USOO8343893B2

(12) United States Patent (10) Patent No.: US 8,343,893 B2 Jeschke et al. (45) Date of Patent: Jan. 1, 2013

(54) SUBSTITUTED ENAMINOCARBONYL FOREIGN PATENT DOCUMENTS COMPOUNDS DE 27 48814 A1 5, 1978 DE 33 14 196 A1 9, 1983 (75) Inventors: Peter Jeschke, Bergisch Gladbach (DE); DE 36 30 046 A1 3, 1988 Thomas Schenke, Bergisch Gladbach DE 36 3.1538 A1 3, 1988 (DE); Robert Velten, Langenfeld (DE); DE 44 17752 A1 11, 1995 EP O 104 876 A2 4f1984 Peter Limmen, Idstein (DE); Olga EP O 302,389 A2 2, 1989 Malsam, Rösrath (DE); Ulrich Görgens, EP O 373 464 A2 6, 1990 Ratingen (DE); Arnd Voerste, Köln EP O 393 453 A2 10, 1990 (DE) EP O 446913 A1 9, 1991 EP O 539 588 A1 5, 1993 (73) Assignee: Bayer Cropscience AG, Monheim (DE) EP O 565 050 A1 10, 1993 EP O 569 947 A1 11, 1993 (*) Notice: Subject to any disclaimer, the term of this EP O7757OO A1 5, 1997 EP O 780 384 A2 6, 1997 patent is extended or adjusted under 35 EP 0 794 180 A1 9, 1997 U.S.C. 154(b) by 57 days. EP 2O39 678 A1 3, 2009 JP 5-239034 A 9, 1993 (21) Appl. No.: 12/817,919 WO WO 97.10226 A1 3, 1997 WO WO99, 55668 A1 11, 1999 (22) Filed: Jun. 17, 2010 WO WO 01/07414 A1 2, 2001 WO WO 2004/082616 A2 9, 2004 (65) Prior Publication Data WO WO 2006/089633 A2 8, 2006 WO WO 2007/095229 A2 8, 2007 US 2010/0324103 A1 Dec. 23, 2010 WO WO 2007 115643 A1 10/2007 WO WO 2007 115644 A1 10/2007 (30) Foreign Application Priority Data WO WO 2007 115646 A1 10/2007 WO WO 2007/149134 A1 12/2007 Jun. 18, 2009 (EP). O9163 137 WO WO 2008/OO9360 A2 1, 2008 (Continued) (51) Int. Cl. ADIN 43/40 (2006.01) OTHER PUBLICATIONS A6 IK3I/435 (2006.01) CO7D 213/08 (2006.01) Grimmett, M.R., and Keene B.R.T. In ... "Advances in Heterocyclic Chemistry.” 43:148-161. A. R. Katritzky (Ed.), Academic Press, (52) U.S. Cl...... 504/244; 514/277:546/250; 546/255 United States (1988). (58) Field of Classification Search ...... 546/250, Hiroi, K., and Kato, F. "Stereochemical studies of the palladium 546/255; 504/244, 250, 514/277 catalyzed rearrangements of chiral 2-alkynyl sulfinates into chiral See application file for complete search history. allenyl sulfones.” Tetrahedron 57:1543-1550, Elsevier Science Ltd., England (2001). Jung, C.-K. et al., “Phosphine-Mediated Reductive Condensation of (56) References Cited Y-Acyloxy Butynoates: A Diversity Oriented Strategy for the Con struction of Substituted Furans.” J. Am. Chem. Soc. 126:41 18-4119, U.S. PATENT DOCUMENTS American Chemical Society, United States (2004). 4,030,994 A 6, 1977 KollonitSch 4, 195,036 A 3, 1980 GoZZO et al. (Continued) 4,631,081 A 12/1986 Watson et al. 4,748,243 A 5, 1988 Becket al. 4,778,896 A 10/1988 Gallenkamp Primary Examiner – Paul V. Ward 4,990,622 A 2f1991 Jelich (74) Attorney, Agent, or Firm — Sterne, Kessler, Goldstein 5,116,993 A 5, 1992 Jelich & Fox PL.L.C. 5,175.301 A 12/1992 Minamida et al. 5, 180,833. A 1/1993 Uneme et al. 5,346,343 A 9, 1994 Babel (57) ABSTRACT 5,420,270 A 5/1995 Chandrakumar et al. 5,679,796 A 10, 1997 Kraatz The present application relates to Substituted enaminocarbo 5,811,555 A 9/1998 Wakasugi et al. nyl compounds of the formula (I) 5,894,073. A 4/1999 Matsuda et al. 6,022.974 A 2/2000 Werbitzky et al. RI A 6,187,927 B1 2/2001 Pitterna 6,252,087 B1 6, 2001 Koch et al. R2 Y -/ 7,230,115 B1 6, 2007 Dolbier et al. 7,393,844 B2 7/2008 Goble et al. 7,687,634 B2 3/2010 LOSo et al. 2003, OO69242 A1 4/2003 Toriyabe et al. B - 2007/0299264 A1 12/2007 Huang et al. O D 2008/0305955 A1 12/2008 Bretschneider et al. 2009,024.7551 A1 10/2009 Jeschke et al. in which A, B, D, R' to Rare each as defined in the descrip 2009,0253749 A1 10/2009 Jeschke et al. tion, to processes for preparation thereof and to the use 2010, 004.8646 A1 2/2010 Jeschke et al. thereof for controlling animal pests. 2010/0204480 A1 8, 2010 Lui et al. 2010/024O705 A1 9, 2010 Jeschke et al. 2011/0306499 A1 12/2011 Bretschneider et al. 18 Claims, No Drawings US 8,343,893 B2 Page 2

FOREIGN PATENT DOCUMENTS David, O., et al., “New Access to Chiral Cycle (D-Oxygenated 3-Enamino Esters by Intramolecular Aminocyclisation Reactions.” WO WO 2008/067911 A1 6, 2008 Heterocycles 62:839-846, Elsevier B.V., Netherlands (2004). OTHER PUBLICATIONS Gassen, K.R., and Baasner, B., "Fluorinated Cyclopropanecarboxylic Acids and Their Derivatives,” Journal of Kinugawa, M., et al., “Facile synthesis of the key intermediate of EO Fluorine Chemistry. 49:127-139, Elsevier Sequoia, Netherlands (1990). 9 via the formation of the indole skeleton using the Nenitzescu Gilchrist, T.L., “Comprehensive Organic Synthesis.” S.V. Ley, (Ed.), reaction.” J. Chem. Soc. Perkin Trans. 1:2677-2678 Chemical Soci 7:748-750, Pergamon Press, England (1992). ety of London, England (1995). Grigg, R., and Savic, V., “Palladium catalysed synthesis of pyrroles Kunes, J., et al., “Synthesis and Antifungal Activity Evaluation of from enamines.” Chem. Commun, 31(35):873-874. The Royal Soci 3-Hetaryl-2,5-Dihydrofuran-2-Ones. An Unusual Fragmentation of ety of Chemistry, England (2000). Pévet, I., et al., “I2,3-Wittig Sigmatropic Rearrangement of Y-Al the Oxazole Ring via 2,3-Selenoxide Shift, 'Collect. Czech. Chem. lyloxy-B-Enaminoesters.” Synlett 5:663-666, Georg Thieme Verlag Commun. 66:1809-1830. Institute of Organic Chemistry and Bio Stuttgart, New York (2003). chemistry, Czech Republic (2001). Prabhakar, P., et al., “A Mild and Efficient Chemoselective Protection Larock, R. C., and Liu, C.-L., “Mercury in Organic Chemistry. 24 of Primary Alcohols as Pivaloyl Esters. Using La(NO)6HO as a Mercuration and Subsequent Carbonylation of 4-Hydroxy-2-alkyn Catalyst under Solvent-free Conditions.” Chemistry Letters 1-ones: A Novel Route to Furans, J. Org. Chem, 48:2151-2158, 36(6):732-733. The Chemical Society of Japan, Japan (2007). American Chemical SocieZy, United States (1983). Raminelli, C., et al., “Kinetic resolution of propargylic and allylic Maezaki, N., et al., “Pd-catalyzed asymmetric sulfinylzincation of alcohols by Candida antarctica lipase (Novozyme 435).” Tetrahe 1-alkynoates using 1-alkynyl Sulfoxides bearing a chiral auxiliary.” dron. Asymmetry 15:3117-3122. Elsevier Ltd., England (2004). Tetrahedron Asymmetry 13:1961-1964. Elsevier Science Ltd., Takahashi.T. et al., “Cationic Polymerization Behavior of Alkoxyal England (2002). lenes. Macromolecules 28:866-869, American Chemical Society, United States (1995). Nishiwaki, N., et al., “Synthesis of N-Modified 4-Aminopyridine-3- Tayama, E., and Hashimoto, R., "A facile synthetic method of O-qua carboxylates by Ring Transformation.” Synlett 9:1437-1439, Georg ternary-f.Y-unsaturated aldehydes via the stereoselective 14-elimi Thieme Verlag, Stuttgart, New York (2006). nation and C-regioselective Ferrier reaction.” Tetrahedron Letters Pesti, J. A., et al., “Efficient Pyridinylmethyl