbothioamide

(96) ##STR00167##

(97) Obtained from N-methyl-6-(trifluoromethyl)pyrimidine-4-carboxamide (19.0 g, 92.6 mmol) and phosphorus pentasulfide (24.7 g, 55.6 mmol) in pyridine (200 ml) according to procedure Example P3, step A-2. The mixture was stirred at reflux temperature for 4.5 hours. The crude material obtained after aqueous workup was used without further purification (16.1 g as a solid), mp 104-106 C. LCMS (method 1): 222 (M+H).sup.+; retention time: 0.95 min. .sup.1H-NMR (CDCl.sub.3, ppm) 3.43 (d, 3H), 8.92 (s, 1H), 9.33 (s, 1H), 10.06 (br s, 1H).

Step A-3: Preparation of ethyl N-methyl-6-(trifluoromethyl)pyrimidine-4-carboximidothioate

(98) ##STR00168##

(99) Obtained from N-methyl-6-(trifluoromethyl)pyrimidine-4-carbothioamide (15.0 g, 67.8 mmol), sodium ethoxide (21 wt % in EtOH) (67.8 mmol, 25 ml) and iodoethane (21.15 g, 135.6 mmol, 11.6 ml) in ethanol (350 ml) according to procedure Example P3, step A-3. The mixture was stirred at room temperature overnight. The crude material obtained after aqueous workup was used without further purification (11.8 g as a liquid). LCMS (method 1): 250 (M+H).sup.+; retention time: 0.96 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.19 (t, 3H), 2.97 (q, 2H), 3.56 (s, 3H), 8.04 (s, 1H), 9.42 (s, 1H).

Step B-1: Preparation of 6-chloro-3-ethylsulfanyl-pyridine-2-carbohydrazide

(100) ##STR00169##

(101) Obtained from methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate (preparation described above, 10.0 g, 43.16 mmol) and hydrazine monohydrate (4.24 ml, 86.3 mmol) in methanol (100 ml) according to procedure Example P3, step B-4. The mixture was stirred at reflux for 26 hours. The residue obtained after workup was triturated in diethyl ether, filtered and dried in vacuo to afford 6-chloro-3-ethylsulfanyl-pyridine-2-carbohydrazide (6.12 g) as a solid, mp 150-151 C. LCMS (method 1): 232/234 (M+H).sup.+; retention time: 0.64 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.41 (t, 3H), 2.92 (q, 2H), 4.02 (d, 2H), 7.36 (d, 1H), 7.62 (d, 1H), 8.76 (br s, 1H).

Step C-1: Preparation of 4-[5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine

(102) ##STR00170##

(103) Obtained from 6-chloro-3-ethylsulfanyl-pyridine-2-carbohydrazide (4.65 g, 20.07 mmol) and ethyl N-methyl-6-(trifluoromethyl)pyrimidine-4-carboximidothioate (5.0 g, 20.06 mmol) in pyridine (50 ml) according to procedure Example P3, step C-1. The mixture was heated in the microwave at 160 C. for 60 minutes (four parallel reactions). The crude material obtained after combined workup was used without further purification (8.04 g as a solid), mp 88-90 C. LCMS (method 1): 401/403 (M+H).sup.+; retention time: 1.01 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.33 (t, 3H), 2.97 (q, 2H), 4.25 (s, 3H), 7.43 (d, 1H), 7.77 (d, 1H), 8.79 (s, 1H), 9.46 (s, 1H).

Step C-2: Preparation of 4-[5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine

(104) ##STR00171##

(105) Obtained from 4-[5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl) pyrimidine (2.5 g, 6.24 mmol) and mCPBA (3.2 g, 13.0 mmol, 70%) in dichloromethane (30 ml) according to procedure Example P3, step C-2. The mixture was stirred at 0-5 C. for 3 hours. The residue obtained after aqueous workup was triturated with diethyl ether, the suspension filtered and the solid dried in vacuo to afford 4-[5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine (2.2 g) as a solid, mp 183-185 C. LCMS (method 1): 433/435 (M+H).sup.+; retention time: 0.94 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.37 (t, 3H), 3.76 (q, 2H), 4.15 (s, 3H), 7.74 (d, 1H), 8.47 (d, 1H), 8.77 (s, 1H), 9.47 (s, 1H).

