USOO9029639B2
(12) United States Patent (10) Patent No.: US 9,029,639 B2 Le VezOuet et al. (45) Date of Patent: May 12, 2015
(54) PYRIDAZINE COMPOUNDS FOR FOREIGN PATENT DOCUMENTS CONTROLLING INVERTEBRATE PESTS CA 2 026 131 3, 1991 (75) Inventors: Ronan Le Vezouet, Mannheim (DE); CN 1711255 12/2005 Sebastian Soergel, Ludwigshafen (DE); (Continued) Christian Defieber, Mannheim (DE); OTHER PUBLICATIONS Steffen Gross, Ludwigshafen (DE); Karsten Koerber, Eppelheim (DE); International Preliminary Report on Patentability issued Jan. 10, 2012, from corresponding International Application No. PCT/ Deborah L. Culbertson, Fuquay Varina, EP2010/059333, filed Jul. 1, 2010. NC (US); Douglas D. Anspaugh, Apex, International Search Report completed Aug. 25, 2010, in Interna NC (US) tional Application No. PCT/EP2010/059333, filed Jul. 1, 2010. Milyutin, A.V., et al. “Synthesis properties and biological activity of (73) Assignee: BASFSE, Ludwigshsafen (DE) 3-pyridylamides of 4-aryl-2-hydroxy-4-oxo-2-butenic (Aroylpyruvic) acids'. Pharmaceutical Chemistry Journal, 1997, p. *) Notice: Subject to anyy disclaimer, the term of this 30-33, vol. 31, No. 1. patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 0 days. Primary Examiner — Jason Sims (21) Appl. No.: 13/382,225 Assistant Examiner — Ibrahim D Bori (74) Attorney, Agent, or Firm — Brinks Gilson & Lione (22) PCT Filed: Jul. 1, 2010 (57) ABSTRACT (86). PCT No.: PCT/EP2010/059333 The present invention relates to pyridazine compounds of S371 (c)(1), formulae I or II and the salts and N-oxides thereof, (2), (4) Date: Jan. 4, 2012 (87) PCT Pub. No.: WO2011/003796 N (I) x w? Yv PCT Pub. Date: Jan. 13, 2011 ul (65) Prior Publication Data A S. US 2012/O110704 A1 May 3, 2012 R1 R x wany (II) Related U.S. Application Data ls (60) Provisional application No. 61/223,100, filed on Jul. 6, A. S.S. 2009. R (51) Int. Cl. AOIH 5/00 (2006.01) wherein C07D 417/12 (2006.01) A is a substituted or unsubstituted oxazole or thiazole or (Continued) imidazole radical; V is C(R) or N; W is C(R") or N; with the proviso that either (52) U.S. Cl. V or W is N. R. R", R. R" are H, halogen, C-C-alkyl and CPC ...... C07D 417/12 (2013.01); A0IN 43/58 the like: X is S, O or NR'', wherein R'' is selected H, (2013.01); A0IN 43/76 (2013.01); A0IN 43/78 C1-Co-alkyl and the like; X is OR", NR'R'', S(O),R’", (2013.01); C07D 403/12 (2013.01); C07D wherein m is 0, 1 or 2, R is C-C-alkyl, C-C-haloalkyl 413/12 (2013.01) and the like, R, R are H, C, -Ca-alkyl, C-C-haloalkyland (58) Field of Classification Search the like, or R'2b and Ri2c together with the nitrogen atom to CPC CO7D 417/122 CO7D 403/12 CO7D which they are bound form a heterocycle, and R is C-C- 413/12. A0N4358, AON 43/78. A01N alkyl, C1-C4-haloalkyl, Ca-C6-cycloalkyland the like; andR s s is H. CN, C-Cio-alkyl and the like. USPC ...... 800,298.514/252.05. 544,238. Theling invertebratepresent invention pests, furtherto a method relates for to protecting a method plant for control propa S ee appl1cauonlication fileIlle fIor completelet searcnh historv.n1Story gation material and/or the plants which grow therefrom, to (56) References Cited plant propagation material, comprising at least one com pound according to the present invention, to a method for U.S. PATENT DOCUMENTS treating or protecting an animal from infestation or infection by parasites and to an agricultural composition containing at 5,360,799 A 1 1/1994 Bachy et al. least one compound according to the present invention. 6,747,041 B1 6/2004 Katsuhira et al. (Continued) 23 Claims, No Drawings US 9,029,639 B2 Page 2
(51) Int. Cl. WO WO 2007.121687 11, 2007 AOIN 43/58 (2006.01) WO WO 2007/139856 12/2007 WO WO 2007/139860 12/2007 AOIN 43/76 (2006.01) WO WO 2008, 116898 10, 2008 AOIN 43/78 (2006.01) WO WO 2009,0273.93 3, 2009 CO7D 403/2 (2006.01) WO WO 2009/086303 T 2009 CO7D 413/2 (2006.01) WO WO 2010/017047 2, 2010 WO WO 2010/023.277 3, 2010 WO WO 2010/034.737 4/2010 (56) References Cited WO WO 2010.034738 4/2010 WO WO 2011/003793 1, 2011 U.S. PATENT DOCUMENTS WO WO 2011/OO9804 1, 2011 2006, OO69132 A1 3, 2006 Armel et al. OTHER PUBLICATIONS 392,939. 3. A. 3. 2. Persson, Tobias, et al., “Pyrazole carboxamides and carboxylic acids 2008.0033513 A1 2, 2008 N.A. a. as protein kinase inhibitors in aberrant eukaryotic signal transduc 2008, OO58389 A1 3/2008 Dunkel et al. tion: induction of growth arrest in MCF-7 cancer cells'. Organic & 2009,0163516 A1 6, 2009 Dunkel et al. Biomolecular Chemistry, 2007, pp. 3963-3970, vol. 5. 2009,0176844 A1 7/2009 Dunkel et al. Sharlow et al., “Development and Implementation of a Miniaturized 2009, O247586 A1 10, 2009 Dunkel et al. High-Throughput Time-Resolved Fluorescence Energy Transfer 2009/0286800 A1 11/2009 Cheruvallath et al. Assay to Identify Small Molecule Inhibitors of Polo-Like Kinase 1.” ASSAY and Drug Development Technologies, vol. 5, No. 6, (2007), FOREIGN PATENT DOCUMENTS pp. 723-735. Office Action dated Jan. 16, 2013, from U.S. Appl. No. 13/120,052, CN 1927838 3, 2007 filed Jul. 20, 2011. CN 101062916 10/2007 Office Action dated May 21, 2013, from U.S. Appl. No. 13/382.229, CN 101062919 10/2007 EP O 419944 4f1991 filed Jan. 4, 2012. EP O573883 12/1993 Office Action dated Nov. 21, 2012, from U.S. Appl. No. 16/674.991, EP 0606175 T 1994 filed Feb. 24, 2010. EP O 89.1975 1, 1999 Office Action dated May 8, 2013, from U.S. Appl. No. 13/386,473, EP 1188 745 3, 2002 filed Jan. 23, 2012. EP 2263455 12/2010 U.S. Environmental Protection Agency, “Insect Repellents: Use and JP 10195072 7, 1998 Effectiveness”.
Invertebrate pests and in particular arthropods and nema (II) todes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large 25 economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests Such as insects, arachnids and nematodes. It is therefore an 30 object of the present invention to provide compounds having wherein a good pesticidal activity and showing a broad activity spec A is an oxazole or thiazole or imidazole radical of formulae trum against a large number of different invertebrate pests, A1, A2 or A3 oxazole, especially against difficult to control insects, arachnids and nematodes. 35 EP 04.19944 describes oxazole- and thioxazolescarboxilic A1 acides derivatives and their use as herbicide is mentioned. R41 WO 2007/068373, WO 2007/068375 and WO 2007/ 068377 describe derivatives of N-aryl- and N-hetarylamides, j \ derived from carboxylic acids comprising a 5- or 6-mem 40 it. -k Z R51 bered carbocycle or heterocycle. These compounds are men tioned to be useful for controlling micro-organisms. (R6) WO 2005/074686 and WO 2005/075411 describe deriva A2 tives of N-arylamides which are mentioned to be useful in R42 control of micro-organismus Such as fungi, bacteria in the 45 phyto-protection. WO 2004/106324, WO 2004/035545 and WO 2005/ 04.0152 describe derivatives of N-aryl- and N-hetarylamides, - Z it. derived from carboxylic acids comprising a 5-membered het (R62). erocycle. These compounds are mentioned to be useful as 50 A3 herbicides. it. WO 2006/074445 describes biologically active hetero pyr N role analogs such as imidazoles, thiazoles, oxazoles, and pyrazoles; their pharmaceutical preparation and their thera peutically administration methods are mentioned. 55 WO 2003/106427, WO 2004/046129 and JP 2007-77106 describe derivatives of N-arylamides, derived from (R63), Pyridazine carboxylic acids. These compounds are men tioned to be useful for combating invertebrate pests. wherein WO 2001/00575 describes derivatives of N-aryl- and 60 # denotes the binding site to the remainder of formulae I or N-hetarylamides, derived from carboxylic acids comprising a II, and wherein 5- or 6-membered heterocycle carrying a further amide-de R', R. Rands R are independently of each other rived function in ortho-position. These compounds are men selected from hydrogen, halogen, CN, NO, C-Co tioned to be useful as insecticides. alkenyl and C-Co-alkynyl, wherein the 3 last men WO 2005/073165 describes derivatives of N-aryl- or 65 tioned radicals may be unsubstituted, may be partially or N-hetarylamides, derived from carboxylic acids comprising fully halogenated or may carry 1, 2 or 3 identical or phenyl or a heterocycle, wherein the N-bound cycle carries a different substituents R. US 9,029,639 B2 3 4 or wherein R', R. RandR are further selected from which, independently of each other, are selected from OR, C(Y)R, C(Y)OR, S(O),R, NR'R'', heterocy halogen, cyano, nitro, C-C-alkyl, C-C-haloalkyl, clyl, heteroaryl, C-Co-cycloalkyl, Cs-Co-cycloalk C-C-alkoxy and C-Ca-haloalkoxy, and wherein enyland phenyl, wherein the five last mentioned radicals R’, R" are independently of each other selected from may be unsubstituted or may carry 1, 2,3,4 or 5 identical 5 hydrogen, C-C-alkyl, C-Ca-haloalkyl, C-C-cy or different substituents R, wherein m is 0, 1, 2 and cloalkyl, C-C-halocycloalkyl, C-C-alkenyl, C-C- wherein haloalkenyl, C-C-alkynyl, C-C-alkylcarbonyl, R. Rare selected from hydrogen, halogen, CN, NO, C-Ca-haloalkylcarbonyl, C-C-alkylsulfonyl, C-C- C-Co-alkyl, C-Co-alkenyl and C-Co-alkynyl, haloalkylsulfonyl, phenyl, phenylcarbonyl, phenylsul wherein the 3 last mentioned radicals may be unsubsti 10 fonyl, hetaryl, hetarylcarbonyl, hetarylsulfonyl, hetero tuted, may be partially or fully halogenated or may carry cyclyl, heterocyclylcarbonyl, heterocyclylsulfonyl, 1, 2 or 3 identical or different substituents R, or wherein hetaryl-C-C-alkyl and heterocyclyl-C-C-alkyl, R, R are further selected from OR, C(Y)R, C(Y) wherein the ring in the twelve last mentioned radicals OR, S(O),R, NRR, heterocyclyl, heteroaryl, may be unsubstituted or may carry 1, 2, 3, 4 or 5 sub Cs-Co-cycloalkyl, Cs-Co-cycloalkenyl and phenyl, 15 stituents which, independently of each other, are wherein the five last mentioned radicals may be unsub selected from halogen, cyano, nitro, C-C-alkyl, stituted or may carry 1, 2, 3, 4 or 5 identical or different C-C-alkoxy and C-Ca-haloalkoxy, or Substituents R, wherein m is 0, 1 or 2, and wherein R’ and R* together with the nitrogen atom to which they R", R, R if present are selected from hydrogen, CN, are bound form a 5- or 6-membered, saturated or unsat NO, C-Co-alkyl, C-Co-alkenyl and C-Co-alkynyl, urated heterocycle, which may carry a further heteroa wherein the three last mentioned radicals may be unsubsti tom being selected from O, S and N as a ring member tuted, may be partially or fully halogenated or may carry 1, 2 atom and wherein the heterocycle may be unsubstituted or 3 identical or different substituents R, or wherein R', R, or may carry 1, 2, 3, 4 or 5 substituents which, indepen R° if present are further selected from OR", C(Y)R’, C(Y) dently of each other, are selected from halogen, cyano, OR, S(OR, NR'R''. C(Y)NR'R'', S(O)NR'R''. C(Y)N- 25 nitro, C-Ca-haloalkyl, C-C-alkoxy and C-Ca-ha RNR'R''. heterocy clyl, heterocyclyl-C-Cs-alkyl, het loalkoxy and wherein eroaryl, heteroaryl-C-C-alkyl, C-Co-cycloalkyl, C-Co R’ is selected from C-C-alkyl, Ca-Ca-cycloalkyl, cycloalkenyl, Cs-Co-cycloalkenyl-C-C-alkyl, phenyl, C-C-halocycloalkyl, C-C-alkenyl, C-C-haloalk phenyl-C-C-alkyl, C-C-alkylen-OR, C-Cs-alkylen enyl, C-C-alkynyl, C-C-alkoxy-C-C-alkyl, phe CN, C-C-alkylen-C(Y)R, C-C-alkylen-C(Y)OR, 30 nyl, hetaryl, heterocyclyl phenyl-C-C-alkyl, hetaryl C-C-alkylen-NR'R''. C-C-alkylen-C(Y)NR'R'', C.-Cs C-C-alkyl and heterocyclyl-C-C-alkyl, wherein the alkylenS(O),R, C-C-alkylen-S(O)NR'R''. C-Cs-alky ring in the six last mentioned radicals may be unsubsti len-C(Y)NRNRR, wherein the last nineteen mentioned tuted or may carry 1, 2, 3, 4 or 5 substituents which, radicals may be unsubstituted or may carry 1, 2, 3, 4 or 5 independently of each other, are selected from halogen, identical or different substituents R or R'' and wherein m is 0, 35 cyano, nitro, C-C-alkyl, C-C-haloalkyl, C-C- 1 or 2; alkoxy and C-Ca-haloalkoxy; Z is O or S for Z=0 or Z is N for Z=1: R" is hydrogen, CN, C-Co-alkyl, C, -Co-haloalkyl, Cs-Co V is C(R) or N: cycloalkyl, C-Co-halocycloalkyl, C-Co-alkenyl, W is C(R") or N: C-C-haloalkenyl, C-Co-alkynyl, C-Co-haloalkynyl, with the proviso that either V or W is N: 40 OR, COY)R, C(Y)ORs, S(O).R, NRR?, C(Y)NR&R, R. R", R' and R" are independently of each other selected S(O)NR'R''. C(Y)NRNR'R'', phenyl, hetaryl, heterocy from hydrogen, halogen, C-C-alkyl, C-C-haloalkyl, clyl, C-C-alkylen-OR, C-C-alkylen-CN. hetaryl-C- C-C-alkoxy, C-C-haloalkoxy, C-C-haloalkylthio. Co-alkyl, heterocyclyl-C-C-alkyl, C-Co-cycloalkyl C-C-alkylsulfinyl, C-C-haloalkylsulfinyl, C-C- C-C-alkyl, C-C-alkylen-C(Y)R’, C, -Co-alkylen-C(Y) alkylsulfonyl, C-C-haloalkylsulfonyl, C-C-cycloalkyl, 45 OR3, C-C-alkylen-NR'R''. C-C-alkylen-C(Y)NR'R'', C-C-halocycloalkyl, C-C-alkenyl, C-Ca-haloalkenyl, C-C-alkylen-S(O).R, C1-Co-alkylenS(O) , NR'R''. C-C-alkynyl or C-C-alkoxy-C-C-alkyl: C-C-alkylen-C(Y)NRNRR, wherein the last sixteen X is S, O or NR", wherein R' is selected from hydrogen, mentioned radicals may be unsubstituted or may carry 1, 2, C-Co-alkyl, C-C-haloalkyl, C-Co-cycloalkyl, 3, 4 or 5 identical or different substituents R or R'' and Cs-Co-cycloalkylmethyl, Cs-Co-halocycloalkyl, 50 wherein m is 0, 1 or 2; C-Co-alkenyl, C-Co-haloalkenyl, C-Co-alkynyl, Y is O or S; C-Co-alkoxy-C-C-alkyl, OR, phenyl, hetaryl, hetero R", R, R are independently of each other selected from cyclyl phenyl-C-C-alkyl, hetaryl-C-C-alkyl, hetero hydrogen, C-C-alkyl, C-Ca-haloalkyl, C-C-cy cyclyl-C-C-alkyl, wherein the ring in, the six last men cloalkyl, C-C-cycloalkyl methyl, C-C-halocycloalkyl, tioned, radicals may be unsubstituted or may carry 1, 2, 3, 55 C-C-alkenyl, C-Ca-haloalkenyl, C-C-alkynyl, C-C- 4 or Substituents which, independently of each other, are, alkoxy-C-C-alkyl, phenyl, hetaryl, heterocyclyl, hetaryl Selected from halogen, cyano, nitro, C-C-alkyl, C-C- C-C-alkyl and heterocyclyl-C-C-alkyl, wherein the haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy; ring in the six last mentioned radicals may be unsubstituted X is OR, NRR, S(O)R’, wherein, m is 0, 1 or 2, or may carry 1, 2, 3, 4 or Substituents which, independently wherein 60 of each other, are selected from halogen, cyano, nitro, R’ is selected from C-C-alkyl, C-C-haloalkyl, C-C- C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy and C-C- cycloalkyl, C-C-halocycloalkyl, C-C-alkenyl, haloalkoxy, C-Ca-haloalkenyl, C-C-alkynyl, C-C-alkoxy-C- R" is selected from C-C-alkyl, C-Ca-haloalkyl, Ca-Ca C-alkyl, phenyl, hetaryl, heterocyclyl phenyl-C-C- cycloalkyl, C-C-cycloalkyl methyl, C-C-halocy alkyl, hetaryl-C-C-alkyl, heterocyclyl-C-C-alkyl, 65 cloalkyl, C-C-alkenyl, C-Ca-haloalkenyl, C-C-alky wherein the ring in the six last mentioned radicals may nyl, C-C-alkoxy-C-C-alkyl, phenyl, hetaryl, be unsubstituted or may carry 1, 2, 3, 4 or substituents heterocyclyl phenyl-C-C-alkyl, hetaryl-C-C-alkyland US 9,029,639 B2 5 6 heterocyclyl-C-C-alkyl, wherein the ring in the six last materials, plants, seeds, soils, Surfaces or spaces, to be pro mentioned radicals may be unsubstituted or may carry 1, 2, tected from pest attack or infestation with a pesticidally effec 3, 4 or 5 substituents which are independently of each other tive amount of a pyridazine compound of formulae I or II Selected from halogen, cyano, nitro, C-C-alkyl, C-C- according to the present invention or a salt or an N-oxide haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy; thereof. R. Rare independently of each other selected from hydro A further aspect of the present invention relates to a method gen, C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, for protecting plant propagation material and/or the plants C-C-cycloalkylmethyl, C-C-halocycloalkyl, C-C- which grow therefrom, which method comprises treating the alkenyl, C-C-haloalkenyl, C-C-alkynyl, C-C- plant propagation material with a pesticidally effective alkoxy-C-C-alkyl, C-C-alkylcarbonyl, C-Ca-ha 10 loalkylcarbonyl, C-C-alkylsulfonyl, C-C- amount of a pyridazine compound of the formulae I or II haloalkylsulfonyl, phenyl, phenylcarbonyl, according to the present invention oran agriculturally accept phenylsulfonyl, hetaryl, hetarylcarbonyl, hetarylsulfonyl, able salt or an N-oxide thereof. heterocyclyl, heterocyclylcarbonyl, heterocyclylsulfonyl, A further aspect of the present invention relates to plant phenyl-C-C-alkyl, hetaryl-C-C-alkyl and heterocy 15 propagation material, comprising at least one compound of clyl-C-C-alkyl, wherein the ring in the twelve last men formulae I or II according to the present invention and/or an tioned radicals may be unsubstituted or may carry 1, 2, 3, 4 agriculturally acceptable salt or an N-oxide thereof. or 5 substituents which, independently of each other, are A further aspect of the present invention relates to a method Selected from halogen, cyano, nitro, C-C-alkyl, C-C- for treating or protecting an animal from infestation or infec haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy; or tion by parasites which comprises bringing the animal in R and R together with the nitrogen atom to which they are contact with a parasiticidally effective amount of a compound bound form a 5- or 6-membered, saturated or unsaturated of the formulae I or II according to the present invention or a heterocycle, which may carry a further heteroatom being veterinarily acceptable salt or an N-oxide thereof. Bringing selected from O, S and N as a ring member atom and the animal in contact with the compound I or II, its salt or the wherein the heterocycle may be unsubstituted or may carry 25 Veterinary composition of the invention means applying or 1, 2, 3, 4 or 5 substituents which are independently of each administering it to the animal. other selected from halogen, cyano, nitro, C-C-alkyl, A further aspect of the present invention relates to an agri C-Ca-haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy; cultural composition containing at least one compound of R°, R" are independently of each other selected from hydro formulae I or II according to the present invention and/or an gen, C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, 30 C-C-halocycloalkyl, C-C-alkenyl, C-Ca-haloalkenyl, agriculturally acceptable salt or an N-oxide thereof and at C-C-alkynyl, C-C-alkoxy-C-C-alkyl, phenyl, least one liquid or solid carrier. hetaryl, heterocyclyl phenyl-C-C-alkyl and hetaryl-C- The radicals attached to the backbone of the compounds of C-alkyl, heterocyclyl-C-C-alkyl, wherein the ring in the formulae I or II may contain one or more centers of chirality. six last mentioned radicals may be unsubstituted or may 35 In this case the compounds of the formulae I or II are present carry 1, 2, 3, 4 or substituents which are independently of in the form of different enantiomers or diastereomers, each other selected from halogen, cyano, nitro, C-C- depending on the Substituents. Compounds of formula II alkyl, C-Ca-haloalkyl, C-C-alkoxy and C-C-ha additionally exist as cis- or trans-isomers with respect to the loalkoxy; N=C axis. The present invention relates to every possible R’ is selected from hydrogen, C-C-alkyl, C-C-haloalkyl, 40 stereoisomer of the compounds of formulae I or II, i.e. to C-C-cycloalkyl, C-C-cycloalkylmethyl, C-C-halo single enantiomers or diastereomers, as well as to mixtures cycloalkyl, C-C-alkenyl, C-C-haloalkenyl, C-C- thereof. alkynyl, C-C-alkoxy-C-C-alkyl, phenyl and phenyl The compounds of formulae I or II may be amorphous or C-C-alkyl wherein the phenyl ring in the two last may exist in one or more different crystalline states (poly mentioned radicals may be unsubstituted or may carry 1, 2, 45 morphs) which may have different macroscopic properties 3, 4 or 5 substituents which are independently of each other such as stability or show different biological properties such selected from halogen, cyano, nitro, C-C-alkyl, C-C- as activities. The present invention relates to amorphousand haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy; crystalline compounds of formulae I or II, mixtures of differ Rare independently of each other selected from cyano, nitro, ent crystalline states of the respective compound I or II, as C-C-alkoxy, C-Ca-haloalkoxy, C-Ca-haloalkylthio. 50 well as amorphous or crystalline salts thereof. C-Ca-haloalkylsulfinyl, C-C-alkylsulfonyl, C-Ca-ha Salts of the compounds of the formulae I or II are prefer loalkylsulfonyl, C-Co-alkylcarbonyl, C-C-cycloalkyl, ably agriculturally and Veterinarily acceptable salts. They can 5- to 7-membered heterocyclyl phenyl, C-C-cy be formed in a customary manner, e.g. by reacting the com cloalkoxy, 3- to 6-membered heterocyclyloxy and phe pound with an acid of the anion in question if the compound noxy, wherein the last 6 mentioned radicals may be unsub 55 of formulae I or II has a basic functionality. stituted or may carry 1, 2,3,4 or 5 radicats R'; and wherein Agriculturally useful salts of the compounds of formulae I R’ is selected fromhalogen, cyano, nitro, C-C-alkyl, C-C- and II encompass especially the acid addition salts of those alkoxy, C-C-haloalkoxy, S(O),R', S(O)NR'R''. C-C- acids whose cations and anions, respectively, have no adverse alkylcarbonyl, C-Ca-haloalkylcarbonyl, C-C-alkoxy effect on the pesticidal action of the compounds of formulae carbonyl, C-Ca-haloalkoxycarbonyl, C-C-cycloalkyl, 60 I or II. C-C-halocycloalkyl, C-C-alkenyl, C-C-haloalkenyl, Anions of useful acid addition salts are primarily chloride, C-C-alkynyl and C-C-alkoxy-C-C-alkyl. bromide, fluoride, hydrogensulfate, Sulfate, dihydrogenphos A further aspect of the present invention relates to a method phate, hydrogenphosphate, phosphate, nitrate, bicarbonate, for controlling invertebrate pests which method comprises carbonate, hexafluorosilicate, hexafluorophosphate, ben treating the pests, their food supply, their habitat or their 65 Zoate, and the anions of C-C-alkanoic acids, preferably breeding ground or a plant, seed, soil, area, material or envi formate, acetate, propionate and butyrate. They can be ronment in which the pests are growing or may grow, or the formed by reacting compounds of formulae I and II with an US 9,029,639 B2 7 8 acid of the corresponding anion, preferably of hydrochloric 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO acid, hydrobromic acid, Sulfuric acid, phosphoric acid or 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, nitric acid. WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) Veterinarily acceptable salts of the compounds of formulae or imidazolinones (see e.g. U.S. Pat. No. 6,222,100, WO I and II encompass especially the acid addition salts which are 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO known and accepted in the art for the formation of salts for 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, Veterinary use. Suitable acid addition salts, e.g. formed by WO 03/13225, WO 03/14356, WO 04/16073); enolpyru compounds of formulae I or II containing a basic nitrogen vylshikimate-3-phosphate synthase (EPSPS) inhibitors, such atom, e.g. an amino group, include salts with inorganic acids, as glyphosate (see e.g. WO92/00377); glutamine synthetase for example hydrochlorids, Sulphates, phosphates, and 10 (GS) inhibitors, such as glufosinate (see e.g. EP-A-0242236, nitrates and salts of organic acids for example acetic acid, EP-A-242246) or oxynil herbicides (see e.g. U.S. Pat. No. maleic acid, e.g. the monoacid salts or diacid salts of maleic 5,559,024) as a result of conventional methods of breeding or acid, dimaleic acid, fumaric acid, e.g. the monoacid salts or genetic engineering. Several cultivated plants have been ren diacid salts of fumaric acid, difumaric acid, methane Sulfenic dered tolerant to herbicides by conventional methods of acid, methane Sulfonic acid, and Succinic acid. 15 breeding (mutagenesis), for example Clearfield(R) Summer The term “N-oxide’ includes any compound of formulae I rape (Canola) being tolerant to imidazolinones, e.g. or II which has at least one tertiary nitrogen atom that is imaZamox. Genetic engineering methods have been used to oxidized to an N-oxide moiety. render cultivated plants, such as soybean, cotton, corn, beets The term “invertebrate pest” as used herein encompasses and rape, tolerant to herbicides, such as glyphosate and glu animal populations, such as insects, arachnids and nema fosinate, some of which are commercially available under, the todes, which may attack plants thereby causing Substantial trade names RoundupReady(R) (glyphosate) and LibertyL damage to the plants attacked, as well as ectoparasites which ink R. (glufosinate). may infest animals, in particular warm blooded animals such The term “cultivated plants' as used hereinfurther includes as e.g. mammals or birds, or other higher animals such as plants that are by the use of recombinant DNA techniques reptiles, amphibians or fish, thereby causing Substantial dam 25 capable to synthesize one or more insecticidal proteins, espe age to the animals infested. cially those known from the bacterial genus bacillus, particu The term "plant propagation material” as used herein larly from bacillus thuringiensis, Such as ?-endotoxins, e.g. includes all the generative parts of the plant Such as seeds and CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, Vegetative plant material Such as cuttings and tubers (e.g. Cry IIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), potatoes), which can be used for the multiplication of the 30 e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of plant. This includes seeds, roots, fruits, tubers, bulbs, rhi bacteria colonizing nematodes, for example Photorhabdus Zomes, shoots, sprouts and other parts of plants. Seedlings spp. or Xenorhabdus spp.: toxins produced by animals, such and young plants, which are to be transplanted after germi as Scorpion toxins, arachnid toxins, wasp toxins, or other nation or after emergence from soil, may also be included. insect-specific neurotoxins; toxins produced by fungi. Such These plant propagation materials may be treated prophylac 35 Streptomycetes toxins, plant lectins, such as pea or barley tically with a plant protection compound either at or before lectins; agglutinins; proteinase inhibitors, such as trypsin planting or transplanting. inhibitors, serine protease inhibitors, patatin, cystatin or The term “plants' comprises any types of plants including papain inhibitors; ribosome-inactivating proteins (RIP). Such “non-cultivated plants’ and in particular “cultivated plants'. as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid The term “non-cultivated plants' refers to any wild type 40 metabolism enzymes. Such as 3-hydroxysteroid oxidase, species or related species or related genera of a cultivated ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, plant. ecdysone inhibitors or HMG-CoA-reductase; ion channel The term “cultivated plants’ as used herein includes plants blockers, such as blockers of sodium or calcium channels; which have been modified by breeding, mutagenesis or juvenile hormone esterase: diuretic hormone receptors (heli genetic engineering. Genetically modified plants are plants, 45 cokinin receptors); Stilben synthase, bibenzyl synthase, chiti which genetic material has been so modified by the use of nases or glucanases. In the context of the present invention recombinant DNA techniques that under natural circum these insecticidal proteins or toxins are to be understood stances cannot readily be obtained by cross breeding, muta expressly also as pre-toxins, hybrid proteins, truncated or tions or natural recombination. Typically, one or more genes otherwise modified proteins. Hybrid proteins are character have been integrated into the genetic material of a genetically 50 ized by a new combination of protein domains, (see, for modified plant in order to improve certain properties of the example WO 02/015701). Further examples of such toxins or plant. Such genetic modifications also include but are not genetically-modified plants capable of synthesizing Such tox limited to targeted post-transtional modification of protein(s) ins are dis-closed, for example, in EP-A 374 753, WO (oligo- or polypeptides) poly for example by glycosylation or 93/007278, WO95/34656, EP-A 427 529, EP-A 451 878, polymer additions such as prenylated, acetylated or farnesy 55 WO 03/018810 and WO 03/052073. The methods for pro lated moieties or PEG moieties (e.g. as disclosed in Biotech ducing Such genetically modified plants are generally known nol Prog. 2001 July-August; 17(4): 720-8. Protein Eng Des to the person skilled in the art and are described, for example, Sel. 2004 January: 17(1):57-66, Nat. Protoc. 2007: in the publications mentioned above. These insecticidal pro 2(5):1225-35, Curr. Opin. Chem. Biol. 2006 October; 10(5): teins contained in the genetically modified plants impart to 487-91. Epub 2006 Aug. 28, Biomaterials. 2001 March: 60 the plants producing these proteins protection from harmful 22(5):405-17, Bioconjug. Chem. 2005 January-February; pests from certain taxonomic groups of arthropods insects, 16(1): 113-21). particularly to beetles (Coleoptera), flies (Diptera), and but The term “cultivated plants' as used hereinfurther includes terflies and moths (Lepidoptera) and to plant parasitic nema plants that have been rendered tolerant to applications of todes (Nematoda). specific classes of herbicides, such as hydroxy-phenylpyru 65 The term “cultivated plants' as used hereinfurther includes vate dioxygenase (HPPD) inhibitors; acetolactate synthase plants that are by the use of recombinant DNA techniques (ALS) inhibitors, such as sulfonylureas (see e.g. U.S. Pat. No. capable to synthesize one or more proteins to increase the US 9,029,639 B2 10 resistance or tolerance of those plants to bacterial, viral or The term “haloalkyl as used herein and in the haloalkyl fungal pathogens. Examples of such proteins are the so-called moieties of haloalkoxy, haloalkylthio, haloalkylcarbonyl, “pathogenesis-related proteins’ (PR proteins, see, for haloalkylsulfonyl and haloalkylsulfinyl, denotes in each case example EP-A 0392 225), plant disease resistance genes (for a straight-chain or branched alkyl group having usually from example potato cultivars, which express resistance genes act- 5 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, ing against Phytophthora infestans derived from the mexican wherein the hydrogen atoms of this group are partially or wild potato Solanum bulbocastanum) or T4-lysozym (e.g. totally replaced with halogenatoms. Preferred haloalkyl moi potato cultivars capable of synthesizing these proteins with eties are selected from C-C-haloalkyl, more preferably increased resistance against bacteria Such as Erwinia amyl from C-C-haloalkyl, in particular from C-C-fluoroalkyl vora). The methods for producing such genetically modified 10 such as fluoromethyl, difluoromethyl, trifluoromethyl, plants are generally, known to the person skilled in the art and are described, for example, in the publications mentioned 1-fluoroethyl 2-fluoroethyl, 2,2-difluoroethyl, 2.2.2-trifluo above. roethyl, pentafluoroethyl, and the like. The term “cultivated plants' as used hereinfurther includes The term “alkoxy” as used herein denotes in each case a plants that are by the use of recombinant DNA techniques 15 straight-chain or branched alkyl group which is bound via an capable to synthesize one or more proteins to increase the oxygen atom and has usually from 1 to 10 carbon atoms, productivity (e.g. bio mass production, grain yield, starch frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon content, oil content or protein content), tolerance to drought, atoms. Examples of an alkoxy group are methoxy, ethoxy, salinity or other growth-limiting environ-mental factors or n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-buty tolerance to pests and fungal, bacterial or viral pathogens of loxy, tert.-butyloxy, and the like. those plants. The term “haloalkoxy” as used herein denotes in each case The term “cultivated plants' as used hereinfurther includes a straight-chain or branched alkoxy group having from 1 to 10 plants that contain by the use of recombinant DNA techniques carbon atoms, frequently from 1 to 4 carbon atoms, prefer a modified amount of substances of content or new substances ably 1 to 3 carbon atoms, wherein the hydrogenatoms of this of content, specifically to improve human or animal nutrition, 25 group are partially or totally replaced with halogen atoms, in for ex-ample oil crops that produce health-promoting long particular fluorine atoms. Preferred haloalkoxy moieties chain omega-3 fatty acids or unsaturated omega-9 fatty acids include C-Ca-haloalkoxy, in particular C-C-fluoroalkoxy, (e.g. Nexera R rape). such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, The term “cultivated plants' as used hereinfurther includes 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2.2.2-tri plants that contain by the use of recombinant DNA techniques 30 fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluo a modified amount of substances of content or new substances roethoxy, 2,2-dichloro-2-fluorethoxy, 2.2.2-trichloroethoxy, of content, specifically to improve raw material production, pentafluoroethoxy and the like. for example potatoes that produce increased amounts of amy The term “cycloalkyl as used herein and in the cycloalkyl lopectin (e.g. Amflora R potato). moieties of cycloalkoxy and cycloalkylmethyl denotes in The organic moieties mentioned in the above definitions of 35 each case a mono- or bicyclic cycloaliphatic radical having the variables are—like the term halogen—collective terms usually from 3 to 10 carbonatoms or 3 to 6 carbonatoms, such for individual listings of the individual group members. The as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo prefix C-C, indicates in each case the possible number of heptyl, cyclooctyl, bicyclo[2.1.1 hexyl, bicyclo[3.1.1 heptyl, carbon atoms in the group. bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl. The term halogen denotes in each case fluorine, bromine, 40 The term “halocycloalkyl as used herein and in the halo chlorine or iodine, in particular fluorine, chlorine or bromine. cycloalkyl moieties of halocycloalkylmethyl denotes in each The term “alkyl as used herein and in the alkyl moieties of case a mono- or bicyclic cycloaliphatic radical having usually alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl from 3 to 10 carbonatoms or 3 to 6 carbonatoms, wherein at and alkoxyalkyl denotes in each case a straight-chain or least one, e.g. 1,2,3,4 or 5 of the hydrogenatoms are replaced branched alkyl group having usually from 1 to 10 carbon 45 by halogen, in particular by fluorine or chlorine. Examples atoms, frequently from 1 to 6 carbonatoms, preferably 1 to 4 are 1- and 2-fluorocyclopropyl, 1.2-, 2.2- and 2,3-difluorocy carbon atoms and in particular from 1 to 3 carbon atoms. clopropyl, 1.2.2-trifluorocyclopropyl. 