Functionalization: Syn 48:7950-7952, Elsevier Ltd., England (2007). thesis of 10, 10-Bis(2-fluoro-4-pyridinyl)methyl-9(10H)- Tisler, M., and Stanovnik, B., in "Advances in Heterocyclic Chem anthracenone (DMP 543), an Acetylcholine Release Enhancing istry.” A. R. Katritzky (Ed.) 9:285-291, Academic Press, United Agent.” J. Org. Chem. 65:7718-7722, American Chemical Society, States (1968). United States (2000). Tisler, M., et al., “Pyridazines and their Benzo Derivatives,” in Com Beholz, L. G. et al., “Formation of Dihydropyridone- and Pyridone prehensive Heterocyclic Chemistry 3(2B):18-20, Academic Press, Based PeptideAnalogs through AZa-Annulation off-Enamino Ester United States (1984). and Amide Substrates with O-Amido Acrylate Derivatives.” J. Org. Van Der Eycken, E., et al., “Synthesis of (E)-5-(2-arylvinyl)-2- Chem. 62: 1033-1042, American Chemical Society, United States (hetero)arlpyridines, (E)-2-(2-arylvinyl)-5- (1997). methoxycarbonylpyridines and (EE)-2,5-bis(2-arylvinyl)pyridines Cabanal-Duvillard, I., and Berrien, J.-F. "A Simple Access to Key as polarity and pH probes.” J. Chem. Soc., Perkin Trans. 2:928-937. Pyridine Building Blocks.” Heterocyclic Communications 5(3):257 The Society of Chemistry, England (2002). 262, De Gruyter, Germany (1999). Yamamoto, Y, et al., “Synthesis of arylboronates via Cp*RuCl Cheeseman, G.W.H., and Wrstiuk, E.S.G., in "Advances in Hetero catalyzed cycloaddition of alkynylboronates.” Tetrahedron 62:4294 cyclic Chemistry.” A. R. Katritzky (Ed.) 22:390-392, Academic 4305, Elsevier Ltd., England (2006). Press, United (1978). English language Abstract of German Patent Publication No. DE 3 Clasby, M. C., et al., “Himbacine derived thrombin receptor antago 314 196 A1, European Patent Office, espacenet database World nists: Discovery of a new tricyclic core.” Bioorganic & Medicinal wide (2001). Chemistry Letters (17):3647-3651, Elsevier Ltd., England (2007). English language Abstract of German Patent Publication No. DE 4 Comer, E., and Murphy, W.S., “The bromoquinone annulation reac 417752 A1, European Patent Office, espacenet database World tion: a formal total synthesis of EO9.” Arkivoc vii.286-296, Arkat wide (2001). USA, Inc, United States (2003). English language Abstract of Japanese Patent Publication No. Covarrubias-Zuniga, A., et al., “Synthesis of Resorcinols Via a 5-239034 A. Japanese Patent Office, Patent & Utility Model Gazette Michael Addition-Dieckman Cyclization Sequence of Dimethyl 1,3- DB, Patent Abstracts of Japan (1993). Acetonedicarboxylate Anion With Alkyl Alkynoates.” Synthetic International Search Report for International Application No. PCT/ Communications 28(18):3461-3469, Marcel Dekker, Inc., United EP2010/003395, European Patent Office, Netherlands, mailed on States (1998). Sep. 30, 2010. US 8,343,893 B2 1. 2 SUBSTITUTED ENAMINOCARBONYL D is a T-R radical in which COMPOUNDS T is oxygen, Sulphur or optionally Substituted nitrogen, and R is hydrogen, formyl, C-C-alkyl, C-C-alkoxy-C-C- The present application relates to Substituted enaminocar alkyl, halo-C-C-alkoxy-C-C-alkyl, C-C-alkoxy-C- bonyl compounds, to processes for preparation thereof and to C-alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, the use thereof for controlling animal pests, especially those C-C-alkenyl, C-C-cycloalkyl, C-C-alkynyl, C-C- which damage plants, in particular arthropods, especially alkoxycarbonyl, C-C-cycloalkyloxycarbonyl, aryl, insects. hetaryl, heterocyclyl, C-C-alkylcarbonyl, aryl-C-C- Substituted enaminocarbonyl compounds, for example alkyl, hetaryl-C-C-alkyl, halo-C-C-alkylcarbonyl, Y-allyloxy-B-enamino esters are known (cf. I. Pevet et al., 10 arylcarbonyl, C-C-alkylsulphonyl, halo-C-C-alkylsul Synlett 5, 663-666, 2003), and some are used as intermediates phonyl, aryl-C-C-aryloxy-C-C-alkyl, arylsulphonyl or for the synthesis of different heterocycles, for example of tri-C-C-alkylsilyl, where the groups are optionally Sub 3,4,5-trifunctionalized pyridines, N-methyldioxoindoles, stituted; indole-3-carboxylic acid derivatives or pyrroles (cf. Y-meth R" is hydrogen, C-C-alkyl, C-C-alkenyl, C-C-alkynyl, oxy-f-enamino methyl esters: N. Nishiwaki et al., Synlett 9, 15 C-C-cycloalkyl, C-C-cycloalkyl-C-C-alkyl, halo 1437-1439, 2006: E. Comer, W. S. Murphy, ARKIVOC C-C-alkyl, halo-C-C-alkenyl, halo-C-C-cycloalkyl, (Gainesville, Fla., USA) 7, 286-296, 2003; M. Kinugawa et halo-C-C-cycloalkyl-C-C-alkyl, C-C-alkoxy oraryl al., J. Chem. Soc., Perkin Trans. 1: Org. and Bio-Organic C-C-alkyl, Chem. 21, 2677-2678, 1995; EP 565 050 A1: Y-methoxy-3- R is hydrogen or halogen; and enamino methyl esters with B-vinyl bromidefunctionality: R. R is hydrogen or C1-Co-alkyl. Grigg, V. Savic Chem. Commun. (Cambridge) 10, 873-874, In a first embodiment, the invention relates to enaminocar 2000). bonyl compounds of the formula (I) in which EP-A1-2039678 describes a process for preparing 4-ami A is a heterocycle of the following formula nobut-2-enolides, in which specific Substituted enaminocar 25 bonyl compounds are used as intermediates. WO2007/115643 describes cyclic enaminocarbonyl com pounds, which are proposed for control of pests. Modern crop protection compositions have to meet many requirements, for example in relation to level, duration and 30 range of their action and possible use. Questions of toxicity play a role, as does the question of application rate and that of economic viability. The search for new crop protection com in which positions can therefore never be considered to be complete, X is halogen (preferably fluorine, chlorine or bromine), and there is a constant need for new compounds with 35 C-C-alkyl or halo-C-C-alkyl, preferably CHF, CHF improved properties. CF, CHCF, CHCHF, CHCHF, and It is an object of the present invention to provide com Y is halogen (preferably fluorine, chlorine or bromine), pounds which take account of the abovementioned aspects. C-C-alkyl, halo-C-C-alkyl, preferably CHF, CHF, It has now been found that, Surprisingly, particular Substi CF, CHCF, CHCHF, CHCHF, halo-C-C-alkoxy, tuted enaminocarbonyl compounds and the N-oxides and 40 preferably OCHF, OCHF, OCF, OCHCF, salts thereof are especially Suitable for controlling animal OCHCHF, OCHCHF, azido or cyano; pests and can therefore be used particularly efficiently in the A is preferably one of the following heterocycles: 5,6- agrochemical sector and in the animal health sector. dibromopyrid-3-yl, 6-bromo-5-chloropyrid-3-yl, These enaminocarbonyl compounds are characterized by 6-bromo-5-fluoropyrid-3-yl, 5-chloro-6-iodopyrid-3- 45 y1, 5,6-dichloropyrid-3-yl, 6-chloro-5-fluoropyrid-3-yl, the formula (I) 5-bromo-6-chloropyrid-3-yl, 6-chloro-5-methylpyrid 3-yl, 6-chloro-5-difluoromethylpyrid-3-yl, 6-chloro-1, 4-pyridazin-3-yl, 2-chloropyrimid-5-yl and 