Step C-3: Preparation of 4-[5-[6-(3-chloro-1,2,4-triazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine (Compound P48)

(106) ##STR00172##

(107) A solution of 4-[5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl) pyrimidine (300 mg, 0.693 mmol) and 3-chloro-1H-1,2,4-triazole (107.6 mg, 1.04 mmol) in pyridine (3 ml) under argon was heated in the microwave at 120 C. for 30 minutes. After cooling, the reaction mixture was poured onto iced water (20 ml), the suspension filtered and the solid washed with cold water. This residue was dissolved in dichloromethane, dried over sodium sulfate, filtered and concentrated to dryness to afford the title compound 4-[5-[6-(3-chloro-1,2,4-triazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine (compound P48) as a solid, mp 261-263 C. LCMS (method 1): 500/502 (M+H).sup.+; retention time: 0.96 min. .sup.1H-NMR (CDCl.sub.3, ppm) 1.38 (t, 3H), 3.72 (q, 2H), 4.14 (s, 3H), 8.25 (d, 1H), 8.73 (d, 1H), 8.79 (s, 1H), 9.07 (s, 1H), 9.48 (s, 1H).

Example P13

Preparation of 3-ethylsulfonyl-6-(3-fluorophenyl)-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (Compound P50)

(108) ##STR00173##

(109) In a microwave vial, a mixture of 6-chloro-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (300 mg, 0.695 mmol), (3-fluorophenyl)boronic acid (150 mg, 1.042 mmol) and an aqueous 2M sodium carbonate solution (1.04 ml, 2.0M, 2.08 mmol) in 1,2-dimethoxyethane (3 ml) was purged with argon for 10 minutes. Bis(triphenylphosphine) palladium(II) dichloride (5 mg, 0.007 mmol) was then added, and the mixture was stirred in the microwave at 110 C. for 30 minutes. The reaction mixture was diluted with ethyl acetate, the organic phase washed several times with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified over silica by flash column chromatography (ethyl acetate gradient in cyclohexane) and the fractions containing product were combined and concentrated. The residue was triturated with diethyl ether, the suspension filtered and the solid dried in vacuo to afford 3-ethylsulfonyl-6-(3-fluorophenyl)-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine (compound P50) as a solid (85 mg), mp 182-184 C. LCMS (method 1): 492 (M+H).sup.+, retention time 1.07 min. 1H-NMR (CDCl3, ppm) 1.40 (t, 3H), 3.86 (q, 2H), 4.11 (s, 3H), 7.24 (m, 1H), 7.43 (m, 1H), 7.49-7.62 (m, 3H), 8.67 (d, 1H), 8.71 (s, 1H), 8.88 (d, 1H), 9.19 (d, 1H).

(110) TABLE-US-00015 TABLE P Examples of compounds of formula (I) LCMS Compound R.sub.t [M + H].sup.+ No. Structures (min) (measured) Method Mp ( C.) P1 1.97 476/478 2 147-149 P2 1.81 508/510 2 234-235 P3 1.54 432 2 121-123 P4 1.43 464 2 174-176 P5 1.84 500 2 P6 1.71 532 2 172-174 P7 0 1.59 498/500 2 166-168 P8 1.54 444 2 162-165 P9 1.38 476 2 191-193 P10 2.06 510 2 P11 1.16 542 1 206-208 P12 0.97 424 1 67-70 P13 1.09 468 1 P14 0.97 489 1 P15 0.90 489 1 P16 1.02 489 1 P17 0 0.94 464 1 197-198 P18 1.10 510/512 1 273-275 P19 1.03 501 1 268-270 P20 1.02 501 1 270-272 P21 1.04 500 1 158-160 P22 1.03 500 1 223-225 P23 0.99 500 1 179-181 P24 1.10 509/511 1 172-174 P25 1.11 509/511 1 229-231 P26 1.09 509/511 1 145-147 P27 00 0.97 499/501 1 P28 01 1.04 498/500 1 P29 02 1.53 438 2 solid P30 1.04 457 1 solid P31 1.25 510 1 174-175 P32 03 1.17 542 1 solid P33 04 1.17 466 1 94-95 P34 05 1.10 498 1 183-184 P35 06 1.78 530 2 solid P36 07 1.60 514 2 solid P37 08 0.89 465 1 133-135 P38 09 1.01 438 1 179-181 P39 0 0.89 476 1 145-147 P40 0.85 465 1 207-209 P41 0.97 499/501 1 136-138 P42 0.96 490 1 229-231 P43 0.94 490 1 235-237 P44 0.94 491 1 205-207 P45 0.94 500/502 1 233-235 P46 0.84 466 1 solid P47 0.85 466 1 245-247 P48 0.96 500/502 1 261-263 P49 0.95 491 1 242-244 P50 1.07 492 1 182-184 P51 1.06 493 1 201-203 P52 1.04 493 1 197-199 P53 1.07 492 1 167-169 P54 0 0.84 477 1 solid P55 0.98 464 1 solid P56 1.07 498/500 1 251-253 P57 0.91 464 1 226-228 P58 0.96 439 1 129-131 P59 0.94 477 1 solid