2.2.3,3-tetrafluorocy Examples of an alkyl group are methyl, ethyl, n-propyl, iso clpropyl, 1- and 2-chlorocyclopropyl, 1.2-, 2.2- and 2.3- propyl. n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-me dichlorocyclopropyl, 1.2.2-trichlorocyclopropyl. 2.2.3,3- thylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpro 50 tetrachlorocyclpropyl, 1-2- and 3-fluorocyclopentyl, 1.2-, pyl, 1-ethylpropyl. n-hexyl, 1,1-dimethylpropyl, 1.2- 2.2-, 2.3-, 3.3-, 3.4-, 2,5-difluorocyclopentyl, 1-, 2- and dimethylpropyl. 1-methylpentyl, 2-methylpentyl, 3-chlorocyclopentyl, 1.2-, 2.2-, 2.3-, 3.3-, 3,4-, 2,5-dichloro 3-methylpentyl, 4-methylpentyl, 1,1-dinnethylbutyl, 1.2- cyclopenty1 and the like. dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2.3- The term “alkenyl as used herein denotes in each case a dimethylbutyl, 3.3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 55 singly unsaturated hydrocarbon radical having usually 2 to 1.1.2-trimethylpropyl, 1.2.2-trimethylpropyl. 1-ethyl-1-me 10, preferably 2 to 4 carbonatoms, e.g. vinyl, allyl (2-propen thylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methyl 1-yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methyl hexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-me prop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, thylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 3-penten-1-yl 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-eth 1-propylpentyl. n-octyl, 1-methyloctyl, 2-methylheptyl, 60 ylprop-2-en-1-yl and the like. 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpen The term “alkynyl as used herein denotes in each case a tyl and 2-propylpentyl. singly unsaturated hydrocarbon radical having usually 2 to The term “alkylene' (or alkanediyl) as used herein in each 10, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl case denotes an alkyl radical as defined above, wherein one (2-propyn-1-yl), 1-propyn-1-yl, 1-methylprop-2-yn-1-yl), hydrogen atom at any position of the carbon backbone is 65 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 3-pentyn-1-yl, replaced by one further binding site, thus forming a bivalent 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl, 1-ethylprop-2-yn-1- moiety. y1 and the like. US 9,029,639 B2 11 12 The term “alkoxyalkyl as used herein refers to alkyl usu The term “haloalkylsulfonyl as used herein refers to an ally comprising 1 to 4 carbon atoms, wherein 1 carbon atom alkylsulfonyl group as defined above wherein the hydrogen carries an alkoxy radical usually comprising 1 to 10, in par atoms are partially or fully substituted by fluorine, chlorine, ticular 1 to 4, carbon atoms as defined above. Examples are bromine and/or iodine. CHOCH, CH, OCHs, n-propoxymethyl, CH, OCH The term "heterocyclyl includes in general 5-, 6-, 7- or (CH), n-butoxymethyl, (1-methylpropoxy)-methyl, (2-me 8-membered monocyclic heterocyclic radicals and 8 to 10 thylpropoxy)methyl, CH, OC(CH), 2-(methoxy)ethyl, membered bicyclic heterocyclic radicals, the mono- and bicy 2-(ethoxy)ethyl 2-(n-propoxy)-ethyl, 2-(1-methylethoxy)- ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl 2-(2- clic radicals may be saturated, partially unsaturated or unsat 10 urated. The mono- and bicyclic heterocyclic radicals usually methylpropoxy)-ethyl, 2-(1,1-dimethylethoxy)-ethyl, comprise 1, 2, 3 or 4 heteroatoms selected from N, O and Sas 2-(methoxy)-propyl. 2-(ethoxy)-propyl. 2-(n-propoxy)-pro ring members. pyl, 2-(1-methylethoxy)-propyl. 2-(n-butoxy)-propyl. 2-(1- methylpropoxy)-propyl. 2-(2-methylpropoxy)-propyl, 2-(1, Examples of saturated or unsaturated 5- or 6-membered 1-dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)- heterocyclic radicals comprise Saturated or unsaturated, non propyl, 3-(n-propoxy)-propyl, 3-(1-methylethoxy)-propyl. 15 aromatic heterocyclic rings, such as pyrrolidinyl, pyrazolinyl, 3-(n-butoxy)-propyl, 3-(1-methylpropoxy)-propyl, 3-(2-me pyrazolidinyl, imidazolinyl, pyrrolinyl, pyrazolidinyl, pyra thylpropoxy)-propyl. 3-(1,1-dimethylethoxy)-propyl, Zolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3- 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n-propoxy)-butyl, dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidi 2-(1-methylethoxy)-butyl, 2-(n-butoxy)-butyl, 2-(1-methyl nyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, propoxy)-butyl, 2-(2-methylpropoxy)-butyl, 2-(1,1-dimeth isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl. ylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n- piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahy propoxy)-butyl, 3-(1-methylethoxy)-butyl, 3-(n-butoxy)- dropyranyl, 1.3- and 1,4-dioxanyl, thiopyranyl, dihydrothi butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)- opyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and butyl, 3-(1,1-dimethylethoxy)-butyl, 4-(methoxy)-butyl, 25 the like. Examples for heterocyclic ring also comprising 1 or 4-(ethoxy)-butyl, 4-(n-propoxy)-butyl, 4-(1-methylethoxy)- 2 carbonyl groups as ring members comprise pyrrolidin-2- butyl, 4-(n-butoxy)-butyl, 4-(1-methylpropoxy)-butyl, 4-(2- only, pyrrolidin-2,5-dionyl, imidazolidin-2-only, oxazolidin methylpropoxy)-butyl, 4-(1,1-dimethylethoxy)-butyl and the 2-only, thiazolidin-2-only and the like. like. The term “hetaryl' includes monocyclic 5- or 6-membered The term “alkylcarbonyl (alkyl-C(=O)—), as used 30 heteroaromatic radicals comprising as ring members 1,2,3 or herein refers to a straight-chain or branched saturated alkyl 4 heteroatoms selected from N, O and S. Examples of 5- or group as define above comprising 1 to 10 carbon atoms 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, (=C-Co-alkylcarbonyl), preferably 1 to 4 carbon atoms 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, (=C-C-alkylcarbonyl) attached through the carbon atom pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2 of the carbonnyl group at any position in the alkyl group. 35 or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or 3-pyr The term “haloalkylcarbonyl as used herein refers to, an rolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4 alkylcarbonyl group as defined above wherein the hydrogen or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiaz atoms are partially or fully substituted by fluorine, chlorine, olyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or bromine and/or iodine. 40 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2 The term “alkylthio “(also alkylsulfanyl or alkyl-S )’ as or 5-1,3,4 oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or used herein refers to a straight-chain or branched saturated 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiaz alkyl group comprising 1 to 10 carbon atoms (=C-Co olyl, e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadia alkylthio), preferably 1 to 4 carbon atoms (=C-C-alky Zol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, e.g. 1H-, 2H- or lthio) as defined above, which is attached via a sulfur atom at 45 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H-, or 4H-1.2. any position in the alkyl group. 4-triazolyl and tetrazolyl, i.e. 1H- or 2H-tetrazolyl. The term “haloalkylthio’ as used herein refers to an alky The term “hetaryl also includes bicyclic 8- to 10-mem lthio group as defined above wherein the hydrogenatoms are partially or fully substituted by fluorine, chlorine, bromine bered heteroaromatic radicals comprising as ring members 1, and/or iodine. 50 2 or 3 heteroatoms selected from N, O and S, wherein a 5- or The term “alkylsulfinyl (also alkylsulfoxyl or alkyl-S 6-membered heteroaromatic ring is fused to a phenyl ring or (=O)—), as used herein refers to a straight-chain or branched to a 5- or 6-membered heteroaromatic radical. Examples of a saturated alkyl group as define above comprising 1 to 10 5- or 6-membered heteroaromatic ring fused to a phenyl ring carbon atoms (=C-Co-alkylsulfinyl), preferably 1 to 4 car or to a 5- or 6-membered heteroaromatic radical include bon atoms (=C-C-alkylsulfinyl) attached through the Sul 55 benzofuranyl, benzothienyl, indolyl, indazolyl, benzimida fur atom of the Sulfinyl group at any position in the alkyl Zolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, group. benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1.8-naph The term “haloalkylsulfinyl as used herein refers to an thyridyl, pteridyl, pyrido 3,2-dipyrimidyl or pyridoimida alkylsulfinyl group as defined above wherein the hydrogen Zolyl and the like. These fused hetaryl radicals may be bonded atoms are partially or fully substituted by fluorine, chlorine, 60 to the remainder of the molecule via any ring atom of 5- or bromine and/or iodine. 6-membered heteroaromatic ring or via a carbon atom of the The term “alkylsulfonyl (also alkyl-S(=O) ) as used fused phenyl moiety. herein refers to a straight-chain or branched Saturated alkyl The terms “phenylalkyland “phenoxyalkyl refers to phe group comprising 1 to 10 carbon atoms (=C-Co-alkylsul nyl or phenoxy, respectively, which are bound via an alkyl fonyl), preferably 1 to 4 carbon atoms (—C-C-alkylsulfo 65 group, in particular a methyl group (hetarylmethyl), to the nyl), as defined above, which is attached via the sulfur atom of remainder of the molecule, examples including benzyl, the Sulfonyl group at any position in the alkyl group. 1-phenylethyl 2-phenylethyl 2-phenoxyethyl and the like. US 9,029,639 B2 13 14 The terms "heterocyclylalkyl and “hetarylalkyl refers to heterocyclyl or hetaryl, respectively, as defined above which are bound via an alkyl group, in particular a methyl group R N (I.A) (heterocyclylmethyl or hetarylmethyl, respectively), to the XI 2 remainder of the molecule. A N Rt. The remarks made below as to preferred embodiments of the variables of the compounds of formulae Ior II are valid on R1 R their own as well as preferably in combination with each R N (II.A) other. The remarks made below concerning preferred 10 X2 21 embodiments of the variables further are valid concerning the compounds of formulae I or II as well as concerning the uses N and methods according to the invention and the composition A 1s Rt. according to the present invention. R A first preferred embodiment of the invention relates to the 15 pyridazine compounds of the formula I, to their salts and to wherein A, X, X, R', R, R" and R" independently from their N-oxides. each are as defined herein. Among the compounds of the formula I, preference is Among the compounds of formulae I and II preference is given to those compounds, whereinX is oxygen. These com further given to those compounds, wherein Wis CR" with R" pounds are hereinafter also referred to as compounds of for being hydrogen, i.e. W is CH. mula I". Among the compounds of formulae I and II preference is Among the compounds of the formula I, preference is further given to those compounds selected from 4-pyridazine further given to those cornpounds, wherein R' is hydrogen, substituted compounds of formulae I.B or II.B CN, C-Co-alkyl, C-Co-haloalkyl, C-Co-alkenyl, 25 C-Co-haloalkenyl, C-Co-alkynyl, C-Co-alkoxy-C-C- (I.B) alkyl, C-C-alkylene-CN, OR, C(Y)R’, C(Y)OR or S(O), N R R". Preferably, R is hydrogen, C, -Co-alkyl, C, -Co-ha XI N22 loalkyl, C-C-alkylene-CN. heterocyclyl-C-C-alkyl, hetaryl-C-C-alkyl, C-C-alkylen-OR' or C-Co-cy 30 cloalkyl-C-C-alkyl. More preferably R' is hydrogen, --Ns. C-C-alkyl, C-C-haloalkyl or C-C-alkoxy-C-C-alkyl. RI R In particular R' is hydrogen or C-C-alkyl. (II.B) 2 N R Another embodiment of the invention relates to pyridazine 35 X2 N21 compounds of the formula II, to the salts and N-oxides thereof and to the methods and uses of Such compounds. In the Als 1s Rt. compounds of the formula II, preference is given to those compounds, wherein X in formula II is OR or SR". In R these compounds R* is preferably C1-Co-alkyl, C-C-alk 40 enyl, C-C-alkynyl, C-Cs-cycloalkylmethyl or C-C- wherein A, X, X, R', R, R and R" independently from alkoxy-C-Cio-alkyl. Another embodiment of the invention each are as defined herein. relates to compounds of the formula II, wherein X is Among the compounds of formulae I and II preference is NR'R''. In these compounds R and R are preferably further given to those compounds, wherein V is CR' with R' selected, independently of each other, from C-C-alkyl, 45 being hydrogen, i.e. V is CH. C-C-cycloalkylmethyl or C-C-alkoxy-C-Cio-alkyl or Among the compounds of formulae I and II preference is RandR, together with the nitrogenatom to which they are further given to those compounds, wherein R. R'' and R", if attached, form a saturated, nitrogen-bound 5- or 6-membered present, are selected independently of each other from hydro heterocycle which may comprise a further heteroatom gen, methyl, difluoromethyl, trifluoromethyl, methoxy, dif selected from O, Sand N, e.g. NR'R' being 1-pyrrolidinyl, 50 luoromethoxy or trifluoromethoxy. More preferably, prefer 1-piperidinyl, 1-piperazinyl, 4-morpholinyl or 4-thiomor ence is given to those compounds, wherein at least two of the pholinyl. radicals R. R', R or R", if present, are hydrogen. Among the compounds of formulae I and Il preference is Most particularly, preference is given to those compounds, given to those compounds, wherein R' is selected from wherein R. R. R. and R", if present, are hydrogen. hydrogen, halogen, 55 Another preferred embodiment of the invention relates to C-C-alkyl, C-C-haloalkyl, C-C-cycloalkyl, C-C- pyridazine compounds of formulae I and II, to the salts and halocycloalkyl, C-C-alkenyl, C-Ca-haloalkenyl, C-C- N-oxides thereof and to the methods and uses of such com alkynyl and C-C-alkoxy-C-C-alkyl. pounds, wherein A is a radical A1. Among the compounds, wherein A is A1, preference is given to compounds of the Among the compounds of formulae I and II preference is 60 formula I, wherein X', R', R, R", R and R" are as defined given to those compounds, wherein R is selected from hydro above and in particular have one of the preferred meanings. gen, halogen, C-C-alkyl: C-C-haloalkyl, C-C-cy Among the compounds of formulae I and II, wherein A is cloalkyl, C-C-halocycloalkyl, C-C-alkenyl, Ca-Ca-ha A1, preference is given to those compounds, wherein R' is loalkenyl, C-C-alkynyl and C-C-alkoxy-C-C-alkyl. selected from hydrogen, halogen, CN, C-C-alkyl and Among the compounds of formulae I and II preference is 65 C-Co-alkenyl, wherein the two last mentioned radicals may further given to those compounds selected from 4-pyridazine be unsubstituted, may be partially or fullyhalogenated or may substituted compounds of formulae I.A or II. A carry 1, 2 or 3 identical or different substituents selected from US 9,029,639 B2 15 16 C-C-alkoxy, C-Ca-haloalkoxy, C-C-cycloalkyl, hetaryl, from C-C-cycloalkyl, C-C-hetaryl and phenyl, wherein phenyl and phenoxy, wherein the last three mentioned radi the three last mentioned radicals may be unsubstituted or may cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals carry 1, 2, 3, 4 or 5 identical or different substituents selected selected from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C- from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy, alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C- C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C-ha haloalkylsulfonyl, or wherein R' is further selected from loalkylsulfonyl. C-C-cycloalkyl, Cs-C-hetaryl and phenyl, wherein the three last mentioned radicals may be unsubstituted or may Preferably, R is selected from hydrogen, C-C-alkyl, carry 1, 2, 3, 4 or 5 identical or different substituents selected C-C-cycloalkyl-C-C-alkyl, heterocyclyl-C-C-alkyl, from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy, 10 C-C-alkoxy-C-C-alkyl and C-C-alkyl-CN. Preferably C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-Ca-ha R' is selected from hydrogen, C-C-alkyl, C-Ca-haloalkyl, loalkylsulfonyl. C-C-cycloalkyl, C-C-halocycloalkyl and phenyl, Preferably R' is selected from hydrogen, halogen, CN, wherein phenyl may be unsubstituted or may carry 1, 2, 3, 4 C-C-alkyl, C-C-haloalkyl, C-C-cycloalkyl, C-C-ha or 5 radicals selected from halogen, C-C-alkyl, C-Ca-ha locycloalkyl and phenyl, wherein phenyl may be unsubsti 15 loalkyl, C-C-alkoxy and C-Ca-haloalkoxy. More prefer tuted or may carry 1, 2, 3, 4 or 5 radicals selected from ably R' if present is hydrogen, C-C-alkyl or C-C-ha halogen, C-C-alkyl, C-C-alkoxy and C-Ca-haloalkoxy. loalkyl. In particular R' if present is hydrogen or C-C- Preferably R' is selected from hydrogen, halogen, CN, alkyl. C-Ca-haloalkyl, C-C-cycloalkyl and C-C-halocy cloalkyl. More preferably, R' is selected from hydrogen, Examples of suitable radicals A1 are the radicals of formu halogen, C-C-alkyl, C-C-haloalkyl, C-C-cycloalkyl lae A1.a, Al...b. Al.c. A1.d. A1.e., A1.f. A1.g., A1.h, Al.i. Alk, and C-Ca-halocycloalkyl. Most preferably R' is selected A1.1, A1.m, Al...n, Al.o, Alp, A1.d, A1.r, A1.s, Al..t, Al.u. from hydrogen, C-C-alkyl, C-C-haloalkyl and C-C-cy A1V, A1,w, A1.x, Aly and A1.Z., wherein Z is O and R', R' cloalkyl. Even more preferably R' is hydrogen or C-C- is a radical as defined in one line of table A. (radicals A1.a1 alkyl. In particular R' is hydrogen. 25 A1.a81 to A1.Z1-A1.Z81): Among the compounds of formulae I and II, wherein A is A1, preference is further given to those compounds, wherein TABLE A R" is selected from hydrogen, halogen, CN, C-Co-alkyl A1.a. and C-C-alkenyl, wherein the 2 last mentioned radicals N may be unsubstituted, may be partially or fully halogenated or 30 may carry 1, 2 or 3 identical or different substituents selected from C-C-alkoxy, C-C-haloalkoxy, C-C-cycloalkyl, H 4 Z ya R51 hetaryl, phenyl and phenoxy, wherein the last three men tioned radicals may be unsubstituted or may carry 1, 2, 3, 4 or A1.b 5 radicals selected from halogen, C-C-alkyl, C-C-alkoxy, 35 CH C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-Ca-ha N loalkylsulfonyl, or wherein R is further selected from C-C-cycloalkyl, Cs-C-hetaryl and phenyl, wherein the it. 4 Z R51 three last mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4 or 5 identical or different substituents selected 40 from halogen, C-C-alkyl, C-C-alkoxy, C-Ca-ha A1.c loalkoxy, C-C-alkylsulfonyl and C-Ca-haloalkylsulfonyl. CFH2 Preferably R' is selected from hydrogen, halogen, CN, N C-C-alkyl, C-C-cycloalkyl, C-C-halocycloalkyl and phenyl, wherein phenyl may be unsubstituted or may carry 1, 45 it. -4 Z ) R51 2, 3, 4 or 5 radicals selected from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy. Pref A1.d erably R' is selected from hydrogen, halogen, CN, C-C- CF2H haloalkyl, C-C-cycloalkyl and C-C-halocycloalkyl. More N preferably, R is selected from hydrogen, halogen, C1-C4 50 alkyl, C-Ca-haloalkyl, C-C-cycloalkyl and C-C-halocy cloalkyl. Most preferably R' is selected from hydrogen, it. -( Z ) R51 C-C-alkyl, C-C-haloalkyl and C-Cs-cycloalkyl. Even more preferably R' is hydrogen or C-C-alkyl. In particular A1.e R" is hydrogen. 55 CF Among the compounds of formulae I and II, wherein A is N A1, preference is further given to those compounds, wherein in R' if present is selected from hydrogen, C1-Co-alkyl and it. -( Z ) R51 C-Co-alkenyl, wherein the two last mentioned radicals may be unsubstituted, may be partially or fully halogenated or may 60 carry 1, 2 or 3 identical or different substituents selected from A1.f C-C-alkoxy, C-Ca-haloalkoxy, C-C-cycloalkyl, hetaryl, CN phenyl and phenoxy, wherein the last three mentioned radi cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals selected from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C- 65 alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C- haloalkylsulfonyl, or wherein R' if presentis further selected
US 9,029,639 B2 25 26 -continued loalkyl, C-C-alkoxy, C-C-haloalkoxy, C-C-alkylsulfo nyl and C-C-haloalkylsulfonyl, or wherein R' is further selected from C-C-cycloalkyl, Cs-Co-hetaryl and phenyl, wherein the three last mentioned radicals may be unsubsti - ) tuted or may carry 1, 2, 3, 4 or 5 identical or different sub stituents selected from halogen, C-C-alkyl, C-C-ha loalkyl, C-C-alkoxy, C-C-haloalkoxy, C-C- alkylsulfonyl and C-C-haloalkylsulfonyl. Preferably R' is selected from hydrogen, halogen, CN, C-C-alkyl, C-C- 10 haloalkyl, C-C-cycloalkyl, C-C-halocycloalkyl and phe nyl, wherein phenyl may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals selected from halogen, C-C-alkyl, C-C- haloalkyl, C-C-alkoxy and C-C-haloalkoxy; in particular R" is selected from hydrogen, halogen, CN, C-C-alkyl, 15 C-C-haloalkyl, C-C-cycloalkyl and C-C-halocy cloalkyl. Preferably R' is selected from hydrogen, halogen, CN, C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, C-C-ha locycloalkyl and phenyl, wherein phenyl may be unsubsti tuted or may carry 1, 2, 3, 4 or 5 radicals selected from halogen, C-C-alkyl, C-C-haloalkyl, C-C-alkoxy and C-C-haloalkoxy. Preferably R' is selected from hydrogen, halogen, CN, C-C-alkyl, C-Ca-haloalkyl, C-C-cy cloalkyl and C-C-halocycloalkyl. More preferably, R is A1.8 25 selected from hydrogen, halogen, C-C-alkyl, C-Ca-ha loalkyl, C-C-cycloalkyl and C-C-halocycloalkyl. Most preferably R' is selected from hydrogen, C-C-alkyl, C-C-haloalkyl and C-C-cycloalkyl. Even more prefer ably R' is hydrogen or C-C-alkyl. In particular R' is 30 hydrogen. Among the compounds of formulae I and II, wherein A is A further embodiment of the invention relates to A2, preference is further given to those compounds, wherein pyridazine compounds of formulae I and II, to the salts and R’ is selected from hydrogen, halogen, CN, C-Co-alkyl N-oxides thereof and to the methods and uses of such com and C-Co-alkenyl, wherein the two last mentioned radicals pounds, wherein A is a radical A2. Among the compounds of 35 may be unsubstituted, may be partially or fullyhalogenated or formulae I and II, wherein A is a radical A2, preference is may carry 1, 2 or 3 identical or different substituents selected given to compounds of the formulae I or II, wherein X', R', from C-C-alkoxy, C-Ca-haloalkoxy, C-C-cycloalkyl, R. R", Rand R" are as defined above and in particular have hetaryl, phenyl and phenoxy, wherein the last three men one of the preferred meanings. tioned radicals may be unsubstituted or may carry 1, 2, 3, 4 or Among the compounds of formulae I and II, wherein A is 40 5 radicals selected from halogen, C-C-alkyl, C-C-ha A2, preference is given to those compounds, wherein R is loalkyl, C-C-alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfo selected from hydrogen, halogen, CN, and C-Co-alkenyl, nyl and C-C-haloalkylsulfonyl, or wherein R’ is further wherein the 2 last mentioned radicals may be unsubstituted, selected from C-C-cycloalkyl, Cs-Co-hetaryl and phenyl, may be partially or fully halogenated or may carry 1, 2 or 3 wherein the three last mentioned radicals may be unsubsti identical or different substituents selected from C-C- 45 tuted or may carry 1, 2, 3, 4 or 5 identical or different sub alkoxy, C-Ca-haloalkoxy, C-C-cycloalkyl, hetanjl, phenyl stituents selected from halogen, C-C-alkyl, C-C-alkoxy, and phenoxy, wherein the last three mentioned radicals may C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C-ha be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals selected loalkylsulfonyl. from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy, Preferably R’ is selected from hydrogen, halogen, CN, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-Ca-ha 50 C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, C-C-ha loalkylsulfonyl, or wherein R is further selected from locycloalkyl and phenyl, wherein phenyl may be unsubsti C-C-cycloalkyl, Cs-C-hetaryl and phenyl, wherein the tuted or may carry 1, 2, 3, 4 or 5 radicals selected from three last mentioned radicals may be unsubstituted or may halogen, C-C-alkyl, C-C-alkoxy and C-Ca-haloalkoxy. carry 1, 2, 3, 4 or 5 identical or different substituents selected Preferably, R’ is selected from hydrogen, halogen, C-C- from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy, 55 alkyl, C-Ca-haloalkyl, C-C-cycloalkyl and C-C-halocy C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C-ha cloalkyl. Most preferably R’ is selected from hydrogen, loalkylsulfonyl. C-C-alkyl, C-C-haloalkyl and C-Cs-cycloalkyl. More Among the compounds of formulae I and II, wherein A is preferably R is hydrogen, C-C-alkyl or C-Ca-haloalkyl. A2, preference is given to those compounds, wherein R is Even more preferably R’ is hydrogen or C-C-alkyl. In selected from hydrogen, halogen, CN, C-C-alkyl and 60 particular R is hydrogen. C-C-alkenyl, wherein the 2 last mentioned radicals may be Among the compounds of formulae I and II, wherein A is unsubstituted, may be partially or fully halogenated or may A2, preference is further given to those compounds, wherein carry 1, 2 or 3 identical or different substituents selected from R’ if present is selected from hydrogen, C-Co-alkyl and C-C-alkoxy, C-C-haloalkoxy, C-C-cycloalkyl, Cs-C- C-Co-alkenyl, wherein the two last mentioned radicals may heteroaryl, phenyl and phenoxy, wherein the last three men 65 be unsubstituted, may be partially or fullyhalogenated or may tioned radicals may be unsubstituted or may carry 1, 2, 3, 4 or carry 1, 2 or 3 identical or different substituents selected from 5 radicals selected from halogen, C-C-alkyl, C-C-ha C-C-alkoxy, C-C-haloalkoxy, C-C-cycloalkyl, hetaryl, US 9,029,639 B2 27 28 phenyl and phenoxy, wherein the last three mentioned radi -continued cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals A2.ah selected from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C- Br alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C- haloalkylsulfonyl, or wherein Rifpresentis further selected j from C-C-cycloalkyl, Cs-C-hetaryl and phenyl, wherein R52 4 Z it. the three last mentioned radicals may be unsubstituted or may A2.ai carry 1, 2, 3, 4 or 5 identical or different substituents selected I from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C-ha 10 loalkylsulfonyl. Preferably, R is selected from hydrogen, C-C-alkyl, - Z it. C-Ca-haloalkyl, C-C-cycloalkyl-C-C-alkyl, heterocy A2.ak clyl-C-C-alkyl, C-C-alkoxy-C-C-alkyl and C-C- CN alkyl-CN. Preferably R if present is selected from hydro 15 gen, C-C-alkyl, C-C-cycloalkyl, C-C-halocycloalkyl j \ and phenyl, wherein phenyl may be unsubstituted or may R52 4 Z it. carry 1, 2, 3, 4 or 5 radicals selected from halogen, C-C- A2.al alkyl, C-Ca-haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy. CHCH More preferably R if present is selected from hydrogen, halogen, CN, C-C-cycloalkyl and C-C-halocycloalkyl. In particular R if present is hydrogen. Examples of suitable radicals A2 are the radicals of formu R52 4. Z it. lae A2.aa, A2.ab, A2.ac, A2.ad, A2.ae, A2.af, A2.ag, A2.ah, A2.am A2.ai, A2.ak, A2.al, A2.am, A2.an and A2.ao, wherein Z is O 25 (CH2)2CH3 and R is a radical as defined in one line of table A (radicals A2.aa1-A2.aa81 to A2.aol-A2.ao81): } \ - Z it. A2.an A2.aa 30 CH(CH3) - ty, it. A2.ab - Z it. CH3 35 A2.ao - , it. A2.ac 40 j \ CHF R52 4. Z it. j \ - , it. Analogue to the above listed structures, examples of Suit A2.ad 45 able radicals A2 are the radicals of formulae A2.aa', A2.ab', CHF A2.ac', A2.ad', A2.ae', A2.af, A2.ag, A2.ah', A2.ai', A2.ak A2.al', A2.am'', A2.an' and A2.ao', wherein Z is S and R is a j \ radical as defined in one line of table A (radicals A2.aa' 1-A2.aa'81 to A2.ao' 1-A2.ao'81). - , it. 50 A2.ae CF j \ - , it. 55 -> A2.af CH A2.ab' F 3
- , it. 60 - , it. A2.ag A2.ac' C CHF
- , it. 65
US 9,029,639 B2 37 38 -continued Preferably R is selected from hydrogen, halogen, CN, A2.ha C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, C-C-ha locycloalkyl and phenyl, wherein phenyl may be unsubsti tuted or may carry 1, 2, 3, 4 or 5 radicals selected from - Z ) halogen, C-C-alkyl, C-C-haloalkyl, C-C-alkoxy and C-C-haloalkoxy. Preferably R is selected from hydrogen, halogen, CN, C-C-alkyl, C-Ca-haloalkyl, C-C-cy A cloalkyl and C-C-halocycloalkyl. More preferably, R is selected from hydrogen, halogen, C-C-alkyl, C-Ca-ha A further embodiment of the invention relates to 10 loalkyl, C-C-cycloalkyl and C-C-halocycloalkyl. Most pyridazine compounds of formulae I and II, to the salts and preferably R is selected from hydrogen, C-C-alkyl, N-oxides thereof and to the methods and uses of such com C-C-haloalkyl and C-C-cycloalkyl. Even more prefer pounds, wherein A is a radical A3. Among the compounds of ably R is hydrogen or C-C-alkyl. In particular R is the formulae I and II, wherein A is a radical A3, preference is hydrogen. given to compounds of the formulae I or II, wherein X', R', 15 Among the compounds of formulae I and II, wherein A is R. R. R. and R" are as defined above and in particular have A3, preference is further given to those compounds, wherein one of the preferred meanings. R" if present is selected from hydrogen, C1-Co-alkyl and Among the compounds of formulae I and II, wherein A is C-Co-alkenyl, wherein the two last mentioned radicals may A3, preference is given to those compounds, wherein R is be unsubstituted, may be partially or fullyhalogenated or may selected from hydrogen, halogen, CN, C-C-alkyl and carry 1, 2 or 3 identical or different substituents selected from C-Co-alkenyl, wherein the 2 last mentioned radicals may be C-C-alkoxy, C-C-haloalkoxy, C-C-cycloalkyl, hetaryl, unsubstituted, may be partially or fully halogenated or may phenyl and phenoxy, wherein the last three mentioned radi carry 1, 2 or 3 identical or different substituents selected from cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals C-C-alkoxy, C-Ca-haloalkoxy, C-C-cycloalkyl, hetaryl, 25 selected from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C- phenyl and phenoxy, wherein the last three mentioned radi alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C- cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals haloalkylsulfonyl, or wherein Rifpresentis further selected selected from halogen, C-C-alkyl, C-C-haloalkyl, C-C- from C-C-cycloalkyl, C-C-hetaryl and phenyl, wherein alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C- the three last mentioned radicals may be unsubstituted or may haloalkylsulfonyl, or wherein R is further selected from 30 carry 1, 2, 3, 4 or 5 identical or different substituents selected C-C-cycloalkyl, Cs-C-hetaryl and phenyl, wherein the from halogen, C-C-alkyl, C-C-alkoxy, C-C-ha three last mentioned radicals may be unsubstituted or may loalkoxy, C-C-alkylsulfonyl and C-Ca-haloalkylsulfonyl. carry 1, 2, 3, 4 or 5 identical or different substituents selected Preferably, R is selected from hydrogen, C-C-alkyl, from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy, C-Ca-haloalkyl, C-C-cycloalkyl-C-C-alkyl, heterocy C-Ca-haloalkoxy, C-C-alkylsulfonyl and C-C-ha 35 clyl-C-C-alkyl, C-C-alkoxy-C-C-alkyl and C-C- loalkylsulfonyl. alkyl-CN. Preferably R if present is selected from hydro Preferably R' is selected from hydrogen, halogen, CN, gen, C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, C-C- C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, C-C-ha halocycloalkyl and phenyl, wherein phenyl may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals selected locycloalkyl and phenyl, wherein phenyl may be unsubsti from halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy tuted or may carry 1, 2, 3, 4 or 5 radicals selected from 40 halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy and and C-Ca-haloalkoxy. More preferably R if present is C-C-haloalkoxy. More preferably R' is selected from hydrogen, C-Ca-alkyl or C-Ca-haloalkyl. In particular R' hydrogen, halogen, CN, C-C-alkyl, C-C-cycloalkyl and if present is hydrogen or C-C-alkyl. Cs-Ca-halocycloalkyl. More preferably, R is selected from Examples of suitable radicals A3 are the radicals of formu hydrogen, halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-cy 45 lae A3.aa, A3.ab, A3.ac, A3.ad, A3.ae, A3.af, A3..ag, A3.ah, cloalkyl and C-Ca-halocycloalkyl. Most preferably R' is A3.ai, A3.ak, A3...al, A3.am, A3...an and A3.ao, wherein Z is O selected from hydrogen, C-C-alkyl, C-C-haloalkyl and and R is a radical as defined in one line of table A (radicals Cs-Cs-cycloalkyl. Even more preferably R' is hydrogen or A3.aa1-A3.aa81 to A3.aol-A3.ao81): C-C-alkyl. In particular R' is hydrogen. Among the compounds of formulae I and II, wherein A is 50 A3, preference is further given to those compounds, wherein it. A3.aa in R is selected from hydrogen, halogen, CN, C-Co-alkyl and C-Co-alkenyl, wherein the 2 last mentioned radicals N may be unsubstituted, may be partially or fully halogenated or \ may carry 1, 2 or 3 identical or different substituents selected 55 R53 4. Z from C-C-alkoxy, C-C-haloalkoxy, C-C-cycloalkyl, it. A3.ab hetaryl, phenyl and phenoxy, wherein the last three men tioned radicals may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals selected from halogen, C-C-alkyl, C-Ca-ha \ loalkyl, C-C-alkoxy, C-Ca-haloalkoxy, C-C-alkylsulfo 60 R53 4. Z CH nyl and C-C-haloalkylsulfonyl, or wherein R is further selected from C-C-cycloalkyl, C-C-hetaryl and phenyl, it. A3.ac wherein the three last mentioned radicals may be unsubsti tuted or may carry 1, 2, 3, 4 or 5 identical or different sub stituents selected from halogen, C-C-alkyl, C-Ca-ha 65 j \ loalkyl, C-C-alkoxy, C-Ca-haloalkoxy, C-C- R53 4. Z CHF alkylsulfonyl and C-Ca-haloalkylsulfonyl.
