SAXENA ROHIT (IN)
PABBA JAGADISH (IN)
SHINDE BHARAT UTTAMRAO (IN)
DHAGE GANESH RAOSAHEB (IN)
PATWA ADITYA (IN)
HEGADE PRASHANT BHANUDAS (IN)
SARAGUR RAVIKUMAR SURYANARAYANA (IN)
KLAUSENER ALEXANDER G M (DE)
WO2021069567A1 | 2021-04-15 | |||
WO2019197468A1 | 2019-10-17 | |||
WO2013024003A1 | 2013-02-21 | |||
WO2013024009A1 | 2013-02-21 | |||
WO2013024004A1 | 2013-02-21 | |||
WO2021099303A1 | 2021-05-27 | |||
WO2020002563A1 | 2020-01-02 | |||
WO2020053364A1 | 2020-03-19 | |||
WO2020053365A2 | 2020-03-19 | |||
WO2020079198A1 | 2020-04-23 | |||
WO2020094363A1 | 2020-05-14 | |||
WO2019197468A1 | 2019-10-17 | |||
WO2019201835A1 | 2019-10-24 | |||
WO2019202077A1 | 2019-10-24 | |||
WO2019206799A1 | 2019-10-31 | |||
WO2021013720A1 | 2021-01-28 | |||
WO2019196468A1 | 2019-10-17 | |||
WO2017192385A1 | 2017-11-09 | |||
WO2016156129A1 | 2016-10-06 | |||
WO2017153200A1 | 2017-09-14 | |||
WO2019072906A1 | 2019-04-18 | |||
WO2016198644A1 | 2016-12-15 | |||
WO2016039623A1 | 2016-03-17 | |||
WO2015192923A1 | 2015-12-23 | |||
WO2011028115A1 | 2011-03-10 | |||
WO2007067042A1 | 2007-06-14 | |||
WO2001078507A2 | 2001-10-25 | |||
WO1992000377A1 | 1992-01-09 | |||
WO1992011376A1 | 1992-07-09 | |||
WO1992014827A1 | 1992-09-03 | |||
WO1991019806A1 | 1991-12-26 | |||
WO1991013972A1 | 1991-09-19 | |||
WO2003086075A1 | 2003-10-23 |
EP3165092A1 | 2017-05-10 | |||
EP3158864A1 | 2017-04-26 | |||
CA2940002A1 | 2015-08-27 | |||
US20060150489A1 | 2006-07-13 | |||
US20040237395A1 | 2004-12-02 | |||
EP2229808A1 | 2010-09-22 | |||
EP1795071A1 | 2007-06-13 | |||
EP1273219A1 | 2003-01-08 | |||
EP1247436A1 | 2002-10-09 | |||
NL1012918C2 | 2001-02-27 | |||
CA2083415A1 | 1993-05-22 | |||
EP0242236A1 | 1987-10-21 | |||
EP0242246A1 | 1987-10-21 | |||
EP0257993A2 | 1988-03-02 | |||
US5013659A | 1991-05-07 | |||
EP0142924A2 | 1985-05-29 | |||
EP0193259A1 | 1986-09-03 |
CHEM. EUR. J., vol. 27, 2021, pages 17293 - 17321
J. AM. CHEM. SOC., vol. 142, 2020, pages 15445 - 15453
ANGEW. CHEM. INT. ED., vol. 43, 2004, pages 1132 - 1136
ORG. LETT, vol. 3, 2001, pages 119 - 122
SYNTHESIS, 2007, pages 393 - 399
J. ORG. CHEM., vol. 72, 2007, pages 4067 - 4072
THE J. ORG. CHEM., vol. 61, 1996, pages 3849 - 3862
SYNLETT, vol. 28, no. 19, 2017, pages 2525 - 2538
THE J. ORG. CHEM., vol. 70, 2005, pages 6904 - 6906
J. HETEROCYCLIC CHEM, vol. 49, 2012, pages 442
"Technical Monograph", May 2008, CROPLIFE INTERNATIONAL
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
KNOWLES: "New developments in crop protection product formulation or in Agrow Reports DS243", T AND IN F INFORMA, 2005
MCCUTCHEON'S: "Emulsifiers and Detergents, McCutcheon's Directories", vol. 1, 2008, GLEN ROCK
KNOWLES: "Adjuvants and additives, in the Agrow Reports DS256", TAND F INFORMA UK, 2006
CLAIMS: 1. A compound of formula (I), Formula (I) wherein, ring-A represents phenyl or 5-6-membered hetero-aromatic ring; wherein the ring-A may be optionally substituted with one R1′ and/or one or more R1; R1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, SF5, C1-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, C1-C6-alkyl-C3-C8-cycloalkyl, C1-C6-haloalkyl-C3- C8-cycloalkyl, OR4, S(O)0-2R4, NR′R″, C(=O)-R″, C1-C6-alkyl-C(=O)-R″, C(=O)-NR′R″, S(O)0-2- NR′R″, C1-C6-alkyl-C(=O)-NR′R″, CR′=NR″, phenyl, phenyl-C1-C6-alkyl, C3-C8-heterocyclyl, and C3- C8-heterocyclyl-C1-C6-alkyl; wherein each group of R1 is optionally substituted with one or more groups consisting of halogen, CN, R″, OR″, S(O)0-2R″, N(R′R″) and Si(R′)3; or two R1 together with the atoms to which they are attached may form a 5- to 10- membered aromatic or non-aromatic heterocyclic ring; wherein one or more heteroatoms of said ring are selected from N, O or S; the ring may be optionally substituted with one or more halogen; R1′ represent a group wherein, D represents a radical selected from the group consisting of a direct bond, -CRaRb- and - C(=O)-; Ra and Rb is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6- alkyl, C1-C6- haloalkyl, and C3-C8-cycloalkyl; R7a is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, C1-C6-alkyl-C(=O)-R″, C6-C10-aryl, C6-C10-aryl-C1-C6-alkyl, C3- C8-heterocyclyl, C3-C8-heterocyclyl-C1-C6-alkyl, and NRcRd; Rc and Rd is independently selected from the group consisting of hydrogen and C1-C6-alkyl; R7b is selected from the group consisting of C1-C6-alkyl and C3-C6-cycloalkyl; wherein each group of R7a and R7b are independently may optionally be substituted with one or more groups consisting of halogen, CN, R″, OR″, S(O)0-2R″, NR′R″, Si(R′)3, COOR′ and CON(R′)2; or R7a and R7b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)0-2 and Si(R′)2, may form a 3- to 6-membered ring, which for its part may optionally be substituted by one or more groups consisting of halogen, CN, R″, OR″, SR″, NR′R″, Si(R′)3, COOR′ and CONR′R″; R2 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, OR4, C1-C6-alkyl-OR4, (C=O)-R″, C3-C8-cycloalkyl, C3-C8- halocycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, and C3-C8-halocycloalkyl-C1-C6-alkyl; R3a and R3b is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C1-C6- alkyl-S(O)0-2-C1-C6-alkyl and C1-C6-alkyl-O-C1-C6-alkyl; or R3a and R3b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S may form a 3- to 4-membered ring, which for its part may optionally be substituted by one or more groups consisting of halogen, CN, R″, OR″, SR″, NR′R″, Si(R′)3,; R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, NR′R″, C(=O)-R″, C1-C6-alkyl-C(=O)-R″, C6-C10-aryl, C6-C10-aryl-C1-C6-alkyl, and C3-C8-heterocyclyl; wherein each group of R4 may optionally be substituted with one or more groups consisting of halogen, CN, R″, OR″, S(O)0-2R″, N(R′R″) and Si(R′)3; ring-B is selected from the group consisting of ring triazolyl and pyrazinyl; wherein each ring-B is optionally substituted with one or more R5; R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, OR′, C1-C6-alkyl-OR′, C3-C6-cycloalkyl, SCN, SF5, NR′R′′, S(O)0-2R′, and C(=O)-R″; ring-C is selected from the group consisting of phenyl and 5-6 membered heteroaromatic ring wherein said phenyl and heteroaromatic ring may optionally be substituted with one R6′ or one or more R6; wherein R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C6-alkyl, C2- C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, OR4, C1-C6-alkyl- OR′, C3-C4-cycloalkyl, SCN, SF5, NR′R′′, S(O)0-2R′, C(=O)-R″, and CR′=NR″; wherein each group of R5 and R6 may be optionally substituted with one or more groups consisting of halogen, CN, R″, OR″, S(O)0-2R″, N(R′R″), and Si(R′)3; R6′ represent a group, wherein, D′ represents a radical selected from the group consisting of a direct bond, -CRaRb- and -C(=O)- ; Ra and Rb is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6- alkyl, C1-C6- haloalkyl, and C3-C8-cycloalkyl; R8a is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, C1-C6-alkyl-C(=O)-R″, C6-C10-aryl, C6-C10-aryl-C1-C6-alkyl, C3- C8-heterocyclyl, C3-C8-heterocyclyl-C1-C6-alkyl, and NRcRd; Rc and Rd is independently selected from the group consisting of hydrogen and C1-C6-alkyl; R8b is selected from the group consisting of C1-C6-alkyl and C3-C6-cycloalkyl; wherein each group of R8a and R8b are independently may optionally be substituted with one or more groups consisting of halogen, CN, R″, OR″, S(O)0-2R″, NR′R″, Si(R′)3, COOR′ and CON(R′)2; or R8a and R8b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)0-2 and Si(R′)2, may form a 3- to 6-membered ring, which for its part may optionally be substituted by one or more groups consisting of halogen, CN, R″, OR″, SR″, NR′R″, Si(R′)3, COOR′ and CONR′R″; R′ is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, and C3-C8-cycloalkyl; wherein alkyl, alkenyl and cycloalkyl groups may optionally be substituted by one or more halogen; R″ is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, C3- C8-cycloalkyl, N(R′)2, OR′, phenyl, benzyl, and C3-C6-heterocyclyl; each group of R″ may optionally be substituted by one or more groups selected from the group consisting of halogen, R′, CN, OR′, S(O)0- 2R′, N(R′)2, Si(R′)3, COOR′, and CON(R′)2; wherein, the compound of formula (I) always includes at least one of R1′ or R6′; and/or N-oxides, metal complexes, stereo-isomers, polymorphs or the agriculturally acceptable salts thereof. 2. The compound of formula (I) according to claim 1, wherein, ring-A represents phenyl, pyridinyl, pyrazolyl, thiazolyl, thienyl ring, , or ; wherein, * denotes the point of attachment to the carbonyl group; wherein, each ring-A may optionally be substituted with one R1′ and/or one or more R1. 3. The compound of formula (I) according to claim 1, wherein, ring-B is selected from the group consisting of ring B-1 and ring B-2; wherein, # denotes the point of attachement to the amine linker part and $ denotes the point of attachement to ring-C; wherein each ring-B is optionally substituted with one or more R5. 4. The compound of formula (I) according to claim 1, wherein, ring-C is pyridinyl, pyrimidinyl, pyrazinyl, pyrazolyl or thiazolyl; wherein each ring-C is optionally substituted with one R6′ or one or more R6. 5. The compound of formula (I) according to any one of the claims 1, 2, 3 or 4 wherein, ring-A is pyridinyl, pyrazolyl, thiazolyl or thienyl ring; wherein each ring-A is optionally substituted with one R1′ and/or one or more R1; ring-B is pyrazinyl; wherein said pyrazinyl ring is optionally substituted with one or more R5; ring-C is pyridinyl, pyrimidinyl, pyrazinyl, pyrazolyl or thiazolyl; wherein each ring-C is optionally substituted with one R6′ or one or more R6. 6. The compound of formula (I) according to any one of the claims 1, 2, 3 or 4 wherein, ring-A is pyridinyl, pyrazolyl, thiazolyl or thienyl ring; wherein each ring-A is optionally substituted with one R1′ and/or one or more R1; ring-B is triazolyl; wherein said triazolyl ring optionally substituted with one or more R5; ring-C is pyridinyl, pyrimidinyl, pyrazinyl, pyrazolyl or thiazolyl; wherein each ring-C is optionally substituted with one R6′ or one or more R6. 7. The compound of formula (I) according to any one of the claims 1, 2, 3 or 4 wherein, ring-A is phenyl; wherein said phenyl ring is optionally substituted with one R1′ and/or one or more R1; ring-B is triazolyl; wherein said triazolyl ring is optionally substituted with one or more R5; ring-C is pyridinyl, pyrimidinyl, pyrazinyl, pyrazolyl or thiazolyl; wherein each ring-C is optionally substituted with one R6′ or one or more R6. 8. The compound of formula (I) according to any one of the claims 1, 2, 3 or 4 wherein, ring-A is phenyl; wherein, said phenyl ring is optionally substituted with one R1′ and/or one or more R1; ring-B is pyrazinyl; wherein said pyrazinyl ring is optionally substituted with one or more R5; ring-C is pyridinyl, pyrimidinyl, pyrazinyl, pyrazolyl or thiazolyl; wherein each ring-C is optionally substituted with one R6′ or one or more R6. 9. The compound of formula (I) according to any one of the claims 1-8 wherein, R1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C6-alkyl, C1-C6- haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, C1-C6-alkyl-C3-C8- cycloalkyl, C1-C6-haloalkyl-C3-C8-cycloalkyl, OR4, and S(O)0-2R4; wherein each group of R1 is optionally substituted with one or more groups consisting of halogen, CN and C1-C3-alkyl; R1′ represent a group wherein, D represents a direct bond; R7a is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C6-C10- aryl, C6-C10-aryl-C1-C6-alkyl, C3-C8-heterocyclyl, C3-C8-heterocyclyl-C1-C6-alkyl, and NRcRd; R7b is selected from the group consisting of C1-C6-alkyl and C3-C6-cycloalkyl; wherein each group of R7a and R7b are independently may optionally be substituted with one or more groups consisting of halogen, CN and C1-C6-alkoxy; or R7a and R7b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O) and C(=S), may form a 3- to 6-membered non aromatic heterocyclic ring; Rc and Rd is independently selected from the group consisting of hydrogen and C1-C6-alkyl; R2 is selected from the group consisting of hydrogen and C1-C3-alkyl; R3a is hydrogen; R3b is C1-C3-alkyl; R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkyl-C3-C8-cycloalkyl, and C3-C8-heterocyclyl; R5 is selected from the group consisting of hydrogen, halogen, cyano, C1-C3-alkyl, and C1-C3-haloalkyl; R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C6-alkyl, C1-C6- haloalkyl, O-C1-C6-alkyl, and C3-C4-cycloalkyl; R6′ represent a group, wherein, D′ represents a radical selected from the group consisting of a direct bond, -CRaRb- and - C(=O)-; Ra and Rb is independently selected from the group consisting of hydrogen, halogen, cyano, and C1-C6- alkyl; R8a is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C6-C10- aryl, C6-C10-aryl-C1-C6-alkyl, C3-C8-heterocyclyl, C3-C8-heterocyclyl-C1-C6-alkyl, and NRcRd; Rc and Rd is independently selected from the group consisting of hydrogen and C1-C6-alkyl; R8b is selected from the group consisting of C1-C6-alkyl and C3-C6-cycloalkyl; wherein each group of R8a and R8b are independently may optionally be substituted with one or more groups consisting of halogen, CN, C1-C3-alkyl or O-C1-C3-alkyl; or R8a and R8b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O) and C(=S), may form a 3- to 6-membered non aromatic heterocyclic ring; R′ is selected from the group consisting of hydrogen, C1-C6-alkyl, and C3-C8-cycloalkyl; wherein alkyl, alkenyl and cycloalkyl groups may optionally be substituted by one or more halogen; R″ is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, N(R′)2, OR′, phenyl, benzyl, and C3-C6-heterocyclyl; each group of R″ may optionally be substituted by one or more groups selected from the group consisting of halogen, R′, CN, C1-C6-alkyl, and C1-C6- haloalkyl; wherein, the compound of formula (I) always includes at least one of R1′ or R6′; and/or N-oxides, metal complexes, stereo-isomers, polymorphs or the agriculturally acceptable salts thereof. 