(111) TABLE-US-00016 TABLE Z Examples of intermediates of formula (IX), (IX-p), (XVII) and (Iab) LCMS Compound R.sub.t [M + H].sup.+ No. Structures (min) (measured) Method Mp ( C.) Z1 1.04 444/446 1 122-123 Z2 1.03 476/478 1 173-175 Z3 1.03 445/447 1 108-110 Z4 0.96 477/479 1 solid Z5 solid Z6 150-152 Z7 1.01 401/403 1 88-90 Z8 0.94 433/435 1 183-185 Z9 0.83 442 1 234-236 Z10 0 0.88 437 1 216-221 Z11 0.85 438 1 203-204

(112) The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use. Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

(113) The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation TX means one compound selected from the group consisting of the compounds described in Tables 1 to 12 and Table P of the present invention):

(114) an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,

(115) an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin (202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate (872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin (46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternative name) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX, brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50439 (development code) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX, chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate (975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX, chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel (alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name) (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton (278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX, fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil (1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim (360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron (370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512 (compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternative name) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp-DDT (219)+TX, parathion (615)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes (traditional name) (1347)+TX, polynactins (alternative name) (653)+TX, proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite (671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos (711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX, sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam (alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX, tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox (alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternative name) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion (847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

(116) an algicide selected from the group of substances consisting of bethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX,

(117) an anthelmintic selected from the group of substances consisting of abamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

(118) an avicide selected from the group of substances consisting of chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copper dioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name) (169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione (1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline (611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole (658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX, tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

(119) a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12)+TX, Agrobacterium radiobacter (alternative name) (13)+TX, Amblyseius spp. (alternative name) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX, Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis (alternative name) (33)+TX, Aphidius colemani (alternative name) (34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographa californica NPV (alternative name) (38)+TX, Bacillus firmus (alternative name) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX, Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveria bassiana (alternative name) (53)+TX, Beauveria brongniartii (alternative name) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX, Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonella GV (alternative name) (191)+TX, Dacnusa sibirica (alternative name) (212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa (scientific name) (293)+TX, Eretmocerus eremicus (alternative name) (300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastix dactylopii (alternative name) (488)+TX, Macrolophus caliginosus (alternative name) (491)+TX, Mamestra brassicae NPV (alternative name) (494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhizium anisopliae var. acridum (scientific name) (523)+TX, Metarhizium anisopliae var. anisopliae (scientific name) (523)+TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp. (alternative name) (596)+TX, Paecilomyces fumosoroseus (alternative name) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741)+TX, Steinernema bibionis (alternative name) (742)+TX, Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae (alternative name) (742)+TX, Steinernema glaseri (alternative name) (742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernema riobravis (alternative name) (742)+TX, Steinernema scapterisci (alternative name) (742)+TX, Steinernema spp. (alternative name) (742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848)+TX,

(120) a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

(121) a chemosterilant selected from the group of substances consisting of apholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan (alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid [CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX, thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name) [CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN]+TX,

(122) an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX, 14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin (alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX, codlelure (alternative name) [CCN]+TX, codlemone (alternative name) (167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl 4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name) [CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternative name) (420)+TX, grandlure (421)+TX, grandlure I (alternative name) (421)+TX, grandlure II (alternative name) (421)+TX, grandlure III (alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX, hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol (alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX, lineatin (alternative name) [CCN]+TX, litlure (alternative name) [CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX, megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternative name) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternative name) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX, sordidin (alternative name) (736)+TX, sulcatol (alternative name) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B.sub.1 (alternative name) (839)+TX, trimedlure B.sub.2 (alternative name) (839)+TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX,

(123) an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide [CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX, oxamate [CCN] and picaridin [CCN]+TX,

(124) an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935)+TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/Chemical Abstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX, 2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX, acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX, allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX, alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX, aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin (alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillus thuringiensis delta endotoxins (alternative name) (52)+TX, barium hexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer 22/190 (development code) (893)+TX, Bayer 22408 (development code) (894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX, beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin (76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name) (909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate (alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX, bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX, butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate (932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternative name) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone (963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos (131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform [CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos (990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternative name)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX, cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX, clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate [CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate (1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS 708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos (184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin (188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate (alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX, d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon (1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos (243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron (250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX, dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin (1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam (1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan (1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion (1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX, doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone (alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX, empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX, eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX, etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion (309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternative name) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX, fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX, flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX, flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX, gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, GY-81 (development code) (423)+TX, halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD (1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos [CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX, hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX, imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX, iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX, isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin (1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX, isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name) (473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I (alternative name) [CCN]+TX, juvenile hormone II (alternative name) [CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan (1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX, methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternative name) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform (alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin [CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX, naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170 (development code) (1306)+TX, NC-184 (compound code)+TX, nicotine (578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram (579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron (585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075)+TX, O,O,O,O-tetrapropyl dithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name) (593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl (609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp-DDT (219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX, parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX, pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name) (623)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX, phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX, phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX, pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name) (1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX, precocene I (alternative name) [CCN]+TX, precocene II (alternative name) [CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos (1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl (1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos (686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin (1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen (708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX, quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, rafoxanide (alternative name) [CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (development code) (723)+TX, RU 25475 (development code) (1386)+TX, ryania (alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX, sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129 (development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX, sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide (623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate [CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX, spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulprofos (1408)+TX, tar oils (alternative name) (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX, teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos (777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX, thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap (803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name) [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate (818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX, trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX, trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX, vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine (alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302 (compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternative name)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901 (development code) (858)+TX, cyantraniliprole [736994-63-19+TX, chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX, cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX, spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX, sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin [915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim (disclosed in WO 2012/092115)+TX, fluxametamide (WO 2007/026965)+TX, epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin [1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chloroprallethrin [399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalodiamide [1262605-53-7]+TX, tioxazafen [330459-31-9]+TX, broflanilide [1207727-04-5]+TX, flufiprole [704886-18-0]+TX, cyclaniliprole [1031756-98-5]+TX, tetraniliprole [1229654-66-3]+TX, guadipyr (described in WO2010/060231)+TX, cycloxaprid (described in WO2005/077934)+TX,