US 9,029,639 B2 51 52 -continued A very preferred embodiment of the invention relates to compounds of the formula I and to the salts and N-oxides it. thereof, wherein X" is O. These compounds are hereinafter also referred to as compounds I'. j \ 5 - , CN (I) CF A3.fl. it. 10 j \ ls, S. Rt. -, CHCH RI R CF 15 In formula I", the variables A. R. R. R", V and W are as defined herein. A3.fm Among the compounds of the formula I", preference is it. given to those compounds, wherein at least one of the radicals R", R, R", V and W. preferably at least two of the radicals R', R. R", V and W, and more preferably all of the radicals R', R, R", V and Whave one of the preferred meanings. Among the compounds of the formula I", preference is -, (CH2)2CH3 further given to those compounds, wherein A is a radical A1, CF e.g. a radical, selected from the oxazole radicals Al...al to A3.fn 25 A1.Z81. it. Among the compounds of the formula I", preference is further given to those compounds, wherein A is a radical A1, j \ e.g. a radical, selected from the thiazole radicals A1.a' 1 to A1781 -, CH(CH3)2 30 Among the compounds of the formula I", preference is CF further given to those compounds, wherein A is a radical A1, it. e.g. a radical, selected from the imidazole radicals A1.a" 1 to A1.7" 81 A particularly preferred embodiment of the invention 35 relates to compounds of formula I.A and to the salts and - , N-oxides thereof, wherein CF (I.A) 40 Further examples of suitable radicals A3 are the radicals of formulae A3.&1, A3.&2, A33 wherein Zis N, R is CHCF and R is respectively CH, CF and CHF: N Rt. RI R
A is a radical A1, as defined herein, in particular a radical A1, wherein R', Rhave the preferred meanings, in particular an oxazole radical of the formulae Al...a to A1.Z., e.g. a 50 radical selected from the oxazole radicals A1.al to A1.Z81; R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, most preferably hydrogen, methyl or ethyl; R1 is further most preferably propyl, iso-propyl, butyl, iso butyl, tert-butyl, CHC(CH), CH-CH=CH, 55 CH-CH=CC1, CH-CH=CBr, CHCHF, CHCHCl, CHCHBr, CHCHF, CHCHCl, CHCHBr, CHCF, CHCN, CHOCH, CHOCHCH, CHCHCN, CHCHCN, CHCHOCH, CHCHOCHCH, ethyl cyclopropane, ethyl-cyclobutane, 2-methyl-oxetane, 3-ethyl-oxetane, 3-methyl-thietane, 3-methyl-thietane 1,1- dioxide, ethyl-cyclopentane, 2-ethyl-tetrahydro-furan, 3-ethyl-tetrahydro-furan, methyl-cyclopropane, methyl cyclobutane, 2-methyl-oxetane, 3-methyl-oxetane, 3-me thyl-thietane, 3-thietane 1,1-dioxide, cyclopentane, 2-me 65 thyl-tetrahydro-furan, tetrahydro-furan, toluene, 2-methyl-furan, 3-methyl-furan, 2-ethyl-thiophene, 3-me thyl-thiophene, 5-ethyl-isothiazole, 4-ethyl-isothiazole, US 9,029,639 B2 53 54 3-methyl-isothiazole, 3-methyl-isoxazole, 5-methyl-ox Table 13: Compounds of the formula I.A and the salts and azole, 2-ethyl-oxazole, 5-ethyl-thiazole, 2-ethyl-thiazole, N-oxides thereof, wherein R. R. R" and R" are hydrogen 4-ethyl-thiazole, 5-methyl-1H-pyrazole, 4-ethyl-1H-pyra and wherein A is selected from the radicals A1.g1 to zole, 3-methyl-1H-pyrazole; 5-ethyl-1-methyl-1H-pyra A1.g.81. zole, 4-ethyl-1-methyl-1H-pyrazole, 3-ethyl-1-methyl 5 Table 14: Compounds of the formula I.A and the salts and 1H-pyrazole, 5-methyl-1H-imidazole, 4-ethyl-1H N-oxides thereof, wherein R' is methyl, R', R" and R" are imidazole, 2-methyl-1H-imidazole, 5-ethyl-1-methyl-1H hydrogen and wherein A is selected from the radicals imidazole, 2-ethyl-1-methyl-1H-imidazole, 1,4-dimethyl Alg1 to A1.g.81. 1H-imidazole, 2-methyl-4,5-dihydro-oxazole, 2-ethyl-4, Table 15: Compounds of the formula I.A and the salts and 5-dihydro-thiazole, 2-ethyl-4,5-dihydro-1H-imidazole, 10 N-oxides thereof, wherein R', R, R" and R" are hydrogen 2-ethyl-1-methyl-4,5-dihydro-1H-imidazole; and wherein A is selected from the radicals A1.h1 to R. R', and R" are independently from each other selected A1.h81. from hydrogen, methyl, difluoromethyl, trifluoromethyl, Table 16: Compounds of the formula I.A and the salts and methoxy, difluoromethoxy and trifluoromethoxy; and N-oxides thereof, wherein R' is methyl, R', R" and R" are wherein preferably at least one, more preferably 2 or 3, of 15 hydrogen and wherein A is selected from the radicals the radicals R. R', and R" are hydrogen. A1.h1 to A1.h81. Examples of compounds of this particularly preferred Table 17: Compounds of the formula I.A and the salts and embodiment are the compounds given in the following tables N-oxides thereof, wherein R', R, R" and R" are hydrogen 1 to 50. and wherein A is selected from the radicals A1.i1 to A1.181. Table 1: Compounds of the formula I.A and the salts and Table 18: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.al to hydrogen and wherein A is selected from the radicals A1.il A1a81. to A1.181. Table 2: Compounds of the formula I.A and the salts and Table 19: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 25 N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals A1.al and wherein A is selected from the radicals A1.k1 to to A1.a81. A1 k81. Table 3: Compounds of the formula I.A and the salts and Table 20: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.b1 to 30 hydrogen and wherein A is selected from the radicals A1.b81. A1.k1 to A1.k81. Table 4: Compounds of the formula I.A and the salts and Table 21: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A1.11 to A1b1 to A1.b81. 35 A1.181. Table 5: Compounds of the formula I.A and the salts and Table 22: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.c1 to hydrogen and wherein A is selected from the radicals A1.c81. A1.11 to A1.181. Table 6: Compounds of the formula I.A and the salts and 40 Table 23: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals A1.c1 and wherein A is selected from the radicals A1 m1 to to A1.c81. A1.m.81. Table 7: Compounds of the formula I.A and the salts and Table 24: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen 45 N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.d1 to hydrogen and wherein A is selected from the radicals A1.d81. A1.m.1 to A1.m.81. Table 8: Compounds of the formula I.A and the salts and Table 25: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R" and R" are hydrogen hydrogen and wherein A is selected from the radicals 50 and wherein A is selected from the radicals A1.nl to A1.d1 to A1.d81. A1 n81. Table 9: Compounds of the formula I.A and the salts and Table 26: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.el to hydrogen and wherein A is selected from the radicals A1.e81. 55 A1.nl to A1.n81. Table 10: Compounds of the formula I.A and the salts and Table 27: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals A1.e1 and wherein A is selected from the radicals A1.ol to to A1.e81. A1081. Table 11: Compounds of the formula I.A and the salts and 60 Table 28: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1f1 to hydrogen and wherein A is selected from the radicals A1f81. A1.o1 to A1.o81. Table 12: Compounds of the formula I.A and the salts and Table 29: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals A1.f1 and wherein A is selected from the radicals A1-p1 to to A1.f31. A1.p81. US 9,029,639 B2 55 56 Table 30: Compounds of the formula I.A and the salts and Table 47: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A1.y1 to A1. p1 to A1.p81. A1 y81. Table 31: Compounds of the formula T.A and the salts and 5 Table 48: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.d1 to hydrogen and wherein A is selected from the radicals A1.d81. A1.y1 to A1.y81. Table 32: Compounds of the formula I.A and the salts and Table 49: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A1. Z1 to A1.d1 to A1.d81. Table 33: Compounds of the formula I.A and the salts and A1.Z81. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 50: Compounds of the formula I.A and the salts and and wherein A is selected from the radicals A1 r1 to 15 N-oxides thereof, wherein R' is methyl, R', R" and R" are A1.r81. hydrogen and wherein A is selected from the radicals A1.z1 Table 34: Compounds of the formula I.A and the salts and to A1.Z81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Further examples of compounds of this particularly pre hydrogen and wherein A is selected from the radicals A1 r1 ferred embodiment are the compounds in analogy to the com to A1 r81. pounds listed in table 1 to 50 wherein R' is a radical repre Table 35: Compounds of the formula I.A and the salts and sented by each individual line (85 to 160) of the following N-oxides thereof, wherein R', R, R" and R" are hydrogen table B: and wherein A is selected from the radicals A1.s 1 to A1. S81. TABLE B Table 36: Compounds of the formula I.A and the salts and 25 N-oxides thereof, wherein R' is methyl, R', R" and R" are Line Radical R' 85 CHCH hydrogen and wherein A is selected from the radicals A1.s 1 86 propyl to A1.s81. 87 iso-propyl Table 37: Compounds of the formula I.A and the salts and 88 butyl N-oxides thereof, wherein R', R', R" and R" are hydrogen 30 89 iso-butyl and wherein A is selected from the radicals A1. t1 to A1.t81. 90 tert-butyl 91 CHC(CH3) Table 38: Compounds of the formula I.A and the salts and 92 CHCH-CH N-oxides thereof, wherein R' is methyl, R', R" and R" are 93 CH-CH=CC1, hydrogen and wherein A is selected from the radicals A1.t1 94 CH-CH=CBr, to A1 t81. 35 95 CHCHF 96 CHCHCl Table 39: Compounds of the formula I.A and the salts and 97 CHCH-Br N-oxides thereof, wherein R', R, R" and R" are hydrogen 98 CHCHF and wherein A is selected from the radicals A1.ul to 99 CHCHCl, A1.u81. OO CHCHBr, 40 O1 CHCF Table 40: Compounds of the formula I.A and the salts and O2 CHCN N-oxides thereof, wherein R' is methyl, R', R" and R" are O3 CHOCH hydrogen and wherein A is selected from the radicals O4 CHOCHCH A1.ul to A1.u81. 05 CHCHCN O6 CH(Me)CHCN Table 41: Compounds of the formula I.A and the salts and O7 2-methoxyethyl N-oxides thereof, wherein R', R', R" and R" are hydrogen 45 O8 2-ethoxyethyl and wherein A is selected from the radicals A1. V1 to 09 cyclopropylmethyl A1.V81. 10 cyclobutylmethyl 11 cyclopentylmethyl Table 42: Compounds of the formula I.A and the salts and 12 oxetan-2-ylmethyl N-oxides thereof, wherein R' is methyl, R', R" and R" are 13 oxetan-3-ylmethyl hydrogen and wherein A is selected from the radicals 50 14 oxolan-2-ylmethyl A1V1 to A1.V81. 15 oxolan-3-ylmethyl 16 thiethan-3-ylmethyl Table 43: Compounds of the formula I.A and the salts and 17 1,1-dioxathiethan-3-ylmethyl N-oxides thereof, wherein R', R, R" and R" are hydrogen 18 cyclopropy and wherein A is selected from the radicals A1.w 1 to 19 cyclobutyl A1.w81. 55 2O cyclopenty 21 oxetan-2-y Table 44: Compounds of the formula I.A and the salts and 22 oxetan-3-y N-oxides thereof, wherein R' is methyl, R', R" and R" are 23 oxolan-2-y hydrogen and wherein A is selected from the radicals 24 oxolan-3-y A1.w1 to A1.w81. 25 thiethan-3-yl 26 1,1-dioxathiethan-3-yl Table 45: Compounds of the formula I.A and the salts and 60 27 benzyl N-oxides thereof, wherein R', R', R" and R" are hydrogen 28 2-furylmethyl and wherein A is selected from the radicals A1.X1 to 29 3-furylmethyl A1X81. 30 2-thienylmethyl 31 3-thienylmethyl Table 46: Compounds of the formula I.A and the salts and 32 isothiazol-3-ylmethyl N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 33 isothiazol-4-ylmethyl hydrogen and wherein A is selected from the radicals 34 isothiazol-5-ylmethyl A1X1 to A1X81. US 9,029,639 B2 57 58 TABLE B-continued Table 55: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen Line Radical R' and wherein A is selected from the radicals A1.c' 1 to A1.c' 35 isoxazol-3-ylmethyl 81. 36 oxazol-2-ylmethyl 5 Table 56: Compounds of the formula I.A and the salts and 37 oxazol-5-ylmethyl 38 oxazol-4-ylmethyl N-oxides thereof, wherein R' is methyl, R', R" and R" are 39 hiazol-2-ylmethyl hydrogen and wherein A is selected from the radicals A1.c' 40 hiazol-4-ylmethyl 1 to A1.c'81. 41 hiazol-5-ylmethyl Table 57: Compounds of the formula I.A and the salts and 42 H-pyrazol-3-ylmethyl 10 43 H-pyrazol-4-ylmethyl N-oxides thereof, wherein R', R, R" and R" are hydrogen 44 2H-pyrazol-3-ylmethyl and wherein A is selected from the radicals A1.d' 1 to A1.d' 45 -methyl-1H-pyrazol-3- 81. yImelny 46 -methyl-1H-pyrazol-4- Table 58: Compounds of the formula I.A and the salts and yImelny 15 N-oxides thereof, wherein R' is methyl, R', R" and R" are 47 2-methyl-2H-pyrazol-3- hydrogen and wherein A is selected from the radicals A1.d' yImelny 48 H-imidazol-2-ylmethyl 1 to A1.d'81. 49 H-imidazol-4-ylmethyl Table 59: Compounds of the formula I.A and the salts and 50 H-imidazol-5-ylmethyl 51 -methyl-1H-imidazol-2- N-oxides thereof, wherein R', R, R" and R" are hydrogen yImelny and wherein A is selected from the radicals A1.e' 1 to A1.e' 52 -methyl-1H-imidazol-4- 81. yImelny Table 60: Compounds of the formula I.A and the salts and 53 -methyl-1H-imidazol-5- yImelny N-oxides thereof, wherein R' is methyl, R', R" and R" are S4 oxazolin-2-ylmethyl hydrogen and wherein A is selected from the radicals A1.e' 55 hiazolin-2-ylmethyl 25 1 to A1.e'81. 56 H-imidazolin-2-ylmethyl 57 -methyl-1H-imidazolin-2- Table 61: Compounds of the formula I.A and the salts and yImelny N-oxides thereof, wherein R. R. R" and R" are hydrogen 58 -phenylpyrazol-4-ylmethyl and wherein A is selected from the radicals A1.f. 1 to A1.f 59 5-methylfuran-2-ylmethyl 81. 60 5,5-dimethyltetrahydrofuran 30 2-ylmethyl Table 62: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are Another particular preferred embodiment relates to com hydrogen and wherein A is selected from the radicals A1.f pounds of the formula I.A and to the salts and N-oxides 1 to A1f 81. thereof, wherein 35 Table 63: Compounds of the formula I.A and the salts and A is a radical A1, as defined herein, in particular a radical A1, N-oxides thereof, wherein R. R. R" and R" are hydrogen wherein R', R have the preferred meanings, in particular and wherein A is selected from the radicals A1.g. 1 to A1.g a thiazole radical of the formulae Ala' to A1.Z', e.g. a 81. radical selected from the thiazole radicals A1.a' 1 to A1.Z.' Table 64: Compounds of the formula I.A and the salts and 81: R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C-alkyl, 40 N-oxides thereof, wherein R' is methyl, R', R" and R" are most preferably hydrogen, methyl or ethyl; hydrogen and wherein A is selected from the radicals A1.g R" is further most preferably represented by a radical as 1 to A1.g'81. defined in each line of table B; Table 65: Compounds of the formula I.A and the salts and R. R', and R" are independently from each other selected N-oxides thereof, wherein R', R, R" and R" are hydrogen from hydrogen, methyl, difluoromethyl, trifluoromethyl, 45 and wherein A is selected from the radicals A1.h' 1 to A1.h' methoxy, difluoromethoxy and trifluoromethoxy; and 81. wherein preferably at least one, more preferably 2 or 3, of the Table 66: Compounds of the formula I.A and the salts and radicals R. R', and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', Rand R" are Examples of compounds of this particularly preferred hydrogen and wherein A is selected from the radicals A1.h' embodiment are the compounds given in the following tables 50 1 to A1.h' 81. 51 to 100 Table 67: Compounds of the formula I.A and the salts and Table 51: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.i' 1 to Ali' and wherein A is selected from the radicals A1.a' 1 to A1.a' 81. 81. 55 Table 52: Compounds of the formula I.A and the salts and Table 68: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.a' hydrogen and wherein A is selected from the radicals A1.i' 1 to A1.a'81. 1 to Ali'81. Table 53: Compounds of the formula I.A and the salts and 60 Table 69: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.b' 1 to A1.b' and wherein A is selected from the radicals A1.k 1 to A1.k. 81. 81. Table 54: Compounds of the formula I.A and the salts and Table 70: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.b' hydrogen and wherein A is selected from the radicals A1.k. 1 to A1.b' 81. 1 to A1.k'81. US 9,029,639 B2 59 60 Table 71: Compounds of the formula I.A and the salts and Table 87: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A1.1' 1 to A1.1" and wherein A is selected from the radicals A1.t' 1 to A1.t' 81. 81. Table 72: Compounds of the formula I.A and the salts and 5 Table 88: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.1" hydrogen and wherein A is selected from the radicals A1.t' 1 to A1.1' 81. 1 to A1.t'81. Table 73: Compounds of the formula I.A and the salts and Table 89: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 10 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.m' 1 to and wherein A is selected from the radicals A1.u' 1 to A1.u' Alm'81. 81. Table 74: Compounds of the formula I.A and the salts and Table 90: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 15 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.m' hydrogen and wherein A is selected from the radicals A1.u' 1 to A1.m'81. 1 to A1.u' 81. Table 75: Compounds of the formula I.A and the salts and Table 91: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.n' 1 to A1.n' and wherein A is selected from the radicals A1.v 1 to A1.v' 81. 81. Table 76: Compounds of the formula I.A and the salts and Table 92: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.n' hydrogen and wherein A is selected from the radicals A1.v. 1 to A1 n' 81. 25 1 to A1 v 81. Table 77: Compounds of the formula I.A and the salts and Table 93: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.o' 1 to A1.o' and wherein A is selected from the radicals A1.w' 1 to 81. A1.w'81. 30 Table 94: Compounds of the formula I.A and the salts and Table 78: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.w' hydrogen and wherein A is selected from the radicals A1.o' 1 to A1.w'81. 1 to A1.O' 81. Table 95: Compounds of the formula I.A and the salts and Table 79: Compounds of the formula I.A and the salts and 35 N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen and wherein A is selected from the radicals A1.x 1 to A1.x and wherein A is selected from the radicals A1.p' 1 to A1.p' 81. 81. Table 96: Compounds of the formula I.A and the salts and Table 80: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are 40 hydrogen and wherein A is selected from the radicals A1.x hydrogen and wherein A is selected from the radicals A1.p' 1 to A1X" 81. 1 to A1.p'81. Table 97: Compounds of the formula I.A and the salts and Table 81: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.y1 to A1.y and wherein A is selected from the radicals A1.d 1 to A1.d 45 81. 81. Table 98: Compounds of the formula I.A and the salts and Table 82: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.y hydrogen and wherein A is selected from the radicals A1.d' 1 to A1.y'81. 1 to A1.d'81. 50 Table 99: Compounds of the formula I.A and the salts and Table 83: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A1.Z 1 to A1.Z.' and wherein A is selected from the radicals A1.r 1 to A1.r 81. 81. Table 100: Compounds of the formula I'...A and the salts and 55 N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 84: Compounds of the formula I.A and the salts and hydrogen and wherein A is selected from the radicals A1.z N-oxides thereof, wherein R' is methyl, R', R" and R" are 1 to A1.Z 81. hydrogen and wherein A is selected from the radicals A1.r Further examples of compounds of this particularly pre 1 to A1.r'81. ferred embodiment are the compounds of tables 51A to 100A Table 85: Compounds of the formula I.A and the salts and 60 wherein R, R" and R' are hydrogen and wherein A is as N-oxides thereof, wherein R', R, R" and R" are hydrogen defined in tables 51 to 100 and wherein R' is a radical repre and wherein A is selected from the radicals A1.s' 1 to A1.s' sented by each individual line (85 to 160) of table B. 81. Another particular preferred embodiment relates to com Table 86: Compounds of the formula I.A and the salts and pounds of the formula I'...A and to the salts and N-oxides N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 thereof, wherein hydrogen and wherein A is selected from the radicals A1.s' A is a radical A1, as defined herein, in particular a radical A1, 1 to A1.s' 81. wherein R', Rhave the preferred meanings, in particular US 9,029,639 B2 61 62 an imidazole radical of the formulae A1.a' to A1.Z', e.g. a Table 114: Compounds of the formula I'...A and the salts and radical selected from the thiazole radicals A1.a' to A1.Z." N-oxides thereof, wherein R' is methyl, R', R" and R" are 81: hydrogen and wherein A is selected from the radicals A1.g" R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, 1 to A1.g" 81. most preferably hydrogen, methyl or ethyl; 5 Table 115: Compounds of the formula I'...A and the salts and R" is further most preferably represented by a radical as N-oxides thereof, wherein R', R, R" and R" are hydrogen defined in each line of table B; and wherein A is selected from the radicals A1.h" 1 to R. R', and R" are independently from each other selected A1.h" 81. from hydrogen, methyl, difluoromethyl, trifluoromethyl, Table 116: Compounds of the formula I'...A and the salts and methoxy, difluoromethoxy and trifluoromethoxy; and 10 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals A1.h" wherein preferably at least one, more preferably 2 or 3, of the 1 to A1.h" 81. radicals R. R', and R" are hydrogen. Table 1 17: Compounds of the formula I'...A and the salts and Examples of compounds of this particularly preferred N-oxides thereof, wherein R. R. R" and R" are hydrogen embodiment are the compounds given in the following tables 15 and wherein A is selected from the radicals Ali" 1 to Ali" 101 to 150 81. Table 101: Compounds of the formula I'...A and the salts and Table 118: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R' and R" are hydrogen and N-oxides thereof, wherein R' is methyl, R', R" and R" are wherein A is selected from the radicals A1.a" 1 to A1.a"81. hydrogen and wherein A is selected from the radicals A1.i" Table 102: Compounds of the formula I'...A and the salts and 1 to A1.1" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 119: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.a" N-oxides thereof, wherein R', R, R" and R" are hydrogen 1 to A1.a" 81. and wherein A is selected from the radicals Alk" 1 to Table 103: Compounds of the formula I'...A and the salts and A1 k" 81. N-oxides thereof, wherein R', R, R" and R" are hydrogen 25 Table 120: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A1.b" 1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A1.b" 81. hydrogen and wherein A is selected from the radicals A1.k" Table 104: Compounds of the formula I'...A and the salts and 1 to A1 k" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 121: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.b" 30 N-oxides thereof, wherein R. R. R" and R" are hydrogen 1 to A1.b" 81. and wherein A is selected from the radicals A1.1" 1 to A1.1" Table 105: Compounds of the formula I.A and the salts and 81. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 122: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A1.c" 1 to A1.c" N-oxides thereof, wherein R' is methyl, R', R" and R" are 81. 35 hydrogen and wherein A is selected from the radicals A1.1" Table 106: Compounds of the formula I'...A and the salts and 1 to A1.1" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 123: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.c" N-oxides thereof, wherein R', R, R" and R" are hydrogen 1 to A1.c" 81. and wherein A is selected from the radicals Alm" 1 to Table 107: Compounds of the formula I'...A and the salts and 40 Alm" 81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 124: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A1.d" 1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A1.d" 81. hydrogen and wherein A is selected from the radicals Table 108: Compounds of the formula I'...A and the salts and Alm" 1 to A1.m" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are 45 Table 125: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.d" N-oxides thereof, wherein R', R, R" and R" are hydrogen 1 to A1.d" 81. and wherein A is selected from the radicals A1.n" 1 to Table 109: Compounds of the formula I'...A and the salts and A1n'81. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 126: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A1.e" 1 to A1.e" 50 N-oxides thereof, wherein R' is methyl, R', R" and R" are 81. hydrogen and wherein A is selected from the radicals A1.n" Table 110: Compounds of the formula I'...A and the salts and 1 to A1.n" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 127: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.e" N-oxides thereof, wherein R. R'' and R" are hydrogen and 1 to A1.e" 81. 55 wherein A is selected from the radicals A1.o" 1 to A1.o"81. Table 111: Compounds of the formula I'...A and the salts and Table 128: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.f" 1 to A1.f." hydrogen and wherein A is selected from the radicals A1.o" 81. 1 to A1.O." 81. Table 112: Compounds of the formula I'...A and the salts and 60 Table 129: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R" and R" are hydrogen hydrogen and wherein A is selected from the radicals A1.f." and wherein A is selected from the radicals A1 p" 1 to 1 to A1.f" 81. A1 p"81. Table 113: Compounds of the formula I'...A and the salts and Table 130: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.g" 1 to hydrogen and wherein A is selected from the radicals A1 p" A1.g" 81. 1 to A1 p" 81. US 9,029,639 B2 63 64 Table 131: Compounds of the formula I'...A and the salts and Table 148: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.d" 1 to hydrogen and wherein A is selected from the radicals A1.y" A1.d" 81. 1 to Ally" 81. Table 132: Compounds of the formula I.A. and the salts and 5 Table 149: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals A1.d" and wherein A is selected from the radicals A1.z" 1 to A1.Z." 1 to A1.d" 81. 81. Table 133: Compounds of the formula I'...A and the salts and Table 150: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R, R" and R" are hydrogen and 10 wherein A is selected from the radicals A1.r" 1 to A1.r" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 134: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.z" N-oxides thereof, wherein R' is methyl, R', R" and R" are 1 to A1 Z'81. hydrogen and wherein A is selected from the radicals A1.r" Further examples of compounds of this particularly pre 1 to A1 r" 81. 15 ferred embodiment are the cornpounds of tables 101A to Table 135: Compounds of the formula I'...A and the salts and 150A wherein R, RandR are hydrogen and wherein A is as N-oxides thereof, wherein R', R, R" and R" are hydrogen defined in tables 101 to 126 and wherein R' is a radical and wherein A is selected from the radicals A1.s" 1 to A1.s" represented by each individual line (85 to 160) of table B. 81. Another particular preferred embodiment relates to com Table 136: Compounds of the formula I'...A and the salts and pounds of the formula I'...A and 401 to the salts and N-oxides N-oxides thereof, wherein R' is methyl, R', R" and R" are thereof, wherein hydrogen and wherein A is selected from the radicals A1.s" A is a radical A2, as defined herein, in particular a radical A2, 1 to A1.s" 81. wherein R', Rhave the preferred meanings, in particular Table 137: Compounds of the formula I'...A and the salts and an oxazole radical of the formulae A2.aa to A2.do, e.g. a N-oxides thereof, wherein R', R, R" and R" are hydrogen 25 radical selected from the oxazole radicals A2.aa1-A2.aa81 and wherein A is selected from the radicals A1.t" 1 to A1.t" to A2.dol to A2.do81; 81. R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, Table 138: Compounds of the formula I'...A and the salts and most preferably hydrogen, methyl or ethyl; N-oxides thereof, wherein R' is methyl, R', R" and R" are R" is further most preferably represented by a radical as hydrogen and wherein A is selected from the radicals A1.t" 30 defined in each line of table B; 1 to A1t'81. R. R" and R" are selected independently of each other from Table 139: Compounds of the formula I'...A and the salts and hydrogen, methyl, difluoromethyl, trifluoromethyl, meth N-oxides thereof, wherein R', R', R" and R" are hydrogen oxy, difluoromethoxy and trifluoromethoxy; and wherein and wherein A is selected from the radicals A1.u" 1 to preferably at least one, more preferably two or three of the A1 u" 81. 35 radicals R. R'' and R" are hydrogen. Table 140: Compounds of the formula I'...A and the salts and Examples of compounds of this particular preferred N-oxides thereof, wherein R' is methyl, R', R" and R" are embodiment are the compounds given in the following tables hydrogen and wherein A is selected from the radicals A1.u" 151 to 176. 1 to A1.u" 81. Table 151: Compounds of the formula I'...A and the salts and Table 141: Compounds of the formula I'...A and the salts and 40 N-oxides thereof, wherein R. R'' and R" are hydrogen and N-oxides thereof, wherein R', R, R" and R" are hydrogen wherein A is selected from the radicals A2.aal to A2.aa81. and wherein A is selected from the radicals A1.v" 1 to Table 152: Compounds of the formula I'...A and the salts and A1V'81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 142: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are 45 A2.aal to A2.aa81. hydrogen and wherein A is selected from the radicals A1.v." Table 153: Compounds of the formula I'...A and the salts and 1 to A1V'81. N-oxides thereof, wherein R. R. R" and R" are hydrogen Table 143: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.ab1 to N-oxides thereof, wherein R', R', R" and R" are hydrogen A2.ab81. and wherein A is selected from the radicals A1.w" 1 to 50 Table 154: Compounds of the formula I'...A and the salts and A1.w'81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 144: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.ab1 to A2.ab81. hydrogen and wherein A is selected from the radicals Table 155: Compounds of the formula I'...A and the salts and A1.w' 1 to A1.w'81. 55 N-oxides thereof, wherein R, R" and R" are hydrogen and Table 145: Compounds of the formula I'...A and the salts and wherein A is selected from the radicals A2.ac1 to A2.ac81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 156: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A1.x" 1 to N-oxides thereof, wherein R', is methyl, R', R" and R" are A1X" 81. hydrogen and wherein A is selected from the radicals Table 146: Compounds of the formula I'...A and the salts and 60 A2.ac1 to A2.ac81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 157: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A1.x" N-oxides thereof, wherein R', RandR are hydrogen and 1 to A1X" 81. wherein A is selected from the radicals A2.ad 1 to A2.ad81. Table 147: Compounds of the formula I'...A and the salts and Table 158: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A1.y" 1 to hydrogen and wherein A is selected from the radicals A1.y" 81. A2.ad 1 to A2.ad81. US 9,029,639 B2 65 66 Table 159: Compounds of the formula I'...A and the salts and Table 176: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.ael to hydrogen and wherein A is selected from the radicals A2.ae81. A2.aol to A2.ao81. Table 160: Compounds of the formula I'...A and the salts and 5 Further examples of compounds of this particularly pre N-oxides thereof, wherein R' is methyl, R', R" and R" are ferred embodiment are the compounds of tables 151A to hydrogen and wherein A is selected from the radicals 176A wherein R, RandR are hydrogen and wherein A is as A2.ael to A2.ae81. defined in tables 153 to 180 and wherein R' is a radical Table 161: Compounds of the formula I'...A and the salts and represented by each individual line (85 to 160) of table B. N-oxides thereof, wherein R', R, R" and R" are hydrogen 10 Another particular preferred embodiment relates to com and wherein A is selected from the radicals A2.af1 to pounds of the formula I'...A and to the salts and N-oxides A2.af31. thereof, wherein Table 162: Compounds of the formula I'...A and the salts and A is a radical A2, as defined herein, in particular a radical A2, N-oxides thereof, wherein R' is methyl, R', R" and R" are 15 wherein R', Rhave the preferred meanings, in particular hydrogen and wherein A is selected from the radicals a thiazole radical of the formulae A2.aa' to A2.do', e.g. a A2.af1 to A2.af31. radical selected from the thiazole radicals A2.aa' 1-A2.aa' Table 163: Compounds of the formula I'...A and the salts and 81 to A2.do' 1 to A2.do' 81; N-oxides thereof, wherein R', R, R" and R" are hydrogen R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, and wherein A is selected from the radicals A2.agl to most preferably hydrogen, methyl or ethyl; A2.ag81. R" is further most preferably represented by a radical as Table 164: Compounds of the formula I'...A and the salts and defined in each line of table B; N-oxides thereof, wherein R' is methyl, R', R" and R" are R. R" and R" are selected independently of each other from hydrogen and wherein A is selected from the radicals hydrogen, methyl, difluoromethyl, trifluoromethyl, meth A2.agl to A2.ag81. 