2-chloro-1, (I) 3-thiazol-5-yl. 50 In a second embodiment, the invention relates to enami nocarbonyl compounds of the formula (I) in which A is pyrid-2-yl; pyrid-4-yl; or pyrid-3-yl which is optionally 6-substituted by fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl or trifluo 55 romethoxy; pyridazin-3-yl which is optionally 6-substi tuted by chlorine or methyl; pyrazin-3-yl: 2-chloropyrazin in which 5-yl: 1,3-thiazol-5-yl which is optionally 2-substituted by A is an optionally Substituted heterocycle; chlorine or methyl; tetrahydrofuryl; pyrimidinyl; pyra B is a Z R radical in which Zolyl; thiophenyl, oxazolyl; isoxazolyl: 1,2,4-oxadiazolyl, Z is oxygen, Sulphur or optionally Substituted nitrogen, and 60 isothiazolyl: 1,2,4-triazolyl: 1,2,5-thiadiazolyl which is R" is hydrogen, C-C-alkyl, C-C-alkoxy-C-C-alkyl, optionally substituted by fluorine, chlorine, bromine, C-C-alkylthio-C-C-alkyl, halo-C-C-alkyl, cyano cyano, nitro, or is Substituted by in each case optionally C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C-cy fluoro- and/or chlorine-substituted C-C-alkyl, C-C- cloalkyl, Ca-Co-dicycloalkyl, tri-C-C-alkylsilyl, tri-C- alkylthio, or C-C-alkylsulphonyl, preferably pyrid-3-yl Co-alkylsilyl-C-C-alkyl, hetaryl, hetaryl-C-C-alkyl, 65 which is 6-substituted by fluorine, chlorine, bromine, optionally Substituted aryl, aryl-C-C-alkyl or aryl-C- methyl or trifluoromethyl or trifluoromethoxy, i.e. 6-fluo Co-alkoxy-C-C-alkyl; ropyrid-3-yl, 6-chloropyrid-3-yl, 6-bromopyrid-3-yl and US 8,343,893 B2 3 4 6-trifluoromethylpyrid-3-yl, 6-methylpyrid-3-yl, 6-trif enesulphonyl, trimethylsilyl, triethylsilyl, triisopropylsi luoromethoxypyrid-3-yl, or 2-methyl-1,3-thiazol-5-yl, lyl, dimethylisopropylsilyl or tert-butyldimethylsilyl: 2-chloro-1,3-thiazol-5-yl, 2-chloro-1,3-thiazol-5-yl, more preferably methylcarbonyl, ethylcarbonyl, tert-bu 2-chloropyrazin-5-yl, 6-chloro-1,4-pyridazin-3-yl, 6-me tylcarbonyl or methoxycarbonyl: thyl-1,4-pyridazin-3-yl, 5 R" is hydrogen, C-C-alkyl, C-C-alkenyl, C-C-alkynyl, A is preferably 6-fluoropyrid-3-yl, 6-chloropyrid-3-yl, C-C-cycloalkyl, C-C-cycloalkyl-C-C-alkyl, C-C- 6-bromopyrid-3-yl, 6-chloro-1,4-pyridazin-3-yl or alkoxy, aryl-C-C-alkyl or fluoro-substituted C-C- 2-chloro-1,3-thiazol-5-yl. alkyl, C-C-alkenyl, C-C-cycloalkyl or C-C-cy In a third embodiment, the invention relates to enaminocar cloalkyl-C-C-alkyl, preferably methyl, ethyl, allyl, bonyl compounds of the formula (I) in which A is as defined 10 propargyl, 2-fluoroethyl, 2,2-difluoroethyl, cyclopropyl. in the first or second embodiment and in which 2-fluorocyclopropyl or methoxy, more preferably methyl, B is a Z R radical in which cyclopropyl or 2.2-difluoroethyl; Z is oxygen or Sulphur, preferably oxygen, and R’ is hydrogen, fluorine or chlorine; and R" is hydrogen, C-C-alkyl, C-C-alkoxy-C-C-alkyl, R is hydrogen or C1-Co-alkyl. C-C-alkylthio-C-C-alkyl, halo-C-C-alkyl, cyano 15 C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C-cy The invention further comprises a process for preparing the cloalkyl, di-C-C-cycloalkyl-C-C-alkyl, tri-C-C- inventive compounds, comprising the following reaction alkylsilyl, tri-C-C-alkylsilyl-C-C-alkyl, hetaryl, steps hetaryl-C-C-alkyl, aryl-C-C-alkyl, aryl-C-C-alky (a) reacting a compound of the formula (II) loxy-C-C-alkyl, phenyl or a nitro-, halogen-, C-C- alkoxy-, C-C-alkylthio-, C-C-alkylsulphinyl- or C-C-alkylsulphonyl-substituted phenyl, preferably (II) hydrogen, methyl, ethyl, n-propyl, iso-propyl. n-butyl, iso butyl, sec-butyl, tent-butyl, methoxyethyl, methylthiom ethyl, 2-methylthioethyl, 2.2.2-trichloroethyl, 2-chloroet 25 R3 hyl, 2-bromoethyl, 2-iodoethyl, 2-cyanoethyl, allyl, methallyl, 3-buten-1-yl, propargyl, cyclopentyl, cyclo with a compound of the formula (III) hexyl, dicyclopropylmethyl, trimethylsilyl, di-tert-butyl methylsilyl, iso-propyldimethylsilyl, trimethylsilylm ethyl, 2-(2-pyridyl)ethyl, 4-picolyl, benzyl, 30 (III) 4-methoxybenzyl, 2,4-dimethoxybenzyl, 4-bromobenzyl, O 4-methylsulphinylbenzyl, 4-nitrobenzyl, benzyloxym ethyl, 4-methylthiophenyl, 4-nitro-phenyl or 2,3,4,5,6- X-G pentafluorophenyl, more preferably hydrogen, methyl, B ethyl or iso-propyl; 35 D is a T-R radical in which in which T is oxygen, Sulphur or optionally Substituted nitrogen, pref B, D and R are each as defined here and LG is a suitable erably oxygen, and leaving group, especially halo-C-C-alkoxy, C-Cs-al R is hydrogen, formyl, C-C-alkyl, C-Ca-alkoxy-C-C- kanoyloxy, mercapto, C-C-alkylthio, halo-C-C-alky alkyl, halo-C-C-alkoxy-C-C-alkyl, C-C-alkoxy-C- 40 lthio orhalogen; LG is preferably C-Cs-alkoxy, especially C-alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, methoxy, ethoxy or iso-propoxy, preferably in the presence C-C-alkenyl, C-C-cycloalkyl, C-C-alkynyl, C-C- of a basic auxiliary and of a diluent, to give a compound of alkoxycarbonyl, C-C-cycloalkyloxycarbonyl, optionally the formula (IV); and substituted aryl, tetrahydropyran-2-yl, 3-bromotetrahy (b) reacting a compound of the formula (IV) dropyran-2-yl, tetrahydrothiopyran-2-yl, 1,4-dioxan-2-yl, 45 tetrahydrofuranyl, C-C-alkylcarbonyl, optionally Substi tuted aryl-C-C-alkyl, hetaryl-C-C-alkyl, halo-C-C- (IV) alkylcarbonyl, optionally Substituted arylcarbonyl, C-C- O D alkylsulphonyl, halo-C-C-alkylsulphonyl, optionally Substituted aryl-C-C-alkyloxy-C-C-alkyl, optionally 50 B R3 Substituted aryloxy-C-C-alkyl, optionally substituted arylsulphonyl or tri-C-C-alkylsilyl; preferably hydro gen, formyl, methyl, ethyl, n-propyl, iso-propyl. n-butyl, with a compound of the formula (V) iso-butyl, sec-butyl, tert-butyl, allyl, methoxymethyl, 1-ethoxyethyl, tert-butoxymethyl, methylthiomethyl, 55 HN(R)-CH-A (V) methoxyethoxymethyl, 1-(2-chloroethoxy)ethyl, 1-me in which B, D, A and R' and Rare each as defined here, thyl-1-methoxyethyl, cyclopropyl, cyclobutyl, propargyl, preferably in the presence of a diluent. methoxycarbonyl, ethoxycarbonyl, cyclopropyloxycarbo The invention further comprises a composition for control nyl, phenyl, tetrahydropyran-2-yl, methylcarbonyl, ethyl ling animal pests, preferably arthropods, especially insects, carbonyl, n-propylcarbonyl, iso-propylcarbonyl, tert-bu 60 which includes at least one inventive compound in an insec tylcarbonyl, trifluoromethylcarbonyl, ticidally effective amount. 