10. The compound of formula (I) according to claim 1, wherein, ring-A represents phenyl, pyridinyl, pyrazolyl, thiazolyl, thienyl ring, , or ; wherein the ring-A may be optionally substituted with one R1′ and/or one or more R1; R1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C3-alkyl, C1-C3- haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, C1-C6-alkyl-C3-C8- cycloalkyl, C1-C6-haloalkyl-C3-C8-cycloalkyl, OR4, and S(O)0-2R4; wherein each group of R1 is optionally substituted with one or more groups consisting of CN and C1-C3-alkyl; R1′ represent a group wherein, D represents a direct bond; R7a is C1-C3-alkyl; R7b is C1-C3-alkyl; or R7a and R7b substituents together with the atom to which they are attached may form a 3- to 6- membered non aromatic heterocyclic ring; R2 is selected from the group consisting of hydrogen, methyl, ethyl, and (n or iso) propyl; R3a is hydrogen; R3b is methyl; ring-B is selected from the group consisting of ring B-1 and ring B-2; wherein, # denotes the point of attachement to the amine linker part and $ denotes the point of attachement to ring-C; wherein each ring-B is optionally substituted with one or more R5; R5 is selected from the group consisting of hydrogen, methyl, ethyl, and (n or iso) propyl; ring-C represents pyridinyl, pyrimidinyl, pyrazinyl, pyrazolyl or thiazolyl wherein said rings may optionally be substituted with one R6′ or one or more R6; wherein R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C3-alkyl, and C1-C3-haloalkyl; R6′ represents a group, wherein, D′ represents a radical selected from the group consisting of a direct bond, -CRaRb- and - C(=O)-; Ra and Rb is hydrogen; R8a is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, cyclohexyl, phenyl, benzyl, and NRcRd; Rc and Rd is C1-C3-alkyl; R8b is C1-C3-alkyl; or R8a and R8b substituents together with the atom to which they are attached may form a 3- to 6- membered non aromatic heterocyclic ring; wherein, the compound of formula (I) always include at least one of R1′ or R6′; and/or N-oxides, metal complexes, stereo-isomers, polymorphs or the agriculturally acceptable salts thereof. 11. A composition comprising the compound of formula (I) or agriculturally acceptable salts, metal complexes, stereo-isomers, polymorphs or N-oxides thereof according to claim 1 and at least one additional component selected from the group consisting of surfactants and auxiliaries. 12. The composition according to claim 11, wherein the said composition additionally comprises at least one biological active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers or nutrients. 13. The composition according to claim 11, wherein the said compound of formula (I) ranges from 0.1 % to 99 % by weight with respect to the total weight of the composition. 14. A combination comprising a biologically effective amount of the compound of formula (I) according to claim 1 and at least one additional biological active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients. 15. A method for combating insects and mite pests comprising contacting the insects and mite pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the insect and mite pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from a pest attack or an infestation with a biologically effective amount of a compound of formula (I), salts, stereo-isomers, polymorphs, metal complexes, N-oxides compositions or combinations thereof according to claim 1 or 11 or 14. 16. A method for protecting crops from attack or infestation by insects and mite pests comprises contacting the crop with the compound of formula (I), agriculturally acceptable salts, stereo-isomers, polymorphs, metal complexes, N-oxides composition or combination thereof according to claim 1 or 11 or 14. 17. The method according to claim 15 or 16, wherein the said method comprises applying effective dosages of a compound of formula (I) in amounts ranging from 1 gai to 5000 gai per hectare in agricultural or horticultural crops. 18. A method for the protection of seeds, plants and plant parts from soil insects and of the seedlings roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pre- germination with the compound of formula (I), salts, stereo-isomers, polymorphs, metal complexes, N- oxides composition or combination thereof according to claim 1 or 11 or 14. 19. Use of a compound of formula (I) or salts, metal complexes, N-oxides, stereo-isomers, polymorphs, composition or combination thereof according to claim 1 or 11 or 14, for combating insects and mite pests in agricultural crops, horticultural crops, household and vector control and parasites on animals. 20. The use of a compound of formula (I) according to claim 19, wherein the said agricultural crops are cereals, corn, sorghum, bajra, rice, soybean, oil seeds and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers, other vegetables and ornamentals. 21. A seed comprising a compound of formula (I) or salts, metal complexes, N-oxides, stereo-isomers, polymorphs, composition or combination thereof according to claim 1 or 11 or 14, wherein the amount of the compound of formula (I) in the said seed is ranging from 0.0001 % to 1 % by weight. |
wherein, "-----" represents the point of attachment to the remainder of the molecule. Depending on the nature of the substituents, the compounds of formula (I), and the intermediates thereof may be present either in pure form or as mixtures of different possible isomeric forms such as stereoisomers or constitutional isomers. The various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, and geometric isomers. Depending on the nature of the substituents, the compounds of formula (I) and intermediates thereof, as mentioned in the general schemes, can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents. The invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions. The syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art. In another embodiment, the present invention provides a process for the preparation of the compound of formula (I) or the salts thereof. The compounds of formula (I), including their stereoisomers, salts, and N-oxides, and their precursors in the synthesis process, can be prepared by the methods described above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or the respective precursor or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula (I) can advantageously be prepared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described. The reaction mixtures are worked up in a customary manner, e.g. by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion. If individual compounds (I) cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds (I). However, if the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e.g. under the action of light, acids or bases). Such conversions may also take place after use, e.g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled. In one embodiment, the present invention provides a composition for controlling or preventing invertebrate pests. The composition comprises a biologically effective amount of the compound of formula (I) agriculturally acceptable salts, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries. In yet another embodiment, the composition additionally comprises at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers or nutrients. In yet another embodiment, the present invention provides a compound of formula (I) or its N-oxides and salts into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", in the Technical Monograph No.2, 6 th Ed. May 2008, CropLife International. The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation or in Agrow Reports DS243, T and in F Informa, London, 2005. Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers or binders. Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; dimethyl sulfoxide; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon′s, Vol.1: Emulsifiers and Detergents, McCutcheon′s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar- based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugarbased surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homeor copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines. Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, in the Agrow Reports DS256 and in Tand F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. Suitable anti- freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and watersoluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azoand phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types and their preparation are: i) Water-soluble concentrates (SL, LS) 10-60 wt% of a compound (I) or an N-oxide or salt thereof and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water. ii) Dispersible concentrates (DC) 5-25 wt% of a compound (I) or an N-oxide or salt thereof and 1-10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion. iii) Emulsifiable concentrates (EC) 15-70 wt% of a compound I or an N-oxide or salt thereof and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES) 5-40 wt% of a compound (I) or an N-oxide or salt thereof and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS) In an agitated ball mill, 20-60 wt% of a compound (I) or an N-oxide or salt thereof are comminuted with the addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added. vi) Water-dispersible granules and water-soluble granules (WG, SG) 50-80 wt% of a compound (I) or an N-oxide or salt thereof are ground finely with the addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS) 50-80 wt% of a compound (I) or an N-oxide or salt thereof are ground in a rotor-stator mill with the addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance. viii) Gel (GW, GF) In an agitated ball mill, 5-25 wt% of a compound (I) or an N-oxide or salt thereof are comminuted with the addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. ix) Microemulsion (ME) 5-20 wt% of a compound (I) or an N-oxide or salt thereof are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion. x) Microcapsules (CS) An oil phase comprising 5-50 wt% of a compound I or an N-oxide or salt thereof, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a dior triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(methyl acrylate) microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound of formula (I), according to the present invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 - 10 wt%. The wt% relate to the total CS composition, xi) Dustable powders (DP, DS) 1-10 wt% of a compound I or an N-oxide or salt thereof are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin. xii) Granules (GR, FG) 0.5-30 wt% of a compound I or an N-oxide or salt thereof is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed. xiii) Ultra-low volume liquids (UL) 1-50 wt% of a compound I or an N-oxide or salt thereof are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon. The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1 -1 wt% colorants. In one another embodiment, the present invention provides agrochemical compositions with the compound of formula (I), which comprise an active substance content between 0.01 and 95% by weight, preferably between 0.1 and 90%, and more preferably between 1 and 70 %, in particular between 10 and 60 by weight of active substance. The active substances are employed in a purity from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two- to-tenfold dilution, active substance concentrations from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Applications can be carried out before or during sowing. Methods for applying or treating compounds of formula (I) and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in- furrow application methods of the propagation material. Preferably, the compound of formula (I) or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that the germination is not induced, e. g. by seed dressing, pelleting, coating and dusting. When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.02 to 0.9 kg per ha, in particular from 0.05 to 0.75 kg per ha. In the treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance from 0.1 to 1000 g, preferably from 1 to 500 g, more preferably from 5 to 200 g and most preferably from 10 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material. Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners, antibiotics, fertilizers, nutrients and biostimulants) may be added to the active substances or the compositions comprising them as premix or, if appropriate, not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the present invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1. The user can apply the composition according to the present invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the present invention is thus obtained. Usually, 20 to 6000 liters, preferably 35 to 1000 litres, more preferably 50 to 500 liters, of the ready-to-use spray liquor are applied per hectare of the agricultural useful area. According to one embodiment, individual components of the composition according to the present invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate. The compounds and compositions of the present invention are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits. The compounds of the present invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a wide spectrum of agronomic and non-agronomic invertebrate pests. The compounds of the present invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which can be used against insecticide resistant pests such as insects and mites, and are well tolerated by warm-blooded species, fish and plants. In the context of the present invention "invertebrate pest control" means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest; related expressions are defined analogously. As referred to in the present invention, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other stylommatophora. The term "nematode" includes all of the helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. The compounds of the present invention display activity against economically important agronomic, forest, greenhouse, nursery, ornamentals, turfgrass, food and fiber, public and animal health, domestic and commercial structure, household, and stored product pests. These include larvae of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hubner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni Hubner), tobacco budworm (Heliothis virescens Fabricius); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworm (Herpetogramma licarsisalis Walker)); leafrohers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus)); nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella gemnanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)); foliar feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scaribaeidae (e.g., Japanese beetle (Popillia japonica Newman) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition it includes: adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius)); adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whitefiies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g., Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also included are adults and larvae of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)), flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)), rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae, ticks in the order Ixodidae (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus) and scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), house cricket (Acheta domesticus Linnaeus), mole crickets (Gryllotalpa spp.)); adults and immatures of the order Diptera including leafminers, midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F.femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chiysomya spp., Phonnia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), botflies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman) and other foliar feeding thrips; insect pests of the order Hymenoptera including ants (e.g., red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Fδrster), odorous house ant (Tapinoma sessile Say)), bees (including carpenter bees), hornets, yellow jackets and wasps; insect pests of the order Isoptera including the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder) and other termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes cams De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurystemus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephatides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch and Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus). Activity also includes members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofllaria immitis Leidy in dogs, Anoplocephala peifoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.). The compounds of the present invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hubner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoveipa armigera Hύbner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis and Schiffeπnύller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hubner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hύbner (cabbage looper) and Tula absoluta Meyrick (tomato leafminer)). Compounds of the present invention also have commercially significant activity on members from the order Homoptera including: Acyrthisiplionpisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (tarnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosipum euphorbiae Thomas (pqtato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii, Boyer de Fonscolombe (black citrus aphid), and Toxoptera citiicida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows and Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris, (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAfee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla). These compounds also have activity on members from the order Hemiptera including: Acrostemum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-S chaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolrius Palisot deBeauvois (one-spotted stink bug), Graptόsthetus spp. (complex of seed bugs), Leptoglossus corculus Say (leaf- footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus DaEas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insects which are controlled by compounds of formula (I) of the present invention include: Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthothήps citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius). Particularly, the compounds of formula (I), their N-oxides, their stereo-isomers, their polymorphs and their salts are especially suitable for efficiently combating the following pests: Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Chilo infuscatellus, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Earias vittella, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Helicoverpa armigera, Helicoverpa virescens, Helicoverpa zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Leucinodes orbonalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scirpophaga incertulas, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Spodoptera exigua, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis; and Beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica undecimpunctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria; flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa; termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus; cockroaches (Blattaria Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile; crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa; fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera oleoptrata, millipedes (Diplopoda), e.g. Narceus spp., Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon allinae, Menacanthus stramineus and Solenopotes capillatus. Collembola (springtails), e.g. Onychiurus ssp. The compounds of formula (I) of the present invention are also suitable for controlling Nematodes: plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species. The compounds of formula (I) and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis. In one embodiment of the present invention, the present invention provides the compounds of formula (I) which are useful for controlling insects selected form sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species: Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, Diptera: Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa; Hemiptera, in particular aphids: Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii. In one embodiment, the present invention of the compound of formula (I) is useful for controlling diamondback moth (Plutella xylostella), american bollworm Hύbner (Helicoveipa armigera), fall armyworm (Spodoptera frugiperdd), tobacco cutworm, cluster caterpillar Fabricius (Spodoptera litura), western flower thrips (Frankliniella occidentalis), potato leafhopper (Empoasca fabae), cotton melon aphid (Aphis gossypii), green peach aphid (Myzus persicae), brown planthopper Stal (Nilaparvata lugens), and sweetpotato whitefly (Bemisia tabaci). In one embodiment, the present invention provides a composition comprising a biologically effective amount of the compound of formula (I) and at least one additional biological active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, nutrients and biostimulants. The compounds used in the composition and in combination with the compound of formula (I) are also termed as active compatible compounds. The known and reported fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics and nutrients can be combined with at least one compound of the formula (I) of the present disclosure. For example, fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, nutrients disclosed and reported in WO2016156129 and/or WO2017153200 can be combined with at least one compound of formula (I) of the present disclosure. The fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients reported in WO2016156129 and or WO2017153200 are incorporated herein by way of reference as non-limiting examples to be combined with at least one compound of the formula (I) of the present disclosure. Particularly, the compounds of the present invention can be mixed with at least one additional biological active compatible compound (mixing partner) which includes but is not limited to insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural utility. Examples of such biologically active compounds or agents/mixing partners with which the compound of formula (I) of the present invention can be combined/formulated are disclosed in WO2019072906A1 (page 27 to 37). In one embodiment, the biological agents for mixing with compounds of the present invention include Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi. In certain instances, combinations with other invertebrate pest control compounds or agents, having a similar spectrum of control but a different mode of action, will be particularly advantageous for resistance management. Thus, compositions of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar spectrum of control but a different mode of action. Contacting a plant genetically modified to express a plant protection compound (e.g., protein) or the locus of the plant with a biologically effective amount of a compound of the invention can also provide a broader spectrum of plant protection and be advantageous for resistance management. In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the compositions ranges from 0.1 % to 99 % by weight with respect to the total weight of the composition, preferably from 5 % to 50 % by weight with respect to the total weight of the composition. The present invention furthermore provides a method of combating invertebrate pests, said method comprising contacting the invertebrate pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the invertebrate pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a biologically effective amount of the compound of formula (I) or agriculturally acceptable salts, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof, composition or combination thereof. Invertebrate pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of the present invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar- and soil-inhabiting invertebrates and protection of agronomic and/or nonagronomic crops, comprising contacting the invertebrates or their environment with a biologically effective amount of one or more of the compounds of the present invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. A preferred method of contact is by spraying. Alternatively, a granular composition comprising a compound of the present invention can be applied to the plant foliage or the soil. Compounds of the present invention are effective in delivery through plant uptake by contacting the plant with a composition comprising a compound of the present invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Other methods of contact include application of a compound or a composition of the present invention by direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds of the present invention can be incorporated into baits that are consumed by the invertebrates or within devices such as traps and the like. Granules or baits comprising between 0.01-5 % active ingredient, 0.05-10 % moisture retaining agent(s) and 40-99 % vegetable flour are effective in controlling soil insects at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact. The compounds of the present invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader, stickers, adjuvants, other solvents, and synergists such as piperonyl butpxide often enhance compound efficacy. The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the pest′s life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/ hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control. The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests. The animal pest, i.e. the arthropods, gastropods, and nematodes, the plant, soil or water in which the plant is growing can be contacted with compounds of formula (I), their N-oxides and salts or composition(s) containing them by any application method known in the art. As used herein, "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant). The compounds of the present invention or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of at least one compound of the present invention. The term "crop" refers both to growing and harvested crops. The compounds of the invention are also suitable for use in combating or controlling animal pests. Therefore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the invention. In one embodiment, the present invention