(125) a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,

(126) a nematicide selected from the group of substances consisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene (233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX, abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz [CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX, cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX, dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate (262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX, GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX, ivermectin (alternative name) [CCN]+TX, kinetin (alternative name) (210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrothecium verrucaria composition (alternative name) (565)+TX, NC-184 (compound code)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin (1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name) (210)+TX, fluensulfone [318290-98-1]+TX,

(127) a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

(128) a plant activator selected from the group of substances consisting of acibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720)+TX,

(129) a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu (880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX, bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX, bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX, chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX, coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX, crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX, fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadine hydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogen cyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX, magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX, norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,

(130) a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX, farnesol with nerolidol (alternative name) (324)+TX, MB-599 (development code) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,

(131) an animal repellent selected from the group of substances consisting of anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene (chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX, thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX,

(132) a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

(133) a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,

(134) and biologically active compounds selected from the group consisting of azaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole [125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate [101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole [178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX, propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX, tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX, triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole [99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol [12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX, bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol [23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX, fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph [81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim [110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil [74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl [71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX, R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl [77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX, debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole [148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline [24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX, procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid [188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX, flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin [5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide [130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3] [112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin [131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin [361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin [133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin [248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin [175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb [12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX, thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX, captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid [1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX, tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX, copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX, coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper [53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX, nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX, iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl [57018-04-9]+TX, acibenzo-lar-S-methyl [135158-54-2]+TX, anilazine [101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S [2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX, chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil [57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX, diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb [87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-L190 (Flumorph) [211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX, etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone [161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX, ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid [126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol [10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid) [120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron [66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX, probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid [189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen [124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX, tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX, isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (disclosed in WO 2007/048556)+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3,4,5-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343)+TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7]+TX,1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8]+TX; lancotrione [1486617-21-3], florpyrauxifen [943832-81-3], ipfentrifluconazole[1417782-08-1], mefentrifluconazole [1417782-03-6], quinofumelin [861647-84-9], chloroprallethrin [399572-87-3], cyhalodiamide [1262605-53-7], fluazaindolizine [1254304-22-7], fluxametamide [928783-29-3], epsilon-metofluthrin [240494-71-7], epsilon-momfluorothrin [1065124-65-3], pydiflumetofen [1228284-64-7], kappa-bifenthrin [439680-76-9], broflanilide [1207727-04-5], dicloromezotiaz [1263629-39-5], dipymetitrone [16114-35-5], pyraziflumid [942515-63-1] and kappa-tefluthrin [391634-71-2]; and