4-nitrophenylcarbonyl, 2,4-dinitrophenyl, 4-nitrophenyl, The invention further comprises the use of an inventive benzyl, 4-methoxybenzyl, 2,4-dimethoxybenzyl, 3,4- compound for controlling animal pests in the agrochemical dimethoxybenzyl, 4-nitrobenzyl, 2,6-dichlorobenzyl, sector (plant pests) and/or in the animal health sector, and to 4-methoxybenzyloxymethyl, 4-nitrobenzyloxymethyl, 65 a method for controlling animal pests, characterized in that an 2-picolyl, 4-picolyl, methylsulphonyl, ethylsulphonyl, inventive compound oran inventive composition is allowed to 4-methoxyphenyl, trifluoromethylsulphonyl, para-tolu act on the pests and/or their habitat. US 8,343,893 B2 5 6 The inventive compounds may, depending on the type of which is saturated, unsaturated or heteroaromatic and may be Substituents, be present as geometric and/or as optically unsubstituted or substituted, where the bonding site is local active isomers or corresponding isomer mixtures in different ized on one ring atom. Unless defined differently, the hetero compositions. These stereoisomers are, for example, enanti cyclic ring preferably contains 3 to 9 ring atoms, especially 3 omers, diastereomers, atropisomers or geometric isomers. to 6 ring atoms, and one or more, preferably 1 to 4, especially The invention thus comprises pure stereoisomers and any 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from desired mixtures of these isomers. the group consisting of N, O, and S, although two oxygen In the general formula (I) and all other formulae in the atoms should not be directly adjacent. Examples of hetero present invention, the alkyl, alkoxy, haloalkyl, haloalkoxy, cyclyl groups are tetrahydropyran-2-yl, tetrahydrothiopyran alkylamino, alkylsulphinyl and alkylsulphonyl radicals, and 10 2-yl, 1,4-dioxan-2-yl and tetrahydrofuranyl. the corresponding unsaturated and/or Substituted radicals in The term heteroaryl or hetaryl is understood in the context the carbon skeleton, may each be straight-chain or branched of the present invention to mean systems as defined above and substituted or unsubstituted. Unless stated specifically, under "heterocyclyl', but which are heteroaromatic, i.e. area the lower carbon skeletons are preferred for these radicals, for fully unsaturated aromatic heterocyclic compound and are example having 1 to 6 carbon atoms, especially 1 to 4 carbon 15 substituted or unsubstituted. atoms, or in the case of unsaturated groups having 2 to 6 Unless defined differently, “substituted in the context of carbon atoms, especially 2 to 4 carbon atoms. the present invention means that the corresponding group Alkyl radicals, including in the combined definitions such may be substituted by one or more substituents, and indepen as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl; dently by one or more identical or different substituents. propyl Such as n- or iso-propyl; butyl Such as n-, iso-, tert- or Substituted radicals, such as a substituted alkyl, alkenyl, 2-butyl; pentyl such as n-pentyl, iso-penty1 and neo-pentyl: alkynyl, cycloalkyl, cycloalkenyl, aryl, phenyl, benzyl, het hexyl Such as n-hexyl, iso-hexyl, 3-methylpentyl, 2.2-dim erocyclyl and hetoaryl radical, are, for example a Substituted ethylbutyl and 2,3-dimethylbutyl; and heptyl such as n-hep radical derived from the unsubstituted base skeleton, where tyl, 1-methylhexyl and 1,4-dimethylpenty1. the Substituents are, for example, one or more, preferably 1, 2 Alkenyl and alkynyl radicals are defined as the possible 25 or 3, radicals from the group of halogen, alkoxy, alkylthio. unsaturated radicals corresponding to the alkyl radicals; hydroxyl, amino, nitro, carboxyl or a group equivalent to the where at least one double bond or triple bond, preferably one carboxyl group, cyano, isocyano, azido, alkoxycarbonyl, double bond or triple bond, is present. Alkenyl is, for alkylcarbonyl, formyl, carbamoyl, mono- and dialkylami example, vinyl, 1-allyl, 1-methylprop-2-en-1-yl, 2-methyl nocarbonyl, Substituted amino, such as acylamino, mono- and prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3- 30 dialkylamino, trialkylsilyl and optionally substituted en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, cycloalkyl, optionally Substituted aryl, optionally Substituted ethynyl, propargyl/propynyl, but-2-yn-1-yl, but-3-yn-1-yl heterocyclyl, where each of the latter cyclic groups may also and 1-methylbut-3-yn-1-yl. They may be substituted or be bonded via heteroatoms or divalent functional groups as unsubstituted. for the alkyl radicals mentioned, and alkylsulphinyl, includ Cycloalkyl groups are, for example, cyclopropyl, cyclobu 35 ing both enantiomers of the alkylsulphonyl group, alkylsul tyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The phonyl, alkylphosphinyl, alkylphosphonyl and, in the case of cycloalkyl groups may occur in bi- or tricyclic form. They cyclic radicals (="cyclic base skeleton'), also alkyl, may be substituted or unsubstituted. haloalkyl, alkylthioalkyl, alkoxyalkyl, optionally substituted When haloalkyl groups and haloalkyl radicals of mono- and dialkylaminoalkyl and hydroxyalkyl, the term haloalkoxy, haloalkenyl, haloalkynyl interalia are specified, 40 “substituted radicals, such as substituted alkyl, etc., the lower carbon skeletons are preferred for these radicals, for includes, as Substituents, in addition to the Saturated hydro example having 1 to 6 carbon atoms or 2 to 6, especially 1 to carbonaceous radicals mentioned, corresponding unsaturated 4 carbon atoms or preferably 2 to 4 carbon atoms, as are the aliphatic and aromatic radicals, such as optionally Substituted corresponding unsaturated and/or Substituted radicals, each alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alky in Straight-chain or branched form in the carbon skeleton, and 45 nylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenyl substituted or unsubstituted. Examples are trifluoromethyl, carbonyl, alkynylcarbonyl, mono- and dialkenylaminocarbo difluoromethyl, 2.2.2-trifluoroethyl, trifluoroallyl and nyl, mono- and dialkynylaminocarbonyl, mono- and 1-chloroprop-1-yl-3-yl. dialkenylamino, mono- and dialkynylamino, trialkenylsilyl, Halogen is fluorine, chlorine, bromine or iodine. trialkynylsilyl, optionally substituted cycloalkenyl, option Haloalkyl, -alkenyl, -alkynyl, -cycloalkyl, -alkylsulphonyl 50 ally Substituted cycloalkynyl, phenyl, phenoxy, etc. In the and -alkylcarbonyl mean alkyl, alkenyl, alkynyl, cycloalkyl, case of Substituted cyclic radicals with aliphatic moieties in alkylsulphonyl and alkylcarbonyl partly or fully substituted the ring, cyclic systems with those Substituents bonded to the by halogen, preferably by fluorine, chlorine or bromine, espe ring by a double bond, for example by an alkylidene group cially by fluorine and/or chlorine, e.g. monohaloalkyl, perha Such as methylidene or ethylidene or an oxo group, imino loalkyl, CF, CHF CHF, CFCF CHFCHCl, CC1, 55 group or Substituted imino group, are also included. CHCl, CHCHCl; haloalkoxy is, for example, OCF, The substituents mentioned by way of example (“first sub OCHFOCHF, CFCFO, OCHCF and OCHCHCl; the stituent level') can, when they contain hydrocarbonaceous same applies to haloalkenyl, -alkynyl, -cycloalkyl, -alkylsul moieties, optionally be further substituted there (“second phonyl and -alkylcarbonyl, and other halogen-substituted substituent level'), for example by one of the substituents as radicals. 