provides a method for protecting crops from an attack or infestation by invertebrate pests, which comprises contacting the crop with a biologically effective amount of the compound or the composition of the present invention, stereo-isomer, polymorph, N-oxide or salt thereof. The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with an insecticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects. In one embodiment, the present invention provides a method for the protection of seeds from soil insects and of the seedlings roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pre-germination with the compound or the composition of the present invention, N- oxide or salt thereof. Furthermore, the present invention provides a method for treating or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a biologically effective amount of compound or composition of the present invention, stereo- isomer, polymorph, N-oxide or veterinary acceptable salt thereof. For use in treating crop plants, the rate of application (applying effective dosages) of the compound of the present invention may be in the range of 1g a.i .to 2000g a.i. per hectare in agricultural or horticultural crops, preferably from 10 g to 600 g per hectare, more preferably from 50 g to 500 g per hectare. The compounds and the compositions of the present invention are particularly useful in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens. Particularly, the compound or the composition of the present invention are useful in protecting agricultural crops such as cereals, corn, sorghum, bajra, rice, soybean, oil seeds and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers, other vegetables and ornamentals. The compounds of the present invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait or plant part). The compounds of the present invention may also be applied against non-crop invertebrate pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of the present invention are preferably used in a bait composition. As used herein, the term "non-crop insect pest" refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches. The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics. The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art. For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5 weight % of active compound. Formulations of compounds of the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases. The oil spray formulations differ from the aerosol recipes in that no propellants are used. For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %. The compounds of the present invention and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems. The methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula (I) and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-diethyl- meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2- methylpiperine, (2hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl4- oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-1-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene. The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets. The compounds of the present invention and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electrie wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of the present invention are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of an application against ants doing harm to crops, wooden dwellings or human beings, a compound of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like. 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. Digital Technologies The compounds of the invention can be used in combination with models e.g. embedded in computer programs for site specific crop management, satellite farming, precision farming or precision agriculture. Such models support the site specific management of agricultural sites with data from various sources such as soils, weather, crops (e.g. type, growth stage, plant health), weeds (e.g. type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield etc. with the purpose to optimize profitability, sustainability and protection of the environment. In particular, such models can help to optimize agronomical decisions, control the precision of pesticide applications and record the work performed. As an example, the compounds of the invention can be applied to a crop plant according to an appropriate dose regime if a model models the development of a pest and calculates that a threshold has been reached for which it is recommendable to apply the compound of the invention to the crop plant. Commercially available systems which include agronomic models are e.g. FieldScriptsTM from The Climate Corporation, XarvioTM from BASF, AGLogicTM from John Deere, etc. The compounds of the invention can also be used in combination with smart spraying equipment such as e.g. spot spraying or precision spraying equipment attached to or housed within a farm vehicle such as a tractor, robot, helicopter, airplane, unmanned aerial vehicle (UAV) such as a drone, etc. Such an equipment usually includes input sensors (such as e.g. a camera) and a processing unit configured to analyze the input data and configured to provide a decision based on the analysis of the input data to apply the compound of the invention to the crop plants (respectively the weeds) in a specific and precise manner. The use of such smart spraying equipment usually also requires positions systems (e.g. GPS receivers) to localize recorded data and to guide or to control farm vehicles; geographic information systems (GIS) to represent the information on intelligible maps, and appropriate farm vehicles to perform the required farm action such as the spraying. In an example, pests can be detected from imagery acquired by a camera. In an example the pests can be identified and/or classified based on that imagery. Such identification and / classification can make use of image processing algorithms. Such image processing algorithms can utilize machine learning algorithms, such as trained neutral networks, decision trees and utilize artificial intelligence algorithms. In this manner, the compounds described herein can be applied only where needed. Seed treatment The present invention further provides a seed comprising the compounds of the present invention, particularly in an amount ranging from about 0.0001% to about 1% by weight of the seed before treatment. The compounds of the present invention are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect and mite pests and the resulting plant′s roots and shoots against soil pests and foliar insects. The compounds of the present invention are particularly useful for the protection of the seed from soil pests and the resulting plant′s roots (white grub, termites, wireworms) and shoots against soil pests and foliar insects. The protection of the resulting plant′s roots and shoots is preferred. More preferred is the protection of resulting plant′s shoots from piercing and sucking insects, wherein the protection from aphids, jassids, thrips and white flies is most preferred. The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedling roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the present invention thereof. Particularly preferred is a method, wherein the plant′s roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids. The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds. The term 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 present invention also comprises seeds coated with or containing the active compound. The seeds can be coated with seed coating compositions containing the compounds of the present invention. For example, seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, WO2007067042, EP1795071, EP1273219, WO200178507, EP1247436, NL1012918 and CA2083415. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the propagation product is (re)planted, it may absorb the active ingredient along with moisture. Suitable seed is seeds of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize/sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens. In addition, the compounds of the present invention may be used for treating seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods. For example, the compounds of the present invention can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP242236, EP242246) (WO92/00377) (EP257993, US5013659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP142924, EP193259). Furthermore, the compound of the present invention can be used for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO92/11376, WO92/14827, WO91/19806) or of transgenic crop plants having a modified fatty acid composition (WO91/13972). The seed treatment application of the compound of the present invention is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants. Compositions which are especially useful for seed treatment are e.g.: A. Soluble concentrates (SL, LS) B. Emulsions (EW, EO, ES) C. Suspensions (SC, OD, FS) D. Water-dispersible granules and water-soluble granules (WG, SG) E. Water-dispersible powders and water-soluble powders (WP, SP, WS) F. Gel-Formulations (GF) G. Dustable powders (DP, DS) Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. In one embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water. Especially FS formulations of compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g.0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g.1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight. Seed treatment formulations may additionally comprise binders and optionally colorants. Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo and copolymers, polyethyleneamines, polyethyleneamides and polyethylenepyrimidines, polysaccharides like celluloses, tylose and starch, polyolefin homo and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers. Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108. An example of a gelling agent is carrageen (Satiagel ® ). In the treatment of seed, the application rates of the compounds of the present invention are generally from 0.1 g to 5 kg per 100 kg of seed, preferably from 1 g to 1 kg per 100 kg of seed, more preferably from 1 g to 200 g per 100 kg of seed and in particular from 5 g to 150 g per 100 kg of seeds and 10 g to 100g per 100 kg of seed. The present invention therefore also provides to seeds comprising a compound of formula (I), or an agriculturally useful salt of the compound of formula (I), as defined herein. The amount of the compound of formula (I) or the agriculturally useful salt thereof will in general vary from 0.1 g to 5 kg per 100 kg of seed, preferably from 1 g to 1 kg per 100 kg of seed, more preferably from 1 g to 200 g per 100 kg of seed and in particular from 5 g to 150 g per 100 kg of seeds and 10 g to 100 g per 100 kg of seeds. Animal health The present invention also provides an agricultural and/or veterinary composition comprising at least one compound of formula (I). In one embodiment, the present invention provides the use of the compound of formula (I), agriculturally acceptable salts, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides, composition or combination thereof, for combating invertebrate pests in agricultural crops and/or horticultural crops or parasites on animals. The compounds of formula (I), their N-oxides and/or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals. The present invention also provides a compositions containing a parasiticidally effective amount of at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof and an acceptable carrier, for combating parasites in and on animals. The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically, or parenteral administering or applying to the animals a parasiticidally effective amount of a compound of the present invention or a composition comprising it. The present invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of the present invention or a composition comprising it. Activity of compounds against agricultural pests does not suggest their suitability for control of endo and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling. Surprisingly it has now been found that compounds of the present invention are suitable for combating endo and ectoparasites in and on animals. Compounds of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in animals including warm-blooded animals and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as freshand salt-water fish as trout, carp and eels. Compounds of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats. Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas. The compounds of the present invention and compositions comprising them are suitable for systemic and/or non-systemic control of ecto and/or endoparasites. They can be active against all or some stages of development. The compounds of the present invention are especially useful for combating ectoparasites. The compounds of the present invention are especially useful for combating parasites of the following orders and species, respectively: fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides cams, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, cockroaches (Blattaria Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pi pi ens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp, Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus, Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp, Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp. Roundworms Nematoda: Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae,) Trichuris spp., Capillaria spp, Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp, Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale, Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi, Camallanida, e.g. Dracunculus medinensis (guinea worm) Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp, Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp, Planarians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria a lata, Paragonimus spp., and Nanocyetes spp, Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp. The compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida. In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating mosquitoes. In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating flies. In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating fleas. The use of the compounds of the present invention and compositions containing them for combating ticks is still another embodiment of the present invention. The compounds of the present invention are also especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians). In one embodiment, the administration of the compounds of the present invention can be carried out both prophylactically and therapeutically. In another embodiment, administration of the compounds of the present invention is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally. For oral administration to warm-blooded animals, compounds of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the compounds of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of the present invention, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day. Alternatively, the compounds of the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention may be formulated into an implant for subcutaneous administration. In addition, the compound of the present invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of the present invention. The compounds of the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound of the present invention. In addition, the compounds of the present invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep. Suitable preparations are: Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels; Emulsions and suspensions for oral or dermal administration; semi-solid preparations; Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base; Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles. The compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methylpyrrolidone, 2-pyrrolidone, and mixtures thereof. The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection. Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester. Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol. Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the used concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary. Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary. Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof. Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above. Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers and adhesives are added. Suitable solvents are for example, water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, dimethylformamide, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or noctylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2- dimethyl-4-oxy-methylene-1 ,3-dioxolane or glycerol formal. Suitable colorants are for example, all colorants permitted for the use on animals and which can be dissolved or suspended. Suitable absorption-promoting substances are for example, dimethyl sulfoxide, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides or fatty alcohols. Suitable antioxidants are for example, sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole or tocopherol. Suitable light stabilizers are for example, novantisolic acid. Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates or natural polymers such as alginates, gelatin. Emulsions can be administered orally, dermally or as injections. Emulsions are either of the water-in-oil type or of the oil- in-water type. They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances. Suitable hydrophobic phases (oils) are: Liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length C 1 -C 12 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, monoand diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C 16 -C 18 , isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C 12 -C 18 , isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof. Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof. Suitable emulsifiers are for example, non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin. Suitable anionic surfactants are for example, sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; suitable cation-active surfactants are cetyltrimethylammonium chloride. Suitable further auxiliaries are for example, substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned. Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers. Liquid suspending agents are all homogeneous solvents and solvent mixtures. Suitable wetting agents (dispersants) are the emulsifiers given above. Other auxiliaries which may be mentioned are those given above. Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity. For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form. Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches. Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above. Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose. In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of death, retardation of development, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the present invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like. The compositions which can be used in the present invention generally comprise from about 0.001 to 95% of the compound of the present invention. Generally, it is favorable to apply the compounds of the present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day. Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight. Preparations diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight. Furthermore, the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight. In a one embodiment, the compositions comprising the compounds of the present invention are applied dermally/topically. In another embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils. Generally, it is favorable to apply solid formulations which release compounds of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks. For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of the present invention. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 2003086075. Positive crop response: The compounds of the present invention not only control insect and mite pests effectively but also induce a positive crop response such as plant growth enhancement effects like enhanced root growth, enhanced tolerance to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality of plant products, higher number of productive tillers, enhanced resistance to fungi, insects, pests and the like, which results in higher yields. Without further elaboration, it is believed that any person skilled in the art who is using the preceding description can utilize the present invention to its fullest extent. The following examples are therefore to be interpreted as merely illustrative and not limiting of the disclosure in any way whatever. CHEMISTRY EXAMPLES: The following examples set forth the manner and process of making compounds of the present invention without representing any limitations thereof. Synthesis of the intermediate tert-butyl 6-hydrazinylnicotinate Step-1: Synthesis of tert-butyl 6-chloronicotinate To a stirred solution of 6-chloronicotinic acid (10 g, 63.5 mmol) and 4-dimethylaminopyridine (DMAP, 0.66 g, 5.4 mmol) in tetrahydrofuran (150 mL), Boc-anhydride (36.8 mL, 159 mmol) was added at 70 °C. The resulting reaction mixture was stirred at 70 °C for 4 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude compound which was purified by column chromatography to obtain tert-butyl 6-chloronicotinate (12 g, 56.2 mmol, 88 % yield). 1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.83 (d, J = 2.0 Hz, 1H), 8.24 (s, 1H), 7.76 (dd, J = 8.9, 2.3 Hz, 1H), 1.49 (s, 9H); LCMS [M+H]: 213. Step-2: Synthesis of tert-butyl 6-hydrazinylnicotinate To a stirred solution of tert-butyl 6-chloronicotinate (10 g, 46.8 mmol) in t-butanol (100 mL), hydrazine hydrate (23.91 mL, 468 mmol) was added at 85 °C. The resulting reaction mixture was stirred at 85 °C for 5h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a sticky crude compound which was diluted with methyl tert-butyl ether (100 mL) and washed with water (50 mL) and brine solution (50 mL). The organic layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain tert-butyl 6-hydrazinylnicotinate (9.5 g, 45.4 mmol, 97 % yield). 1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.47 (d, J = 2.0 Hz, 1H), 8.28 (s, 1H), 7.80 (dd, J = 8.9, 2.3 Hz, 1H), 6.69 (d, J = 8.8 Hz, 1H), 4.35 (s, 2H), 1.49 (s, 9H); LCMS [M+H]: 209.95. Scheme 9
Preparation example: Synthesis of (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl-1H-1,2,4-triazol-1- yl)-N-(dimethyl(oxo)-λ 6 -sulfanylidene) nicotinamide (1) Step-1: Synthesis of (S)-N-(1-amino-1-oxopropan-2-yl)-3-chloro-5-(trifluoromethyl ) benzamide To a stirred solution of 3-chloro-5-(trifluoromethyl) benzoic acid (1 g, 4.45 mmol) in N,N- dimethylformamide (20 mL), N,N-diisopropylethylamine (2.33 mL, 13.4 mmol) was added, followed by the addition of 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyri dinium 3-oxid hexafluorophosphate (2.54 g, 6.7 mmol). The reaction mixture was stirred for 5-10 min, after which (S)-2- aminopropanamide hydrochloride (0.77 g, 6.2 mmol) was added portion wise. The resulting reaction mixture was stirred for 2-3 h at 25 °C. After the completion of the reaction, the reaction mixture was quenched by the addition of water (10 mL) and extracted with ethyl acetate (25 mL x 2 ). The combined organic layers were washed with water (20 mL) followed by brine (25 mL), dried over anhydrous sodium sulphate and concentrated under reduced pressure, to obtain a crude compound, which was suspended in a mixture of dichloromethane (20 mL) and hexane (20 mL) and stirred for 10 min. The precipitated solid was isolated by filtration and dried under vacuum to get (S)-N-(1-amino-1-oxopropan-2-yl)-3-chloro-5- (trifluoromethyl) benzamide (1.1 g, 3.7 mmol, 84 % yield) as an off-white solid. 1 H-NMR(400 MHz, DMSO- d 6 ) δ 8.87 (d, J = 2.0 Hz, 1H), 8.25 (s, 1H), 8.20 (dd, J = 8.9, 2.3 Hz, 1H), 8.09 (d, J = 8.8 Hz, 1H), 7.05 (s, 2H), 4.45 (m, 1H), 1.34 (d, J = 6.8 Hz, 3H); LCMS [M+H]: 294.95. Step-2: Synthesis of tert-butyl (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl- 1H-1,2,4-triazol-1-yl) nicotinate To a suspension of (S)-N-(1-amino-1-oxopropan-2-yl)-3-chloro-5-(trifluoromethyl ) benzamide (2 g, 6.79 mmol) in dichloromethane (30 mL), 1,1-dimethoxy-N, N-dimethylethan-1-amine (1.60 mL, 10.8 mmol) was added, and the resulting mixture was stirred under reflux for 1 h. After the completion of the reaction, the reaction mixture was cooled to 25 °C and concentrated to get a crude compound which was dissolved in a mixture of 1,4-dioxane (20 mL), acetic acid (10 mL), followed by the addition of tert-butyl-6- hydrazenyl-nicotinate (1.63 g, 7.81 mmol) at 25 °C. The resulting reaction mixture was stirred at 100 °C for 2 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to get a crude sticky compound, which was dissolved in ethyl acetate (150 mL) and washed subsequently by water (50 mL) and brine (50 mL). The organic layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to get a crude compound, which was purified by column chromatography to obtain tert-butyl (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido)ethyl)-3-methyl- 1H-1,2,4-triazol-1-yl)nicotinate as an off-white solid (2.6 g, 5.1 mmol, 75 % yield). 1 H-NMR(400 MHz, DMSO-d 6 ) δ 9.36 (d, J = 7.1 Hz, 1H), 8.92 (q, J = 1.0 Hz, 1H), 8.41 (dd, J = 8.6, 2.4 Hz, 1H), 8.11 (d, J = 1.5 Hz, 1H), 8.05-8.04 (m, 2H), 7.92 (dd, J = 8.6, 0.7 Hz, 1H), 6.11-6.04 (m, 1H), 2.32 (d, J = 13.2 Hz, 3H), 1.71-1.61 (m, 3H), 1.55-1.49 (m, 9H); LCMS [M+H]: 510.05. Step-3: Synthesis of (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl-1H-1,2,4- triazol-1-yl) nicotinic acid To a stirred solution of tert-butyl (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl- 1H-1,2,4-triazol-1-yl) nicotinate (2.6 g, 5.10 mmol) in dichloromethane (20 mL), trifluoroacetic acid (7.86 mL, 102 mmol) was added at 25 °C, and the resulting mixture was stirred for 5-6 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a sticky residue, which was suspended in water (50 mL) and extracted twice with ethyl acetate (150 mL x 2 ). The combined organic layers were washed with brine (50 mL), dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl- 1H-1,2,4-triazol-1-yl) nicotinic acid as an off-white solid (2 g, 4.4 mmol, 86 % yield), 1 H-NMR(400 MHz, DMSO-d 6 ) δ 13.59 (s, 1H), 9.40 (d, J = 7.1 Hz, 1H), 8.98 (dd, J = 2.4, 0.7 Hz, 1H), 8.48 (dd, J = 8.6, 2.2 Hz, 1H), 8.16 (s, 1H), 8.10 (s, 1H), 8.06 (s, 1H), 7.95 (dd, J = 8.6, 0.7 Hz, 1H), 6.14-6.07 (m, 1H), 2.35 (s, 3H), 1.64 (d, J = 6.8 Hz, 3H); LCMS [M+H]: 454.05 Step-4: Synthesis of (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl-1H-1,2,4- triazol-1-yl)-N-(dimethyl(oxo)-λ 6 -sulfanylidene)nicotinamide (1) To a stirred solution of (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl-1H-1,2,4- triazol-1-yl) nicotinic acid (200 mg, 0.4 mmol) in N,N-dimethylformamide (2 mL), N,N- diisopropylethylamine (0.23 mL, 1.3 mmol) was added, followed by the addition of 1- [bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridi nium 3-oxid hexafluorophosphate (251 mg, 0.7 mmol). The reaction mixture was stirred for 5-10 min, followed by the addition of iminodimethyl-λ 6 - sulfanone (61.6 mg, 0.7 mmol) at 25 °C. The resulting reaction mixture was stirred at the same temperature for 2-3 h. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3x30 mL) followed by brine (2x30 mL). The organic layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude compound, which was purified by column chromatography to obtain (S)-6-(5-(1-(3-chloro-5-(trifluoromethyl) benzamido) ethyl)-3-methyl-1H-1,2,4-triazol-1-yl)-N-(dimethyl(oxo)-λ 6 -sulfanylidene) nicotinamide as an off-white solid (182 mg, 0.3 mmol, 78 % yield). 1 H-NMR(400 MHz, DMSO- d 6 ) δ 9.38 (d, J = 7.3 Hz, 1H), 9.00 (d, J = 2.1 Hz, 1H), 8.47 (dd, J = 8.6, 2.1 Hz, 1H), 8.15 (s, 1H), 8.11 (s, 1H), 8.05 (s, 1H), 7.90 (d, J = 8.6 Hz, 1H), 6.13-6.06 (m, 1H), 3.49 (t, J = 15.0 Hz, 6H), 2.33 (s, 3H), 1.61 (d, J = 7.0 Hz, 3H); LCMS [M+H]: 529 Preparation examples: Synthesis of (S)-N-(1-(1-(5-((diethyl(oxo)-λ 6 -sulfaneylidene)amino)pyridin-2-yl)-1H-1,2,4-triazol-5 - yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (16): Step 1: Synthesis of 2-hydrazineyl-5-iodopyridine To a stirred solution of 2-chloro-5-iodopyridine (5 g, 20.8 mmol) in ethanol (20 mL), hydrazine hydrate (17.06 mL, 209 mmol) was added, and the resuting reaction mixture was stirred at 90 °C for 72 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product which was recrystallized using dichloromethane/hexane to obtain 2-hydrazinyl-5-iodopyridine (3.33 g, 14.2 mmol, 67 % yield) as a grey solid. 1 H-NMR(400 MHz, Chloroform-D) δ 7.27 (d, J = 1.2Hz, 1H), 7.70 (dd, J = 8.4, 2.4 Hz, 1H), 6.61 (dd, J = 8.4, 0.8 Hz, 1H), 5.80 (s, 1H), 3.78 (s, 2H); LCMS (M+H): 235 Step 2: Synthesis of tert-butyl (S)-(1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl) carbamate To a stirred solution of tert-butyl (S)-(1-amino-1-oxopropan-2-yl) carbamate (2.22 g, 11.8 mmol) in dichloromethane (16 mL), 1,1-dimethoxy-N,N-dimethylmethanamine (2.35 mL, 17.7 mmol) was added, and the resulting reaction mixture was refluxed for 1h, cooled to 25 °C and concentrated under reduced pressure to remove the solvent. Then the reaction mixture was dissolved in a mixture of 1,4-dioxane (50 mL) and acetic acid (50 mL), followed by the addition of 2-hydrazineyl-5-iodopyridine (3.33 g, 14.2 mmol). The reaction mixture was then stirred at 90 °C for 4 h. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate (100 mL), quenched by the addition of saturated sodium bicarbonate (NaHCO 3, 100 mL) solution and washed with brine (50 mL). The organic layer was dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude compound which was purified by column chromatography to obtain tert-butyl (S)-(1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5- yl) ethyl) carbamate (3.1 g, 7.5 mmol, 63 % yield). 1 H-NMR (400 MHz, Chloroform-D) δ 8.71 (dd, J = 1.6, 0.8 Hz, 1H), 8.17 (dd, J = 8.4, 2.4 Hz, 1H), 7.74 (dd, J = 8.4, 0.4 Hz, 1H), 5.87 (m, 1H), 5.57 (s, 1H), 1.55 (d, J = 6.8 Hz, 3H), 1.36 (s, 9H). LCMS (M+H): 416. Step 3: Synthesis of (S)-1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethan-1-amine 2,2,2- trifluoroacetate To a stirred solution of tert-butyl (S)-(1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl) carbamate (6.14 g, 14.8 mmol) in dichloromethane (100 mL), trifluoroacetic acid (8.1 ml, 105 mmol) was added dropwise at 0 °C, and the resulting reaction mixture was stirred at 25 °C for 24 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain (S)-1-(1-(5- iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethan-1-amine 2,2,2-trifluoroacetate (4.54 g, 19.3 mmol, 93 % yield) as a dark brownish solid. LCMS (M+H): 315. Step 4: Synthesis of (S)-N-(1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl)-3,5- bis(trifluoromethyl) benzamide To a stirred solution of 3,5-bis(trifluoromethyl)benzoic acid (2.346 g, 9.09 mmol) in N,N- dimethylformamide (40 mL), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyri dinium 3- oxid hexafluorophosphate (3.46 g, 9.1 mmol) was added at 25 °C, and the resulting reaction mixture was stirred for 15 min, after which N,N-diisopropylethylamine (4.10 mL, 23.5 mmol) and (S)-1-(1-(5- iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethan-1-amine 2,2,2-trifluoroacetate (3.25 g, 7.6 mmol) were added to the reaction mixture. The resulting reaction mixture was stirred at 25 °C for 3 h. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate (100 mL), washed twice with water (75 mL x 2) and concentrated under reduced pressure to obtain a crude compound which was purified by column chromatography to obtain (S)-N-(1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl)-3,5- bis(trifluoromethyl)benzamide (3.15 g, 5.7 mmol, 74.8 % yield) as brownish solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.79 (dd, J = 2.4, 0.8 Hz, 1H), 8.27 (s, 2H), 8.24 (dd, J = 8.4, 2.4 Hz, 1H), 8.00 (s, 1H), 7.99 (s, 1H), 7.89-7.77 (m, 1H), 6.41-6.34 (m, 1H), 1.72 (d, J = 6.8 Hz, 3H) LCMS (M+H): 555 Step 5: Synthesis of (S)-N-(1-(1-(5-((diethyl(oxo)-λ 6 -sulfaneylidene)amino)pyridin-2-yl)-1H-1,2,4- triazol-5-yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (16): A solution of (S)-N-(1-(1-(5-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl)-3,5- bis(trifluoromethyl)benzamide (400 mg, 0.77 mmol) and diethyl(imino)-λ 6 -sulfanone (112 mg, 0.92 mmol) in toluene (8 mL) was degassed with nitrogen for 10 min followed by the addition of palladium acetate (Pd (OAc)2, 25.8 mg, 0.12 mmol), xantphos (155 mg, 0.27 mmol) and cesium carbonate (500 mg, 1.5 mmol). The resuting mixture was stirred for 24 h at 120 °C. After the completion of the reaction, the heterogeneous reaction mixture was cooled to 25 °C and diluted with ethyl acetate (25 mL). The resulting reaction mixture was filtered through a pad of celite and washed with a saturated sodium bicarbonate solution (10 mL). The organic layer was separated, dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain (S)-N-(1-(1-(5- ((diethyl(oxo)-λ 6 -sulfaneylidene) amino) pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl)-3,5- bis(trifluoromethyl)benzamide (212 mg, 0.42 mmol, 53.7 % yield) as a white solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.47 (d, J = 7.3 Hz, 1H), 8.45 (d, J = 6.1 Hz, 2H), 8.37 (s, 2H), 8.30 (s, 1H), 8.10 (s, 1H), 5.90-5.83 (m, 1H), 3.42 (qd, J = 7.4, 3.7 Hz, 4H), 1.62 (d, J = 7.0 Hz, 3H), 1.23 (td, J = 7.3, 2.8 Hz, 6H). LCMS (M+H): 550. Synthetic Scheme 11 Preparation example: Example-3: Synthesis of (S)-3-((1-oxidotetrahydro-λ 6 -thiophen-1-ylidene)amino)-5- (trifluoromethyl)-N-(1-(1-(5-(trifluoromethyl)pyridin-2-yl)- 1H-1,2,4-triazol-5-yl)ethyl)benzamide (31) Step 1: Synthesis of 3-bromo-5-(trifluoromethyl)benzoic acid To a suspension of N-bromosuccinimide (2.67 g, 14.99 mmol) in conc. sulfuric acid (1.49 mL, 27.0 mmol), a solution of 3-(trifluoromethyl) benzoic acid (1.9 g, 9.9 mmol) in trifluoro acetic acid (5 mL) was added at 25 °C. The resulting reaction mixture was stirred at 60 °C for 6 h. After the completion of the reaction, the reaction mixture was poured into water (75 mL) under vigorous stirring. The resulting suspension was filtered then dried under reduced pressure to obtain 3-bromo-5-(trifluoromethyl) benzoic acid (2.6 g, 9.6 mmol, 97 % yield). 1 H-NMR (400 MHz, DMSO-D6) δ 13.81 (s, 1H), 8.30 (d, J = 1.5 Hz, 1H), 8.27-8.27 (m, 1H), 8.13 (d, J = 0.5 Hz, 1H); LCMS (M-H): 266.30. Step 2: Synthesis of ethyl 3-bromo-5-(trifluoromethyl) benzoate To a stirred solution of 3-bromo-5-(trifluoromethyl) benzoic acid (5 g, 18.59 mmol) in ethanol (50 mL), conc. sulfuric acid (H 2 SO 4 , 4.95 mL, 93 mmol) was added dropwise at 25 °C. The resulting reaction mixture was refluxed for 16 h. After the completion of the reaction, ethanol was evaporated under reduced pressure to obtain a crude product which was was diluted with ethyl acetate (75 mL). The organic layer was washed with water (100 mL) and a saturated aqueous sodium bicarbonate solution (50 mL). The organic layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain ethyl 3- bromo-5-(trifluoromethyl) benzoate (5 g, 16.83 mmol, 91 % yield) as a liquid. 1 H-NMR (400 MHz, CHLOROFORM-D) δ 8.35 (t, J = 1.3 Hz, 1H), 8.23-8.22 (m, 1H), 7.94-7.93 (m, 1H), 4.42 (q, J = 7.2 Hz, 2H), 1.42 (t, J = 7.2 Hz, 3H). Step 3: Synthesis of ethyl 3-((1-oxidotetrahydro-λ 6 -thiophen-1-ylidene) amino)-5- (trifluoromethyl)benzoate A 10 ml vial equipped with a magnetic stirring bar was charged with palladium (II) acetate (28.3 mg, 0.1 mmol) and xantphos (170 mg, 0.3 mmol) under an inert atmosphere. Then, toluene (5 mL) was added, followed by the addition of ethyl 3-bromo-5-(trifluoromethyl) benzoate (250 mg, 0.8 mmol), 1- iminotetrahydro-1H-λ 6 -thiophene 1-oxide (120 mg, 1.0 mmol) and caesium carbonate (384 mg, 1.2 mmol). The resulting mixture was degassed using nitrogen. The resulting reaction mixture was heated at 120 °C for 45 min under microwave irradiation. After that, the reaction mixture was allowed to cool to 25 °C, diluted with ethyl acetate (20 mL), filtered through a pad of celite, and the obtained solid material was rinsed with ethyl acetate (10 mL). The filtrate was concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain ethyl 3-((1-oxidotetrahydro-λ 6 -thiophen- 1-ylidene) amino)-5-(trifluoromethyl) benzoate (230 mg, 0.7 mmol, 82 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 7.86 (s, 2H), 7.46 (s, 1H), 4.38 (q, J = 7.1 Hz, 2H), 3.43-3.36 (m, 2H), 3.27-3.20 (m, 2H), 2.40-2.22 (m, 4H), 1.40 (q, J = 6.7 Hz, 3H); LCMS (M+H): 336.15 Step 4: Synthesis of 3-((1-oxidotetrahydro-λ 6 -thiophen-1-ylidene) amino)-5-(trifluoromethyl)benzoic acid To a stirred solution of ethyl 3-((1-oxidotetrahydro-λ 6 -thiophen-1-ylidene) amino)-5-(trifluoromethyl) benzoate (4.7 g, 14.02 mmol) in tetrahydrofuran (30 mL) and water (7.5 mL), lithium hydroxide monohydrate (0.70 g, 16.8 mmol) was added at 25 °C, and the resulting reaction mixture was stirred at 25 °C for 12 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure and then acidified with 5% aqueous hydrochloride solution. The aqueous layer was extracted with ethyl acetate (80 mL x 2). The combined organic layers were dried over anhydrous sodium sulphate (Na2SO4) and then concentrated under reduced pressure to obtain 3-((1-oxidotetrahydro-λ 6 -thiophen-1- ylidene) amino)-5-(trifluoromethyl) benzoic acid (4.0 g, 13.0 mmol, 93 % yield) as a solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 13.40 (s, 1H), 7.70 (d, J = 1.7 Hz, 1H), 7.65 (s, 1H), 7.33 (t, J = 1.6 Hz, 1H), 3.45-3.38 (m, 2H), 3.34 (d, J = 7.1 Hz, 1H), 3.29 (d, J = 7.3 Hz, 1H), 2.28-2.17 (m, 2H), 2.15-2.05 (m, 2H); LCMS (M-H): 305.90 Step 5: Synthesis of (S)-3-((1-oxidotetrahydro-λ 6 -thiophen-1-ylidene)amino)-5-(trifluoromethyl)-N- (1-(1-(5-(trifluoromethyl)pyridin-2-yl)-1H-1,2,4-triazol-5-y l)ethyl)benzamide (31) To a stirred solution of 3-((1-oxidotetrahydro-λ 6 -thiophen-1-ylidene) amino)-5-(trifluoromethyl) benzoic acid (415 mg, 1.351 mmol) in in N,N-dimethylformamide (8 mL), 1-[bis(dimethylamino)methylene]-1H- 1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate (514 mg, 1.351 mmol) was added at 25 °C. After 20 minutes, a solution of -(S)-1-(1-(5-(trifluoromethyl) pyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethan-1- amine 2,2,2-trifluoroacetate (400 mg, 1.126 mmol) in N,N-dimethylformamide (2 mL) and N,N- diisopropylethylamine (0.59 mL, 3.38 mmol) were added to the reaction mixture and the stirring was continued for 12 h at 25°CC. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate (30 mL) and washed with water (50 mL), followed by an aqueous sodium bicarbonate solution (50 mL). The organic layer was dried over anhydrous sodium sulphate and then concentrated under reduced pressure to obtain a crude product which was purified using preparative HPLC to obtain (S)-3-((1- oxidotetrahydro-λ 6 -thiophen-1-ylidene) amino)-5-(trifluoromethyl)-N-(1-(1-(5-(trifluoromethyl) pyridin- 2-yl)-1H-1,2,4-triazol-5-yl) ethyl) benzamide (254 mg, 0.46 mmol, 41.3 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 8.87 (q, J = 1.0 Hz, 1H), 8.18-8.13 (m, 2H), 7.99 (s, 1H), 7.61 (s, 2H), 7.41 (s, 1H), 7.37 (d, J = 8.1 Hz, 1H), 6.39 (dt, J = 14.9, 6.8 Hz, 1H), 3.42-3.36 (m, 2H), 3.27-3.20 (m, 2H), 2.41-2.22 (m, 4H), 1.70 (d, J = 6.8 Hz, 3H); LCMS (M+H): 547.2. Synthetic Scheme 13 Preparation example: Example-4: Synthesis of (S)-N-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)pyridin-2- yl)pyrazin-2-yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (103) Step-1: Synthesis of tert-butyl ((2S)-4-(5-bromopyridin-2-yl)-3-hydroxy-4-oxobutan-2-yl)carb amate To a stirred solution of tert-butyl (S)-(1-oxopropan-2-yl)carbamate (10 g, 57.7 mmol) in dichloromethane (100 mL), 5-bromopicolinaldehyde (13.96 g, 75 mmol) and thiazolium, 5-(2-hydroxyethyl)-4-methyl-3- (phenylmethyl)-bromide (3.63 g, 11.55 mmol) were added followed by the addition of N,N- diisipropylethylamine (20.17 mL, 115 mmol) under a nitrogen atmosphere. The resulting reaction mixture was stirred at 25 °C for 1.5 h. After the completion of the reaction, the reaction mixture was quenched with a saturated ammonium chloride solution (150 mL) and extracted with dichloromethane (500 mL x 2). The combined organic layers were washed with brine solution (250 mL), dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain tert-butyl ((2S)-4-(5-bromopyridin-2-yl)-3-hydroxy-4-oxobutan-2-yl)carb amate (17 g, 47.3 mmol, 82 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 8.72 (d, J = 1.7 Hz, 1H), 8.03- 7.93 (m, 1H), 7.88 (d, J = 8.3 Hz, 1H), 5.24 (d, J = 5.6 Hz, 1H), 4.63 (d, J = 9.3 Hz, 1H), 4.46-4.39 (m, 1H), 3.68 (d, J = 6.1 Hz, 1H), 1.37 (d, J = 6.8 Hz, 3H), 1.32 (d, J = 16.1 Hz, 9H); LCMS [M+H]: 360.2. Step-2: Synthesis of tert-butyl (S)-(4-(5-bromopyridin-2-yl)-3,4-dioxobutan-2-yl)carbamate To a stirred solution of tert-butyl ((2S)-4-(5-bromopyridin-2-yl)-3-hydroxy-4-oxobutan-2-yl)carb amate (10.5 g, 29.2 mmol) in dichloromethane (50 mL) and tetrahydrofuran (50 mL), dess-Martinperiodinane (18.60 g, 43.8 mmol) was added portion wise at 0 °C, and the resulting mixture was stirred at 25 °C for 2 h. After the completion of the reaction, the reaction mixture was quenched cautiously with a saturated sodium bicaronate solution (100 mL) and the aqueous layer was extracted with ethyl acetate (200 mL x 2). The combined organic layers were washed with brine solution (100 mL x 2), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain tert-butyl (S)-(4-(5-bromopyridin-2- yl)-3,4-dioxobutan-2-yl)carbamate (10 g, 28.0 mmol, 96 % yield) as yellow gum. 1 H-NMR (400 MHz, CHLOROFORM-D) δ 8.77 (d, J = 2.0 Hz, 1H), 8.05 (dd, J = 8.3, 2.2 Hz, 1H), 7.95 (dd, J = 8.3, 0.5 Hz, 1H), 5.10 (d, J = 4.9 Hz, 1H), 4.87 (t, J = 7.1 Hz, 1H), 1.46 (d, J = 7.1 Hz, 3H), 1.37-1.29 (m, 9H); LCMS: [M+H]: 358.2. Step-3: Synthesis of tert-butyl (S)-(1-(3-(5-bromopyridin-2-yl)pyrazin-2-yl)ethyl)carbamate To a stirred solution of tert-butyl (S)-(4-(5-bromopyridin-2-yl)-3,4-dioxobutan-2-yl)carbamate (11 g, 30.8 mmol) in ethanol (150 mL), ethane-1,2-diamine (7.20 mL, 108 mmol) was added, and the resulting reaction mixture was stirred at 25 °C for 60 h in the presence of air. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain tert-butyl (S)-(1-(3-(5-bromopyridin-2-yl)pyrazin-2-yl)ethyl)carbamate (4.5 g, 11.87 mmol, 38.5 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 8.78 (q, J = 1.1 Hz, 1H), 8.55 (dd, J = 11.5, 2.4 Hz, 2H), 8.01-7.95 (m, 2H), 5.76-5.67 (m, 2H), 1.52 (d, J = 6.4 Hz, 3H), 1.41 (d, J = 12.5 Hz, 9H); LCMS: [M+H]: 380.2. Step-4: Synthesis of tert-butyl (S)-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)pyridin-2- yl)pyrazin-2-yl)ethyl)carbamate To a stirred suspension of tert-butyl (S)-(1-(3-(5-bromopyridin-2-yl)pyrazin-2-yl)ethyl)carbamate (2.9 g, 7.65 mmol) in toluene (30 mL), iminodimethyl-λ 6 -sulfanone (1.068 g, 11.47 mmol) and potassium phosphate tribasic (3.25 g, 15.29 mmol) were added slowly. The resulting reaction mixture was degassed with nitrogen for 10 min followed by the addition of Pd2(dba) 3 (1.050 g, 1.147 mmol) and xantphos (1.549 g, 2.68 mmol). The resulting reaction mixture was stirred at 105 °C for 16 h. After the completion of the reaction, the reaction mixture was filterd through a celite bed, the celite bed was washed with ethyl acetate (200 mL x 2) and the filtrate was concentrated to get a crude sticky compound which was purified by column chromatography to obtain tert-butyl (S)-(1-(3-(5-((dimethyl(oxo)-λ 6 - sulfaneylidene)amino)pyridin-2-yl)pyrazin-2-yl)ethyl)carbama te (2.7 g, 6.90 mmol, 90 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 8.50 (dd, J = 6.8, 2.4 Hz, 2H), 8.45 (dd, J = 2.7, 0.7 Hz, 1H), 7.93-7.91 (m, 1H), 7.53 (dd, J = 8.4, 2.6 Hz, 1H), 5.89 (s, 1H), 5.76 (t, J = 7.5 Hz, 1H), 3.26-3.23 (m, 6H), 1.51 (d, J = 6.6 Hz, 3H), 1.40 (s, 9H); LCMS: [M+H]: 392. Step-5: Synthesis of (S)-((6-(3-(1-aminoethyl)pyrazin-2-yl)pyridin-3-yl)imino)dim ethyl-λ 6 -sulfanone tris(2,2,2-trifluoroacetate) To a stirred solution of tert-butyl (S)-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)pyridin-2- yl)pyrazin-2-yl)ethyl)carbamate (3 g, 7.66 mmol) in dichloromethane (10 mL), trifluoroacetic acid (5.90 mL, 77 mmol) was added slowly, and the resulting reaction mixture was stirred at 25 °C for 16 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude gum which was triturated with hexane and concentrated under reduced pressure to obtain (S)-((6-(3-(1- aminoethyl)pyrazin-2-yl)pyridin-3-yl)imino)dimethyl-λ 6 -sulfanone tris(2,2,2-trifluoroacetate) (4.85 g, 7.66 mmol, quantitative yield) as alight brown gum. LCMS [M+H]: 292. Step-6: Synthesis of (S)-N-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)pyridin-2-yl)pyrazin-2- yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (103) To a stirred solution of 3,5-bis(trifluoromethyl)benzoic acid (194 mg, 0.751 mmol) in N,N- dimethylformamide (3 mL), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyri dinium 3-oxid hexafluorophosphate (285 mg, 0.751 mmol) and N,N-diisopropylethylamine (0.30 ml, 1.733 mmol) were added, and the resulting mixture was stirred at 25 °C for 10-15 min followed by the addition of (S)-((6-(3- (1-aminoethyl)pyrazin-2-yl)pyridin-3-yl)imino)dimethyl-λ 6 -sulfanone bis(2,2,2-trifluoroacetate) (300 mg, 0.578 mmol) and the reaction mixture was further stirred at 25 °C for 16 h. After the completion of the reaction, the reaction mixture was poured into water (50 mL) and the aqueous layer was extracted with ethyl acetate (50 x 2 mL). The combined organic layers were washed with brine solution (50 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by preparative HPLC to obtain (S)-N-(1-(3-(5-((dimethyl(oxo)-λ 6 - sulfaneylidene)amino)pyridin-2-yl)pyrazin-2-yl)ethyl)-3,5-bi s(trifluoromethyl)benzamide (60 mg, 0.113 mmol, 19.55 % yield) as an off-white solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.38 (d, J = 7.1 Hz, 1H), 8.58 (dd, J = 3.5, 2.6 Hz, 2H), 8.45 (s, 2H), 8.27 (dd, J = 2.8, 0.6 Hz, 2H), 7.91 (dd, J = 8.6, 0.7 Hz, 1H), 7.49 (dd, J = 8.6, 2.7 Hz, 1H), 6.05-5.98 (m, 1H), 3.32 (s, 6H), 1.64 (d, J = 6.8 Hz, 3H); LCMS [M+H]: 431.6. Synthetic Scheme 14
Preparation example: Example-5: Synthesis of N-((1S)-1-(1-(4-(((ethyl(methyl)amino)(methyl)(oxo)-λ 6 - sulfaneylidene)amino)pyridin-2-yl)-1H-1,2,4-triazol-5-yl)eth yl)-3,5-bis(trifluoromethyl)benzamide (200) Step 1: Synthesis of O-([1,1'-biphenyl]-4-yl)hydroxylamine To a stirred solution of sodium hydride (7.05 g, 176 mmol) in N,N-dimethylformamide (1000 ml), [1,1'- biphenyl]-4-ol (25 g, 147 mmol) was added at 0 °C and the resulting reaction mixture was stirred at 0 °C for 30 min. To this reaction mixture (aminooxy)diphenylphosphine oxide (34.3 g, 147 mmol) was added at 0 °C portion wise and the reaction mixture was stirred further at 25 °C for 16 h. After the completion of the reaction, the mixture was diluted with water (200 mL) at 0 °C and the aqueous layer was extracted with ethyl acetate (500 mL x 3). The combined organic layers were washed with saturated sodium chloride solution (1000 mL x 2), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain O-([1,1'-biphenyl]-4-yl)hydroxylamine (26 g, 140 mmol, 96 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 7.59-7.49 (m, 4H), 7.43-7.39 (m, 2H), 7.35-7.28 (m, 1H), 7.21 (dt, J = 9.5, 2.5 Hz, 2H), 5.89 (s, 2H). Step 2: Synthesis of (([1,1'-biphenyl]-4-yloxy)imino)- λ 4 -sulfanone To a stirred solution of O-([1,1'-biphenyl]-4-yl)hydroxylamine (26 g, 140 mmol) in diethyl ether (1000 mL), triethylamine (39.1 mL, 281 mmol) was added, and the resulting reaction mixture was stirred at 25 °C for 15 min. To the reaction mixture, thionyl chloride (10.76 mL, 147 mmol) was added dropwise at 0 °C and was stirred at same temperature for 2-3 h. After completion of the reaction, the reaction mixture was diluted with methyl tertiary-butyl ether (250 mL). The precipitate was filtered to obtain a crude solid which was washed with methyl tertiary-butyl ether (100 mL) to obtain (([1,1'-biphenyl]-4-yloxy)imino)-λ4- sulfanone (16 g, 69.2 mmol, 49.3 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 7.62-7.58 (m, 2H), 7.57-7.54 (m, 2H), 7.46-7.41 (m, 2H), 7.37- 7.33 (m, 3H). Step 3: Synthesis of N-ethyl-N-methylmethanesulfonimidamide To a stirred solution of (([1,1'-biphenyl]-4-yloxy)imino)-λ4-sulfanone (2 g, 8.65 mmol) in tetrahydrofuran (20 mL), methylmagnesium iodide (4.32 mL, 8.65 mmol) was added dropwise at -78 °C over 5 min, and the resulting reaction mixture was stirred at -78 °C for 10 min. To the reaction mixture, N- methylethanamine (0.511 g, 8.65 mmol) was added dropwise over 5 min at -78 °C and the mixture stirred at the same temperature for further 15 min. Then the reaction mixture was stirred at 25 °C for another1 h. After the completion of the reaction, the reaction mixture was quenched with a saturated ammonium chloride solution (20 mL) and extracted with ethyl acetate (25 mL x 3). The combined organic layers were washed with brine solution (25 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was was purified by column chromatography to obtain N-ethyl-N-methylmethanesulfonimidamide (0.3 g, 2.202 mmol, 25.5 % yield). 1 H-NMR (400 MHz, CHLOROFORM-D) δ 3.40-3.19 (m, 5H), 2.88-2.86 (m, 3H), 2.41-2.01 (brs, 1H), 1.20 (t, J = 7.0 Hz, 3H). Step 4: Synthesis of N-((1S)-1-(1-(4-(((ethyl(methyl)amino)(methyl)(oxo)-λ 6 - sulfaneylidene)amino)pyridin-2-yl)-1H-1,2,4-triazol-5-yl)eth yl)-3,5-bis(trifluoromethyl)benzamide (200) To a stirred solution of (S)-N-(1-(1-(4-iodopyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethyl )-3,5- bis(trifluoromethyl)benzamide (0.35 g, 0.630 mmol) in 1,4-dioxane (5 mL), N-ethyl-N- methylmethanesulfonimidamide (0.129 g, 0.946 mmol) and potassium phosphate tribasic (0.401 g, 1.9 mmol) were added with caution. The reaction mixture was degassed with nitrogen for 15 min, followed by the addition of xantphos (0.128 g, 0.221 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.085 g, 0.095 mmol) The resulting reaction mixture was stirred at 120 °C for 1 h under microwave irradiation.After the completion of the reaction, the reaction mixture was filtered, and washed with ethyl acetate (30 mL). The organic layer was concentrated under reduced pressure to obtain a crude product which was purified by preparative HPLC to obtain N-((1S)-1-(1-(4-(((ethyl(methyl)amino)(methyl)(oxo)-λ 6 - sulfaneylidene)amino)pyridin-2-yl)-1H-1,2,4-triazol-5-yl)eth yl)-3,5-bis(trifluoromethyl)benzamide (0.080 g, 0.142 mmol, 22.52 % yield). 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.55-9.51 (m, 1H), 8.45 (s, 2H), 8.30 (s, 1H), 8.22 (t, J = 5.7 Hz, 1H), 8.08 (s, 1H), 7.39-7.36 (m, 1H), 6.92 (td, J = 3.7, 1.9 Hz, 1H), 6.09-6.02 (m, 1H), 3.21-3.13 (m, 5H), 2.76 (d, J = 2.8 Hz, 3H), 1.66-1.60 (m, 3H), 1.05 (q, J = 7.4 Hz, 3H); LCMS (M+H): 564.1. Synthetic Scheme 15 Preparation example: Example 6: Synthesis of N-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)-1H-pyrazol-1- yl)pyrazin-2-yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (196) Step-1: Synthesis of 1-(3-chloropyrazin-2-yl)ethan-1-one: To a stirred solution of 2,3-dichloropyrazine (20 g, 134 mmol)) in toluene (100 mL), tributyl(1- ethoxyvinyl)stannane (50.9 g, 141 mmol) and bis(triphenylphosphine)palladium(II) chloride (4.71 g, 6.71 mmol) were added slowly and the resulting reaction mixture was stirred at 110 °C for 6 h. After the completion of the reaction, the reaction mixture was filtered through a pad of celite. The filtrate was concentrated under reduced pressure to obtain a residue which was dissolved in acetonitrile (60 mL) followed by the dropwise addition of concentrated hydrochloric acid (20 mL). The resulting reaction mixture was allowed to stir at 25 °C for 18 h. After the completion of the reaction, the reaction mixture was filtered through a pad of celite. The filterate was diluted with water (200 mL) and extracted with ethyl acetate (200 mL x 3). The combined organic layers were washed with brine solution (100 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain 1-(3-chloropyrazin-2-yl)ethan-1-one (16 g, 102 mmol, 76 % yield) as pale yellowish solid; 1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.5 (d, J = 44 Hz, 2H), 7.38 (d, J = 45 Hz, H), 2.71 (s, 3H); LCMS[M+H]: 156.9. Step-2: Synthesis of 1-(3-chloropyrazin-2-yl)ethan-1-amine: To a stirred solution of 1-(3-chloropyrazin-2-yl)ethan-1-one (16 g, 102 mmol) in methanol (150 mL), ammonium acetate (118 g, 1.538 mol) was added, and the resulting mixture was stirred for 10 min at 25 °C. Then sodium cyanoborohydride (NaBH 3 CN), (9.6 g, 153 mmol) was added at 25 °C and the reaction mixture was stirred for further 12 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude residue. The resulting residue was neutralized with a 1N sodium hydroxide (NaOH) solution and the aqueous layer was extracted with ethyl acetate (EtOAc) (200 mL x 3). The combined organic layers were washed with brine solution (100 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain 1-(3-chloropyrazin-2-yl)ethan-1-amine (3.5 g, 22.4 mmol, 22 % yield) as a brownish gel and used for the next transformation immediately; LCMS: 194.8 [M] + . Step-3: Synthesis of N-(1-(3-chloropyrazin-2-yl)ethyl)-3,5-bis(trifluoromethyl)be nzamide: To a stirred solution of 3,5-bis(trifluoromethyl)benzoic acid (7.5 g, 29.1 mmol) in N,N-dimethylformamide (50 mL), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyri dinium 3-oxide hexafluorophosphate (11.1 g, 29.1 mmol) were slowly added, and the resulting reaction mixture was stirred at 25 °C for 0.5 h. Then N,N-diisopropylethylamine (15.2 mL, 87.3 mmol) and a solution of 1-(3- chloropyrazin-2-yl)ethan-1-amine (3.5 g, 22.4 mmol) in N,N-dimethylformamide (20 mL) were added and the reaction mixture was allowed to be stirred at 25 °C for further 16 h. After the completion of the reaction, the reaction mixture was diluted with water (100 mL) and the aqueous layer was extracted with ethyl acetate (200 mL x 3). The combined organic layers were washed with a saturated solution of sodium bicarbonate (100 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain N-(1-(3-chloropyrazin-2- yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (3.0 g, 7.66 mmol, 34 % yield) as a pale yellow solid. 