25 oxy, difluoromethoxy and trifluoromethoxy; and wherein Table 165: Compounds of the formula I'...A and the salts and preferably at least one, more preferably two or three of the N-oxides thereof, wherein R', R, R" and R" are hydrogen radicals R. R'' and R" are hydrogen. and wherein A is selected from the radicals A2.ail to Examples of compounds of this particular preferred A2.ai81. embodiment are the compounds given in the following tables Table 166: Compounds of the formula I'...A and the salts and 30 N-oxides thereof, wherein R' is methyl, R', R" and R" are 177 to 202. hydrogen and wherein A is selected from the radicals Table 177: Compounds of the formula I'...A and the salts and A2.ail to A2.ai81. N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A2.aa' 1 to Table 167: Compounds of the formula I'...A and the salts and A2.aa'81. N-oxides thereof, wherein R. R' and R" are hydrogen and 35 wherein A is selected from the radicals A2.ak1 to A2.ak81. Table 178: Compounds of the formula I'...A and the salts and Table 168: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.aa' 1 to A2.aa'81. A2.ak1 to A2.ak81. 40 Table 179: Compounds of the formula I'...A and the salts and Table 169: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R. R' and R" are hydrogen and and wherein A is selected from the radicals A2.ab' 1 to wherein A is selected from the radicals A2.all to A2.al81. A2.ab'81. Table 170: Compounds of the formula I'...A and the salts and Table 180: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 45 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.all to A2.al81. A2.ab' 1 to A2.ab' 81. Table 171: Compounds of the formula I'...A and the salts and Table 181: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R' and R" are hydrogen and N-oxides thereof, wherein R. R. R" and R" are hydrogen wherein A is selected from the radicals A2.am1 to 50 and wherein A is selected from the radicals A2.ac' 1 to A2.am81. A2.ac'81. Table 172: Compounds of the formula I'...A and the salts and Table 182: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.am1 to A2.am81. 55 A2.ac' 1 to A2.ac'81. Table 173: Compounds of the formula I'...A and the salts and Table 183: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', RandR are hydrogen and and wherein A is selected from the radicals A2.an1 to wherein A is selected from the radicals A2.ad 1 to A2.ad' A2.an81. 81. Table 174: Compounds of the formula I'...A and the salts and 60 Table 184: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.an1 to A2.an81. A2.ad 1 to A2.ad 81. Table 175: Compounds of the formula I'...A and the salts and Table 185: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A2.aol to and wherein A is selected from the radicals A2.ae' 1 to A2.ao81. A2.ae'81. US 9,029,639 B2 67 68 Table 186: Compounds of the formula I'...A and the salts and Table 202: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.ae'1 to A2.ae'81. A2.ao' 1 to A2.ao'81. Table 187: Compounds of the formula I'...A and the salts and 5 Further examples of compounds of this particularly pre N-oxides thereof, wherein R', R, R" and R" are hydrogen ferred embodiment are the compounds of tables 177A to and wherein A is selected from the radicals A2.af. 1 to 202A wherein R, RandR are hydrogen and wherein A is as A2.af 81. defined in tables 176 to 202 and wherein R' is a radical Table 188: Compounds of the formula I'...A and the salts and represented by each individual line (85 to 160) of table B. N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 Another particular preferred embodiment relates to com hydrogen and wherein A is selected from the radicals A2.af pounds of the formula I'...A and to the salts and N-oxides 1 to A2.af 81. thereof, wherein Table 189: Compounds of the formula I'...A and the salts and A is a radical A2, as defined herein, in particular a radical A2, N-oxides thereof, wherein R', R', R" and R" are hydrogen 15 wherein R. R. R. have the preferred meanings, in and wherein A is selected from the radicals A2.ag 1 to particular an imidazole radical of the formulae A2.aa" to A2.ag 81. A2.do, e.g. a radical selected from the imidazole radicals Table 190: Compounds of the formula I'...A and the salts and A2.aa" 1-A2.aa" 81 to A2.dol to A2.do81; N-oxides thereof, wherein R' is methyl, R', R" and R" are R" is hydrogen, Craralkyl or Cra-4-alkoxy-C-C2-alkyl, most hydrogen and wherein A is selected from the radicals preferably hydrogen, methyl or ethyl; A2.ag 1 to A2.ag 81. R" is further most preferably represented by a radical as Table 191: Compounds of the formula I'...A and the salts and defined in each line of table B; N-oxides thereof, wherein R', R, R" and R" are hydrogen R. R" and R" are selected independently of each other from and wherein A is selected from the radicals A2.ai' 1 to hydrogen, methyl, difluoromethyl, trifluoromethyl, meth A2.ai'81. 25 oxy, difluoromethoxy and trifluoromethoxy; and wherein Table 192: Compounds of the formula I'...A and the salts and preferably at least one, more preferably two or three of the N-oxides thereof, wherein R' is methyl, R', R" and R" are radicals R. R'' and R" are hydrogen. hydrogen and wherein A is selected from the radicals A2.ai' Examples of compounds of this particular preferred 1 to A2.ai'81. embodiment are the compounds given in the following tables Table 193: Compounds of the formula I'...A and the salts and 30 2O3 to 313. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 203: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.ak 1 to N-oxides thereof, wherein R. R. R" and R" are hydrogen A2.ak'81. and wherein A is selected from the radicals A2.aa" 1 to Table 194: Compounds of the formula I'...A and the salts and 35 A2.aa" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 204: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.ak 1 to A2.ak'81. hydrogen and wherein A is selected from the radicals Table 195: Compounds of the formula I'...A and the salts and A2.aa" 1 to A2.aa" 81. N-oxides thereof, wherein R', R, R" and R" are hydrogen 40 Table 205: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.al 1 to N-oxides thereof, wherein R, R" and R" are hydrogen and A2.al' 81. wherein A is selected from the radicals A2.ab" 1 to A2.ab" Table 196: Compounds of the formula I'...A and the salts and 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 206: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals A2.al' 45 N-oxides thereof, wherein R' is methyl, R', R" and R" are 1 to A2.al' 81. hydrogen and, wherein A is selected from the radicals Table 197: Compounds of the formula I'...A and the salts and A2.ab" 1 to A2.ab" 81. N-oxides thereof, wherein R. R' and R" are hydrogen and Table 207: Compounds of the formula I'...A and the salts and wherein A is selected from the radicals A2.am' 1 to A2.am' N-oxides thereof, wherein R. R. R" and R" are hydrogen 81. 50 and wherein A is selected from the radicals A2.ac" 1 to Table 198: Compounds of the formula I'...A and the salts and A2.ac" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 208: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.am' 1 to A2.am'81. hydrogen and wherein A is selected from the radicals 55 A2.ac" 1 to A2.ac" 81. Table 199: Compounds of the formula I'...A and the salts and Table 209: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R', RandR are hydrogen and and wherein A is selected from the radicals A2.an' 1 to wherein A is selected from the radicals A2.ad" 1 to A2.ad" A2.an'81. 81. Table 200: Compounds of the formula I'...A and the salts and 60 Table 210: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.an'1 to A2.an'81. A2.ad" 1 to A2.ad" 81. Table 201: Compounds of the formula I'...A and the salts and Table 211: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A2.ao' 1 to and wherein A is selected from the radicals A2.ae" 1 to A2.ao'81. A2.ae" 81. US 9,029,639 B2 69 70 Table 212: Compounds of the formula I'...A and the salts and Table 228: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.ae" 1 to A2.ae" 81. A2.ao" 1 to A2.ao" 81. Table 213: Compounds of the formula I.A and the salts and 5 Table 229: Compounds of the formula I.A. and the Salts and N-oxides thereof, wherein R', R" and R" are hydrogen and N-oxides thereof, wherein R', R, R" and R" are hydrogen wherein A is selected from the radicals A2.af" 1 to A2.af." and wherein A is selected from the radicals A2.bal to 81. A2.ba81. Table 214: Compounds of the formula I'...A and the salts and Table 230: Compounds of the formula I'...A and the salts and 10 N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.bal to A2.ba81. A2.af" 1 to A2.af" 81. Table 231: Compounds of the formula I'...A and the salts and Table 215: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen 15 and wherein A is selected from the radicals A2.bbl to and wherein A is selected from the radicals A2.ag" 1 to A2.bb81. A2.ag" 81. Table 232: Compounds of the formula I'...A and the salts and Table 216: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.bb1 to A2, bb81. A2.ag" 1 to A2.ag" 81. Table 233: Compounds of the formula I'...A and the salts and Table 217: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A2.bc1 to and wherein A is selected from the radicals A2.ai" 1 to A2.bc81. A2.ai" 81. 25 Table 234: Compounds of the formula I'...A and the salts and Table 218: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.bc1 to A2.bc81. A2.ai" 1 to A2.ai" 81. Table 235: Compounds of the formulaI'...A and, the salts and 30 N-oxides thereof, wherein R', IT, R" and R" are hydrogen Table 219: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.bd1 to N-oxides thereof, wherein R', R, R" and R" are hydrogen A2.bd81. and wherein A is selected from the radicals A2.ak" 1 to Table 236: Compounds of the formula I'...A and the salts and A2.ak" 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 220: Compounds of the formula I'...A and the salts and 35 hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.bd1 to A2.bd81. hydrogen and wherein A is selected from the radicals Table 237: Compounds of the formula I'...A and the salts and A2.ak" 1 to A2.ak" 81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 221: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.bel to N-oxides thereof, wherein R', R" and R" are hydrogen and 40 A2.be81. wherein A is selected from the radicals A2.al" 1 to A2.al" Table 238: Compounds of the formula I'...A and the salts and 81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 222: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.bel to A2.be81. hydrogen and wherein A is selected from the radicals 45 Table 239: Compounds of the formula I'...A and the salts and A2.al" 1 to A2.al" 81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 223: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.bfl to N-oxides thereof, wherein R', R', R" and R" are hydrogen A2.bf81. and wherein A is selected from the radicals A2.am" 1 to Table 240: Compounds of the formula I'...A and the salts and A2.am" 81. 50 N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 224: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.bf1 to A2.bf81. hydrogen and wherein A is selected from the radicals Table 241: Compounds of the formula I'...A and the salts and A2.am" 1 to A2.am" 81. N-oxides thereof, wherein R. R. R" and R" are hydrogen 55 and wherein A is selected from the radicals A2.bg1 to Table 225: Compounds of the formula I'...A and the salts and A2.bg.81. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 242: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.an" 1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.an" 81. hydrogen and wherein A is selected from the radicals Table 226: Compounds of the formula I'...A and the salts and 60 A2.bg1 to A2.bg.81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 243: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R, R" and R" are hydrogen and A2.an" 1 to A2.an" 81. wherein A is selected from the radicals A2.bill to A2.bi81. Table 227: Compounds of the formula I'...A and the salts and Table 244: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N" oxides thereof, wherein R' is methyl, R. R" and R" are and wherein A is selected from the radicals A2.ao" 1 to hydrogen and wherein A is selected from the radicals A2.ao" 81. A2.bi1 to A2.bi81. US 9,029,639 B2 71 72 Table 245: Compounds of the formula I'...A and the salts and Table 262: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.bk1 to hydrogen and wherein A is selected from the radicals A2. bk81. A2.cd1 to A2.cd81. Table 246: Compounds of the formula I'...A and the salts and 5 Table 263: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R is methyl, R', R" and R" are N-oxides thereof, wherein R, R" and R" are hydrogen and hydrogen and wherein A is selected from the radicals wherein A is selected from the radicals A2.cel to A2.ce81. A2. bk1 to A2. bk81. Table 264: Compounds of the formula I'...A and the salts and Table 247: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R', R, R" and R" are hydrogen A2.cel to A2.ce81. and wherein A is selected from the radicals A2.bl1 to Table 265: Compounds of the formula I'...A and the salts and A2.bl81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 248: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.cf1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are 15 A2.cf31. hydrogen and wherein A is selected from the radicals Table 266: Compounds of the formula I'...A and the salts and A2.bl1 to A2.b181. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 249: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R', R" and R" are hydrogen and A2.cf1 to A2.cf31. wherein A is selected from the radicals A2.bm1 to Table 267: Compounds of the formula I'...A and the salts and A2.bm81. N-oxides thereof, wherein R. R. R" and R" are hydrogen Table 250: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.cg1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.cg81. hydrogen and wherein A is selected from the radicals Table 268: Compounds of the formula I'...A and the salts and A2.bm1 to A2.bm81. 25 N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 251: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R, R" and R" are hydrogen and A2.cg1 to A2.cg81. wherein A is selected from the radicals A2.bn1 to A2.bn81. Table 269: Compounds of the formula I'...A and the salts and Table 252: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are 30 and wherein A is selected from the radicals A2.cil to hydrogen and wherein A is selected from the radicals A2.c181. A2.bn1 to A2.bn81. Table 270: Compounds of the formula I'...A and the salts and Table 253: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A2.bol to 35 A2.cil to A2.ci81. A2.bo81. Table 271: Compounds of the formula I'...A and the salts and Table 254: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.ck1 to hydrogen and wherein A is selected from the radicals A2.ck81. A2.bol to A2.bo81. 40 Table 272: Compounds of the formula I"A and the salts and Table 255: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R', R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A2.cal to A2.ck1 to A2.ck81. A2.ca81. Table 273: Compounds of the formula I'...A and the salts and Table 256: Compounds of the formula I'...A and the salts and 45 N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.cl1 to hydrogen and wherein A is selected from the radicals A2.c181. A2.cal to A2.ca81. Table 274: Compounds of the formula I'...A and the salts and Table 257: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen 50 hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A2.cb1 to A2.c11 to A2.c181. A2.cb81. Table 275: Compounds of the formula I'...A and the salts and Table 258: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.cm1 to hydrogen and wherein A is selected from the radicals 55 A2.cm81. A2.cb1 to A2.cb81. Table 276: Compounds of the formula I'...A and the salts and Table 259: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A2.cc1 to A2.cm1 to A2.cm81. A2.cc81. 60 Table 277: Compounds of the formula I'...A and the salts and Table 260: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.cn1 to hydrogen and wherein A is selected from the radicals A2.cn81. A2.cc1 to A2.cc81. Table 278: Compounds of the formula I'...A and the salts and Table 261: Compounds of the formula I'...A and the salts and 65 N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R' and R" are hydrogen and hydrogen and wherein A is selected from the radicals wherein A is selected from the radicals A2.cd1 to A2.cd81. A2.cn1 to A2.cn81. US 9,029,639 B2 73 74 Table 279: Compounds of the formula I'...A and the salts and Table 296: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.col to hydrogen and wherein A is selected from the radicals A2.co81. A2.di 1 to A2.di81. Table 280: Compounds of the formula I.A. and the salts and 5 Table 297: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A2.dk1 to A2.co.1 to A2.co81. A2.dk81. Table 281: Compounds of the formula I'...A and the salts and Table 298: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 10 and wherein A is selected from the radicals A2.dal to N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.da81. hydrogen and wherein A is selected from the radicals Table 282: Compounds of the formula I'...A and the salts and A2.dk1 to A2.dk81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 299: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals 15 N-oxides thereof, wherein R. R. R" and R" are hydrogen A2.dal to A2.da81. and wherein A is selected from the radicals A2.dll to Table 283: Compounds of the formula I'...A and the salts and A2.dl31. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 300: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.db1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.db81. hydrogen and wherein A is selected from the radicals Table 284: Compounds of the formula I'...A and the salts and A2.dll to A2.dl31. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 301: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R', R, R" and R" are hydrogen A2.db1 to A2.db81. and wherein A is selected from the radicals A2.dm1 to Table 285: Compounds of the formula, I'...A and the salts and 25 A2.dm81. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 302: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.dc1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.dc81. hydrogen and wherein A is selected from the radicals Table 286: Compounds of the formula I'...A and the salts and A2.dm1 to A2.dm81. N-oxides thereof, wherein R' is methyl, R', R" and R" are 30 hydrogen and wherein A is selected from the radicals Table 303: Compounds of the formula I'...A and the salts and A2.dc1 to A2.dc81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 287: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.dn1 to N-oxides thereof, wherein R', R, R" and R' are hydrogen A2.dn81. and wherein A is selected from the radicals A2.dd 1 to 35 Table 304: Compounds of the formula I'...A and the salts and A2.dd81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 288: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A2.dn1 to A2.dn81. hydrogen and wherein A is selected from the radicals Table 305: Compounds of the formula I'...A and the salts and A2.dd 1 to A2.dd81. 40 N-oxides thereof, wherein R. R. R" and R" are hydrogen Table 289: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A2.dol to N-oxides thereof, wherein R', R" and R" are hydrogen, and A2.do81. wherein A is selected from the radicals A2.del to A2.de31. Table 306: Compounds of the formula I'...A and the salts and Table 290 Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are 45 hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.dol to A2.do81. A2.del to A2.de81. Table 307: Compounds of the formula I'...A and the salts and Table 291: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen and wherein A is selected from the radicals A2.eal to and wherein A is selected from the radicals A2.df1 to 50 A2.ea81. A2.df&1. Table 308: Compounds of the formula I'...A and the salts and Table 292: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are, hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.eal to A2.ea81. A2.df1 to A2.df81. 55 Table 293: Compounds of the formula I'...A and the salts and Table 309: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A2.dg1 to and wherein A is selected from the radicals A2.fa1 to A2.dg81. A2.fa81. Table 294: Compounds of the formula I'...A and the salts and 60 Table 310: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A2.dg1 to A2.dg81. A2.fa1 to A2.fa81. Table 295: Compounds of the formula I'...A and the salts and Table 311: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A2.di 1 to and wherein A is selected from the radicals A2.gal to A2.di81. A2.ga81. US 9,029,639 B2 75 76 Table 312: Compounds of the formula I'...A and the salts and Table 322: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R'' and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.ael to A2.gal to A2.ga81. A3.ae81. Table 313: Compounds of the formula I'...A and the salts and 5 Table 323: Compounds of the formula I"A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A2.hal to hydrogen and wherein A is selected from the radicals A2.ha81. A3.ael to A3..ae81. Further examples of compounds of this particularly pre Table 324: Compounds of the formula I'...A and the salts and ferred embodiment are the compounds of tables 203A to 10 N-oxides thereof, wherein R', R, R" and R" are hydrogen 313A wherein R. R'' and Rare hydrogen and wherein A is as, and wherein A is selected from the radicals A3...af1 to defined in tables 203 to 313 and wherein R' is a radical A3.af31. represented by each individual line (85 to 160) of table B. Table 325: Compounds of the formula I'...A and the salts and Another particular preferred embodiment relates to com 15 N-oxides thereof, wherein R' is methyl, R', R" and R" are pounds of formula I.A and to the salts and N-oxides thereof, hydrogen and wherein A is selected from the radicals wherein A3.af1 to A3.af31. A is a radical A3, as defined herein, in particular a radical A3, Table 326: Compounds of the formula I'...A and the salts and wherein R, R have the preferred meanings, more par N-oxides thereof, wherein R', R, R" and R" are hydrogen ticularly an oxazole radical of the formulae A3.aa to A3...do, and wherein A is selected from the radicals A3...ag1 to e.g. a radical selected from the oxazole radicals A3.aal A3.ag81. A3.aa81 to A3...do1-A3...do81; Table 327: Compounds of the formula I'...A and the salts and R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, N-oxides thereof, wherein R' is methyl, R', R" and R" are most preferably hydrogen, methyl or ethyl; hydrogen and wherein A is selected from the radicals R" is further most preferably represented by a radical as 25 A3.agl to A3...ag&1. defined in each line of table B; Table 328: Compounds of the formula I'...A and the salts and R. R' and R" are selected independently of each other from N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen, methyl, difluoromethyl, trifluoromethyl, meth and wherein A is selected from the radicals A3.ahl to oxy, difluoromethoxy and trifluoromethoxy; and wherein A3.ah81. preferably at least one, more preferably 2 or 3, of the 30 Table 329: Compounds of the formula I'...A and the salts and radicals R. R" and R" are hydrogen. N-oxides thereof, wherein R' is methyl, R', R" and R" are Examples of compounds of this particular preferred hydrogen and wherein A is selected from the radicals embodiment are the compounds given in the following tables A3.ahl to A3..ah81. 314 to 341. Table 330: Compounds of the formula I'...A and the salts and 35 N-oxides thereof, wherein R', R" and R" are hydrogen and Table 314: Compounds of the formula I'...A and the salts and wherein A is selected from the radicals A3.ail to A3.ai81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 331: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3.aal to N-oxides thereof, wherein R' is methyl, R', R" and R" are A3.aa81. hydrogen and wherein A is selected from the radicals Table 315: Compounds of the formula LA and the salts and 40 A3.ail to A3.ai81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 332: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R. R. R" and R" are hydrogen A3.aal to A3..aa81. and wherein A is selected from the radicals A3.ak1 to Table 316: Compounds of the formula I'...A and the salts and A3.ak81. N-oxides thereof, wherein R', R', R" and R" are hydrogen 45 Table 333: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3.ab1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A3.ab81. hydrogen and wherein A is selected from the radicals Table 317: Compounds of the formula LA and the salts and A3.ak1 to A3.ak81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 334: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals 50 N-oxides thereof, wherein R', R, R" and R" are hydrogen A3ab1 to A3...ab81. and wherein A is selected from the radicals A3...all to Table 318: Compounds of the formula I'...A and the salts and A3a181. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 335: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3.ac1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are 55 hydrogen and wherein A is selected from the radicals A3.ac81. A3..all to A3a181. Table 319: Compounds of the formula I'...A and the salts and Table 336: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.am1 to A3.ac1 to A3.ac81. 60 A3.am81. Table 320: Compounds of the formula I'...A and the salts and Table 337: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R, R" and R" are hydrogen and N-oxides thereof, wherein R' is methyl, R', R" and R" are wherein A is selected from the radicals A3.ad 1 to A3.ad81. hydrogen and wherein A is selected from the radicals Table 321: Compounds of the formula I'...A and the salts and A3.am1 to A3.am81. N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 Table 338: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R. R'' and R" are hydrogen and A3.ad 1 to A3...ad81. wherein A is selected from the radicals A3..an1 to A3...an81. US 9,029,639 B2 77 78 Table 339: Compounds of the formula I'...A and the salts and Table 349: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3..an1 to A3...an81. A3.ad 1 to A3.ad 81. Table 340: Compounds of the formula I'...A and the salts and 5 Table 350: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.aol to and wherein A is selected from the radicals A3.ae' 1 to A3..ao81. A3.ae'81. Table 341: Compounds of the formula I'...A and the salts and Table 351: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.aol to A3..ao81. A3.ae'1 to A3..ae'81. Further examples of compounds of this particularly pre Table 352: Compounds of the formula I'...A and the salts and ferred embodiment are the compounds of tables 314A to 15 N-oxides thereof, wherein R. R. R" and R" are hydrogen 341A wherein R, R" and Rare hydrogen and wherein A is as and wherein A is selected from the radicals A3.af. 1 to defined in tables 314 to 341 and wherein R' is a radical A3af 81. represented by each individual line (85 to 160) of table B. Table 353: Compounds of the formula I'...A and the salts and Another particular preferred embodiment relates to com N-oxides thereof, wherein R' is methyl, IR%R" and R" are pounds of formula I.A and to the salts and N-oxides thereof, hydrogen and wherein A is selected from the radicals A3...af wherein 1 to A3.af 81. A is a radical A3, as defined herein, in particular a radical A3, Table 354: Compounds of the formula I'...A and the salts and wherein R, R have the preferred meanings, more par N-oxides thereof, wherein R', R, R" and R" are hydrogen ticularly a thiazole radical of the formulae A3.aa' to A3...do', and wherein A is selected from the radicals A3..ag 1 to e.g. a radical selected from the thiazole radicals A3.aa' 25 A3.ag 81. 1-A3.aa'81 to A3...do' 1-A3...do' 81; Table 355: Compounds of the formula I'...A and the salts and R" is hydrogen, C1-C4-alkyl or C-C-alkoxy-C-C2-alkyl, N-oxides thereof, wherein R' is methyl, R', R" and R" are most preferably hydrogen, methyl or ethyl; hydrogen and wherein A is selected from the radicals R" is further most preferably represented by a radical as A3.ag 1 to A3...ag 81. defined in each line of table B; 30 Table 356: Compounds of the formula I'...A and the salts and R. R" and R" are selected independently of each other from N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen, methyl, difluoromethyl, trifluoromethyl, meth and wherein A is selected from the radicals A3.ah' 1 to oxy, difluoromethoxy and trifluoromethoxy; and wherein A3.ah'81. preferably at least one, more preferably 2 or 3, of the Table 357: Compounds of the formula I'...A and the salts and radicals R. R'' and R" are hydrogen. 35 N-oxides thereof, wherein R' is methyl, R', R" and R" are Examples of compounds of this particular preferred hydrogen and wherein A is selected from the radicals embodiment are the compounds given in the following tables A3.ah' 1 to A3..ah'81. 342 to 369. Table 358: Compounds of the formula I'...A and the salts and Table 342: Compounds of the formula I'...A and the salts and 40 N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.ai' 1 to and wherein A is selected from the radicals A3.aa' 1 to A3.ai'81. A3..aa' 81. Table 359: Compounds of the formula I'...A and the salts and Table 343: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are 45 hydrogen and wherein A is selected from the radicals A3.ai' hydrogen and wherein A is selected from the radicals 1 to A3.ai'81. A3..aa' 1 to A3..aa' 81. Table 360: Compounds of the formula I'...A and the salts and Table 344: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen and wherein A is selected from the radicals A3.ak 1 to and wherein A is selected from the radicals A3.ab' 1 to 50 A3.ak'81. A3...ab' 81. Table 361: Compounds of the formula I'...A and the salts and Table 345: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.ak 1 to A3..ak'81. A3.ab' 1 to A3..ab' 81. 55 Table 346: Compounds of the formula I'...A and the salts and Table 362: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3.ac' 1 to and wherein A is selected from the radicals A3...al 1 to A3.ac'81. A3a181. Table 347: Compounds of the formula I'...A and the salts and 60 Table 363: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and RY are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...al' A3.ac' 1 to A3.ac'81. 1 to A3..al' 81. Table 348: Compounds of the formula I'...A and the salts and Table 364 Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.ad 1 to and wherein A is selected from the radicals A3.am' 1 to A3.ad 81. A3.am'81. US 9,029,639 B2 79 80 Table 365: Compounds of the formula LA and the salts and Table 375: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.am' 1 to A3.am'81. A3.ac" 1 to A3.ac" 81. Table 366: Compounds of the formula I'...A and the salts and 5 Table 376: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein I".A is selected from the radicals A3...an' 1 to and wherein A is selected from the radicals A3.ad" 1 to A3..an'81. A3.ad" 81. Table 367: Compounds of the formula I'...A and the salts and Table 377: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 N-oxides thereof, wherein R' is methyl, IR, R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3..an'1 to A3...an'81. A3.ad" 1 to A3...ad" 81. Table 368: Compounds of the formula I'...A and the salts and Table 378: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen 15 N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3.ao' 1 to and wherein A is selected from the radicals A3.ae" 1 to A3..ao'81. A3.ae" 81. Table 369: Compounds of the formula I'...A and the salts and Table 379: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3..ao' 1 to A3..ao'81. A3.ae" 1 to A3..ae" 81. Further examples of compounds of this particularly pre Table 380: Compounds of the formula I'...A and the salts and ferred embodiment are the compounds of tables 342A to N-oxides thereof, wherein R', R, R" and R" are hydrogen 369A wherein R. R' and R" are hydrogen and wherein A is as and wherein A is selected from the radicals A3...af" 1 to defined in tables 342 to 369 and wherein R' is a radical 25 A3.af" 81. represented by each individual line (85 to 160) of table B. Table 381: Compounds of the formula I'...A and the salts and Another particular preferred embodiment relates to com N-oxides thereof, wherein R' is methyl, R', R" and R" are pounds of formula I.A and to the salts and N-oxides thereof, hydrogen and wherein A is selected from the radicals wherein A3.af" 1 to A3..af" 81. A is a radical A3, as defined herein, in particular a radical A3, 30 Table 382: Compounds of the formula I'...A and the salts and wherein R, R have the preferred meanings, more par N-oxides thereof, wherein R', R, R" and R" are hydrogen ticularly an imidazole radical of the formulae A3.aa" to and wherein A is selected from the radicals A3...ag" 1 to A3.fo, e.g. a radical selected from the thiazole radicals A3.ag" 81. A3.aa" 1-A3.aa" 81 to A3..fo1-A3.fo81; Table 383: Compounds of the formula I'...A and the salts and R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C-alkyl, 35 N-oxides thereof, wherein R' is methyl, R', R" and R" are most preferably hydrogen, methyl or ethyl; hydrogen and wherein A is selected from the radicals R" is further most preferably represented by a radical as A3.ag" 1 to A3...ag" 81. defined in each line of table B; Table 384: Compounds of the formula I'...A and the salts and R. R" and R" are selected independently of each other from 40 N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen, methyl, difluoromethyl, trifluoromethyl, meth and wherein A is selected from the radicals A3.ah" 1 to oxy, difluoromethoxy and trifluoromethoxy; and wherein A3.ah" 81. preferably at least one, more preferably 2 or 3, of the Table 385: Compounds of the formula I'...A and the salts and radicals R. R" and R" are hydrogen. N-oxides thereof, wherein R' is methyl, R', R" and R" are Examples of compounds of this particular preferred 45 hydrogen and wherein A is selected from the radicals embodiment are the compounds given in the following tables A3.ah" 1 to A3..ah" 81. 