60 defined for the first substituent level. Corresponding further Aryl is a mono-, bi- or polycyclic aromatic system, for substituent levels are possible. The term “substituted radical” example phenyl or naphthyl, preferably phenyl. Aryl may be preferably encompasses only one or two Substituent levels. substituted or unsubstituted. Preferred substituents for the substituent levels are, for A heterocyclic radical (heterocyclyl) contains at least one example, amino, hydroxyl, halogen, nitro, cyano, isocyano, heterocyclic ring (carbocyclic ring in which at least one 65 mercapto, isothiocyanato, carboxyl, carboxamide, SFs, ami carbon atom is replaced by a heteroatom, preferably by a noSulphonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alky heteroatom from the group consisting of N, O, S. P. B. Si, Se), nyl, monoalkylamino, dialkylamino, N-alkanoylamino, US 8,343,893 B2 7 8 alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkeny In a further emphasized group of compounds of the for loxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycar mula (I), R is hydrogen, B is iso-propoxy and A is 6-chloro bonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynyl 5-methylpyrid-3-yl. carbonyl, arylcarbonyl, alkylthio. cycloalkylthio. In a further emphasized group of compounds of the for alkenylthio, cycloalkenylthio, alkynylthio, alkylsulphenyl, mula (I), R is hydrogen, B is iso-propoxy and A is 6-chloro alkylsulphinyl, including both enantiomers of the alkylsul 5-difluoromethylpyrid-3-yl. phinyl group, alkylsulphonyl, monoalkylaminosulphonyl, In a further emphasized group of compounds of the for dialkylaminosulphonyl, alkylphosphinyl, alkylphosphonyl, mula (I), R and Rare each hydrogen, B is iso-propoxy and including both enantiomers for alkylphosphinyl and alky A is 6-chloropyrid-3-yl. lphosphonyl, N-alkylaminocarbonyl, N,N-dialkylaminocar 10 bonyl, N-alkanoylaminocarbonyl, N-alkanoyl-N-alkylami In a further emphasized group of compounds of the for nocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio. mula (I), R and Rare each hydrogen, B is iso-propoxy and arylthio, arylamino, benzylamino, heterocyclyl and trialkyl A is 6-bromopyrid-3-yl. silyl. In a further emphasized group of compounds of the for As already mentioned, preferred radicals having carbon 15 mula (I), R and Rare each hydrogen, B is iso-propoxy and atoms are those having 1 to 6 carbon atoms, preferably 1 to 4 A is 6-fluoropyrid-3-yl. carbon atoms, especially 1 or 2 carbon atoms. Preference is In a further emphasized group of compounds of the for generally given to Substituents from the group of halogen, e.g. mula (I), R and Rare each hydrogen, B is iso-propoxy and fluorine, chlorine and bromine, (C-C)-alkyl, preferably A is 6-trifluoromethylpyrid-3-yl. methyl or ethyl, (C-C)-haloalkyl, preferably trifluorom In a further emphasized group of compounds of the for ethyl, (C-C)-alkoxy, preferably methoxy or ethoxy, (C- mula (I), R and Rare each hydrogen, B is iso-propoxy and C)-haloalkoxy, nitro and cyano. A is 2-chloro-1,3-thiazol-5-yl. Optionally substituted aryl or heteroaryl is preferably phe In a further emphasized group of compounds of the for nylor heteroaryl, which is unsubstituted or mono- or polysub mula (I), R and Rare each hydrogen, B is iso-propoxy and stituted, preferably up to trisubstituted, by identical or differ 25 A is 5,6-dibromopyrid-3-yl. ent radicals from the group of halogen, (C-C)-alkyl, (C- In a further emphasized group of compounds of the for C)-cycloalkyl, (C-C)-alkoxy, (C-C)-haloalkyl, (C-C)- mula (I), R and Rare each hydrogen, B is iso-propoxy and haloalkoxy, (C-C)-alkylthio, cyano and nitro, e.g. ortho A is 6-bromo-5-chloropyrid-3-yl. meta- and para-tolyl, dimethylphenyls, 2-, 3- and 4-chlo In a further emphasized group of compounds of the for rophenyl, 2-, 3- and 4-trifluoromethyl and 2-, 3- and 4-trichlo 30 mula (I), R and Rare each hydrogen, B is iso-propoxy and rmethylphenyl, 2.4-, 3.5-, 2.5- and 2,3-dichlorophenyl, A is 6-bromo-5-fluoropyrid-3-yl. ortho-, meta- and para-methoxyphenyl. In a further emphasized group of compounds of the for In one emphasized group of compounds of the formula (I), mula (I), R and Rare each hydrogen, B is iso-propoxy and R is hydrogen, B is iso-propoxy and A is 6-chloropyrid-3-yl. A is 5-chloro-6-iodopyrid-3-yl. In a further emphasized group of compounds of the for 35 In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 6-bro mula (I), R and Rare each hydrogen, B is iso-propoxy and mopyrid-3-yl. A is 5,6-dichloropyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 6-fluoro mula (I), R and Rare each hydrogen, B is iso-propoxy and pyrid-3-yl. 40 A is 6-chloro-5-fluoropyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 6-trifluo mula (I), R and Rare each hydrogen, B is iso-propoxy and romethylpyrid-3-yl. A is 5-bromo-6-chloropyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 2-chloro 45 mula (I), R and Rare each hydrogen, B is iso-propoxy and 1,3-thiazol-5-yl. A is 6-chloro-5-methylpyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 5.6- mula (I), R and Rare each hydrogen, B is iso-propoxy and dibromopyrid-3-yl. A is 6-chloro-5-difluoromethylpyrid-3-yl. In a further emphasized group of compounds of the for 50 In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 6-bromo mula (I), R and Rare each hydrogen, B is methoxy and A is 5-chloropyrid-3-yl. 6-chloropyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 6-bromo mula (I), R and Rare each hydrogen, B is methoxy and A is 5-fluoropyrid-3-yl. 55 6-bromopyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 5-chloro mula (I), R and Rare each hydrogen, B is methoxy and A is 6-iodopyrid-3-yl. 6-fluoropyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 5.6- 60 mula (I), R and Rare each hydrogen, B is methoxy and A is dichloropyrid-3-yl. 6-trifluoromethylpyrid-3-yl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 6-chloro mula (I), R and Rare each hydrogen, B is methoxy and A is 5-fluoropyrid-3-yl. 2-chloro-1,3-thiazol-5-yl. In a further emphasized group of compounds of the for 65 In a further emphasized group of compounds of the for mula (I), R is hydrogen, B is iso-propoxy and A is 5-bromo mula (I), R and Rare each hydrogen, B is methoxy and A is 6-chloropyrid-3-yl. 5,6-dibromopyrid-3-yl. US 8,343,893 B2 10 In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R is methyl, R and Rare each hydrogen and B is 6-bromo-5-chloropyrid-3-yl. iso-propoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R is cyclopropyl, R and Rare each hydrogen and 6-bromo-5-fluoropyrid-3-yl. B