(135) microbials including: Acinetobacter lwoffii+TX, Acremonium alternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremonium diospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus (AdoxGV) (Capex)+TX, Agrobacterium radiobacter strain K84 (Galltrol-A)+TX, Alternaria alternate+TX, Alternaria cassia+TX, Alternaria destruens (Smolder)+TX, Ampelomyces quisqualis (AQ10)+TX, Aspergillus flavus AF36 (AF36)+TX, Aspergillus flavus NRRL 21882 (Aflaguard)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX, Azospirillum+TX, (MicroAZ+TX, TAZO B)+TX, Azotobacter+TX, Azotobacter chroocuccum (Azotomeal)+TX, Azotobacter cysts (Bionatural Blooming Blossoms)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart Rhizoboost)+TX, Bacillus licheniformis strain 3086 (EcoGuard+TX, Green Releaf)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe+TX, BioNem-WP+TX, VOTiVO)+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillae (Milky Spore Powder)+TX, Bacillus pumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield)+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808 (Sonata+TX, Ballad Plus)+TX, Bacillus spahericus (VectoLex)+TX, Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strain AQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST 713 (CEASE+TX, Serenade+TX, Rhapsody)+TX, Bacillus subtilis strain QST 714 (JAZZ)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro+TX, Rhizopro)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 (Agree)+TX, Bacillus thuringiensis israelensis (BMP123+TX, Aquabac+TX, VectoBac)+TX, Bacillus thuringiensis kurstaki (Javelin+TX, Deliver+TX, CryMax+TX, Bonide+TX, Scutella WP+TX, Turilav WP+TX, Astuto+TX, Dipel WP+TX, Biobit+TX, Foray)+TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone)+TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF/3P)+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari+TX, DiPel)+TX, bacteria spp. (GROWMEND+TX, GROWSWEET+TX, Shootup)+TX, bacteriophage of Clavipacter michiganensis (AgriPhage)+TX, Bakflor+TX, Beauveria bassiana (Beaugenic+TX, Brocaril WP)+TX, Beauveria bassiana GHA (Mycotrol ES+TX, Mycotrol O+TX, BotaniGuard)+TX, Beauveria brongniartii (Engerlingspilz+TX, Schweizer Beauveria+TX, Melocont)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum (TerraMax)+TX, Brevibacillus brevis+TX, Bacillus thuringiensis tenebrionis (Novodor)+TX, BtBooster+TX, Burkholderia cepacia (Deny+TX, Intercept+TX, Blue Circle)+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian Bioherbicide)+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guiffiermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat+TX, Biocure)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova-Cide)+TX, Chaetomium globosum (Nova-Cide)+TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo)+TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea (EndoFine)+TX, Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans WG)+TX, Coniothyrium spp.+TX, Cryptococcus albidus (YIELDPLUS)+TX, Cryptococcus humicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex)+TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD-X)+TX, Cydia pomonella granulovirus (Madex+TX, Madex Plus+TX, Madex Max/Carpovirusine)+TX, Cylindrobasidium laeve (Stumpout)+TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta (Vektor)+TX, Epicoccum nigrum+TX, Epicoccum purpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean/Biofox C)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop+TX, Prestop)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard)+TX, Gliocladium virens (Soilgard)+TX, Granulovirus (Granupom)+TX, Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillus trueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibrio variabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex)+TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar)+TX, Isoflavoneformononetin (Myconate)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidium giganteum (Laginex)+TX, Lecanicillium longisporum (Vertiblast)+TX, Lecanicillium muscarium (Vertikil)+TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus)+TX, Marinococcus halophilus+TX, Meira geulakonigii+TX, Metarhizium anisopliae (Met52)+TX, Metarhizium anisopliae (Destruxin WP)+TX, Metschnikowia fruticola (Shemer)+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot)+TX, Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus 620 (Muscudor)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. (AMykor+TX, Root Maximizer)+TX, Myrothecium verrucaria strain AARC-0255 (DiTera)+TX, BROS PLUS+TX, Ophiostoma piliferum strain D97 (Sylvanex)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus (PFR-97+TX, PreFeRal)+TX, Paecilomyces linacinus (Biostat WP)+TX, Paecilomyces lilacinus strain 251 (MeloCon WG)+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan C9-1)+TX, Pantoea spp.+TX, Pasteuria spp. (Econem)+TX, Pasteuria nishizawae+TX, Penicillium aurantiogriseum+TX, Penicillium billai (Jumpstart+TX, TagTeam)+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop)+TX, phosphate solubilizing bacteria (Phosphomeal)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine)+TX, Pichia anomala+TX, Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX, Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens (Spot-Less Biofungicide)+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis (AtEze)+TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens strain A506 (BlightBan A506)+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae (Bio-Save)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens (Zequanox)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L)+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior)+TX, Pythium paroecandrum+TX, Pythium oligandrum (Polygandron+TX, Polyversum)+TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia (Dormal+TX, Vault)+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor (SARRITOR)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X+TX, Spexit)+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir)+TX, Sporobolomyces roseus+TX, Stenotrophomonas maltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomyces albaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX, Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop)+TX, Streptomyces lydicus (Actinovate)+TX, Streptomyces lydicus WYEC-108 (ActinoGrow)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol)+TX, Trichoderma gamsii (Tenet)+TX, Trichoderma atroviride (Plantmate)+TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai (Mycostar)+TX, Trichoderma harzianum T-22 (Trianum-P+TX, PlantShield HC+TX, RootShield+TX, Trianum-G)+TX, Trichoderma harzianum T-39 (Trichodex)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma spp. LC 52 (Sentinel)+TX, Trichoderma lignorum+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T)+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard)+TX, Trichoderma viride+TX, Trichoderma viride strain ICC 080 (Remedier)+TX, Trichosporon pullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichothecium roseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhiza strain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii (Botry-Zen)+TX, Ustilago maydis+TX, various bacteria and supplementary micronutrients (Natural II)+TX, various fungi (Millennium Microbes)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii (Mycotal+TX, Vertalec)+TX, Vip3Aa20 (VlPtera)+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv. Poae (Camperico)+TX, Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and