370 to 537. Table 386: Compounds of the formula I'...A and the salts and Table 370: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen and wherein A is selected from the radicals A3.ai" 1 to and wherein A is selected from the radicals A3.aa" 1 to 50 A3.ai" 81. A3..aa" 81. Table 387: Compounds of the formula I'...A and the salts and Table 371: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.ai" 1 to A3.ai" 81. A3..aa" 1 to A3..aa" 81. 55 Table 372: Compounds of the formula I'...A and the salts and Table 388: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3.ab" 1 to and wherein A is selected from the radicals A3.ak" 1 to A3...ab'81. A3.ak" 81. Table 373: Compounds of the formula I'...A and the salts and 60 Table 389: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...ab" 1 to A3...ab" 81. A3.ak" 1 to A3..ak" 81. Table 374: Compounds of the formula I'...A and the salts and Table 390: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.ac" 1 to and wherein A is selected from the radicals A3...al" 1 to A3ac'81. A3...al" 81. US 9,029,639 B2 81 82 Table 391: Compounds of the formula I'...A and the salts and Table 407: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...al" 1 to A3...al" 81. A3...be 1 to A3...be81. Table 392: Compounds of the formula I'...A and the salts and 5 Table 408: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.am" 1 to and wherein A is selected from the radicals A3...bfl to A3.am" 81. A3...bf81. Table 393: Compounds of the formula I'...A and the salts and Table 409: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.am" 1 to A3.am" 81. A3...bf1 to A3...bf81. Table 394: Compounds of the formula I'...A and the salts and Table 410: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen 15 N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3...an" 1 to and wherein A is selected from the radicals A3...bg1 to A3..an" 81. A3...bg.81. Table 395: Compounds of the formula I'...A and the salts and Table 411: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3..an" 1 to A3...an" 81. A3...bg1 to A3...bg.81. Table 396: Compounds of the formula I'...A and the salts and Table 412: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.ao" 1 to and wherein A is selected from the radicals A3...bh1 to A3ao'81. 25 A3...bh81. Table 397: Compounds of the formula I'...A and the salts and Table 413: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3..ao" 1 to A3..ao" 81. A3...bh1 to A3...bh81. Table 398: Compounds of the formula I'...A and the salts and 30 Table 414: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3...bal to and wherein A is selected from the radicals A3...bill to A3...ba81. A3...bi81. Table 399: Compounds of the formula I'...A and the salts and Table 415: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 35 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...ba1 to A3...ba81. A3...bi1 to A3...bi81. Table 400: Compounds of the formula I'...A and the salts and Table 416: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 40 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3...bbl to and wherein A is selected from the radicals A3...bk1 to A3...bb81. A3...bk81. Table 401: Compounds of the formula I'...A and the salts and Table 417: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals 45 hydrogen and wherein A is selected from the radicals A3...bb1 to A3...bb81. A3...bk1 to A3...bk81. Table 402: Compounds of the formula I'...A and the salts and Table 418: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3...bc1 to and wherein A is selected from the radicals A3...bl1 to A3...bc81. 50 A3b181. Table 403: Compounds of the formula I'...A and the salts and Table 419: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...bc1 to A3...bc81. A3b11 to A3b181. Table 404: Compounds of the formula I'...A and the salts and 55 Table 420: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3...bd1 to and wherein A is selected from the radicals A3...bm1 to A3...bd81. A3...bm81. Table 405: Compounds of the formula I'...A and the salts and 60 Table 421: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...bd1 to A3...bd81. A3...bm1 to A3...bm81. Table 406: Compounds of the formula I'...A and the salts and Table 422: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3...bel to and wherein A is selected from the radicals A3...bn1 to A3...be81. A3...bn81. US 9,029,639 B2 83 84 Table 423: Compounds of the formula I'...A and the salts and Table 440: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R'' and R" are hydrogen and hydrogen and wherein A is selected from the radicals wherein A is selected from the radicals A3..ch1 to A3...ch81. A3...bn1 to A3...bn81. Table 441: Compounds of the formula I'...A and the salts and Table 424: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3...bol to A3.ch1 to A3...ch81. A3...bo81. Table 442: Compounds of the formula I'...A and the salts and Table 425: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are, 10 and wherein A is selected from the radicals A3.cil to hydrogen and wherein A is selected from the radicals A3.c181. A3...bol to A3...bo81. Table 443: Compounds of the formula I'...A and the salts and Table 426: Compounds of the formula I.A and, the salts and N-oxides thereof, wherein R is methyl, R', R" and R" are N-oxides thereof, wherein R', R', R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3...cal to 15 A3.cil to A3.c181. A3.ca81. Table 444: Compounds of the formula I'...A and the salts and Table 427: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3.ck1 to hydrogen and wherein A is selected from the radicals A3.ck81. A3..cal to A3.ca81. Table 445: Compounds of the formula I'...A and the salts and Table 428: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.cb1 to A3.ck1 to A3.ck81. A3.cb81. Table 446: Compounds of the formula I'...A and the salts and Table 429: Compounds of the formula I'...A and the salts and 25 N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3.cl1 to hydrogen and wherein A is selected from the radicals A3.c181. A3.cb1 to A3.cb81. Table 447: Compounds of the formula I'...A and the salts and Table 430: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R" and R" are, hydrogen 30 hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.cc1 to A3.c11 to A3.c181. A3.cc81. Table 448: Compounds of the formula I'...A and the salts and Table 431: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3.cm1 to hydrogen and wherein A is selected from the radicals 35 A3.cm81. A3.cc1 to A3.cc81. Table 449: Compounds of the formula and the salts and N-ox Table 432: Compounds of the formula I'...A and the salts and ides thereof, wherein R' is methyl, R', R" and R" are hydro N-oxides thereof, wherein R', R, R" and R" are, hydrogen gen and wherein A is selected from the radicals A3.cm1 to and wherein A is selected from the radicals A3.cd1 to A3.cm81. A3.cd81. 40 Table 450: Compounds of the formula I'...A and the salts and Table 433: Compounds of the formula I.A and, the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3.cn1 to hydrogen and wherein A is selected from the radicals A3.cn81. A3.cd1 to A3.cd81. Table 451: Compounds of the formula I'...A and the salts and Table 434: Compounds of the formula I'...A and the salts and 45 N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.cel to A3.cn1 to A3.cn81. A3.ce81. Table 452: Compounds of the formula I'...A and the salts and Table 435: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are 50 and wherein A is selected from the radicals A3.col to hydrogen and wherein A is selected from the radicals A3.co81. A3.ce 1 to A3...ce81. Table 453: Compounds of the formula I'...A and the salts and Table 436: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R', R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.cf1 to 55 A3.co.1 to A3.co81. A3.cf.81. Table 454: Compounds of the formula I'...A and the salts and Table 437: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3...dal to hydrogen and wherein A is selected from the radicals A3...da81. A3.cf1 to A3.cf31. 60 Table 455: Compounds of the formula I'...A and the salts and Table 438: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R" and R" are hydrogen and hydrogen and wherein A is selected from the radicals wherein A is selected from the radicals A3.cg1 to A3.cg81. A3...da1 to A3...da81. Table 439: Compounds of the formula I'...A and the salts and Table 456: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3...db1 to A3.cg1 to A3.cg81. A3...db81. US 9,029,639 B2 85 86 Table 457: Compounds of the formula I'...A and the salts and Table 474: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R. R. R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3.dll to A3...db1 to A3...db81. A3.dl81. Table 458: Compounds of the formula I.A. and the salts and 5 Table 475: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3...dc1 to hydrogen and wherein A is selected from the radicals A3...dc81. A3.dll to A3.dl31. Table 459: Compounds of the formula I'...A and the salts and Table 476: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3...dm1 to A3...dc1 to A3...dc81. Table 460: Compounds of the formula I'...A and the salts and A3...dm81. N-oxides thereof, wherein R', R', R" and R" are hydrogen Table 477: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3...dd 1 to 15 N-oxides thereof, wherein R' is methyl, R', R" and R" are A3...dd81. hydrogen and wherein A is selected from the radicals Table 461: Compounds of the formula I'...A and the salts and A3...dm1 to A3...dm81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 478: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R', R, R" and R" are hydrogen A3...dd 1 to A3...dd81. and wherein A is selected from the radicals A3...dn1 to Table 462: Compounds of the formula I'...A and the salts and A3...dn81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 479: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3...del to N-oxides thereof, wherein R' is methyl, R', R" and R" are A3...de81. hydrogen and wherein A is selected from the radicals Table 463: Compounds of the formula I'...A and the salts and 25 A3...dn1 to A3...dn81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 480: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R. R. R" and R" are hydrogen A3...de 1 to A3...de81. and wherein A is selected from the radicals A3...do1 to Table 464: Compounds of the formula I'...A and the salts and A3...do81. N-oxides thereof, wherein R', R', R" and R" are hydrogen 30 and wherein A is selected from the radicals A3...df1 to Table 481: Compounds of the formula I'...A and the salts and A3...df81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 465: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A3...do1 to A3...do81. hydrogen and wherein A is selected from the radicals 35 Table 482: Compounds of the formula I'...A and the salts and A3...df1 to A3...df81. N-oxides thereof, wherein R. R. R" and R" are hydrogen Table 466: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3...eal to N-oxides thereof, wherein R', R, R" and R" are hydrogen A3...ea81. and wherein A is selected from the radicals A3...dg1 to Table 483: Compounds of the formula I'...A and the salts and A3...dg81. 40 N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 467: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A3...eal to A3...ea81. hydrogen and wherein A is selected from the radicals Table 484: Compounds of the formula I'...A and the salts and A3...dg1 to A3 dg81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 468: Compounds of the formula I'...A and the salts and 45 and wherein A is selected from the radicals A3...eb1 to N-oxides thereof, wherein R', R, R" and R" are hydrogen A3.eb81. and wherein A is selected from the radicals A3...dh1 to Table 485: Compounds of the formula I'...A and the salts and A3...dh81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 469: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are 50 A3.eb.1 to A3...eb81. hydrogen and wherein A is selected from the radicals Table 486: Compounds of the formula I'...A and the salts and A3...dh1 to A3...dh81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 470: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3...ec1 to N-oxides thereof, wherein R', R', R" and R" are hydrogen A3...ec81. and wherein A is selected from the radicals A3...di 1 to 55 A3...di81. Table 487: Compounds of the formula I'...A and the salts and Table 471: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...ec1 to A3...ec81. A3...di 1 to A3...di81. 60 Table 488: Compounds of the formula I'...A and the salts and Table 472: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R" and R" are hydrogen and and wherein A is selected from the radicals A3...ed1 to wherein A is selected from the radicals A3...dk1 to A3...dk81. A3.ed81. Table 473: Compounds of the formula I'...A and the salts and Table 489: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 65 N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...dk1 to A3...dk81. A3.ed1 to A3...ed81. US 9,029,639 B2 87 88 Table 490: Compounds of the formula I'...A and the salts and Table 507: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R', R" and R" are hydrogen N-oxides thereof, wherein R' is methyl, R', R" and R" are and wherein A is selected from the radicals A3...eel to hydrogen and wherein A is selected from the radicals A3...ee81. A3...en1 to A3...en81. Table 491: Compounds of the formula I.A. and the salts and 5 Table 508: Compounds of the formula I.A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R', R, R" and R" are hydrogen hydrogen and wherein A is selected from the radicals and wherein A is selected from the radicals A3...eo1 to A3...eel to A3...ee81. A3...eo81. Table 492: Compounds of the formula I'...A and the salts and Table 509: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 10 and wherein A is selected from the radicals A3...ef1 to N-oxides thereof, wherein R' is methyl, R', R" and R" are A3.ef31. hydrogen and wherein A is selected from the radicals Table 493: Compounds of the formula I'...A and the salts and A3...eo1 to A3...eo81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 510: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals 15 N-oxides thereof, wherein R. R. R" and R" are hydrogen A3.ef1 to A3...ef31. and wherein A is selected from the radicals A3.fa1 to Table 494: Compounds of the formula I'...A and the salts and A3.fa81. N-oxides thereof, wherein R, R" and R" are hydrogen and Table 511: Compounds of the formula I'...A and the salts and wherein A is selected from the radicals A3...egl to A3...eg81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 495: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A3.fa1 to A3.fa81. hydrogen and wherein A is selected from the radicals Table 512: Compounds of the formula I'...A and the salts and A3...egl to A3...eg81. N-oxides thereof, wherein R', R, R" and R" are hydrogen Table 496: Compounds of the formula I'...A and the salts and and wherein A is selected from the radicals A3.fb1 to N-oxides thereof, wherein R', R, R" and R" are hydrogen 25 A3fb81. and wherein A is selected from the radicals A3...ehl to Table 513: Compounds of the formula I'...A and the salts and A3.eh81. N-oxides thereof, wherein R' is methyl, R', R" and R" are Table 497: Compounds of the formula I'...A and the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein R' is methyl, R', R" and R" are A3fb1 to A3..fb81. hydrogen and wherein A is selected from the radicals 30 A3.eh1 to A3...eh81. Table 514: Compounds of the formula I'...A and the salts and Table 498: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen and wherein A is selected from the radicals A3..fc1 to and wherein A is selected from the radicals A3...ei1 to A3.fc81. A3.ei81. 35 Table 515: Compounds of the formula I'...A and the salts and Table 499: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.fc1 to A3..fc81. A3.ei1 to A3...ei81. Table 516: Compounds of the formula I'...A and the salts and Table 500: Compounds of the formula I'...A and the salts and 40 N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3.fd1 to and wherein A is selected from the radicals A3...ek1 to A3.fd81. A3.ek81. Table 517: Compounds of the formula I'...A and the salts and Table 501: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R and R are N-oxides thereof, wherein R' is methyl, R', R" and R" are 45 hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.fd1 to A3..fd81. A3.ek1 to A3...ek81. Table 518: Compounds of the formula I'...A and the salts and Table 502: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R. R. R" and R" are hydrogen N-oxides thereof, wherein R', R', R" and R" are hydrogen and wherein A is selected from the radicals A3...fel to and wherein A is selected from the radicals A3...ell to 50 A3.fe81. A3...el81. Table 519: Compounds of the formula I'...A and the salts and Table 503: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3.fel to A3..fe81. A3...el 1 to A3...el81. 55 Table 504: Compounds of the formula I'...A and the salts and Table 520: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen N-oxides thereof, wherein R. R. R" and R" are hydrogen and wherein A is selected from the radicals A3...em1 to and wherein A is selected from the radicals A3.ffl to A3...em81. A3.f31. Table 505: Compounds of the formula I'...A and the salts and 60 Table 521: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A is selected from the radicals hydrogen and wherein A is selected from the radicals A3...em1 to A3...em81. A3ff1 to A3..f31. Table 506: Compounds of the formula I'...A and the salts and Table 522: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R', R, R" and R" are hydrogen 65 N-oxides thereof, wherein R', R, R" and R" are hydrogen and wherein A is selected from the radicals A3...en1 to and wherein A is selected from the radicals A3.fg1 to A3...en81. A3.fg81. US 9,029,639 B2 89 90 Table 523: Compounds of the formula I'...A and the salts and Another particularly preferred embodiment of the inven N-oxides thereof, wherein R' is methyl, R', R" and R" are tion relates to compounds of formula I.B and to the salts and hydrogen and wherein A is selected from the radicals N-oxides thereof, wherein A3.fg1 to A3..fg81. Table 524: Compounds of the formula I'...A and the salts and 5 (I.B) N-oxides thereof, wherein R', R, R" and R" are hydrogen N R and wherein A is selected from the radicals A3.fh1 to O N21 A3..fh81. Table 525: Compounds of the formula I'...A and the salts and N-oxides thereof, wherein R' is methyl, R', R" and R" are 10 -- N Rt. hydrogen and wherein A is selected from the radicals k R A3.fh1 to A3..fh81. Table 526: Compounds of the formula I'...A and the salts and A is a radical A1, as defined herein, in particular a radical A1, N-oxides thereof, wherein R', R', R" and R" are hydrogen 15 wherein R'' and R have the preferred meanings, in par and wherein A is selected from the radicals A3...fil to ticular an oxazole radical of the formulae A1.a to A1.Z., e.g. A3..f81. a radical selected from the oxazole radicals A1.al to Table 527: Compounds of the formula I'...A and the salts and A1.Z81; N-oxides thereof, wherein R' is methyl, R', R" and R" are R" is hydrogen, C1-C4-alkyl or C-C-alkoxy-C-C2-alkyl, hydrogen and wherein A is selected from the radicals most preferably hydrogen, methyl or ethyl; A3.fi1 to A3.fi81. R" is further most preferably represented by a radical as Table 528: Compounds of the formula I'...A and the salts and defined in each line of table B; N-oxides thereof, wherein R', R, R" and R" are hydrogen R. R' and R are independently of each other selected from and wherein A is selected from the radicals A3.fk1 to hydrogen, methyl, difluoromethyl, trifluoromethyl, meth A3.fk81. 25 oxy, difluoromethoxy and trifluoromethoxy; and wherein Table 529: Compounds of the formula I'...A and the salts and preferably at least one, more preferably 2 or 3, of the N-oxides thereof, wherein R' is methyl, R', R" and R" are radicals R. R', and Rare hydrogen. hydrogen and wherein A is selected from the radicals Examples of compounds of this particularly preferred A3.fk1 to A3..fk81. embodiment are the compounds given in the following tables 30 538 to 588 and tables 538A to 588A. Table 530: Compounds of the formula I'...A and the salts and Tables 538 to 588: Compounds of the formula I.B and the N-oxides thereof, wherein R', R, R" and R" are hydrogen salts and N-oxides thereof, wherein R, R" and Rare hydro and wherein A is selected from the radicals A3...fl1 to gen and wherein A and R' are as defined in tables 1 to 50. A3..f81. Tables 538A to 588A: Compounds of the formula I.B and Table 531: Compounds of the formula I'...A and the salts and 35 the salts and N-oxides thereof, wherein R. R' and R are N-oxides thereof, wherein R' is methyl, R', R" and R" are hydrogen and wherein A and R' are as defined in tables 1A to hydrogen and wherein A is selected from the radicals 5OA. A3..f1 to A3..f81. Another particular preferred embodiment relates to com Table 532: Compounds of the formula I'...A and the salts and pounds of the formula I.B and to the salts and N-oxides N-oxides thereof, wherein R', R, R" and R" are hydrogen 40 thereof, wherein and wherein A is selected from the radicals A3..fm 1 to A is a radical A1, as defined herein, in particular a radical A1, A3.fm81. wherein R'' and R have the preferred meanings, in par Table 533: Compounds of the formula I'...A and the salts and ticularathiazole radical of the formulae A1.a' to A1.z', e.g. N-oxides thereof, wherein R' is methyl, R', R" and R" are a radical selected from the thiazole radicals Ala' 1 to A1.Z.' hydrogen and wherein A is selected from the radicals 45 81: A3.fm 1 to A3.fm81. R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, Table 534: Compounds of the formula I'...A and the salts and most preferably hydrogen, methyl or ethyl; N-oxides thereof, wherein R', R, R" and R" are hydrogen R" is further most preferably represented by a radical as and wherein A is selected from the radicals A3.fn1 to defined in each line of table B; A3.fin81. 50 R. R" and R' are independently of each other selected from Table 535: Compounds of the formula I'...A and the salts and hydrogen, methyl, difluoromethyl, trifluoromethyl, meth N-oxides thereof, wherein R' is methyl, R', R" and R" are oxy, difluoromethoxy and trifluoromethoxy; and wherein hydrogen and wherein A is selected from the radicals preferably at least one, more preferably 2 or 3, of the A3.fn1 to A3.fin81. radicals R. R', and Rare hydrogen. Table 536: Compounds of the formula I'...A and the salts and 55 Examples of compounds of this particularly preferred N-oxides thereof, wherein R', R', R" and R" are hydrogen embodiment are the compounds given in the following tables and wherein A is selected from the radicals A3..fo1 to 589 to 639 and tables 589A to 639A. A3.fo81. Tables 589 to 639: Compounds of the formula I.B and the Table 537: Compounds of the formula and the salts and N-ox salts and N-oxides thereof, wherein R. R'' and Rare hydro ides thereof, wherein R' is methyl, R', R" and R" are hydro 60 gen and wherein A and R' are as defined in tables 51 to 100. gen and wherein A is selected from the radicals A3..fo1 to Tables 589A to 639A: Compounds, of the formula I.B and A3.fo81. the salts and N-oxides thereof, wherein R, R" and R' are Further examples of compounds of this particularly pre hydrogen and wherein A and Ware as defined in tables 51A to ferred embodiment are the cornpounds of tables 370A to 1OOA. 537A wherein R, RandR' are hydrogen and wherein A is as 65 Another particular preferred embodiment relates to com defined in tables 370 to 357 and wherein R' is a radical pounds of the formula I.B and to the salts and N-oxides represented by each individual line (85 to 160) of table B. thereof, wherein US 9,029,639 B2 91 92 A is a radical A2, as defined herein, in particular a radical A2, preferably at least one, more preferably 2 or 3, of the wherein R* and R- have the preferred meanings, in par radicals R', RandR are hydrogen. ticular an oxazole radical of the formulae A2.aa to A2.do, Examples of compounds of this particular preferred e.g. a radical selected from the oxazole radicals A2.aal embodiment are the compounds given in the following tables A2.aa81 to A2.ha1-A2.ha81; 717 to 742 and tables 717A to 742A. R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, Tables 717 to 742: Compounds of the formula I.B and the most preferably hydrogen, methyl or ethyl; salts and N-oxides thereof, wherein R, R" and Rare hydro R" is further most preferably represented by a radical as gen and wherein A and R' are as defined in tables 177 to 202. defined in each line of table B; Tables 717A to 742A: Compounds of the formula I.B and R. R" and R' are selected independently of each other from 10 the salts and N-oxides thereof, wherein R, R" and R' are hydrogen, methyl, difluoromethyl, trifluoromethyl, meth hydrogen and wherein A and R' are as defined in tables 177A oxy, difluoromethoxy and trifluoromethoxy; and wherein to 202A. preferably at least one, more preferably two or three of the Another particular preferred embodiment relates to com radicals R. R'' and Rare hydrogen. 15 pounds of formula I.B and to the salts and N-oxides thereof, Examples of compounds of this particular preferred wherein embodiment are the compounds given in the following tables A is a radical A3, as defined herein, in particular a radical A3, 640 to 690 and thales 640A to 690A. wherein R* and R have the preferred meanings, more Tables 640 to 690: Compounds of the formula I.B and the particularly a thiazole radical of the formulae A3.aa' to salts and N-oxides thereof, wherein R, R" and Rare hydro A3...do', e.g. a radical selected from the thiazole radicals gen and wherein A and R' are as defined in tables 101 to 150. A3.aa' 1-A3.aa'81 to A3...do' 1-A3...do' 81; Tables 640A to 690A: Compounds of the formula I.B and R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, the salts and N-oxides thereof, wherein R. R' and R are most preferably hydrogen, methyl or ethyl; hydrogen and wherein A and R' are as defined in 101A to R" is further most preferably represented by a radical as 15OA. 25 defined in each line of table B; Another particular preferred embodiment relates to com R", R and R are selected independently of each other from pounds of the formula I.B and to the salts and N-oxides hydrogen, methyl, difluoromethyl, trifluoromethyl, meth thereof, wherein oxy, difluoromethoxy and trifluoromethoxy; and wherein A is a radical A2, as defined herein, in particular a radical A2, preferably at least one, more preferably 2 or 3, of the wherein R* and R- have the preferred meanings, in par 30 radicals R', RandR are hydrogen. ticular a thiazole radical of the formulae A2.aa' to A2.do', Examples of compounds of this particular preferred e.g. a radical selected from the thiazole radicals A2.aa' 1-A2.aa'81 to A2.ha' 1-A2.ha'81; embodiment are the compounds given in the following tables R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C2-alkyl, 743 to 760 and tables 743 A to 760A. most preferably hydrogen, methyl or ethyl; 35 Tables 743 to 760: Compounds of the formula I.B and the R" is further most preferably represented by a radical as salts and N-oxides thereof, wherein R. R'' and Rare hydro defined in each line of table B; gen and wherein A and R' are as defined in tables 342 to 369. R. R" and R' are selected independently of each other from Tables 743 A to 760A: Compounds of the formula I.B and hydrogen, methyl, difluoromethyl, trifluoromethyl, meth the salts and N-oxides thereof, wherein R. R' and R are oxy, difluoromethoxy and trifluoromethoxy; and wherein 40 hydrogen and wherein A and R' are as defined in tables 342A preferably at least one, more preferably two or three of the to 369A. radicals R. R'' and Rare hydrogen. The compounds of the formula I, wherein X is O or S Examples of compounds of this particular preferred (compounds I), can be prepared e.g. according to the method embodiment are the compounds given in the following tables depicted in scheme 1 by reacting an activated oxazole, thia 691 to 716 and tables 691A to 716A. 45 Zole or imidazole carboxylic acid derivative II with a 3- or Tables 691 to 716: Compounds of the formula I.B and the 4-aminopyridazine, compound III (see e.g. Houben-Weyl: salts and N-oxides thereof, wherein R. R'' and Rare hydro “Methoden der organ. Chemie' Methods of Organic Chem gen and wherein A and R' are as defined in tables 151 to 176. istry, Georg-Thieme-Verlag, Stuttgart, New York 1985, Vol Tables 691A to 716A: Compounds of the formula I.B and ume E5, pp. 941-1045). Activated oxazole, thiazole or imi the salts and N-oxides thereof, wherein R, R" and R' are 50 dazole carboxylic acid derivatives II are, for example, acyl hydrogen and wherein A and R' areas defined in tables 151A halides, activated esters, anhydrides, acyl azides, wherein X to 176A. is for examplechlorine, fluorine, bromine, para-nitrophenoxy, Another particular preferred embodiment relates to com pentafluorophenoxy, N-hydroxysuccinimides, hydroxyben pounds of formula I.B and to the salts and N-oxides thereof, zotriazol-1-yl. In scheme 1, the radicals A. R', R, R", V and wherein 55 W have the meanings mentioned above and in particular the A is a radical A3, as defined herein, in particular a radical A3, meanings mentioned as being preferred. wherein R* and R have the preferred meanings, more particularly an oxazole radical of the formulae A3.aa to A3...do, e.g. a radical selected from the oxazole, thiazole, or Scheme 1: imidazole radicals A3.aal-A3.aa81 to A3...do1-A3...do81; 60 N R" is hydrogen, C-C-alkyl or C-C-alkoxy-C-C-alkyl, w1 S v most preferably hydrogen, methyl or ethyl; O R" is further most preferably represented by a radical as ul + H NN afn -e- defined in each line of table B; A X R", RandR are selected independently of each other from 65 RI R hydrogen, methyl, difluoromethyl, trifluoromethyl, meth oxy, difluoromethoxy and trifluoromethoxy; and wherein US 9,029,639 B2 93 94 -continued Compounds of formula I, wherein X" is O (compounds I") N and R' is different from hydrogen can also be prepared by O w? alkylating the amides I (in which R" is hydrogen and which can be obtained according to scheme 1 or 2) using Suitable - S. alkylating agents in the presence of bases. R1 R (I) Scheme 3: N The compounds of the formula I, wherein X" is O or S 10 O w1YS n v alkylating (compounds I"), can also be prepared, for example, by react us agent ing the oXZole or thiazole carboxylic acid IV and the 3- or A afn 4-aminopyridazine compound III, in the presence of a cou H R pling agent according to Scheme 2. In scheme 2, the radicals 15 N A. R. R', V and W have the meanings given above and in O Y S v particular the meanings given as being preferred. us 21S. Scheme 2: R1 R N 1S O W n v coupling The oxazole, thiazole or imidazole carboxylic acids IV and H agent -- -e- their activated derivatives II as well as 3- or 4-aminopy us NN 2 Rt. ridazine-compounds III please check if following names are A OH 25 correct are known in the art or are commercially available or RI R can be prepared by methods known from the literature. Compounds of the formula I, wherein X" is different from N oxygen, can be prepared from the compounds of formula I' by O Y S v standard methods: 30 Compounds of the formula I, wherein X" is S, can be 1s. prepared e.g. by reacting a compound of formula I" with R1 R 2.4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4- (I) disulfide orphorphorus pentasulfide according to the method 35 described by M. Jesberger et al. in Synthesis 2003, 1929. Compounds of the formula I, wherein X" is NR", can be Suitable coupling agents are, for example: prepared e.g. by reacting a compound I' with by reacting a coupling agents based on carbodiimides, for example compound I' with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiad N,N'-dicyclohexylcarbodiimide J. C. Sheehan, G. P. iphosphetane-2,4-disulfide to obtain the corresponding thioa Hess, J. Am. Chem. Soc. 1955, 77, 1067), N-(3-dim 40 mide (compound I, wherein X is S) which is then reacted ethylaminopropyl)-N'-ethylcarbodiimide: coupling with an appropriate amine according to the method described agents which form mixed anhydrides with carbonic by V. Glushkov et al. in Pharmaceutical Chemistry Journal esters, for example 2-ethoxy-1-ethoxycarbonyl-1,2-di 2005, 39(10), 533-536. hydroquinoline B. Belleau, G. Malek, J. Amer. Chem. Compounds of formula II, wherein X=SR", can be pre Soc. 1968, 90, 1651), 2-isobutyloxy-1-isobutyloxycar 45 pared by alkylation of the corresponding thioamide (com bonyl-1,2-dihydroquinoline Y. Kiso, H. Yajima, J. pound I, wherein X" is S) by reaction with an alkylating agent Chem. Soc., Chem. Commun. 