is iso-propoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R is ethyl, R and Rare each hydrogen and B is 5-chloro-6-iodopyrid-3-yl. iso-propoxy. In a further emphasized group of compounds of the for 10 In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R is methoxy, RandR are each hydrogen and Bis 5,6-dichloropyrid-3-yl. iso-propoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is 15 mula (I), R' is 2-fluorocyclopropyl, RandR are each hydro 6-chloro-5-fluoropyrid-3-yl. gen and B is iso-propoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R is methyl, R and Rare each hydrogen and B is 5-bromo-6-chloropyrid-3-yl. methoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R' is cyclopropyl, R and Rare each hydrogen and 6-chloro-5-methylpyrid-3-yl. B is methoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R and Rare each hydrogen, B is methoxy and A is mula (I), R is ethyl, R and Rare each hydrogen and B is 6-chloro-5-difluoromethylpyrid-3-yl. 25 methoxy. In a further emphasized group of compounds of the for mula (I), R' is difluoromethyl, R and Rare each hydrogen In a further emphasized group of compounds of the for and B is iso-propoxy. mula (I), R' is difluoromethyl, R and Rare each hydrogen In a further emphasized group of compounds of the for and D is methylcarbonyloxy. mula (I), R is 2-fluoroethyl, R and Rare each hydrogen and 30 In a further emphasized group of compounds of the for B is iso-propoxy. mula (I), R' is 2-fluoroethyl, RandR are each hydrogen and In a further emphasized group of compounds of the for D is methylcarbonyloxy. mula (I), R is 2,2-difluoroethyl, R and Rare each hydrogen In a further emphasized group of compounds of the for and B is iso-propoxy. mula (I), R is 2,2-difluoroethyl, RandR are each hydrogen In a further emphasized group of compounds of the for 35 and D is methylcarbonyloxy. mula (I), R is methyl, R and Rare each hydrogen and B is In a further emphasized group of compounds of the for iso-propoxy. mula (I), R' is difluoromethyl, R and Rare each hydrogen In a further emphasized group of compounds of the for and D is hydroxyl. mula (I), R' is cyclopropyl, R and Rare each hydrogen and In a further emphasized group of compounds of the for B is iso-propoxy. 40 mula (I), R' is 2-fluoroethyl, RandR are each hydrogen and In a further emphasized group of compounds of the for D is hydroxyl. mula (I), R is 2-fluorocyclopropyl, R and Rare each hydro In a further emphasized group of compounds of the for gen and B is iso-propoxy. mula (I), R is 2,2-difluoroethyl, RandR are each hydrogen In a further emphasized group of compounds of the for and D is hydroxyl. mula (I), R is methoxy, RandR are each hydrogen and B is 45 iso-propoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is methyl, R and Rare each hydrogen and B is mula (I), R' is difluoromethyl, R and Rare each hydrogen D is methylcarbonyloxy. and B is methoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for 50 mula (I), R' is cyclopropyl, R and Rare each hydrogen and mula (I), R' is 2-fluoroethyl, RandR are each hydrogen and D is methylcarbonyloxy. B is methoxy. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is ethyl, R and Rare each hydrogen and D is mula (I), R is 2,2-difluoroethyl, R and Rare each hydrogen methylcarbonyloxy. and B is methoxy. 55 In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is methyl, R and Rare each hydrogen and B is mula (I), R is methyl, R and Rare each hydrogen and Dis methoxy. hydroxyl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R' is cyclopropyl, R and Rare each hydrogen and 60 mula (I), R is cyclopropyl, R and Rare each hydrogen and B is methoxy. D is hydroxyl. In a further emphasized group of compounds of the for In a further emphasized group of compounds of the for mula (I), R is 2-fluorocyclopropyl, R and Rare each hydro mula (I), R is ethyl, R and R are each hydrogen and D is gen and B is methoxy. hydroxyl. In a further emphasized group of compounds of the for 65 The radical definitions and explanations given above in mula (I), R is methoxy, RandR are each hydrogen and B is general terms or given as preferred apply correspondingly to methoxy. the end products and to the starting materials and intermedi US 8,343,893 B2 11 12 ates. These radical definitions can be combined with one -continued another as desired, i.e. including between the particular pre C ferred ranges. Preference is given in accordance with the invention to the / \, (E)-isomers of the formula (I). Salts suitable inaccordance with the invention of the inven tive compounds, for example salts with bases or acid addition salts, are all customary nontoxic salts, preferably agricultur CH N-CH ally and/or physiologically acceptable salts, for example salts 10 with bases or acid addition salts. Preference is given to salts HC-( o with inorganic bases, for example alkali metal salts (e.g. O O Sodium, potassium or caesium salts), alkaline earth metal O X-ch salts (e.g. calcium or magnesium salts), ammonium salts or O salts with organic bases, especially with organic amines, for 15 example triethylammonium, dicyclohexylammonium, N,N'- dibenzylethylenediammonium, pyridinium, picolinium or Some compounds of the formula (II) in which the DandR ethanol-ammonium salts, salts with inorganic acids (e.g. radicals are each as defined above can be obtained commer hydrochlorides, hydrobromides, dihydrosulphates, trihydro cially or synthesized by literature methods (cf., for example, compounds of the formula (II) in which D-O-CH(CH), Sulphates, orphosphates), salts with organic carboxylic acids R=H: T. Takahashi, et al., Macromolecules 28, 866-869, or organic Sulphonic acids (e.g. formates, acetates, trifluoro 1995; D=O CO C(CH), R=H: P. Prabhakar et al., acetates, maleates, tartrates, methanesulphonates, benzene Chem. Lett. 36,732-733, 2007; D=O CO CH, R—CH: Sulphonates or 4-toluenesulphonates). AS is well known, ter K Hiroi, F. Kato Tetrahedron 57, 1543-1550, 2001; D=O– tiary amines, for example some of the inventive compounds, 25 CO CH, R=CHs; J. Kunes et al., Coll. Czech. Chem. form N-oxides, which likewise constitute inventive salts. Commun. 66, 1809-1830, 2001: C. Raminelli et al., Tetrahe Preparation processes for the inventive compounds are dron: Asymmetry 15, 3117-3122, 2004 as the (S)-enanti described hereinafter, though they should not be interpreted omer). in a restrictive manner. Further processes for preparing the Some compounds of the formula (III) in which the B radi inventive compounds can be derived in an analogous manner. 