(136) Plant extracts including: pine oil (Retenol)+TX, azadirachtin (Plasma Neem Oil+TX, AzaGuard+TX, MeemAzal+TX, Molt-X+TX, Botanical IGR (Neemazad+TX, Neemix)+TX, canola oil (Lilly Miller Vegol)+TX, Chenopodium ambrosioides near ambrosioides (Requiem)+TX, Chrysanthemum extract (Crisant)+TX, extract of neem oil (Trilogy)+TX, essentials oils of Labiatae (Botania)+TX, extracts of clove rosemary peppermint and thyme oil (Garden insect Killer)+TX, Glycinebetaine (Greenstim)+TX, garlic+TX, lemongrass oil (GreenMatch)+TX, neem oil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX, oregano oil (MossBuster)+TX, Pedaliaceae oil (Nematon)+TX, pyrethrum+TX, Quillaja saponaria (NemaQ)+TX, Reynoutria sachalinensis (Regalia+TX, Sakalia)+TX, rotenone (Eco Roten)+TX, Rutaceae plant extract (Soleo)+TX, soybean oil (Ortho Ecosense)+TX, tea tree oil (Timorex Gold)+TX, thymus oil+TX, AGNIQUE MMF+TX, BugOil+TX, mixture of rosemary sesame peppermint thyme and cinnamon extracts (EF 300)+TX, mixture of clove rosemary and peppermint extract (EF 400)+TX, mixture of clove peppermint garlic oil and mint (Soil Shot)+TX, kaolin (Screen)+TX, storage glucam of brown algae (Laminarin); and

(137) pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone)+TX, Codling Moth Pheromone (Paramount dispenser-(CM)/Isomate C-Plus)+TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone)+TX, Leafroller pheromone (3M MEC-LR Sprayable Pheromone)+TX, Muscamone (Snip7 Fly Bait+TX, Starbar Premium Fly Bait)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable Pheromone)+TX, Peachtree Borer Pheromone (Isomate-P)+TX, Tomato Pinworm Pheromone (3M Sprayable Pheromone)+TX, Entostat powder (extract from palm tree) (Exosex CM)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11 Tetradecatrienyl acetate+TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX, (E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX, Calcium acetate+TX, Scenturion+TX, Biolure+TX, Check-Mate+TX, Lavandulyl senecioate; and