1972, 942: according to the method described by V. Glushkov et al. in coupling agents based on phosphonium salts, for example Pharmaceutical Chemistry Journal 2005, 39(10) 533-536. In (benzotriazol-1-yloxy)tris(dimethylamino)phospho a similar manner, compounds I, wherein X is OR or nium hexafluorophosphate B. Castro, J. R. Domoy, G. 50 NR'R' can be obtained. Compounds of the formula II, Evin, C. Selve, Tetrahedron Lett. 1975, 14, 1219), (ben wherein X=SOR or SOR" can be obtained by oxidation Zotriazol-1-yloxy)tripyrrolidinophosphonium of compounds II with X—SR". hexafluorophosphate J. Coste et al., Tetrahedron Lett. N-oxides of the compounds of formulae I and II, can be 1990, 31, 205: prepared by oxidation of compounds I, according to standard 55 methods of preparing heteroaromatic N-oxides, e.g. by the coupling agents based on uronium salts or having a guani method described by C. Botteghi et al. in Journal of Organo dinium N-oxide structure, for example N.N.N',N'-tet metallic Chemistry 1989, 370, 17-31. ramethyl-O-(1H-benzotriazol-1-yl)uronium hexafluo As a rule, the compounds of formulae I or II can be pre rophosphate R. Knorr, A. Trzeciak, W. Bannwarth, D. pared by the methods described above. If individual com Gillessen, Tetrahedron Lett. 1989, 30, 1927, N.N.N',N'- 60 pounds can not be prepared via the above-described routes, tetramethyl-O-(benzotriazol-1-yl)uronium tetrafluo they can be prepared by derivatization of other compounds I roborate, (benzotriazol-1-yloxy)dipiperidinocarbenium or II or by customary modifications of the synthesis routes hexafluorophosphate S. Chen, J. Xu, Tetrahedron Lett. described. For example, in individual cases, certain com 1992, 33,647: pounds I or II can advantageously be prepared from other coupling agents which form acid chlorides, for example 65 compounds I or II by ester hydrolysis, amidation, esterifica bis-(2-oxooxazolidinyl)phosphinic chloride J. Diago tion, ether cleavage, olefination, reduction, oxidetion and the Mesequer, Synthesis 1980, 547. like. US 9,029,639 B2 95 96 The reaction mixtures are worked up in the customary Capua reticulana, Chematobia brumata, Choristoneura manner, for example by mixing with water, separating the filmiferana, Choristoneura Occidentalis, Cirphis unipuncta, phases, and, if appropriate, purifying the crude products by Cydia pomonella, Dendrolimus pini, Diaphania initidalis, chromatography, for example on alumina or on silica gel. Diatraea grandiosella, Earias insulana, Elasmopalpus Some of the intermediates and end products may be obtained lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia in the form of colorless or pale brown viscous oils which are subterranea, Galleria mellonella, Grapholitha finebrana, freed or purified from volatile components under reduced Grapholitha molesta, Heliothis armigera, Heliothis vire pressure and at moderately elevated temperature. If the inter scens, Heliothis zea, Hellula undalis, Hibernia defoliaria, mediates and end products are obtained as solids, they may be Hyphantria cunea, Hyponomeuta malinellus, Keiferia lyco purified by recrystallization or trituration. 10 persicella, Lambdina fiscellaria, Laphygma exigua, Leucop Due to their excellent activity, the compounds of the gen tera coffeella, Leucoptera scitella, Lithocolletis blancardella, eral formulae I or II may be used for controlling invertebrate Lobesia botrana, Loxostege Sticticalis, Lymantria dispar, pests. Lymantria monacha, Lyonetia clerkella, Malacosoma neus Accordingly, the present invention also provides a method tria, Mamestra brassicae, Orgvia pseudotsugata, Ostrinia for controlling invertebrate pests which method comprises 15 nubilalis, Panolis flammea, Pectinophora gossypiella, treating the pests, their food supply, their habitat or their Peridroma saucia, Phalera bucephala, Phthorinaea Oper breeding ground oracultivated plant, plant propagation mate culella, Phyllocnistis citrella, Pieris brassicae, Plathypena rials (such as seed), Soil, area, material or environment in scabra, Plutella xylostella, Pseudoplusia includens, Rhya which the pests are growing or may grow, or the materials, cionia frustrana, Scrobipalpula absoluta, Sitotroga cere cultivated plants, plant propagation materials (such as seed), alella, Sparganothis pilleriana, Spodoptera frugiperda, soils, Surfaces or spaces to be protected from pest attack or Spodoptera littoralis, Spodoptera litura, Thaumatopoea infestation with a pesticidally effective amount of a com pityocampa, Tortrix viridana, Trichoplusiani and Zeiraphera pound of formulae (I) or (II) or a salt or N-oxide thereof or a Canadensis, composition as defined above. beetles (Coleoptera), for example Agrilus sinuatus, Agri Preferably, the method of the invention serves for protect 25 otes lineatus, Agriotes obscurus, Amphimalus solstitialis, ing plant propagation material (such as seed) and the plant Anisandrus dispar, Anthonomus grandis, Anthonomus which grows therefrom from invertebrate pest attack or infes pomorum, Atomaria linearis, Blastophagus piniperda, Blito tation and comprises treating the plant propagation material phaga undata, Bruchus rufimanus, Bruchus pisorum, Bru (such as seed) with a pesticidally effective amount of a com chus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma pound of formulae (I) or (II) or an agriculturally acceptable 30 trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus salt or N-oxide thereofas defined above or with a pesticidally mapi, Chaetocnema tibialis, Conoderus vespertinus, Crioc effective amount of an agricultural composition as defined eris asparagi, Diabrotica longicornis, Diabrotica 12 punc above and below. The method of the invention is not limited to tata, Diabrotica virgifera, Epillachna varivestis, Epitrix hir the protection of the “substrate' (plant, plant propagation tipennis, Eutinobothrus brasiliensis, Hylobius abietis, materials, Soil material etc.) which has been treated according 35 Hypera brunneipennis, Hypera postica, Ips typographus, to the invention, but also has a preventive effect, thus, for Lema bilineata, Lema melanopus, Leptinotarsa decemlin example, according protection to a plant which grows from a eata, Limonius Californicus, Lissorhoptrus Oryzophilus, Mel treated plant propagation materials (such as seed), the plant anotus communis, Melligethes aeneus, Melolontha hippoc itself not having been treated. astani, Melolontha melolontha, Oulema Oryzae, In the sense of the present invention, “invertebrate pests’ 40 Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon are preferably selected from arthropods and nematodes, more cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., preferably from harmful insects, arachnids and nematodes, Phyllopertha horticola, Phyllotreta memorum, Phyllotreta and even more preferably from insects, acarids and nema striolata, Popillia japonica, Sitona lineatus and Sitophilus todes. granaria, The invention further provides an agricultural composition 45 dipterans (Diptera), for example Aedes aegypti, Aedes for combating Such invertebrate pests, which comprises Such vexans, Anastrephaludens, Anopheles maculipennis, Cerati an amount of at least one compound of the general formulae tis capitata, Chrysomya bezziana, Chrysomya hominivorax, I or II or at least one agriculturally useful salt or N-oxide Chrysomya macellaria, Contarinia sorghicola, Cordylobia thereof and at least one inert liquid and/or Solid agronomi anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus cally acceptable carrier that has a pesticidal action and, if 50 Oleae, Dasineura brassicae, Fannia canicularis, Gasterophi desired, at least one Surfactant. lus intestinalis, Glossina morsitans, Haematobia irritans, Such a composition may contain a single active compound Haplodiplosis equestris, Hyllemyia platura, Hypoderma lin of the formulae Ior II or a salt or N-oxide thereofor a mixture eata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, of several active compounds I or II or their salts according to Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, May the present invention. The composition according to the 55 etiola destructor; Musca domestica, Muscina stabulans, present invention may comprise an individual isomer or mix Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia tures of isomers as well as individual tautomers or mixtures of antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis tautomerS. cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula olera The compounds of the formulae I or II and the pestidicidal cea and Tipula paludosa, compositions comprising them are effective agents for con 60 thrips (Thysanoptera), e.g. Dichromothrips corbetti, Fran trolling arthropod pests and nematodes. Invertebrate pests Kliniella fusca, Frankliniella occidentalis, Frankliniella controlled by the compounds of formulae I or II include for tritici, Scirtothrips citri, Thrips Oryzae, Thrips palmi and example Thrips tabaci, insects from the order of the lepidopterans (Lepidoptera), hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta for example Agrotis ypsilon, Agrotis segetum, Alabama 65 cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Hoplocampa testudinea, Monomorium pharaonis, Solenop Autographa gamma, Bupalus piniarius, Cacoecia murinama, sis geminata and Solenopsis invicta, US 9,029,639 B2 97 98 heteropterans (Heteroptera), e.g. Acrosternum hilare, Blis Stem and foliar nematodes, Aphelenchoides species; Sting sus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, nematodes, Belonolaimus longicaudatus and other Belono Dysdercus intermedius, Eurygaster integriceps, Euschistus laimus species; Pine nematodes, Bursaphelenchus xylophilus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, and other Bursaphelenchus species; Ring nematodes, Cri Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea conema species, Criconemella species, Criconenoides spe insularis and Thyanta perditor, cies, Mesocriconema species; Stem and bulb nematodes, homopterans (Homoptera), e.g. Acyrthosiphon Onobry Dity lenchus destructor, Dity lenchus dipsaci and other Dity chis, Adelges laricis, Aphidula masturti, Aphis fabae, Aphis lenchus species; Awl nematodes, Dolichodorus species; Spi forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, ral nematodes, Heliocotylenchus multicinctus and other Heli Aphis Schneideri, Aphis spiraecola, Aphis Sambuci, Acyrtho 10 cotylenchus species; Sheath and sheathoid nematodes, siphon pisum, Aulacorthum Solani, Bemisia argentifolii, Hemicycliophora species and Hemicriconenoides species; Bemisia tabaci, Brachycaudus cardui, Brachycaudus heli Hirshmanniella species; Lance nematodes, Hoploaimus spe chrysi, Brachycaudus persicae, Brachycaudus prunicola, cies; false rootknot nematodes, Nacobbus species; Needle Brevicoryne brassicae, Capitophorus horni, Cerosiphagos nematodes, Longidorus elongatus and other Longidorus spe sypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfu 15 cies; Pin nematodes, Paratylenchus species; Lesion nema sia nordmannianae, Dreyfusia piceae, Dysaphis radicola, todes, Pratylenchus neglectus, Pratylenchus penetrans, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysa Pratylenchus curvitatus, Pratylenchus goodevi and other phis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus Pratylenchus species; Burrowing nematodes, Radopholus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, similis and other Radopholus species; Reniform nematodes, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Rotylenchus robustus and other Rotylenchus species; Scutel Metopolophium dirhodium, Myzodes persicae, Myzus asca lonema species: Stubby root nematodes, Trichodorus primi lonicus, Myzus cerasi, Myzus persicae, Myzus varians, tivus and other Trichodorus species, Paratrichodorus spe Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bur cies; Stunt nematodes, Tilenchorhynchus claytoni, sarius, Perkinsiella saccharicida, Phorodon humuli, Psylla Tilenchorhynchus dubius and other Tilenchorhynchus spe mali, Psylla pini, Rhopalomyzus ascalonicus, Rhopalosi 25 cies; Citrus nematodes, Tilenchulus species; Dagger nema phum maidis, Rhopalosiphum padi, Rhopalosiphum inser todes, Xiphinema species; and other plant parasitic nematode tum, Sappaphis, mala, Sappaphis mali, Schizaphis grani species. num, Schizoneura lanuginosa, Sitobion avenae, Sogatella In a preferred embodiment of the invention the compounds fircifera Trialeurodes vaporariorum, Toxoptera aurantiand, of formulae I or II are used for controlling insects or arach and Viteus vitifolii; 30 nids, in particular insects of the orders Lepidoptera, termites (Isoptera), e.g. Calotermes flavicollis, Leucote Coleoptera, Thysanoptera and Homoptera and arachnids of rmes flavipes, Reticulitermes flavipes, Reticulitermes lucifit the order Acarina. The compounds of the formulae I or II gus and Termes natalensis, according to the present invention are particularly useful for orthopterans (Orthoptera), e.g. Acheta domestica, Blatta controlling insects of the order Thysanoptera and Homoptera. Orientalis, Blattella germanica, Forficula auricularia, Gryl 35 The compounds of formula formulae Ior II or the pesticidal lotalpa gryllotalpa, Locusta migratoria, Melanoplus bivitta compositions comprising them may be used to protect grow tus, Melanoplus femur-rubrum, Melanoplus mexicanus, Mel ing plants and crops from attack or infestation by invertebrate anoplus sanguinipes, Melanoplus spretus, Nomadacris pests, especially insects, acaridae or arachnids by contacting Septemfasciata, Periplaneta americana, Schistocerca ameri the plant/crop with a pesticidally effective amount of com cana, Schistocerca peregrina, Stauronotus maroccanus and 40 pounds of, formulae I or II. The term “crop' refers both to Tachycines asynamorus, growing and harvested crops. arachnoidea, Such as arachnids (Acarina), e.g. of the fami The compounds of formulae I or II can be converted into lies Argasidae. Ixodidae and Sarcoptidae. Such as Amblvo the customary formulations, for example solutions, emul mma americanum, Amblyomma variegatum, Argas persicus, sions, Suspensions, dusts, powders, pastes and granules. The Boophilus annulatus, Boophilus decoloratus, Boophilus 45 use form depends on the particular intended purpose; in each microplus, Dermacentor Silvarum, Hvalomma truncatum, case, it should ensure a fine and even distribution of the Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, compound according to the invention. Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhi The formulations are prepared in a known manner (see e.g. picephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes for review U.S. Pat. No. 3,060,084, EP-A 707445 (for liquid scabiei, and Eriophyidae spp. Such as Aculus Schlechtendali, 50 concentrates), Browning, "Agglomeration’, Chemical Engi Phyllocoptrata oleivOra and Eriophyes Sheldoni; Tarsonemi neering, Dec. 4, 1967, 147-48, Perry's Chemical Engineers dae spp. Such as Phytonemus pallidus and Polyphagotarson Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages emus latus; Tenuipalpidae spp. Such as Brevipalpus phoeni 8-57 and et seq.WO 91/13546, U.S. Pat. No. 4,172,714, U.S. cis; Tetranychidae spp. Such as Tetranychus cinnabarinus, Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. Tetranychus kanzawai, Tetranychus pacificus, Tetranychus 55 5,180,587, U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, telarius and Tetranychus urticae, Panonychus ulmi, Panony GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman, Weed chus citri, and Oligonychus pratensis, Control as a Science, John Wiley and Sons, Inc., New York, siphonatera, e.g. Xenopsylla cheopsis Ceratophyllus spp. 1961, Hance et al., Weed Control Handbook, 8th Ed., Black The compositions and compounds of formulae I or II are well Scientific Publications, Oxford, 1989 and Mollet, H., useful for the control of nematodes, especially plant parasitic 60 Grubemann, A., Formulation technology, Wiley VCH Verlag nematodes Such as root knot nematodes, Meloidogyne hapla, GmbH. Weinheim (Germany), 2001, 2. D. A. Knowles, Meloidogyne incognita, Meloidogyne javanica, and other Chemistry and Technology of Agrochemical Formulations, Meloidogyne species; Kluwer Academic Publishers, Dordrecht, 1998 (ISBN cyst-forming nematodes, Globodera rostochiensis and 0-7514-0443-8), for example by extending the active com other Globodera species: Heterodera avenae, Heterodera 65 pound with auxiliaries suitable for the formulation of agro glycines, Heterodera Schachtii, Heterodera trifolii, and other chemicals, such as solvents and/or carriers, if desired emul Heterodera species; Seed gall nematodes, Anguina species; sifiers, Surfactants and dispersants, preservatives, anti US 9,029,639 B2 99 100 foaming agents, anti-freezing agents, for seed treatment orange 43, pigment orange 34, pigment orange 5, pigment formulation also optionally colorants and/or binders and/or green 36, pigment green 7, pigment white 6, pigment brown gelling agents. 25, basic violet 10, basic violet 49, acid red 51, acid red 52, Examples of Suitable solvents are water, aromatic solvents acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red (for example Solves.So products, Xylene), paraffins (for 5 108. example mineral oil fractions), alcohols (for example metha An example of a gelling agent is carrageen (Satiagel(R). nol, butanol, pentanol, benzyl alcohol), ketones (for example Powders, materials for spreading and dustable products cyclohexanone, gamma-butyrolactone), pyrrolidones (N-me can be prepared by mixing or concomitantly grinding the thylpyrrolidone NMP, N-octylpyrrollidone NOPI), active Substances with a solid carrier. acetates (glycol diacetate), glycols, fatty acid dimethyla 10 Granules, for example coated granules, impregnated gran mides, fatty acids and fatty acid esters. In principle, Solvent ules and homogeneous granules, can be prepared by binding mixtures may also be used. the active compounds to Solid carriers. Suitable emulsifiers are non-ionic and anionic emulsifiers Examples of solid carriers are mineral earths such as silica (for example polyoxyethylene fatty alcohol ethers, alkylsul gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, fonates and arylsulfonates). 15 bole, loess, clay, dolomite, diatomaceous earth, calcium Sul Examples of dispersants are lignin-sulfite waste liquors fate, magnesium Sulfate, magnesium oxide, ground synthetic and methylcellulose. materials, fertilizers, such as, for example, ammonium Sul Suitable surfactants used are alkali metal, alkaline earth fate, ammonium phosphate, ammonium nitrate, ureas, and metal and ammonium salts of lignoSulfonic acid, naphthale products of vegetable origin, such as cereal meal, tree bark nesulfonic acid, phenolsulfonic acid, dibutylnaphthalene meal, wood meal and nutshell meal, cellulose powders and Sulfonic acid, alkylarylsulfonates, alkyl Sulphates, alkylsul other solid carriers. fonates, fatty alcohol Sulfates, fatty acids and Sulphated fatty In general, the formulations comprise from 0.01 to 95% by alcohol glycol ethers, furthermore condensates of sulfonated weight, preferably from 0.1 to 90% by weight, of the active naphthalene and naphthalene derivatives with formaldehyde, compound(s). In this case, the active compound(s) are condensates of naphthalene or of naphthalenesulfonic acid 25 employed in a purity of from 90% to 100% by weight, pref with phenol and formaldehyde, polyoxyethylene octylphenol erably 95% to 100% by weight (according to NMR spec ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, trum). alkylphenol polyglycol ethers, tributylphenyl polyglycol For seed treatment purposes, respective formulations can ether, tristearylphenyl polyglycol ether, alkylaryl polyether be diluted 2- to 10-fold leading to concentrations in the ready alcohols, alcohol and fatty alcohol ethylene oxide conden 30 to use preparations of 0.01 to 60% by weight active com sates, ethoxylated castor oil, polyoxyethylene alkyl ethers, pound by weight, preferably 0.1 to 40% by weight. ethoxylated polyoxypropylene, lauryl alcohol polyglycol The compounds of formulae I or II can be used as such, in ether acetal, Sorbitol esters, lignoSulfite waste liquors and the form of their formulations or the use forms prepared methylcellulose. therefrom, for example in the form of directly sprayable solu Substances which are suitable for the preparation of 35 tions, powders, Suspensions or dispersions, emulsions, oil directly sprayable solutions, emulsions, pastes or oil disper dispersions, pastes, dustable products, materials for spread sions are mineral oil fractions of medium to high boiling ing, or granules, by means of spraying, atomizing, dusting, point, such as kerosene or diesel oil, furthermore coal tar oils spreading or pouring. The use forms dependentirely on the and oils of vegetable or animal origin, aliphatic, cyclic and intended purposes; they are intended to ensure in each case aromatic hydrocarbons, for example toluene, Xylene, paraf 40 the finest possible distribution of the active compound(s) fin, tetrahydronaphthalene, alkylated naphthalenes or their according to the invention. derivatives, methanol, ethanol, propanol, butanol, cyclohex Aqueous use forms can be prepared from emulsion con anol, cyclohexanone, isophorone, highly polar solvents, for centrates, pastes or wetable powders (sprayable powders, oil example dimethyl sulfoxide, N-methylpyrrolidone or water. dispersions) by adding water. To prepare emulsions, pastes or Also anti-freezing agents such as glycerin, ethylene glycol, 45 oil dispersions, the Substances, as Such or dissolved in an oil propylene glycol and bactericides such as can be added to the or solvent, can be homogenized in water by means of a wet formulation. tings agent, tackifier, dispersant or emulsifier. However, it is Suitable antifoaming agents are for example antifoaming also possible to prepare concentrates composed of active agents based on silicon or magnesium Stearate. Substance, wetting agent, tackifier, dispersant or emulsifier A Suitable preservative is e.g. dichlorophen. 50 and, if appropriate, Solvent or oil, and Such concentrates are Seed treatment formulations may additionally comprise suitable for dilution with water. binders and optionally colorants. The active compound concentrations in the ready-to-use Binders can be added to improve the adhesion of the active preparations can be varied within relatively wide ranges. In materials on the seeds after treatment. Suitable binders are general, they are from 0.0001 to 10%, preferably from 0.01 to block copolymers EO/PO surfactants but also polyvinylalco 55 1% per weight. holsl, polyvinylpyrrolidones, polyacrylates, polymethacry The active compound(s) may also be used Successfully in lates, polybutenes, polyisobutylenes, polystyrene, polyethyl the ultra-low-volume process (ULV), it being possible to eneamines, polyethyleneamides, polyethyleneimines apply formulations comprising over 95% by weight of active (Lupasol R, Polymin(R), polyethers, polyurethans, polyviny compound, or even to apply the active compound without lacetate, tylose and copolymers derived from these polymers. 60 additives. Optionally, also colorants can be included in the formula The following are examples of formulations: tion. Suitable colorants or dyes for seed treatment formula 1. Products for dilution with water for foliar applications. tions are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent For seed treatment purposes, such products may be applied to Red 1, pigment blue 15:4, pigment blue 15:3, pigment blue the seed diluted or undiluted. 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, 65 A) Water-Soluble Concentrates (SL, LS) pigment yellow 13, pigment red 112, pigment red 48:2, pig 10 parts by weight of the active compound(s) are dissolved ment red 48:1, pigment red 57:1, pigment red 53:1, pigment in 90 parts by weight of water or a water-soluble solvent. As US 9,029,639 B2 101 102 an alternative, wetting agents or other auxiliaries are added. I) Dustable Powders (DP, DS) The active compound(s) dissolves upon dilution with water, 5 parts by weight of the active compound(s) are ground whereby a formula-tion with 10% (w/w) of active finely and mixed intimately with 95 parts by weight of finely compound(s) is obtained. divided kaolin. This gives a dustable product having 5% B) Dispersible Concentrates (DC) (w/w) of active compound(s) 20 parts by weight of the active compound(s) are dissolved J) Granules (GR, FG, GG, MG) in 70 parts by weight of cyclohexanone with addition of 10 0.5 parts by weight of the active compound(s) is ground parts by weight of a dispersant, for example polyvinylpyrroli finely and associated with 95.5 parts by weight of carriers, done. Dilution with water gives a dispersion, whereby a for whereby a formulation with 0.5% (w/w) of active 10 cornpound(s) is obtained. Current methods are extrusion, mulation with 20% (w/w) of active compound(s) is obtained. spray-drying or the fluidized bed. This gives granules to be C) Emulsifiable Concentrates (EC) applied undiluted for foliar use. 15 parts by weight of the active compound(s) are dissolved K) ULV Solutions (UL) in 7 parts by weight of xylene with addition of calcium dode 10 parts by weight of the active compound(s) are dissolved cylbenzenesulfonate and castor oil ethoxylate (in each case 5 15 in 90 parts by weight of an organic solvent, for example parts by weight). Dilution with water gives an emulsion, xylene. This gives a product having 10% (w/w) of active whereby a formulation with 15% (w/w) of active compound(s), which is applied undiluted for foliar use. compound(s) is obtained. The compounds of formulae I or II are also suitable for the D) Emulsions (EW, EO, ES) treatment of plant propagation materials (such as seed). Con 25 parts by weight of the active compound(s) are dissolved ventional seed treatment formulations include for example in 35 parts by weight of xylene with addition of calcium flowable concentrates FS, solutions LS, powders for dry treat dodecylbenzenesulfonate and castor oil ethoxylate (in each ment DS, water dispersible powders for slurry treatment WS, case 5 parts by weight). This mixture is introduced into 30 water-soluble powders SS and emulsion ES and EC and gel parts by weight of water by means of an emulsifier machine formulation GF. These formulations can be applied to the (e.g. Ultraturrax) and made into a homogeneous emulsion. 25 seed diluted or undiluted. Application to the seeds is carried Dilution with water gives an emulsion, whereby a formula out before sowing, either directly on the seeds or after having tion with 25% (w/w) of active compound(s) is obtained. pre-germinated the latter E) Suspensions (SC, OD, FS) In a preferred embodiment a FS formulation is used for In an agitated ball mill, 20 parts by weight of the active seed treatment. Typically, a FS formulation may comprise 1 30 to 800 g/l of active ingredient, 1 to 200 g/l Surfactant, 0 to 200 compound(s) are comminuted with addition of 10 parts by g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a weight of dispersants, wetting agents and 70 parts by weight pigment and up to 1 liter of a solvent, preferably water. of water or of an organic solvent to give a fine active com Other preferred FS formulations of compounds of formu pound(s) suspension. Dilution with water gives a stable Sus lae I or II for seed treatment comprise from 0.5 to 80 wt % of pension of the active compound(s), whereby a formulation 35 the active ingredient, from 0.05 to 5 wt % of a wetting agent, with 20% (w/w) of active compound(s) is obtained. from 0.5 to 15 wt % of a dispersing agent, from 0.1 to 5 wt % F) Water-Dispersible Granules and Water-Soluble Gran of a thickener, from 5 to 20 wt % of an anti-freeze agent, from ules (WG, SG) 0.1 to 2 wt % of an anti-foam agent, from 1 to 20 wt % of a 50 parts by weight of the active compound(s) are ground pigment and/or a dye, from 0 to 15 wt % of a sticker/adhesion finely with addition of 50 parts by weight of dispersants and 40 agent, from 0 to 75 wt % of a filler/vehicle, and from 0.01 to wetting agents and made as water-dispersible or water 1 wt % of a preservative. soluble granules by means of technical appliances (for Various types of oils, wetting agents, adjuvants, herbicides, example extrusion, spray tower, fluidized bed). Dilution with fungicides, other pesticides, or bactericides may be added to water gives a stable dispersion or solution of the active com the active ingredients, if appropriate just immediately prior to pound(s), whereby a formulation with 50% (w/w) of active 45 use (tank mix). These agents usually are admixed with the compound(s) is obtained. agents according to the invention in a weight ratio of 1:10 to G) Water-Dispersible Powders and Water-Soluble Powders 10:1. (WP, SPSS, WS) The compounds of formulae I or II are effective through 75 parts by weight of the active compound(s) are ground in both contact (via Soil, glass, wall, bed net, carpet, plant parts a rotor-stator mill with addition of 25 parts by weight of 50 or animal parts), and ingestion (bait, or plant part). dispersants, wetting agents and silica gel. Dilution with water For use against ants, termites, wasps, flies, mosquitoes, gives a stable dispersion or Solution of the active crickets, or cockroaches, compounds of formulae I or II are compound(s), whereby a formulation with 75% (w/w) of preferably used in a bait composition. active compound(s) is obtained. The bait can be a liquid, a solid or a semisolid preparation 55 (e.g. a gel). Solid baits can be formed into various shapes and H) Gel-Formulation (GF) forms suitable to the respective application e.g. granules, In an agitated ball mill, 20 parts by weight of the active blocks, sticks, disks. Liquid baits can be filled into various compound(s) are comminuted with addition of 10 parts by devices to ensure proper application, e.g. open containers, weight of dispersants, 1 part by weight of a gelling agent spraying devices, droplet sources, or evaporation sources. wetting agents and 70 parts by weight of water or of an 60 Gels can be based on aqueous or oily matrices and can be organic solvent to give a fine active compound(s) suspension. formulated to par-ticular necessities in terms of Stickiness, Dilution with water gives a stable suspension of the active moisture retention or aging characteristics. compound(s), whereby a formulation with 20% (w/w) of The bait employed in the composition is a product, which active compound(s) is obtained. is sufficiently attractive to incite insects such as ants, termites, 2. Products to be applied undiluted for foliar applications. 