30 cal is as defined above and LG is, for example, halo-C-C- alkoxy, C-C-alkanoyloxy, mercapto, C-C-alkylthio, halo As shown in reaction scheme 1, inventive compounds can C-Cs-alkylthio. halogen, especially C-Cs-alkoxy (e.g. be obtained by using, in the process for preparing the inven methoxy), can be obtained commercially (e.g. chloroformic tive compounds, in reaction step (a), for example, prop-2-yn esters, acid chlorides) or by literature methods. 1-yl acetate (as compound (II)) and iso-propyl chloroformate 35 Some compounds of the formula (IV) in which the B. D (as compound (III)). The iso-propyl 4-acetoxybut-2-ynecar and R radicals are each as defined above, can be obtained boxylate thus obtained (as compound (IV)) is then reacted in commercially or by literature methods (cf., for example, com reaction step (b) with, for example, N-(6-chloropyridin-3- pounds of the formula (IV) in which B—OCHCHs, D-OH, yl)methylmethan-1-amine (as compound (V)). R—H: B. M. C. Clasby et al., Bioorg Med. Chem. Lett. 13, 40 3647-3651, 2007; B–OCH(CH), D=O CO. O. CH, R=H: R. Tayama, R. Hashimoto Tetrahedron Lett. 48, Reaction Scheme 1 7950-7952, 2007; B–OCH, D=O CO. O. CH, R—H: O. David et al., Heterocycles 62, 839-846, 2004; B—OCH, D=O CH-C=CH, R=H:Y.Yamamoto Tet sts" 45 rahedron Lett. 62, 4294-4305, 2006; B–OCH, D=O C C CH3 (CH4), R=H: A. Covarrubias-Zuniga et al., Synth. Com --- 1st reaction step mun. 28, 3461-3469, 1998: B=OCH, D=O CO CH, i- -( R=H:N. Maezaki et al., Tetrahedron: Asymmetry. 13, 1961 O 1964, 2002; B–OCH, D-tetrahydro-2H-pyran-2-yl-oxy, 50 R—H: R. Larocket al., J. Org. Chem. 48,2151-2158, 1983; H3C B=OCHs, D=O CO-aryl, R=H: Ch.-K. Jung et al., J. Am. Chem. Soc. 126, 41 18-41 19, 2004). In addition, the )—o preparation and use of particular O-Substituted 4-hydroxy HC X = \ CH alkyne-2-carboxylic esters as microbicides has become O b-( 55 known (cf. B=OC.H., D=O CO-n-CH, R=CH: DE O 4417752 A1). 21 C Compounds of the formula (V) in which the A and R' radicals are each as defined above can also be prepared from N compounds of the formula (VI) by literature methods (cf. HC N 60 N-(6-chloropyridin-3-yl)methyl-2,2-difluoroethan-1- amine, N-(6-chloro-5-fluoropyridin-3-yl)methyl-2,2-dif ) O HN luoroethan-1-amine: WO 2007/115646; WO 2008/009360; HC X = \ CH CH cf. scheme 2 below). O O 2nd reaction step Some compounds of the formula (VI) are commercially 65 available, known or can be prepared by known methods (e.g. O 2-chloro-5-chloromethyl-1,3-thiazole: DE 3631538 (1988), EP 446913 (1991), EP 780384 (1997), EP 775 700 (1997), US 8,343,893 B2 13 14 EP 794 180 (1997), WO 9710 226 (1997): 6-chloro-3-chlo lag Stuttgart, p. 648; M. L. Moore in “The Leuckart Reaction' romethylpyridine: DE 3630 046A1 (1988), EP373 464 A2 in: Organic Reactions, vol. 5, 2nd ed. 1952, New York, John (1990), EP373464A2 (1990), EP393 453 A2 (1990), EP569 Wiley & Sons, Inc. London) (cf., for example, also 3-fluoro 947 A1 (1993); 6-chloro-3-bromomethylpyridine: I. Caba nal-Duvillard et al., Heterocycl. Commun. 5, 257-262 (1999); n-propylamine: U.S. Pat. No. 6.252,087 B1; 3,3-difluoro 6-bromo-3-chloromethylpyridine, 6-bromo-3-hydroxymeth prop-2-enylamine hydrochloride: WO 2001/007414A1: 3,3- ylpyridine: U.S. Pat. No. 5,420,270 A (1995); 6-fluoro-3- dichloro-prop-2-enylamine: DE 2747814); 2-chloro-2- chloromethylpyridine: J. A. Pesti et al., J. Org. Chem. 65, fluorocyclopropylamine, 2.2-dichloro-cyclopropylamine: K. 7718-7722 (2000): 6-methyl-3-chloromethylpyridine: EP R. Gassen, B. Baasner, J. Fluorine Chem. 49, 127-139, 1990). 302389 A2, E. v der Eycken et al., J. Chem. Soc., Perkin Trans 10 25,928-937 (2002): 6-trifluoromethyl-3-chloromethylpyri Alternatively, particular amino compounds of the formula dine: WO 2004/082616 A2: 2-chloro-5-chloromethylpyra (VIIa) in which R" is CH R (R-halogenated radical; zine: JP 05239034 A2). halogen-fluorine or chlorine) can also be obtained by reduc General ways of preparing compounds of the formula (VI) ing halogenated carboxamides (VIII) in the presence of Suit are shown in reaction scheme 2. able reducing agents (reaction scheme 4).

Reaction Scheme 2 A-CHO A-CH elein |E-Ital A-CH He- A-COOH - - A-CH-OH oxidation reduction - - A-CH-E (VI) E = Hal, for example chlorine, bromine, iodine; O-tosyl, O-mesyl, A = as defined above

The heterocyclic carboxylic acid (A-COOH) can be con verted by literature methods to the corresponding heterocy 30 Reaction scheme 4 clic hydroxymethyl compounds (A-CH, OH), which are H2N-CO-R - - HN-CH-R then converted by literature methods to activated heterocyclic reduction hydroxymethyl compounds (A-CH-E, E-OTosyl, OMesyl) (VIII) (VIIa) or heterocyclic halomethyl compounds (A-CH-E, E–Hal). R = halogenated radical The latter can also be obtained from corresponding methyl 35 group-containing heterocycles (A-CH-) using Suitable litera ture halogenating agents. An example of a Suitable reducing agent is the known To prepare compounds of the formula (V), it is advanta borane-dimethyl Sulphide complex (cf. also the preparation geous that, for example, compounds of the formula (VI) in of 2-chloro-2-fluoroethan-1-amine from commercially avail which the A and E radicals are each as defined above are 40 able 2-chloro-2-fluoroacetamide). reacted with compounds of the formula (VII) in which the R' Alternatively and in particular cases, preparation of com radical is as defined above in the presence of diluents and in pounds of the formula (V) from the corresponding aldehydes the presence of basic reaction auxiliaries (cf. N-alkylation, (A-CHO) and compounds of the formula (VII) by means of reaction scheme 3). reductive amination is also possible (cf. Houben-Weyl, Meth 45 oden der Organischen Chemie, vol. XI/1, Georg Thieme Ver lag Stuttgart, p. 602). Some of the aldehydes (A-CHO) are Reaction scheme 3 commercially available (cf., for example, 6-chloronicotinal A-CHO dehyde, 6-fluoronicotinaldehyde, 6-bromonicotinaldehyde, 50 2-chloro-1,3-thiazole-5-carbaldehyde) or can be obtained by retic + (VII) literature methods (cf., for example, 6-methylnicotinalde hyde: EP-A2-104876; 2-chloropyrazine-5-carboxaldehyde: RI DE 3314196A1). A-CH2-E + H2N-R A-CH-NH Reaction step (a) of the preparation process according to N-alkylation 55 the invention is preferably performed in the presence of a (VI) (VII) (V) basic reaction auxiliary and in the presence of diluents. Dilu E = Hal, for example chlorine, bromine, iodine; O-tosyl, O-mesyl, ents are used in Such an amount that the reaction mixture A = as defined above remains efficiently stirrable over the entire process. Suitable diluents are all inert organic solvents (e.g. halohydrocarbons, Some of the amino compounds of the formula (VII) can be 60 especially chlorohydrocarbons such as tetrachloroethylene, obtained commercially (cf., for example, 2-fluoroethylamine tetrachloroethane, dichloropropane, methylene chloride, or 2,2-difluoroethylamine)orina manner known perse by the dichlorobutane, chloroform, carbon tetrachloride, trichloro