(138) Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi (Aphelinus-System)+TX, Acerophagus papaya+TX, Adalia bipunctata (Adalia-System)+TX, Adalia bipunctata (Adaline)+TX, Adalia bipunctata (Aphidalia)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX, Amblyseius andersoni (Anderline+TX, Andersoni-System)+TX, Amblyseius califomicus (Amblyline+TX, Spical)+TX, Amblyseius cucumeris (Thripex+TX, Bugline Cucumeris)+TX, Amblyseius fallacis (Fallacis)+TX, Amblyseius swirskii (Bugline Swirskii+TX, Swirskii-Mite)+TX, Amblyseius womersleyi (WomerMite)+TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar)+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralis (Anthocoris-System)+TX, Aphelinus abdominalis (Apheline+TX, Aphiline)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar)+TX, Aphidius ervi (Ervipar)+TX, Aphidius gifuensis+TX, Aphidius matricariae (Aphipar-M)+TX, Aphidoletes aphidimyza (Aphidend)+TX, Aphidoletes aphidimyza (Aphidoline)+TX, Aphytis lingnanensis+TX, Aphytis melinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline)+TX, Bombus spp.+TX, Bombus terrestris (Natupol Beehive)+TX, Bombus terrestris (Beeline+TX, Tripol)+TX, Cephalonomia stephanoderis+TX, Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline)+TX, Chrysoperla carnea (Chrysopa)+TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar)+TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX, Cryptolaemus montrouzieri (Cryptobug+TX, Cryptoline)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa)+TX, Diglyphus isaea (Diminex)+TX, Delphastus catalinae (Delphastus)+TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea (Miglyphus+TX, Digline)+TX, Dacnusa sibirica (DacDigline+TX, Minex)+TX, Diversinervus spp.+TX, Encarsia citrina+TX, Encarsia formosa (Encarsia Max+TX, Encarline+TX, En-Strip)+TX, Eretmocerus eremicus (Enermix)+TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus (Syrphidend)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus (Ercal+TX, Eretline E)+TX, Eretmocerus eremicus (Bemimix)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar+TX, Eretline M)+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga (Spidend)+TX, Feltiella acarisuga (Feltiline)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX, Formononetin (Wirless Beehome)+TX, Franklinothrips vespiformis (Vespop)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle)+TX, Heterorhabditis spp. (Lawn Patrol)+TX, Heterorhabditis bacteriophora (NemaShield HB+TX, Nemaseek+TX, Terranem-Nam+TX, Terranem+TX, Larvanem+TX, B-Green+TX, NemAttack+TX, Nematop)+TX, Heterorhabditis megidis (Nemasys+TX, BioNem+TX, Exhibitline Hm+TX, Larvanem-M)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System+TX, Entomite-A)+TX, Hypoaspis miles (Hypoline M+TX, Entomite-M)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopfi (Leptopar)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar (Natufly)+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N+TX, Macroline+TX, Mirical)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing)+TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar)+TX, Neodryinus typhlocybae+TX, Neoseiulus califomicus+TX, Neoseiulus cucumeris (THRYPEX)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis (NesidioBug+TX, Nesibug)+TX, Ophyra aenescens (Biofly)+TX, Orius insidiosus (Thripor-I+TX, Oriline I)+TX, Orius laevigatus (Thripor-L+TX, Oriline I)+TX, Orius majusculus (Oriline M)+TX, Orius strigicollis (Thripor-S)+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug)+TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis (Spidex+TX, Phytoline P)+TX, Podisus maculiventris (Podisus)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank)+TX, Steinernema carpocapsae (Nematac C+TX, Millenium+TX, BioNem C+TX, NemAttack+TX, Nemastar+TX, Capsanem)+TX, Steinernema feltiae (NemaShield+TX, Nemasys F+TX, BioNem F+TX, Steinernema-System+TX, NemAttack+TX, Nemaplus+TX, Exhibitline Sf+TX, Scia-Rid+TX, Entonem)+TX, Steinernema kraussei (Nemasys L+TX, BioNem L+TX, Exhibitline Srb)+TX, Steinernema riobrave (BioVector+TX, BioVektor)+TX, Steinernema scapterisci (Nematac S)+TX, Steinernema spp.+TX, Steinernematid spp. (Guardian Nematodes)+TX, Stethorus punctillum (Stethorus)+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae (Tricholine B)+TX, Trichogramma brassicae (Tricho-Strip)+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator; and

(139) other biologicals including: abscisic acid+TX, bioSea+TX, Chondrostereum purpureum (Chontrol Paste)+TX, Colletotrichum gloeosporioides (Callego)+TX, Copper Octanoate (Cueva)+TX, Delta traps (Trapline D)+TX, Erwinia amylovora (Harpin) (ProAct+TX, Ni-HIBIT Gold CST)+TX, Ferri-phosphate (Ferramol)+TX, Funnel traps (Trapline Y)+TX, Gallex+TX, Growers Secret+TX, Homo-brassonolide+TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait)+TX, MCP hail trap (Trapline F)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X)+TX, BioGain+TX, Aminomite+TX, Zenox+TX, Pheromone trap (Thripline Ams)+TX, potassium bicarbonate (MilStop)+TX, potassium salts of fatty acids (Sanova)+TX, potassium silicate solution (SD-Matrix)+TX, potassium iodide+potassiumthiocyanate (Enzicur)+TX, SuffOil-X+TX, Spider venom+TX, Nosema locustae (Semaspore Organic Grasshopper Control)+TX, Sticky traps (Trapline YF+TX, Rebell Amarillo)+TX and Traps (Takitrapline y+B)+TX.

(140) The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in The Pesticide Manual [The Pesticide ManualA World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound abamectin is described under entry number (1). Where [CCN] is added hereinabove to the particular compound, the compound in question is included in the Compendium of Pesticide Common Names, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright 1995-2004]; for example, the compound acetoprole is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

(141) Most of the active ingredients described above are referred to hereinabove by a so-called common name, the relevant ISO common name or another common name being used in individual cases. If the designation is not a common name, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a chemical name, a traditional name, a compound name or a development code is used or, if neither one of those designations nor a common name is used, an alternative name is employed. CAS Reg. No means the Chemical Abstracts Registry Number.

(142) The active ingredient mixture of the compounds of formula I selected from Tables 1 to 12 and Table P with active ingredients described above comprises a compound selected from Tables 1 to 12 and Table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

(143) The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

(144) The mixtures comprising a compound of formula I selected from Tables 1 to 12 and Table P 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 selected from Tables 1 to 12 and Table P and the active ingredients as described above is not essential for working the present invention.

(145) The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

(146) The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

(147) The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouringwhich are to be selected to suit the intended aims of the prevailing circumstancesand the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

(148) A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

(149) The compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.

(150) The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

(151) The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).

(152) Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.