65 wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. For seed treatment purposes, such products may be applied to The attractiveness can be manipulated by using feeding the seed diluted or undiluted. stimulants or sex pheromones. Food stimulants are chosen, US 9,029,639 B2 103 104 for example, but not exclusively, from animal and/or plant The impregnation of curtains and bednets is done in gen proteins (meat-, fish- or blood meal, insect parts, egg yolk), eral by dipping the textile material into emulsions or disper from fats and oils of animal and/or plant origin, or mono-, sions of the active compounds of formulae I and II or spraying oligo- or polyorganosaccharides, especially from Sucrose, them onto the nets. lactose, fructose, dextrose, glucose, starch, pectin or even 5 Methods which can be employed for treating the seed are, molasses or honey. Fresh or decaying parts of fruits, crops, in principle, all suitable seed treatment and especially seed plants, animals, insects or specific parts thereof can also serve dressing techniques known in the art, such as seed coating as a feeding stimulant. Sex pheromones are known to be more (e.g. seed pelleting), seed dusting and seed imbibition (e.g. insect specific. Specific pheromones are described in the lit seed soaking). Here, “seed treatment” refers to all methods erature and are known to those skilled in the art. 10 that bring seeds and the compounds of formulae I or II into Formulations of compounds of formulae I or II as aerosols contact with each other, and “seed dressing to methods of (e.g. in spray cans), oil sprays or pump sprays are highly seed treatment which provide the seeds with an amount of the Suitable for the non-professional user for controlling pests compounds of formulae I or II, i.e. which generate a seed Such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol 15 comprising the compound of formulae Ior II. In principle, the recipes are preferably corn-posed of the active compound, treatment can be applied to the seed at any time from the Solvents such as lower alcohols (e.g. methanol, ethanol, pro harvest of the seed to the sowing of the seed. The seed can be panol, butanol), ketones (e.g. acetone, methyl ethyl ketone), treated immediately before, or during, the planting of the paraffin hydrocar-bons (e.g. kerosenes) having boiling ranges seed, for example using the “planter's box’ method. How of approximately 50 to 250° C., dimethyl-formamide, N-me ever, the treatment may also be carried out several weeks or thylpyrrolidone, dimethyl Sulphoxide, aromatic hydrocar months, for example up to 12 months, before planting the bons such as toluene, Xylene, water, furthermore auxiliaries seed, for example in the form of a seed dressing treatment, Such as emulsifiers such as Sorbitol monooleate, oleylethoxy without a substantially reduced efficacy being observed. late having 3 to 7 mol of ethylene oxide, fatty alcohol ethoxy Expediently, the treatment is applied to unsown seed. As late, perfume oils such as ethereal oils, esters of medium fatty 25 used herein, the term “unsown seed' is meant to include seed acids with lower alcohols, aromatic carbonyl compounds, if at any period from the harvest of the seed to the sowing of the appropriate stabilizers such as Sodium benzoate, am-photeric seed in the ground for the purpose of germination and growth surfactants, lower epoxides, triethyl orthoformate and, if of the plant. required, propellants such as propane, butane, nitrogen, com Specifically, a procedure is followed in the treatment in pressed air, dimethyl ether, carbon dioxide, nitrous oxide, or 30 which the seed is mixed, in a suitable device, for example a mixtures of these gases. mixing device for Solid or solid/liquid mixing partners, with The oil spray formulations differ from the aerosol recipes the desired amount of seed treatment formulations, either as in that no propellants are used. such or after previous dilution with water, until the composi The compounds of formulae I or II and their respective tion is distributed uniformly on the seed. If appropriate, this is compositions can also be used in mosquito and fumigating 35 followed by a drying step. coils, Smoke cartridges, vaporizer plates or long-term vapor The compounds of formulae I or II or the enantiomers or izers and also in, moth papers, moth pads or other heat veterinarily acceptable salts thereof are in particular also independent vaporizer systems. Suitable for being used for combating parasites in and on Methods to control infectious diseases transmitted by animals. insects (e.g. malaria, dengue and yellow fever, lymphatic 40 A further object of the present invention is therefore to filariasis, and leishmaniasis) with compounds of formulae Ior provide new methods for controlling parasites in and on ani II and its respective compositions also comprise treating Sur mals. Another object of the invention is to provide safer faces of huts and houses, air spraying and impregnation of pesticides for animals. Another object of the invention is curtains, tents, clothing items, bed nets, tsetse-fly trap or the further to provide pesticides for animals that may be used in like. Insecticidal compositions for application to fibers, fab 45 lower doses than existing pesticides. And another object of ric, knitgoods, nonwovens, netting material or foils and tar the invention is, to provide pesticides for animals, which paulins preferably comprise a mixture including the insecti provide a long, residual control of the parasites. cide, optionally a repellent and at least one binder. Suitable The invention also relates to compositions containing a repellents for exam-ple are N,N-diethyl-meta-toluamide parasiticidally effective amount of compounds of formulae I (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclo 50 or II or the enantiomers or veterinarily acceptable salts hexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethyl thereof and an acceptable carrier, for combating parasites in cyclohexyl)acetic acid lactone, 2-ethyl-1,3-hexandiol, indal and on animals. one, Methylneodecanamide (MNDA), a pyrethroid not used The present invention also provides a method for treating, for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocy controlling, preventing and protecting animals against infes clopent-2-(+)-enyl-H-trans-chrysantemate (Esbiothrin), a 55 tation and infection by parasites, which comprises orally, repellent derived from or identical with plant extracts like topically or parenterally administering or applying to the limonene, eugenol, (+)-Eucamalol (1), (-)-1-epi-eucamalol animals a parasiticidally effective amount of compounds of or crude plant extracts from plants like Eucalyptus maculata, formulae I or II or the enantiomers or, veterinarily acceptable Vitex rotundifolia, Cymbopogan martinii, Cymbopogan cit salts thereof and an acceptable carrier or a composition com ratus (lemon grass), Cymopogan martdus (citronella). Suit 60 prising it. able binders are selected for example from polymers and The present invention also provides a non-therapeutic copolymers of vinyl esters of aliphatic acids (such as such as method for treating, controlling, preventing and protecting vinyl acetate and vinyl versatate), acrylic and methacrylic animals against infestation and infection by parasites, which esters of alcohols, such as butyl acrylate, 2-ethylhexylacry comprises applying to a locus-P a parasiticidally effective late, and methyl acrylate, mono- and diethylenically unsatur 65 amount of a compound of formulae I or II or the enantiomers ated hydrocarbons, such as styrene, and aliphatic diens, such or veterinarily acceptable salts thereof and an acceptable as butadiene. carrier or a composition comprising it. US 9,029,639 B2 105 106 The invention also provides a process for the preparation of phyrus, Anopheles minimus, Anopheles quadrimaculatus, a composition for treating, controlling, preventing or protect Caliphora vicina, Chrysomya bezziana, Chrysomya homini ing animals against infestation or, infection by parasites vorax, Chrysomya macellaria, Chrysops discalis, Chrysops which comprises including a parasiticidally effective amount silacea, Chrysops atlanticus, Cochliomyia hominivorax, of a compound of, formulae I or II or the enantiomers or Cordylobia anthropophaga, Culicoides furens, Culex pipi Veterinarily acceptable salts thereof and an acceptable carrier ens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsa or a composition comprising it. lis, Culiseta inornata, Culiseta melanura, Dermatobia homi The invention relates further to the use of compounds of nis, Fannia canicularis, Gasterophilus intestinalis, Glossina formula I for treating, controlling, preventing or protecting morsitans, Glossina palpalis, Glossina fiscipes, Glossina animals against infestation or infection by parasites. The 10 invention relates also to the use of a compound of formulae I tachinoides, Haematobia irritans, Haplodiplosis equestris, or II or the enanti-omers or veterinarily acceptable salts Hippelates spp., Hypoderma lineata, Leptoconops torrens, thereofand an acceptable carrier or a composition comprising Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria it, for the manufacture of a medicament for the therapeutic pectoralis, Mansonia spp., Musca domestica, Muscina stabu treatment of animals against infections or infestions by para 15 lans, Oestrus ovis, Phlebotomus argentipes, Psorophora sites. columbiae, Psorophora discolor; Prosimulium mixtum, Sar Activity of compounds against agricultural pests does not cophaga haemorrhoidalis, Sarcophaga sp., Simulium vit Suggest their Suitability for control of endo- and ectoparasites tatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atra in and on animals which requires, for example, low, non tus, Tabanus lineola, and Tabanus similis, emetic dosages in the case of oral application, metabolic lice (Phthiraptera), e.g. Pediculus humanus capitis, compatibility with the animal, low toxicity, and a safe han Pediculus humanus corporis, Pthirus pubis, Haematopinus dling. eurysternus, Haematopinus suis, Linognathus vituli, Bovi Surprisingly, it has been found that compounds of formulae cola bovis, Menopon gallinae, Menacanthus stramineus and I or II are Suitable for combating endo- and ectoparasites in Solenopotes capillatus, and on animals. 25 ticks and parasitic mites (Parasitiformes): ticks (Ixodida), Compounds of formulae I or II or the enantiomers or vet e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, erinarily acceptable salts thereof and compositions compris Rhiphicephalus sanguineus, Dermacentor andersoni, Der ing them are preferably used for controlling and preventing macentor variabilis, Amblyomma americanum, Ambryomma infestations and infections animals including warm-blooded maculatum, Orni-thodorus hermsi, Ornithodorus turicata animals (including humans) and fish. They are for example 30 and parasitic mites (Mesostigmata), e.g. Orni-thonyssus Suitable for controlling and preventing infestations and infec bacoti and Dermanyssus gallinae, tions in mammals such as cattle, sheep, Swine, camels, deer, actinedida (Prostigmata) and Acaridida (Astigmata) e.g. horses, pigs, poultry, rabbits, goats, dogs and cats, water Acarapis spp., Cheyletiella spp., OrnithOcheyletia spp., Myo buffalo, donkeys, fallow deer and reindeer, and also in fur bia spp., Psorergates spp., Demodex spp., Trombicula spp., bearing animals such as mink, chinchilla and raccoon, birds 35 Listrophorus spp., Acarus spp., Tvrophagus spp., Calogly Such as hens, geese, turkeys and ducks and fish Such as fresh phus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., and salt-water fish Such as trout, carp and eels. Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres Compounds of formulae I or II or the enantiomers or vet spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes erinarily acceptable salts thereof and compositions compris Spp, ing them are preferably used for controlling and preventing 40 bugs (Heteropterida): Cimex lectularius, Cimex hemi infestations and infections in domestic animals, such as dogs pterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Pan Or CatS. strongylus ssp. and Arilus critatus, Infestations in warm-blooded animals and fish include, but Anoplurida, e.g. Haematopinus spp., Linognathus spp., are not limited to, lice, biting dice, ticks, nasal bots, keds, Pediculus spp., Phtirus spp., and Solenopotes spp. biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, 45 Mallophagida (Suborders Arnblycerina and Ischnocerina), gnats, mosquitoes and fleas. e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola The compounds of formulae I or II or the enantiomers or spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., Veterinarily acceptable salts thereof and compositions com and Felicola spp. prising them are Suitable for systemic and/or non-systemic Roundworms Nematoda: control of ecto- and/or endoparasites. They are active against 50 Wipeworms and Trichinosis (Trichosyringida), e.g. Tri all or some stages of development. chinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., The compounds of formulae I or II are especially useful for Capillaria spp. combating ectoparasites. Rhabditida, e.g. Rhabditis spp., Strongyloides spp., Heli The compounds of formulae I or II are especially useful for cephalobus spp. combating parasites of the following orders and species, 55 Strongylida, e.g. Strongylus spp., Ancylostoma spp., Neca respectively: tor americanus, Bunostomum spp. (Hookworm), Trichos fleas (Siphonaptera), e.g. Ctenocephalides felis, Cteno trongylus spp., Haemonchus contortus., Ostertagia spp., cephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cya penetrans, and Nosopsyllus fasciatus, thostoma spp., Oesophagostomum spp., Stephanurus denta cockroaches (Blattaria—Blattodea), e.g. Blattella ger 60 tus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, manica, Blattella asahinae, Periplaneta americana, Syngamus trachea, Ancylostoma spp., Uncinaria spp., Glob Periplaneta japonica, Periplaneta brunnea, Periplaneta ocephalus spp., Necator spp., Metastrongylus spp., Muelle filigginosa, Periplaneta australasiae, and Blatta Orientalis, rius capillaris, Protostrongylus spp., Angiostrongylus spp., flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes Parelaphostrongylus spp. Aleurostrongylus abstrusus, and albopictus, Aedes vexans, Anastrepha ludens, Anopheles 65 Dioctophyma renale, maculipennis, Anopheles crucians, Anopheles albimanus, Intestinal roundworms (Ascaridida), e.g. Ascaris lumbri Anopheles gambiae, Anopheles freeborni, Anopheles leucos coides, Ascaris suum, Ascaridia galli, Parascaris equorum, US 9,029,639 B2 107 108 Enterobius vermicularis (Threadworm), Toxocara canis, Administration can be carried out both prophylactically Toxascaris leonine, Skriabinema spp., and Oxyuris equi, and therapeutically. Camallanida, e.g. Dracunculus medimensis (guinea worm), Administration of the active compounds is carried out Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., directly or in the form of suitable preparations, orally, topi Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., cally/dermally or parenterally. Setaria spp., Elaeophora spp., Spirocerca lupi, and For oral administration to warm-blooded animals, the com Habronema spp., pounds of formula I or II may be formulated as animal feeds, Thorny headed worms (Acanthocephala), e.g. Acantho animal feed premixes, animal feed concentrates, pills, solu cephalus spp., Macracanthorhynchus hirudinaceus and tions, pastes, Suspensions, drenches, gels, tablets, boluses and Oncicola spp. 10 capsules. In addition, the compounds of formulae I or II may Planarians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides be administered to the animals in their drinking water. For magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis oral administration, the dosage form chosen should provide buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia the animal with 0.01 mg/kg to 100 mg/kg of animal body spp., Alaria alata, Paragonimus spp., and Nanocyetes spp. 15 weight per day of the formulae I or II compound, preferably Cercomeromorpha, in particular Cestoda (Tapeworms), with 0.5 mg/kg to 100 mg/kg of animal body weight per day. e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Alternatively, the compounds of formulae I or II may be Dipylidium caninum, Multiceps spp., Hymenolepis spp., administered to animals parenterally, for example, by intraru Mesocestoides spp., Vampirolepis spp., Moniezia spp., Ano minal, intramuscular, intravenous or Subcutaneous injection. plocephala spp., Sirometra spp., Anoplocephala spp., and The compounds of formulae I or II may be dispersed or Hymenolepis spp. dissolved in a physiologically acceptable carrier for Subcuta The compounds of formulae I or II and compositions con neous injection. Alternatively, the compounds of formulae I taining them are particularly useful for the control of pests or II may be formulated into an implant for Subcutaneous from the orders Diptera, Siphonaptera and Ixodida. administration. In addition the compounds of formulae I or II Moreover, the use of the formulae I or II and compositions 25 may be transdermally administered to animals. For parenteral containing them for combating mosquitoes is especially pre administration, the dosage form chosen should provide the ferred. animal with 0.01 mg/kg to 100 mg/kg of animal body weight The use of the compounds of formulae I or II and compo per day of the compounds of formulae I or II. sitions containing them for combating flies is a further pre The compounds of formulae I or II may also be applied ferred embodiment of the present invention. 30 topically to the animals in the form of dips, dusts, powders, Furthermore, the use of the compounds of formulae I or II collars, medallions, sprays, shampoos, spot-on and pouron and compositions containing them for combating fleas is formulations and in ointments or oil-in-water or water-in-oil especially preferred. emulsions. For topical applica-tion, dips and sprays usually The use of the compounds of formula formulae I or II and contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3 000 compositions containing them for combating ticks is a further 35 ppm of the compounds of formulae I or II. In addition, the preferred embodiment of the present invention. compounds of formulae I or II may be formulated as ear tags The compounds of formulae I or II and compositions con for animals, particularly quadrupeds Such as cattle and sheep. taining them also are especially useful for combating Suitable preparations are: endoparasites (roundworms nematoda, thorny headed worms Solutions such as oral Solutions, concentrates for oral and planarians). 40 administration after dilution, Solutions for use on the skin or The compounds of formulae I or II and compositions con in body cavities, pouring-on formulations, gels; taining them can be effective through both contact (via Soil, Emulsions and Suspensions for oral or dermal administra glass, wall, bed net, carpet, blankets or animal parts) and tion; semi-solid preparations; ingestion (e.g. baits). Formulations in which the active compound is processed in The present invention relates to the therapeutic and the 45 an ointment base or in an oil-in-water or water-in-oil emul non-therapeutic use of cornpounds of formulae I or II and sion base; compositions containing them for controlling and/or com Solid preparations such as powders, premixes or concen bating parasites in and/or on animals. trates, granules, pellets, tablets, boluses, capsules; aerosols The compounds of formulae I or II and compositions con and inhalants, and active compound-containing shaped taining them may be used to protect the animals from attack or 50 articles. infestation by parasites by contacting them with a parasiti Compositions suitable for injection are prepared by dis cally effective amount of compounds of formulae I or II and Solving the active ingredient in a suitable solvent and option compositions containing them. As such, “contacting ally adding further ingredients such as acids, bases, buffer includes both direct contact (applying the pesticidal mixtures/ salts, preservatives, and solubilizers. The solutions are fil compositions directly on the parasite, which may include an 55 tered and filled sterile. indirect contact at it's locus-P, and optionally also adminis Suitable solvents are physiologically tolerable solvents trating the pesticidal mixtures/composition directly on the Such as water, alkanols such as ethanol, butanol, benzyl alco animal) and indirect contact (applying the compounds/com hol, glycerol, propylene glycol, polyethylene glycols, N-me positions to the locus of the parasite). The contact of the thylpyrrolidone, 2-pyrrolidone, and mixtures thereof. parasite through application to its locus is an example of a 60 The active compounds can optionally be dissolved in non-therapeutic use of compounds of formula I. physiologically tolerable vegetable or synthetic oils which “Locus-Pas defined above means the habitat, food supply, are suitable for injection. breeding ground, area, material or environment in which a Suitable solubilizers are solvents which promote the dis parasite is growing or may grow outside of the animal. The Solution of the active compound in the main solvent or pre compounds of the invention can also be applied preventively 65 vent its precipitation. Examples are polyvinylpyrrolidone, to places at which occurrence of the pests or parasites is polyvinyl alcohol, polyoxyethylated castor oil, and polyoxy expected. ethylated sorbitan ester. US 9,029,639 B2 109 110 Suitable preservatives are benzyl alcohol, trichlorobutanol, Emulsions can be administered orally, dermally oras injec p-hydroxybenzoic acid esters, and n-butanol. tions. Oral solutions are administered directly. Concentrates are Emulsions are either of the water-in-oil type or of the administered orally after prior dilution to the use concentra oil-in-water type. tion. Oral Solutions and concentrates are prepared according They are prepared by dissolving the active compound to the state of the art and as described above for injection either in the hydrophobic or in the hydrophilic phase and Solutions, sterile procedures not being necessary. homogenizing this with the solvent of the other phase with the Solutions for use on the skin are trickled on, spread on, aid of Suitable emulsifiers and, if appropriate, other auxilia rubbed in, sprinkled on or sprayed on. ries such as colorants, absorption-promoting Substances, pre Solutions for use on the skin are prepared according to the 10 state of the art and according to what is described above for servatives, antioxidants, light stabilizers, viscosity-enhanc injection solutions, sterile procedures not being necessary. ing Substances. Further suitable solvents are polypropylene glycol, phenyl Suitable Hydrophobic Phases (Oils) are: ethanol, phenoxy ethanol, ester Such as ethyl or butyl acetate, liquid paraffins, silicone oils, natural vegetable oils such as benzyl benzoate, ethers such as alkyleneglycol alkylether, 15 sesame oil, almond oil, casfor oil, synthetic triglycerides Such e.g. dipropylenglycol monomethylether, ketons such as as caprylic/capric biglyceride, triglyceride mixture with Veg acetone, methylethylketone, aromatic hydrocarbons, Veg etable fatty acids of the chain length Cs-C or other specially etable and synthetic oils, dimethylformamide, dimethylac selected natural fatty acids, partial glyceride mixtures of satu etamide, transcutol, Solketal, propylencarbonate, and mix rated or unsaturated fatty acids possibly also containing tures thereof. hydroxyl groups, mono- and diglycerides of the Cs-Co fatty It may be advantageous to add thickeners during prepara acids, fatty acid esters such as ethyl Stearate, di-n-butyryl tion. Suitable thickeners are inorganic thickeners such as adipate, hexyllaurate, dipropylene glycol perlargonate, esters bentonites, colloidal silicic acid, aluminium monostearate, of a branched fatty acid of medium chain length with satu organic thickeners such as cellulose derivatives, polyvinyl rated fatty alcohols of chain length C-Cls, isopropyl alcohols and their copolymers, acrylates and methacrylates. 25 myristate, isopropyl palmitate, caprylic/capric acid esters of Gels are applied to or spread on the skin or introduced into saturated fatty alcohols of chain length C-Cls, isopropyl body cavities. Gels are prepared by treating solutions which Stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, have been prepared as described in the case of the injection waxy fatty acid esters such as synthetic duck coccygeal gland Solutions with Sufficient thickener that a clear material having fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures anointmentlike consistency results. The thickeners employed 30 related to the latter, fatty alcohols such as isotridecyl alcohol, are the thickeners given above. 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and Pour-on formulations are poured or sprayed onto limited fatty acids such as oleic acid and mixtures thereof. areas of the skin, the active compound penetrating the skin Suitable hydrophilic phases are: water, alcohols such as and acting systemically. propylene glycol, glycerol, Sorbitol and mixtures thereof. Pour-on formulations are prepared by dissolving, Suspend 35 Suitable Emulsifiers are: ing or emulsifying the active compound in Suitable skin non-ionic Surfactants, e.g. polyethoxylated castor oil, poly compatible solvents or solvent mixtures. If appropriate, other ethoxylated Sorbitan monooleate, Sorbitan monostearate, auxiliaries such as colorants, bioabsorption-promoting Sub glycerol monostearate, polyoxyethyl Stearate, alkylphenol stances, antioxidants, light stabilizers, adhesives are added. polyglycol ether, ampholytic Surfactants such, as di-sodium Suitable solvents are water, alkanols, glycols, polyethylene 40 N-lauryl-p-iminodipropionate or lecithin; anionic Surfac glycols, polypropylene glycols, glycerol, aromatic alcohols tants, such as sodium lauryl Sulfate, fatty alcohol ether Sul Such as benzyl alcohol, phenylethanol, phenoxyethanol, fates, mono/dialkyl polyglycol ether orthophosphoric acid esters such as ethyl acetate, butyl acetate, benzyl benzoate, ester monoethanolamine salt; cation-active surfactants. Such ethers such as alkylene glycol alkyl ethers such as dipropy as cetyltrimethylammonium chloride. lene glycol monomethyl ether, diethylene glycol mono-butyl 45 Suitable further auxiliaries are: substances which enhance ether, ketones such as acetone, methyl ethyl ketone, cyclic the Viscosity and stabilize the emulsion, Such as carboxym carbonates Such as propylene carbonate, ethylene carbonate, ethylcellulose, methylcellulose and other cellulose and starch aromatic and/or aliphatic hydrocarbons, vegetable or Syn derivatives, polyacrylates, alginates, gelatin, gum arabic, thetic oils, DMF, dimethylacetamide, N-alkylpyrrolidones polyvinylpyrrolidone, polyvinyl alcohol, copolymers of such as N-Methylpyrrolidone, N-butylpyrrolidone or N-oc 50 methyl vinyl ether and maleic anhydride, polyethylene gly tylpyrrolidone, 2-pyrrolidone, 2.2-dimethyl-4-oxy-methyl cols, waxes, colloidal silicic acid or mixtures of the Sub ene-1,3-dioxolane and glycerol formal. stances mentioned. Suitable colorants are all colorants permitted for use on Suspensions can be administered orally or topically/der animals and which can be dissolved or Suspended. mally. They are prepared by Suspending the active compound Suitable absorption-promoting Substances are, for 55 in a Suspending agent, if appropriate with addition of other example, DMSO, spreading oils such as isopropyl myristate, auxiliaries such as wetting agents, colorants, bioabsorption dipropylene glycol pelargonate, silicone oils and copolymers promoting Substances, preservatives, antioxidants, light sta thereof with polyethers, fatty acid esters, triglycerides, fatty bilizers. alcohols. Liquid Suspending agents are all homogeneous solvents Suitable antioxidants are sulfites or metabisulfites such as 60 and solvent mixtures. potassium metabisulfite, ascorbic acid, butylhydroxytoluene, Suitable wetting agents (dispersants) are the emulsifiers butylhydroxyanisole, tocopherol. given above. Suitable light stabilizers are, for example, novantisolic Other auxiliaries which may be mentioned are those given acid. above. Suitable adhesives are, for example, cellulose derivatives, 65 Semi-solid preparations can be administered orally or topi starch derivatives, polyacrylates, natural polymers such as cally/dermally. They differ from the suspensions and emul alginates, gelatin. sions described above only by their higher viscosity. US 9,029,639 B2 111 112 For the production of Solid preparations, the active com which are sufficiently compatible with the compounds of pound is mixed with Suitable excipients, if appropriate with formulae I or II. A detailed list of plastics and elastomers as addition of auxiliaries, and brought into the desired form. well as preparation procedures for the shaped articles is given Suitable excipients are all physiologically tolerable solid e.g. in WO 03/086075. inert Substances. Those used are inorganic and organic Sub Compositions to be used according to this invention may stances. Inorganic Substances are, for example, sodium chlo also contain other active ingredients, for example other pes ride, carbonates Such as calcium carbonate, hydrogencarbon ticides, insecticides, herbicides, fungicides, other pesticides, ates, aluminium oxides, titanium oxide, silicic acids, or bactericides, fertilizers such as ammonium nitrate, urea, argillaceous earths, precipitated or colloidal silica, or phos potash, and Superphosphate, phytotoxicants and plant growth phates. Organic Substances are, for example, Sugar, cellulose, 10 foodstuffs and feeds such as milk powder, animal meal, grain regulators, safeners and nematicides. These additional ingre meals and shreds, starches. dients may be used sequentially or in combination with the Suitable auxiliaries are preservatives, antioxidants, and/or above-described compositions, if appropriate also added only colorants which have been mentioned above. immediately prior to use (tank mix). For example, the plant(s) Other suitable auxiliaries are lubricants and glidants such 15 may be sprayed with a composition of this invention either as magnesium Stearate, Stearic acid, talc, bentonites, disinte before or after being treated with other active ingredients. gration-promoting Substances such as starch or crosslinked These agents can be admixed with the agents used accord polyvinylpyrrolidone, binders such as starch, gelatin or linear ing to the invention in a weight ratio of 1:10 to 10:1. Mixing polyvinylpyrrolidone, and dry binders such as microcrystal the compounds of formulae I or II or the compositions com line cellulose. prising them in the use form as pesticides with other pesti In general, "parasiticidally effective amount’ means the cides frequently results in a broader pesticidal spectrum of amount of active ingredient needed to achieve an observable action. effect on growth, including the effects of necrosis, death, The following list M of pesticides together with which the retardation, prevention, and removal, destruction, or other compounds of formulae I or II the invention can be used and wise diminishing the occurrence and activity of the target 25 with which potential synergistic effects might be produced, is organism. The parasiticidally effective amount can vary for intended to illustrate the possible combinations, but not to the various compounds/compositions used in the invention. A impose any limitation: parasiticidally effective amount of the compositions will also M.1. Organo (thio)phosphates: acephate, azamethiphos, vary according to the prevailing conditions such as desired azinphos-ethyl, azinphosmethyl, chlorethoxyfos, chlorfen parasiticidal effect and duration, target species, mode of 30 Vinphos, chlormephos, chlorpyrifos, chlorpyrifoSmethyl, application, and the like. coumaphos, cyanophos, demeton-5-methyl, diazinon, The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the com dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvin pound of formulae I or II. phos, disulfoton, EPN, ethion, ethoprophos, famphur, Generally, it is favorable to apply the compounds of for 35 fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiaz mulae I or II in total amounts of 0.5 mg/kg to 100 mg/kg per ate, heptenophos, isoxathion, malathion, mecarbam, metha day, preferably 1 mg/kg to 50 mg/kg per day. midophos, methidathion, mevinphos, monocrotophos, naled, Ready-to-use preparations contain the compounds acting omethoate, oxydemeton-methyl, parathion, parathion-me against parasites, preferably ectoparasites, in concentrations thyl, phenthoate, phorate, phosalone, phosmet, phosphami of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 40 don, phoxim, pirimiphos-methyl, profenofos, propetamphos, percent by weight, more preferably from 1 to 50 percent by prothiofos, pyraclofos, pyridaphenthion, quinalphos, Sul weight, most preferably from 5 to 40 percent by weight. fotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, Preparations which are diluted before use contain the com thiometon, triaZophos, trichlorfon, vamidothion; pounds acting againstectoparasites in concentrations of 0.5 to M.2. Carbamates: aldicarb, alanycarb, bendiocarb, benfu 90 percent by weight, preferably of 1 to 50 percent by weight. 45 racarb, butocarboxim, butoxycarboxim, carbaryl, carbofu Furthermore, the preparations comprise the compounds of ran, carbosulfan, ethiofencarb, fenobucarb, formetanate, formulae I or II against endoparasites in concentrations of 10 furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, ppm to 2 percent by weight, preferably of 0.05 to 0.9 percent oxamyl, pirimicarb, propoXur, thiodicarb, thiofanox, tri by weight, very particularly preferably of 0.005 to 0.25 per methacarb. XMC, xylylcarb, triazamate; cent by weight. 50 M.3. Pyrethroids: acrinathrin, allethrin, d-cis-trans In a preferred embodiment of the present invention, the allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioal compositions comprising the compounds of formulae I or II lethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, are applied dermally/topically. cyfluthrin, betacy fluthrin, cyhalothrin, lambda-cyhalothrin, In a further preferred embodiment, the topical application gamma-cyhalothrin, cypermethrin, alphacypermethrin, beta is conducted in the form of compound-containing shaped 55 cypermethrin, theta-cypermethrin, Zeta-cypermethrin, articles such as collars, medallions, ear tags, bands for fixing cyphenothrin, deltamethrin, empenthrin, esfenvalerate, at body parts, and adhesive strips and foils. etofemprox, fenpropathrin, fenvalerate, flucythrinate, flu Generally, it is favorable to apply solid formulations which methrin, tau-fluvalinate, halfenproX, imiprothrin, metof release compounds of formulae I or II in total amounts of 10 luthrin, permethrin, phenothrin, prallethrin, profluthrin, pyre mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most 60 thrin (pyrethrum), resmethrin, RU 15525, silafluofen, preferably 25 mg/kg to 160 mg/kg body weight of the treated tefluthrin, tetramethrin, tralomethrin, transfluthrin, ZXI animal in the course of three weeks. 8901; For the preparation of the shaped articles, thermoplastic M.4. Juvenile hormone mimics: hydroprene, kinoprene, and flexible plastics as well as elastomers and thermoplastic methoprene, fenoxycarb, pyriproxyfen; elastomers are used. Suitable plastics and elastomers are 65 M.5. Nicotinic receptor agonists/antagonists compounds: polyvinyl resins, polyurethane, polyacrylate, epoxy resins, acetamiprid, bensultap, cartap hydrochloride, clothianidin, cellulose, cellulose derivatives, polyamides and polyester dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nico