1H- NMR (400 MHz, CHLOROFORM-D) δ 8.52 (d, J = 2.4 Hz, 1H), 8.39 (d, J = 2.4 Hz, 1H), 8.28 (s, 2H), 8.03 (s, 1H), 7.63 (d, J = 7.3 Hz, 1H), 5.78 (t, J = 7.2 Hz, 1H), 1.63 (d, J = 6.7 Hz, 3H); LCMS (M+H): 397. Step-4: Synthesis of N-(1-(3-(5-bromo-1H-pyrazol-1-yl)pyrazin-2-yl)ethyl)-3,5- bis(trifluoromethyl)benzamide: To a stirred solution of N-(1-(3-chloropyrazin-2-yl)ethyl)-3,5-bis(trifluoromethyl)be nzamide (590 mg, 1.484 mmol), 3-bromo-1H-pyrazole (327 mg, 2.225 mmol) in N,N-dimethylformamide (5 mL), potassium carbonate (615 mg, 4.45 mmol) was added slowly, and the resulting reaction mixture was stirred at 130 °C for 2 h under microwave irradiation. After the completion of the reaction, the reaction mixture was diluted with cold water (15 mL) and the aqueous layer was extracted twice with ethyl acetate (20 x 2 mL). The combined organic layers were washed with brine solution (10 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain N-(1-(3-(5-bromo-1H-pyrazol-1-yl)pyrazin-2-yl)ethyl)-3,5- bis(trifluoromethyl)benzamide (608 mg, 1.196 mmol, 81 % yield) as off-whitish solid; 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.48 (d, J = 6.4 Hz, 1H), 8.73 (d, J = 2.4 Hz, 1H), 8.54 (d, J = 2.2 Hz, 1H), 8.50 (d, J = 2.7 Hz, 1H), 8.46 (s, 2H), 8.28 (s, 1H), 6.79 (d, J = 2.7 Hz, 1H), 5.80-5.74 (m, 1H), 1.63 (d, J = 6.8 Hz, 3H); LCMS: 507.7 [M+H]. Step-5: Synthesis of N-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)-1H-pyrazol-1-yl)pyrazin-2- yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (196) A stirred solution of N-(1-(3-(5-bromo-1H-pyrazol-1-yl)pyrazin-2-yl)ethyl)-3,5- bis(trifluoromethyl)benzamide (250 mg, 0.492 mmol) and iminodimethyl-λ 6 -sulfanone (68.7 mg, 0.738 mmol) in toluene (8 mL), was degassed with nitrogen for 10 min. Tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3) (67.6 mg, 0.074 mmol), xantphos (100 mg, 0.172 mmol) and potassium phosphate tribasic (K3PO4, 313 mg, 1.476 mmol) were added slowly, and the resulting reaction mixture was stirred at 120 °C for 1h under microwave irradiation. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate (20 mL) and passed through a celite column. The organic layer was concentrated under reduced pressure to obtain a crude product which was purified by preparative HPLC to obtain N-(1-(3-(5-((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)-1H-pyrazol- 1-yl)pyrazin-2-yl)ethyl)-3,5-bis(trifluoromethyl)benzamide (152 mg, 0.292 mmol, 59.4 % yield) as a light brownish solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.46 (d, J = 7.0 Hz, 1H), 8.51 (d, J = 2.4 Hz, 3H), 8.37 (dd, J = 15.1, 2.6 Hz, 2H), 8.29 (s, 1H), 6.25-6.19 (m, 1H), 6.08 (d, J = 2.8 Hz, 1H), 3.35 (d, J = 16.2 Hz, 6H), 1.63 (d, J = 6.7 Hz, 3H); LCMS[M+H]: 521.1. Synthetic Scheme 16 Preparation example: Example 7: Synthesis of (S)-3-chloro-N-(1-(1-(5-(((dimethyl(oxo)-λ 6 - sulfaneylidene)amino)methyl)pyridin-2-yl)-1H-1,2,4-triazol-5 -yl)ethyl)-5- (trifluoromethyl)benzamide (187) Step-1: Synthesis of (S)-N-(1-(1-(5-(bromomethyl)pyridin-2-yl)-1H-1,2,4-triazol-5 -yl)ethyl)-3-chloro- 5-(trifluoromethyl)benzamide: To a stirred solution of (S)-3-chloro-N-(1-(1-(5-(methoxymethyl)pyridin-2-yl)-1H-1,2, 4-triazol-5- yl)ethyl)-5-(trifluoromethyl)benzamide (2.0 g, 4.55 mmol) in dichloromethane (20 mL), boron tribromide (6.82 mL, 6.82 mmol) was added and the resulting reaction mixture was stirred at 25 °C for 2 h. After the completion of the reaction, the reaction mixture was diluted with water (30 mL) and the aqueous layer was extracted with ethyl acetate (30 mL x 2). The combined organic layers were washed with brine solution (20 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product which was purified by column chromatography to obtain (S)-N-(1-(1-(5- (bromomethyl)pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethyl)-3-ch loro-5-(trifluoromethyl)benzamide (1.2 g, 2.456 mmol, 54.0 % yield) as a white solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.36 (d, J = 7.1 Hz, 1H), 8.60 (d, J = 1.7 Hz, 1H), 8.15 (s, 1H), 8.13-8.10 (m, 2H), 8.05 (dd, J = 9.7, 0.9 Hz, 2H), 7.86-7.84 (m, 1H), 6.06-5.98 (m, 1H), 4.79 (s, 2H), 1.64-1.61 (m, 3H); LCMS [M+H]: 490. Step-2: (S)-3-chloro-N-(1-(1-(5-(((dimethyl(oxo)-λ 6 -sulfaneylidene)amino)methyl)pyridin-2-yl)-1H- 1,2,4-triazol-5-yl)ethyl)-5-(trifluoromethyl)benzamide (187) To a stirred solution of iminodimethyl-λ 6 -sulfanone (86 mg, 0.921 mmol) in acetonitrile (5 mL), potassium carbonate (127 mg, 0.921 mmol) was added followed by the addition of (S)-N-(1-(1-(5- (bromomethyl)pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethyl)-3-ch loro-5-(trifluoromethyl)benzamide (300 mg, 0.614 mmol) and the resulting reaction mixture was stirred at 80 °C for 3 h. After the completion of the reaction, the reaction mixture was diluted with water (20 mL) and the aqueous layer was extracted with ethyl acetate (20 mL x 2). The combined organic layers were dried over anhydrous sodium sulfate and filtered and concentrated under reduced pressure to obtain a crude product which was purified by preparative HPLC to obtain (S)-3-chloro-N-(1-(1-(5-(((dimethyl(oxo)-λ 6 - sulfaneylidene)amino)methyl)pyridin-2-yl)-1H-1,2,4-triazol-5 -yl)ethyl)-5-(trifluoromethyl)benzamide (135 mg, 0.270 mmol, 43.9 % yield) as a solid. 1 H-NMR (400 MHz, DMSO-d 6 ) δ 9.38 (d, J = 7.1 Hz, 1H), 8.50 (d, J = 1.5 Hz, 1H), 8.13 (s, 1H), 8.11 (s, 1H), 8.09 (s, 1H), 8.05 (s, 1H), 8.00 (dd, J = 8.3, 2.2 Hz, 1H), 7.77 (d, J = 8.6 Hz, 1H), 6.03-5.96 (m, 1H), 4.24 (s, 2H), 3.08 (s, 6H), 1.61 (d, J = 7.1 Hz, 3H); LCMS [M+H]: 501.25. The following compounds (Table-1) of the present invention were obtained using analogous procedures as described in the schemes or in the examples. Table: 1
As described herein, the compounds of formula (I) show insecticidal activities which are exerted with respect to numerous insects that attack on important agricultural crops. The compounds of the present invention were assessed for their activity as described in the following tests: BIOLOGY EXAMPLES: Example A: Helicoverpa armigera The diet incorporation method was used, in which the required quantity of the test compound was weighed and dissolved in a tube containing a solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing. Semi-synthetic diet was incorporated into this solution when the temperature was approximately 50 °C in the bioassay containers. Compound and diet were stirred thoroughly for proper mixing and allowed to cool for 30 min. The solidified diet was cut into equal pieces, and then each piece was transferred into one cell of a bio-assay tray. A single starved third instar larva was released into each of the cells of the bioassay trays and the tray was covered with a lid. The bio-assay trays were then kept under laboratory conditions at a temperature of 25 °C and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of the larvae. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control. The compounds 1 2 11 12 16 17 19 20 22 23 24 25 46 49 53 86 88 93 94 96 97 102 103 105 106 109 126 131 139 140 143 147 148 149 150 152 153 154 156 157 160 161 174 177 178 180 183 186 187 192 200 202 204 208 210 211 213 214 and 216 recorded ≥ 70 per cent mortality @ 300PPM. Example B: Spodoptera litura The diet incorporation method was used, in which the required quantity of the test compound was weighed and dissolved in a tube containing a solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing. Semi-synthetic diet was incorporated into this solution when the temperature was approximately 50 °C in the bioassay containers. Compound and diet were stirred thoroughly for proper mixing and allowed to cool for 30 min. The solidified diet was cut into equal pieces, and then each piece was transferred into one cell of a bio-assay tray. A single starved third instar larva was released into each of the cells of the bioassay trays and the tray was covered with a lid. The bio-assay trays were then kept under laboratory conditions at a temperature of 25 °C and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of the larvae. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control. The compounds 2 12 16 17 19 20 22 23 25 26 30 38 46 86 88 93 94 95 105 106 109 116 121 126 127 131 140 141 143 145 147 148 152 153 154 156 157 158 161 163 164 165 172 174 175 177 180 183 187 188 192 200 204 209 213 and 216 recorded ≥ 70 per cent mortality @ 300PPM. Example C: Plutella xylostella The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing a solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then the mixture was diluted with a 0.01% Triton-X solution to the desired test concentration. Cabbage leaves were dipped in the compound solution for 10 seconds, shade dried for 20 min and then transferred into the cells of bioassay trays. A single second instar larva was released into each cell and the tray was covered with a lid. The bio-assay trays were then kept under laboratory conditions at a temperature of 25 °C and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control. The compounds 2 9 10 11 12 13 15 16 17 18 19 20 22 23 24 25 26 27 28 29 30 33 36 37 38 39 40 43 44 46 48 49 53 54 56 61 63 64 66 76 85 86 88 89 90 91 93 94 95 96 97 98 99 100 102 103 104 105 106 107 108 109 111 112 114 115 116 117 120 121 124 126 127 129 131 133 134 137 139 140 141 143 145 147 148 149 150 151 152 153 154 156 157 158 160 161 164 165 169 172 173 174 175 177 178 179 180 181 182 183 185 186 187 188 190 192 193 194 197 199 200 201 202 203 204 207 208 209 210 211 212 213 214 215 and 216 recorded ≥ 70 per cent mortality @ 300PPM. Example D: Bemisia tabaci The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing a solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then the mixture was diluted with a 0.01% Triton-X solution to the desired test concentration. Brinjal leaves were dipped in the compound solution for 10 seconds; shade dried for 20 min and then placed, with the abaxial side of the leaf up, on 4 ml of a solidified 1 % agar-agar solution in respective perforated container caps. Known numbers of freshly emerged whitefly adults were collected, using a modified aspirator, and released into a perforated container in which the cap containing the treated leaf was placed. The containers were kept in a plant growth chamber at a temperature of 25 °C and relative humidity of 70%. Observations on dead, moribund and alive adults were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund adults and comparing the result to the one of the untreated control. The compound 20 recorded ≥ 70 per cent mortality @ 300PPM. Example E: Myzus persicae The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing a solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then the mixture was diluted with a 0.01% Triton-X solution to the desired test concentration. Capsicum leaves were dipped in the compound solution for 10 seconds, shade dried for 20 min and then placed, with the abaxial side of the leaf up, in single cells of a bio-assay tray containing 4 ml of a solidified 1 % agar-agar solution. Known numbers of third instar nymphs, collected in petri plates, were released into the cell with the treated leaf and the cell was covered with a perforated lid for better aeration. The trays were kept in a plant growth chamber at a temperature of 25 °C and a relative humidity of 70%. Observations on dead, moribund and alive nymphs were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund nymphs and comparing the result with the one of the untreated control. The compounds, 2 3 4 5 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 25 30 38 46 50 53 56 65 86 88 91 93 94 95 96 97 98 99 102 105 106 107 108 109 112 120 124 127 128 134 137 138 140 141 142 143 147 148 149 152 153 154 157 158 160 161 162 163 164 165 170 172 173 174 177 180 186 187 189 200 201 202 203 204 207 208 209 210 211 212 213 214 216 219 221 222 and 227 recorded ≥ 70 per cent mortality @ 300PPM. Example F: Nilaparvata lugens The seedling dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing a solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then the mixture was diluted with a 0.01% Triton-X solution to the desired test concentration. Paddy seedlings were dipped in the compound solution for 10 seconds, shade dried for 20 min and then the seedlings were placed in glass test tubes with the roots kept in water. 15 third instar nymphs were released into each test tube, the tubes were covered with a lid and kept in a plant growth chamber at a temperature of 25 °C and relative humidity of 75%. Observations on dead, moribund and alive nymphs were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund nymphs and comparing the result to the one of the untreated control. The compounds, 9 10 11 12 17 18 19 20 21 22 24 26 50 53 73 86 88 90 91 93 94 95 152 153 158 161 179 185 186 199 200 202 203 204 207 208 209 210 212 216 and 221 recorded ≥ 70 per cent mortality @ 300PPM. Having described the invention with reference to certain preferred embodiments, other embodiments will become apparent to one skilled in the art from the consideration of the specification. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.