BIOLOGICAL EXAMPLES

Example B1

Activity Against Spodoptera littoralis (Egyptian Cotton Leaf Worm)

(153) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feedant effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is when at least one of mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

(154) The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P4, P6, P7, P9, P11, P13, P14, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P32, P35, P37, P38, P39, P41, P42, P40, P44, P45, P48, P50, P52 and P53.

Example B2

Activity Against Spodoptera littoralis (Egyptian Cotton Leaf Worm)

(155) Test compounds were applied by pipette from 10,000 ppm DMSO stock solutions into 24-well plates and mixed with agar. Lettuce seeds were placed on the agar and the multi well plate was closed by another plate which contains also agar. After 7 days the roots have absorbed the compound and the lettuce has grown into the lid plate. The lettuce leafs were now cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil on a humid gel blotting paper and the plate closed with it. The samples were assessed for mortality, anti-feedant effect and growth inhibition in comparison to untreated samples 6 days after infestation.

(156) The following compounds gave an effect of at least 80% in at least one of the three categories (mortality, anti-feedancy, or growth inhibition) at a test rate of 12.5 ppm: P6, P7, P9, P14, P16, P17, P20, P21, P22, P23, P25, P26, P27, P28, P29, P39, P41, P40, P48, P50 and P52.

Example B3

Activity Against Plutella xylostella (Diamond Back Moth)

(157) 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

(158) The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P6, P7, P8, P9, P11, P13, P14, P16, P17, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P32, P35, P37, P38, P39, P41, P40, P45, P48, P50, P52, P53 and P54.

Example B4

Activity Against Diabrotica Balteata (Corn Root Worm)

(159) Maize sprouts, placed on an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.

(160) The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P5, P6, P7, P8, P9, P11, P13, P14, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P32, P34, P35, P36, P37, P38, P39, P41, P40, P45, P46, P47, P48, P50, P52, P53 and P54.

Example B5

Activity Against Myzus persicae (Green Peach Aphid)

(161) Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.

(162) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P4, P6, P7, P9, P11, P12, P13, P14, P16, P17, P20, P21, P22, P23, P26, P27, P28, P29, P34, P37, P39, P41, P40, P43, P45, P46, P47, P48, P50, P52 and P54.

Example B6

Activity Against Myzus persicae (Green Peach Aphid)

(163) Roots of pea seedlings infested with an aphid population of mixed ages were placed directly in the aqueous test solutions prepared from 10,000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings in test solutions.

(164) The following compounds resulted in at least 80% mortality at a test rate of 24 ppm: P9, P12, P14, P15, P17, P23, P27, P29, P36, P37, P39, P41, P40, P43, P44, P45, P46, P47 and P54.

Example B7

Activity Against Frankliniella occidentalis (Western Flower Thrips)

(165) Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.

(166) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P3, P6, P7, P8, P9, P13, P14, P17, P21, P22, P23, P26, P27, P28, P41, P40, P45, P46, P48, P50, P52 and P54.

Example B8

Activity Against Bemisia tabaci (Cotton White Fly)

(167) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation.

(168) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P6, P14, P17, P27 P32, P37, P40, P45 and P48.

Example B9

Activity Against Euschistus heros(Neotropical Brown Stink Bug)

(169) Soybean leaf on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf were infested with N-2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

(170) The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P3, P4, P6, P7, P9, P11, P14, P17, P20, P21, P22, P23, P24, P25, P26, P27, P28, P37, P39, P41, P40, P45, P47, P48, P50, P52 and P54.

Example B10

Activity Against Tetranychus urticae (Two-Spotted Spider Mite)

(171) Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation.

(172) The following compound resulted in at least 80% mortality at an application rate of 200 ppm: P19.

Example B11

Activity Against Aedes aegypti (Yellow Fever Mosquito)

(173) Test solutions, at an application rate of 200 ppm in ethanol, were applied to 12-well tissue culture plates. Once the deposits were dry, five, two to five days old adult female Aedes aegypti were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.

(174) The following compounds gave at least 80% control of Aedes aegypti after 48 h and/or 24 h: P7, P17, P22, P26, P27, P39 and P40.

Example B12

Activity Against Thrips tabaci (Onion Thrips)

(175) Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf discs were infested with a thrips population of mixed ages. The samples were assessed for mortality 6 days after infestation.

(176) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P6, P7, P13, P14, P15, P17, P22, P23, P25, P26, P27, P29, P32, P41, P42, P40 and P45.

Example B13

Activity Against Anopheles stephensi (Indian Malaria Mosquito)

(177) Test solutions, at an application rate of 200 ppm in ethanol, were applied to 12-well tissue culture plates. Once the deposits were dry, five, two to five day old adult female Anopheles stephensi were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.

(178) The following compounds gave at least 80% control of Anopheles stephensi after 48 h and/or 24 h: P17, P22, P26, P27 and P39.