US 9,029,639 B2 115 116 CF (CH),C(CN)CH (CF)CF (2-(2.2.3.3.4.4.5.5.5- amine derivatives Such as aldimorph, dodine, dodemorph, Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononi fenpropimorph, fenpropidin, guazatline, iminoctadine, trile), CF (CF). CHC(CN)-CH(CF)CFH (2-(2,2,3,3,4, spiroxamin, tridemorph, 4.4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro anilinopyrimidines such as pyrimethanil, mepanipyrim or pentyl)-malononitrile), CFCFCHC(CN),CH (CF), cyrodinyl, CFH (2-(2.2.3.3.4.4.5.5-Octafluoro-pentyl)-2-(2,2,3,3,3- antibiotics such as cycloheximid, griseofulvin, kasugamy pentafluoro-propyl)-malononitrile), CFHCFCFCFCHC cin, natamycin, polyoxin or streptomycin, (CN),CHCHCFCF (2-(2,2,3,3,4,4,5,5-octafluoropen azoles such as bitertanol, bromoconazole, cyproconazole, tyl)-2-(3.3.4.4.4-pentafluorobutyl)-malonodinitrile), CF difenoconazole, diniconazole, epoxiconazole, fenbucona 10 Zole, fluculiconazole, flusilaZole, hexaconazole, imazalil, (CH),C(CN)CH (CF)CFH (2-(2.2.3.3.4.4.5.5- metconazole, myclobutanil, penconazole, propiconazole, octafluoropentyl)-2-(3,3,3-trifluoro-butyl)-malononitrile); prochloraz, prothioconazole, tebuconazole, triadimefon, tri M.26. Microbial disruptors: Bacillus thuringiensis subsp. adimenol, triflumizol, triticonazole, flutriafol, Israelensi, Bacillus sphaericus, Bacillus thuringiensis Subsp. dicarboximides such as iprodion, mycloZolin, procymi Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thu 15 don, VincloZolin, ringiensis Subsp. Tenebrionis, dithiocarbamates Such as ferbam, nabam, maneb, manco The commercially available compounds of the group M Zeb, metam, metiram, propineb, polycarbamate, thiram, may be found in The Pesticide Manual, 14th Edition, British Ziram, Zineb, Crop Protection Council (2006) among other publications. heterocyclic compounds such as anilazine, benomyl, bos Thioamides of formula M6.1 and their preparation have calid, carbendazim, carboxin, oxycarboxin, cyaZofamid, been described in WO 98/28279. Lepimectin is known from dazomet, dithianon, famoxadon, fenamidon, fenarimol, Agro Project, PJB Publications Ltd, November 2004. Ben fuberidazole, flutolanil, furametpyr, isoprothiolane, clothiaz and its preparation have been described in mepronil, nuarimol, probenazole, produinazid, pyrifenox, EP-A1454621. Methidathion and Paraoxon and their prepa pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluza ration have been described in Farm Chemicals Handbook, 25 mid, thiophanate-methyl, tiadinil, tricyclazole, triforine, Volume 88, Meister Publishing Company, 2001. Acetoprole copper fungicides such as Bordeaux mixture, copper and its preparation have been described in WO 98/28277. acetate, copper oxychloride, basic copper Sulfate, Metaflumizone and its preparation have been described in nitrophenyl derivatives such as binapacryl, dinocap, EP-A1 462456. Flupyrazofos has been described in Pesticide dinobuton, nitrophthalisopropyl. 30 phenylpyrroles such as fenpiclonil or fludioxonil, Sulfur, Science 54, 1988, p. 237-243 and in U.S. Pat. No. 4,822,779. other fungicides such as acibenzolar-5-methyl, benthia Pyrafluprole and its preparation have been described in JP valicarb, carpropamid, chlorothalonil, cyflufenamid, 2002 193709 and in WO 01/00614. Pyriprole and its prepara cymoxanil, diclomezin, diclocymet, diethofencarb, edifen tion have been described in WO98/.45274 and in U.S. Pat. No. phos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, fer 6,335,357. Amidoflumet and its preparation have been 35 imzone, fluaZinam, fosetyl, fosetyl-aluminum, iprovalicarb, described in U.S. Pat. No. 6,221,890 and in JP 21.010907. hexachlorobenzene, metrafenon, pencycuron, propamocarb, Flufenerim and its preparation have been described in WO phthalide, toloclofoS-methyl, quintoZene, Zoxamid, 03/007717 and in WO 03/007718. AKD 1022 and its prepa strobilurins such as azoxystrobin, dimoxystrobin, enes ration have been described in U.S. Pat. No. 6,300,348. Chlo troburin, fluoxastrobin, kresoximmethyl, me-tominostrobin, ranthraniliprole has been described in WO 01/70671, WO 40 orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb or 03/015519 and WO 05/118552. Cyantraniliprole has been trifloxystrobin, described in WO 01/70671, WO 04/067528 and WO Sulfenic acid derivatives such as captafol, captan, dichlof 05/118552. The anthranilamides M 24.1 to M24.6 have been luanid, folpet, tolylfluanid, described in WO 2008/72743 and WO 200872783. The cinnemamides and analogs such as dimethomorph, flume phthalamide M21.1 is known from WO 2007/101540. Cyflu 45 tover or flumorph. metofen and its preparation have been described in WO The invertebrate pest, i.e. arthropodes and nematodes, the 04/080180. The aminoquinazolinone compound pyriflu plant, soil or water in which the plant is growing can be quinazon has been described in EPA 1097932. Sulfoximine contacted with the compound(s) of formulae I or II or com Sulfoxaflor has been described in WO 2006/060029 and WO position(s) containing them by any application method 50 known in the art. As such, “contacting includes both direct 2007/149134. The alkynylether compound M22.1 is contact (applying the compounds/compositions directly on described e.g. in JP 2006131529. Organic sulfur compounds the invertebrate pest or plant—typically to the foliage, stem or have been described in WO 2007060839. The carboxamide roots of the plant) and indirect contact (applying the com compound M 22.2 is known from WO 2007/83394. The pounds/compositions to the locus of the invertebrate pest or oxazoline compounds M 22.3 to M22.6 have been described 55 plant). in WO 2007/074789. The furanon compounds M 22.7 to M Moreover, invertebrate pests may be controlled by contact 22.16 have been described eg. in WO 2007/115644. The ing the target pest, its food Supply, habitat, breeding ground or pyripyropene derivative M-22.17 has been described in WO its locus with a pesticidally effective amount of compounds of 2008/66153 and WO 2008/108491. The pyridazin compound formulae I or II. As such, the application may be carried out M22.18 has been described in JP 2008/115155. The malono 60 before or after the infection of the locus, growing crops, or nitrile compounds have been described in WO 02/089579 harvested crops by the pest. WO 02/090320, WO 02/090321, WO 04/006677, WO "Locus in general means a habitat, breeding ground, cul 05/068423, WO 05/068432 and WO 05/063694. tivated plants, plant propagation material (such as seed), Soil, Fungicidal mixing partners are in particular those selected area, material or environment in which a pest or parasite is from the group consisting of 65 growing or may grow. acylalanines Such as benalaxyl, metalaxyl, ofurace, oxa In general “pesticidally effective amount’ means the dixyl, amount of active ingredient needed to achieve an observable US 9,029,639 B2 117 118 effect on growth, including the effects of necrosis, death, seed, preferably from 1 g to 5 kg per 100 kg of seed, in retardation, prevention, and removal, destruction, or other particular from -1 g to 200 g per 100 kg of seed. wise diminishing the occurrence and activity of the target The present invention is now illustrated in further detail by organism. The pesticidally effective amount can vary for the the following, examples. various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also I. PREPARATION EXAMPLES vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, The procedures described in the following preparation mode of application, and the like. examples were used to prepare further compounds of formu The compounds of formulae I or II and the compositions 10 lae I and II by appropriate modification of the starting mate comprising said compounds can be used for protecting rial. The resulting compounds, together with physical data, wooden materials such as trees, board fences, sleepers, etc. are listed in the table C below. and buildings such as houses, outhouses, factories, but also Products were characterized by HPLC (High Performance construction materials, furniture, leathers, fibers, vinyl liquid Chromatography Mass Spectrometry). HPLC was car articles, electric wires and cables etc. from ants and/or ter 15 ried out using an analytic RP-18 column (Chromolith Speed mites, and for controlling ants and termites from doing harm ROD from Merck KgaA, Germany) which was operated at to crops or human being (e.g. when the pests invade into 40° C. Acetonitrile with 0.1% by volume of a trifluoroacetic houses and public facilities). The compounds of are applied acid/water mixture and 0.1% by volume of trifluoroacetic not only to the Surrounding soil Surface or into the under-floor acid served as mobile phase; flow rate: 1.8 ml/min and injec soil in order to protect wooden materials but it can also be tion Volume: 2 ul. applied to lumbered articles such as surfaces of the under floor concrete, alcove posts, beams, plywood, furniture, etc., Example 1 wooden articles such as particle boards, halfboards, etc. and vinyl articles Such as coated electric wires, vinyl sheets, heat 2-Chloro-thiazole-4-carboxylic acid insulating material Such as styrene foams, etc. In case of 25 methyl-pyridazin-4-yl-amide application againstants doing harm to crops or human beings, the ant controller of the present invention is applied to the 2-Chlorothiazole-4-carboxylic acid crops or the Surrounding soil, or is directly applied to the nest of ants or the like. 14.0 g (73.1 mmol) of 2-chlorothiazole-4-carboxylic acid The compounds of formulae I and II can also be applied 30 ethyl ester were slowly added to a solution of 11.0 g (0.17 preventively to places at which occurrence of the pests is mol, 85% purity) of potassium hydroxide in ethanol/water expected. (1:3, 200 ml) at 0°C. The reaction mixture was stirred at room The compounds of formulae I or II may also be used to temperature for 16 h, diluted with water and washed twice protect growing plants from attack or infestation by pests by with diethyl ether. The aqueous layer was acidified (pH 5.5) contacting the plant with a pesticidally effective amount of 35 with conc. HCl and stirred at room temperature for three days. compounds of formula I or II. As such, "contacting includes The formed precipitate was collected by filtration and dried at both direct contact (applying the compounds/compositions 40° C. under vacuum to yield 7.0 g (56%, 95% purity) of the directly on the pest and/or plant—typically to the foliage, title compound as a brown solid. stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or 40 2-Chloro-thiazole-4-carboxylic acid plant). methyl-pyridazin-4-yl-amide In the case of Soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges 200 mg (1.2 mmol) of 2-chlorothiazole-4-carboxylic acid from 0.0001 to 500g per 100 m, preferably from 0.001 to 20 and 96.1 mg (0.9 mmol) of pyridazin-4-yl-amine were dis g per 100 m. 45 solved in 6 ml dimethyl formamide. 0.15 mL (1.1 mmol) of Customary application rates in the protection of materials triethylamine followed by 382 mg (0.73 mmol) of 1H-Ben are, for example, from 0.01 g to 1000 g of active compound Zotriazol-1-yloxytri-pyrrolidinophosphonium hexafluoro perm treated material, desirably from 0.1 g to 50g perm. phosphate (PyBOP) were added and the reaction mixture was Insecticidal compositions for use in the impregnation of stirred at room temperature for 16 h. Brine was added and the materials typically contain from 0.001 to 95% by weight, 50 reaction mixture was extracted three times with dichlo preferably from 0.1 to 45% by weight, and more preferably romethane. The combined organic layers were dried over from 1 to 25% by weight of at least one repellent and/or sodium sulfate, filtered and the solvent was removed under insecticide. reduced pressure. The obtained residue was purified by flash For use in bait compositions, the typical content of active column chromatography (silica, gradient elution cyclohex ingredient is from 0.001% by weight to 15% by weight, 55 ane, ethyl acetate, methanol) to give 200 mg (61%. 95% desirably from 0.001% by weight to 5% by weight of active purity) of the title compound. compound. For use in spray compositions, the content of active ingre Example 2 dient is from 0.001 to 80% by weight, preferably from 0.01 to 50% by weight and most preferably from 0.01 to 15% by, 60 2-Methyl-thiazole-4-carboxylic acid weight. methyl-pyridazin-4-yl-amide For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 250 mg (1.8 mmol) of 2-Methyl-thiazole-4-carboxylic g to 4000 g per hectare, desirably from 25 g to 600 g per acid were suspended in 20 mL of toluene and two drops of hectare, more desirably from 50 g to 500 g per hectare. 65 dimethylformamide were added to the mixture. 0.16 mL of In the treatment of seed, the application rates of the active thionylchloride (2.2 mmol) were added at room temperature ingredients are generally from 0.1 g to 10 kg, per 100 kg of and the reaction mixture was stirred at 65° C. for two hours. US 9,029,639 B2 119 120 After removal of the solvent, toluene was added and the were allowed to transfer overnight to accomplish an infesta evaporation was repeated. The obtained residue was then tion of 80-100 aphids perplant and the host leaf was removed. dissolved in 10 mL of dichloromethane and the solution was The infested plants were then sprayed by an automated elec added dropwise to a solution containing 166 mg pyridazin trostatic plant sprayer equipped with an atomizing spray 4-yl-amine (1.8 mmol) and 0.27 ml triethylamine (1.9 mmol) nozzle. The plants were dried in the sprayer fume hood, in 40 ml dichloromethane. The mixture was stirred at room removed from the sprayer, and then maintained in a growth temperature for 16 h and the solvent was removed under room under fluorescent lighting in a 24-hr photoperiod at 25° vacuum. The obtained residue was purified by flash column C. and 20-40% relative humidity. Aphid mortality on the chromatography (silica, gradient elution cyclohexane, ethyl treated plants, relative to mortality on untreated control acetate, methanol) to give 50 mg (13%, 99% purity) of the 10 plants, was determined after 5 days. title compound. In this test, the compounds 2, 4, 6, and 11 respectively, at Compounds of the formula I and the salts or N-oxides 300 ppm showed a mortality of at least 75% in comparison thereof, wherein R, R" and Ware CH, V is N and X is O are with untreated controls. hereinafter referred to as compounds I'. Aa. 15 II.2 Activity Against Green Peach Aphid (Myzus persicae, Mixed Life Stages) (I.Aa) The active compounds were formulated in cyclohexanone as a 10.0000 ppm solution supplied in 1.3 ml ABgene(R) tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% --N acetone:50% water (v/v). A nonionic surfactant (Kinetic R) R was included in the solution at a volume of 0.01% (v/v). Bell pepper plants at the first true-leaf stage were infested Compounds of formula I.Aa prepared according to the 25 prior to treatment by placing heavily infested leaves from the above mentioned method together with their physico-chemi main colony on top of the treatment plants. Aphids were cal data are compiled in table C below. R' and A in each case allowed to transfer overnight to accomplish an infestation of have the meanings given in the corresponding line of table C. 30-50 aphids perplant and the host leaves were removed. The infested plants were then sprayed by an automated electro TABLE C 30 static plant sprayer equipped with an atomizing spray nozzle. Compounds of formula I.Aa prepared according to the The plants were dried in the sprayerfume hood, removed, and above-mentioned method then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C. and 20-40% relative humid physico ity. Aphid mortality on the treated plants, relative to mortality chemical 35 data: on untreated controt plants, was determined after 5 days. Example R' A. rt. min In this test, the compounds 2, 4, and 11 respectively, at 300 1 H 2-methyl-5-trifluoromethyloxazol-4-yl 1.883 ppm showed a mortality of at least 75% in comparison with 2 H 2,4-dimethyloxazol-5-yl 1.264 untreated controls. 3 H 2,5-dimethyloxazol-4-yl 1468 4 H 2,4-dimethylthiazol-5-yl 1.465 40 II.3 Activity Against Cowpea Aphid (Aphis craccivora) 5 methyl 2-methylthiazol-4-yl 1.288 The active compounds were formulated in 50:50 (vol: Vol) 6 H 2-methylthiazol-4-yl 1.090 7 H 5-bromothiazol-4-yl 1560 acetone: water. The test Solution was prepared at the day of 8 methyl 5-bromothiazol-4-yl 1430 SC. 9 H 2-phenylthiazol-4-yl 2.406 10 methyl 2-phenylthiazol-4-yl 2.315 45 Potted cowpea plants colonized with 100-150 aphids of 11 H 4-methylthiazol-5-yl 1.263 various stages were sprayed after the pest population had 12 H 2-(4-chlorophenyl)oxazol-4-yl 2.537 been recorded. Population reduction was assesed after 24,72, 13 methyl 2-(4-chlorophenyl)oxazol-4-yl 2.524 and 120 hours. 14 methyl 2-chlorothiazol-4-yl 1606 15 H 5-methyl-3-(2,2,2-trifluoro-ethyl)-3H- 1.278 In this test, the compounds 2, 3, 5, 6 and 7, respectively, at imidazol-4-yl 50 300 ppm showed a mortality of at least 90% in comparison with untreated controls. rt, = HPLC retention time II.4 Activity Against Vetch Aphid (Megoura viciae) The active compounds were formulated in 1:3 (vol: Vol) II. EVALUATION OF PESTICIDAL ACTIVITY DMSO:water with different concentrations of formulated 55 compounds. II.1 Activity Against Cotton Aphid (Aphis gossypii, Mixed Life Stages) Bean leaf disks were placed into, microtiterplates filled The active compounds were formulated in cyclohexanone with 0.8% agar-agar and 2.5 ppm OPUSTM. The leaf disks as a 10.0000 ppm solution supplied in 1.3 ml ABgeneR tubes. were sprayed with 2.5ul of the test solution and 5 to 8 adult These tubes were inserted into an automated electrostatic 60 aphids were placed into the microtiterplates which were then sprayer equipped with an atomizing nozzle and they served as closed and kept at 23+1° C. and 50+5% relative humidity stock solutions for which lower dilutions were made in 50% under fluorescent light for 6 days. Mortality was assessed on acetone:50% water (v/v). A nonionic surfactant (Kinetic R) the basis of vital, reproduced, aphids. Aphid mortality and was included in the solution at a volume of 0.01% (v/v). fecundity was then visually assessed. Cotton plants at the cotyledon stage were infested with 65 In this test, the compounds 4, 6 and 7, respectively at a aphids prior to treatment by placing a heavily infested leaf concentration of the test solution of 2500 mg/L showed a from the main aphid colony on top of each cotyledon. Aphids mortality of at least 90%. US 9,029,639 B2 121 122 II.5 Activity Against Green Peach Aphid (Myzus persicae) radicals may be unsubstituted, may be partially or For evaluating control of green peach aphid (Myzus persi fully halogenated or may carry 1, 2 or 3 identical or cae) through systemic means the test unit consisted of different substituents R. 96-well-microtiter plates containing liquid artificial diet or wherein R', R, R and R are selected from the under an artificial membrane. group consisting of OR', SR, C(Y)R’, C(Y)OR, The compounds were formulated using a solution contain S(O).R. NR'R''. heterocyclyl, Cs-Co-cycloalkyl, ing 75% v/v water and 25% v/v DMSO. Different concentra Cs-Co-cycloalkenyl and phenyl, wherein the four tions of formulated compounds were pipetted into the aphid last mentioned radicals may be unsubstituted or may diet, using a custom built pipetter, at two replications. After carry 1, 2, 3, 4 or 5 identical or different substituents 10 R; application, 5 to 8 adult aphids were placed on the artificial R and Rare selected from the group consisting of membrane inside the microtiter plate wells. The aphids were hydrogen, halogen, CN, NO, C-Co-alkyl, C-Co then allowed to suck on the treated aphid diet and incubated at alkenyl and C-Co-alkynyl, wherein the three last about 23+1° C. and about 50+5% relative humidity for 3 days. mentioned radicals may be unsubstituted, may be par Aphid mortality and fecundity was then visually assessed. 15 tially or fully halogenated or may carry 1, 2 or 3 In this test, compounds 2, 4, 6 and 7, respectively, at 2500 identical or different substituents R*, ppm showed 100% mortality in comparison with untreated or wherein R and R are selected from the group controls. consisting of OR: SR, C(Y)R, C(Y)Or, S(O).R., NR'R''. heterocyclyl, Cs-Co-cycloalkyl, Cs-Co-cy The invention claimed is: cloalkenyl and phenyl, wherein the four last men 1. A compound of formula (I) tioned radicals may be unsubstituted or may carry 1, 2, 3, 4 or 5 identical or different substituents R, and wherein (I) N R', R', and Rare selected from the group consisting x w?N v 25 of hydrogen, CN, NO, C-Co-alkyl, C-Co-alkenyl and C-Co-alkynyl, wherein the three last mentioned radicals may be unsubstituted, may be partially or ul 1. Rt. fully halogenated or may carry 1, 2 or 3 identical or R1 R different substituents R. 30 or wherein R', R, R are selected from the group consisting of OR', SR, C(Y)R, C(Y)OR, S(O).R., wherein NRR, C(Y)NR&R', S(O)NR'R', C(Y)NR'NRR, A is an oxazole orthiazole orimidazole radical of formulae heterocyclyl, C-Co-cycloalkyl, Cs-Co-cycloalk A1, A2 or A3, enyland phenyl, wherein the four last mentioned radi 35 cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 identical or different substituents R': A1 V is N: R41 W is C(R"); with R" being hydrogen: R is selected from the group consisting of hydrogen, halo 40 gen, C-C-alkyl, C-C-haloalkyl, C-C-alkoxy, it. - Z R51 C-C-haloalkoxy, C-C-alkylthio, C-C-haloalky lthio, C-C-alkylsulfinyl, C-C-haloalkylsulfinyl, (R6) C-C-alkylsulfonyl, C-C-haloalkylsulfonyl, C-C- A2 cycloalkyl, C-C-halocycloalkyl, C-C-alkenyl, R42 45 C-Ca-haloalkenyl, C-C-alkynyl and C-C-alkoxy C-C-alkyl; RandR'' are selected independently of each other from the R52 4. Z it. group consisting of hydrogen, methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy and trifluo (R62), 50 romethoxy; A3 X' is O: it. R" is hydrogen, C1-Co-alkyl, C1-Co-haloalkyl, C-Ca alkylene-CN. heterocyclyl-C-C-alkyl, hetaryl-CCs alkyl, C-C-alkylen-OR or C-Co-cycloalkyl-C-C- j \ 55 alkyl: R53 - Z R43 m is 0, 1, or 2: Y is O or S: (R63). R", R” and R are independently of each other selected from the group consisting of hydrogen, C-C-alkyl, wherein 60 C-Ca-haloalkyl, C-C-cycloalkyl, C-C-cycloalkyl # denotes the binding site to the remainder of formula I; methyl, C-C-halocycloalkyl, C-C-alkenyl, C-C- Z is O or S for Z=O or haloalkenyl, C-C-alkynyl, C-C-alkoxy-C-C- Z is N for Z=1: alkyl, phenyl, hetaryl, phenyl-C-C-alkyl and hetaryl R', R, R and R are independently of each other C-C-alkyl, wherein the aromatic ring in the four last selected from the group consisting of hydrogen, halo 65 mentioned radicals may be unsubstituted or may carry 1, gen, CN, NO, C-Co-alkyl, C-Co-alkenyl and 2, 3, 4 or substituents which, independently of each C-Co-alkynyl, wherein the three last mentioned other, are selected from the group consisting of halogen, US 9,029,639 B2 123 124 cyano, nitro, C-C-alkyl, C-Ca-haloalkyl, C-C- loxy and phenoxy, wherein the last 6 mentioned radicals alkoxy and C-C-haloalkoxy: may be unsubstituted or may carry 1, 2, 3, 4 or 5 radicals R" is selected from the group consisting of C-C-alkyl, R'; and wherein C-Ca-haloalkyl, C-C-cycloalkyl, C-C-cycloalkyl R’ is selected from the group consisting of halogen, cyano, methyl, C-C-halocycloalkyl, C-C-alkenyl, C-C- nitro, C-C-alkyl, C-C-haloalkyl, C-C-alkoxy, haloalkenyl, C-C-alkynyl, C-C-alkoxy-C-C- C-Ca-haloalkoxy, C-C-alkylthio, C-Ca-haloalky alkyl, phenyl, hetaryl, phenyl-C-C-alkyl and hetaryl lthio, C-C-alkylsulfinyl, C-Ca-haloalkylsulfinyl, C-C-alkyl, wherein the aromatic ring in the four last C-C-alkylsulfonyl, C-Ca-haloalkylsulfonyl, C-C- mentioned radicals may be unsubstituted or may carry 1, alkylcarbonyl, C-Ca-haloalkylcarbonyl, C-C-cy 2, 3, 4 or 5 substituents which are independently of each 10 cloalkyl, C-C-halocycloalkyl, C-C-alkenyl, C-C- other selected from the group consisting of halogen, haloalkenyl, C-C-alkynyl and C-C-alkoxy-C-C- cyano, nitro, C-C-alkyl, C-Ca-haloalkyl, C-C- alkyl: alkoxy and C-Ca-haloalkoxy; wherein said heterocyclyl is a Saturated, partially unsatur RandR are independently of each other selected from the 15 ated or unsaturated 5-, 6-, 7- or 8-membered monocyclic group consisting of hydrogen, C-C-alkyl, C-Ca-ha heterocyclic radical or a saturated, partially unsaturated loalkyl, C-C-cycloalkyl, C-C-cycloalkylmethyl, or unsaturated 8 to 10 membered bicyclic heterocyclic C-C-halocycloalkyl, C-C-alkenyl, C-C-haloalk radical; wherein the monocyclic and bicyclic heterocy enyl, C-C-alkynyl, C-C-alkoxy-C-C-alkyl, clic radicals comprise, as ring members, 1, 2, 3 or 4 C-C-alkylcarbonyl, C-Ca-haloalkylcarbonyl, C-C- heteroatoms selected from the group consisting of N, O alkylsulfonyl, C-Ca-haloalkylsulfonyl, phenyl, phenyl and S; carbonyl, phenylsulfonyl, hetaryl, hetarylcarbonyl, and hetarylsulfonyl, phenyl-C-C-alkyl and hetaryl-C-C- wherein said hetaryl is a monocyclic 5- or 6-membered alkyl, wherein the aromatic ring in the eight last men heteroaromatic radical or a bicyclic 8- to 10-membered tioned radicals may be unsubstituted or may carry 1,2,3, 25 heteroaromatic; and wherein the monocyclic and bicy 4 or 5 substituents which, independently of each other, clic heteroaromatic radicals comprise, as ring members, are selected from the group consisting of halogen, 1, 2, 3 or 4 heteroatoms selected from the group consist cyano, nitro, C-C-alkyl, C-C-haloalkyl, C-C- ing of N, O and S; alkoxy and C-Ca-haloalkoxy; or or an agriculturally or veterinally acceptable salt, N-oxide, RandR together with the nitrogenatom to which they are 30 enantiomer or diastereomer thereof. bound form a 5- or 6-membered, saturated or unsatur 2. The compound as claimed in claim 1, wherein R' is ated heterocycle, which may carry a further heteroatom hydrogen or C-C-alkyl. being selected from the group consisting of O, S and N 3. The compound as claimed in claim 1, wherein R and R' as a ring member atom and wherein the heterocycle may are hydrogen. be unsubstituted or may carry 1, 2, 3, 4 or 5 substituents 35 4. The compound as claimed in claim 1, wherein Z is O. which are independently of each other selected from the 5. The compound as claimed in claim 1, wherein Z is S. group consisting of halogen, cyano, nitro, C-C-alkyl, 6. The compound as claimed in claim 1, wherein Z is N. C-Ca-haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy; 7. The compound as claimed in claim 1, wherein A is a RandR" are independently of each otherselected from the radical A1. group consisting of hydrogen, C-C-alkyl, C-C-ha 40 8. The compound as claimed in claim 7, wherein R' is loalkyl, C-C-cycloalkyl, C-C-halocycloalkyl, selected from the group consisting of hydrogen, halogen, C-C-alkenyl, C-Ca-haloalkenyl, C-C-alkynyl, C-C-alkyl, C-C-haloalkyl, C-C-cycloalkyl and C-C- C-C-alkoxy-C-C-alkyl, phenyl, hetaryl, phenyl-C- halocycloalkyl. C-alkyl and hetaryl-C-C-alkyl, wherein the aromatic 9. The compound as claimed in claim 7, wherein R is ring in the four last mentioned radicals may be unsub 45 selected from the group consisting of hydrogen, halogen, stituted or may carry 1, 2, 3, 4 or substituents which are C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl and C-C- independently of each other selected from the group halocycloalkyl. consisting of halogen, cyano, nitro, C-C-alkyl, C-C- 10. The compound as claimed in claim 7, wherein R' is haloalkyl, C-C-alkoxy and C-Ca-haloalkoxy: selected from the group consisting of hydrogen, C-C-alkyl, R is selected from the group consisting of hydrogen, 50 C-Ca-haloalkyl, C-C-cycloalkyl-C-C-alkyl, heterocy C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl, clyl-C-C-alkyl, C-C-alkoxy-C-C-alkyl and C-C- C-C-cycloalkylmethyl, C-C-halocycloalkyl, C-C- alkyl-CN. alkenyl, C-Ca-haloalkenyl, C-C-alkynyl, C-C- 11. The compound as claimed in claim 1, wherein A is a alkoxy-C-C-alkyl, phenyl and phenyl-C-C-alkyl radical A2. wherein the phenyl ring in the two last mentioned radi 55 12. The compound as claimed in claim 11, wherein R is cals may be unsubstituted or may carry 1, 2, 3, 4 or 5 selected from the group consisting of hydrogen, halogen, substituents which are independently of each other C-C-alkyl, C-Ca-haloalkyl, C-C-cycloalkyl and C-C- Selected from the group consisting of halogen, cyano, halocycloalkyl. nitro, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy and 13. The compound as claimed in claim 11, wherein R is C-Ca-haloalkoxy; 60 selected from the group consisting of hydrogen, halogen, Rare independently of each other selected from the group C-C-alkyl, C-C-haloalkyl, C-C-cycloalkyl and C-C- consisting of cyano, nitro, C-C-alkoxy, C-Ca-ha halocycloalkyl. loalkoxy, C-C-alkylthio. C-Ca-haloalkylthio, C-C- 14. The compound as claimed in claim 11, wherein R is alkylsulfinyl, C-Ca-haloalkylsulfinyl, C-C-alkylsul selected from the group consisting of hydrogen, C-C-alkyl, fonyl, C-Ca-haloalkylsulfonyl, C-Co-alkylcarbonyl, 65 C-Ca-haloalkyl, C-C-cycloalkyl-C-C-alkyl, heterocy C-C-cycloalkyl, 5- to 7-membered heterocyclyl phe clyl-C-C-alkyl, C-C-alkoxy-C-C-alkyl and C-C- nyl, C-C-cycloalkoxy, 3- to 6-membered heterocycly alkyl-CN. US 9,029,639 B2 125 126 15. The compound as claimed in claim 1, wherein A is a environment in which the pests are growing or may grow, or radical A3. the materials, plants, seeds, soils, Surfaces or spaces to be 16. The compound as claimed in claim 15, wherein R is protected from pest attack or infestation with a pesticidally selected from the group consisting of hydrogen, halogen, effective amount of a compound of claim 1 or a salt or an C-Ca-haloalkyl, C-C-cycloalkyl and C-C-halocy N-oxide thereof. cloalkyl. 20. The method as claimed in claim 19, wherein the inver 17. The compound as claimed in claim 15, wherein R is tebrate pests are insects. selected from the group consisting of hydrogen, halogen, 21. The method as claimed in claim 20, wherein the inver C-C-alkyl, C-C-haloalkyl, C-C-cycloalkyl and C-C- tebrate pests are insects of the order Homoptera. halocycloalkyl. 10 18. The compound as claimed in claim 15, wherein R is 22. A method for protecting plant propagation material selected from the group consisting of hydrogen, C-C-alkyl, and/or the plants which grow therefrom, which method com C-Ca-haloalkyl, C-C-cycloalkyl-C-C-alkyl, heterocy prises treating the plant propagation material with a pesticid clyl-C-C-alkyl, C-C-alkoxy-C-C-alkyl and C-C- ally effective amount of a compound of claim 1 or an agri alkyl-CN. 15 culturally acceptable salt or an N-oxide thereof. 19. A method for controlling invertebrate pests, wherein, 23. Plant propagation material, treated with at least one the invertebrate pests are arthropod pests, which method.com compound of claim 1 and/or an agriculturally acceptable salt prises treating the pests, their food Supply, their habitat or or an N-oxide thereof. their breeding ground or a plant, seed, soil, area, material or k k k k k