Leuckart-Wallach reaction (e.g. 2-fluoroethylamine: U.S. ethane, trichloroethylene, pentachloroethane, difluoroben Pat. No. 4,030,994 (1977)); compounds of the formula (VII) Zene, 1,2-dichloroethane, chlorobenzene, bromobenzene, in which R" is alkyl can likewise be obtained (primary 65 dichlorobenzene, chlorotoluene, trichlorobenzene: alcohols amines: cf., for example, Houben-Weyl, Methoden der Orga Such as methanol, ethanol, isopropanol, butanol); ethers (e.g. nischen Chemie, vol. XI/1, 4th ed. 1957, Georg Thieme Ver ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, ani US 8,343,893 B2 15 16 sole, phenetole, cyclohexyl methyl ether, dimethyl ether, To perform reaction step (a), generally 0.5 to 4.0 mol, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl preferably 0.5 to 4.0 mol, more preferably 0.5 to 1.0 mol of ether, diisobutyl ether, diisoamyl ether, ethylene glycol dim compound of the general foimula (III) is used per mole of ethyl ether, tetrahydrofuran, dioxane, dichlorodiethyl ether compound of the general formula (II). and polyethers of ethylene oxide and/or propylene oxide); After reaction, the entire reaction mixture of reaction step amines (e.g. trimethyl-, triethyl-, tripropyl-, tributylamine, (a) is partitioned between water and a suitable halohydrocar N-methylmorpholine, pyridine and tetramethylenediamine); bon, for example dichloromethane, and washed with dilute nitrohydrocarbons (e.g. nitromethane, nitroethane, nitropro acid and base. The products obtained after workup can be pane, nitrobenzene, chloronitrobenzene, o-nitrotoluene); purified by recrystallization, vacuum distillation or column nitriles (e.g. acetonitrile, propionitrile, butyronitrile, isobuty 10 chromatography (cf. also the preparation examples). ronitrile, benzonitrile, m-chlorobenzonitrile) and compounds Reaction step (b) is advantageously performed in the pres such as tetrahydrothiophene dioxide and dimethyl sulphox ence of diluents, for which the diluents listed above can be ide, tetramethylene Sulphoxide, dipropyl Sulphoxide, benzyl used. Preference is given to using ethers such as tetrahydro methyl sulphoxide, diisobutyl sulphoxide, dibutyl sulphox furan or dioxane. ide, diisoamyl Sulphoxide; Sulphones such as dimethyl, 15 diethyl, dipropyl, dibutyl, diphenyl, dihexyl, methyl ethyl, In reaction step (b), generally 0.5 to 5.0 mol, preferably 0.5 to 3.0 mol, more preferably 0.5 to 1.5 moland most preferably ethyl propyl, ethyl isobutyl and pentamethylene Sulphone; a slight excess of amino compound of the general formula (V) aliphatic, cycloaliphatic or aromatic hydrocarbons such as is used per mole of compound of the general formula (IV). pentane, hexane, heptane, octane, nonane and technical Diluents are advantageously used in Such an amount that grade hydrocarbons; for example white spirits with compo the reaction mixture remains efficiently stirrable over the nents having boiling points in the range from about 40°C. to entire process. about 250° C., cymene, petroleum fractions within a boiling The reaction time of the process or of reaction step (a) or range from 70° C. to about 190° C., cyclohexane, methylcy (b) is generally from 10 minutes to 48 hours. The reactions are clohexane, petroleum ether, ligroin, octane, benzene, toluene, effected at temperatures between -100° C. and +100° C. chlorobenzene, bromobenzene, nitrobenzene, Xylene; esters 25 preferably between -80° C. and +80° C., particularly at -75° (e.g. methyl, ethyl, butyl, isobutyl acetate, and dimethyl, C. to room temperature. dibutyl, ethylene carbonate); amides (e.g. hexamethylene It is possible in principle to work under standard pressure. phosphoramide, formamide, N-methylformamide, N,N-dim Preference is given to working at standard pressure or at ethylformamide, N,N-dipropylformamide, N,N-dibutylfor pressures up to 15 bar and optionally under protective gas mamide, N-methylpyrrolidone, N-methylcaprolactam, 1,3- 30 dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidine, atmosphere (nitrogen, helium or argon). After the reaction has ended, the entire reaction mixture is octylpyrrolidone, octylcaprolactam, 1,3-dimethyl-2-imida concentrated. The products obtained after workup can be Zolidinedione, N-formyl-piperidine, N,N'-1,4-diformylpip purified in a customary manner by recrystallization, vacuum erazine); ketones (e.g. acetone, acetophenone, methyl ethyl distillation or column chromatography (cf. also the prepara ketone, methylbutyl ketone). It is also possible to use mix 35 tion examples). tures of the aforementioned diluents. The geometric (for example the E or Z isomers) and/or In reaction step (a), the diluents used are preferably ethers, optically active isomers or corresponding isomer mixtures of especially methyl tert-butyl ether and dipropyl ether, tetrahy the formula (I) can of course be separated by a Suitable sepa drofuran and dioxane. ration process, for example by means of column chromatog Reaction step (a) is preferably performed in the presence of 40 raphy, optionally on a chiral phase, or by means of extraction a basis reaction auxiliary (i.e. auxiliary). Especially suitable processes (e.g. Craig partition). are acid binders such as amines, especially tertiary amines, To prepare the inventive compounds in which R is halo and alkali metal and alkaline earth metal compounds. gen, it is alternatively also possible to react compounds of the Examples include the hydroxides, hydrides, oxides, amides formula (I) in which R is hydrogen with halogenating agents and carbonates of lithium, sodium, potassium, magnesium, 45 calcium and barium, and also further basic compounds Such in the presence of basic auxiliaries according to reaction as amidine bases or guanidine bases such as 7-methyl-1.5.7- scheme 5. triazabicyclo[4.4.0dec-5-ene (MTBD); diazabicyclo4.3.0 nonene (DBN), diazabicyclo[2.2.2 octane (DABCO), 1.8- Reaction scheme 5: diazabicyclo5.4.0]undecene (DBU), 50 cyclohexyltetrabutylguanidine (CyTBG), cyclohexyltetram R A ethylguanidine (CyTMG), N.N.N.N-tetramethyl-1,8-naph H VN - / Hal VN-/ thalenediamine, pentamethylpiperidine, tertiary amines Such halogenation as triethylamine, trimethylamine, tribenzylamine, triisopro Her pylamine, tributylamine, tricyclohexylamine, triamylamine, 55 trihexylamine, N,N-dimethylaniline, N,N-dimethyltolui B -R B dine, N,N-dimethyl-p-aminopyridine, N-methylpyrrolidine, O D O D N-methylpiperidine, N-methylimidazole, N-methylpyrazole, N-methylmorpholine, N-methylhexamethylenediamine, In the compounds of the formula (I) required as starting pyridine, 4-pyrrolidinopyridine, 4-dimethylaminopyridine, 60 materials, A, B, D, R' and Rare each as defined above; the quinoline, C-picoline, B-picoline, isoquinoline, pyrimidine, substituent R is hydrogen. acridine, N.N.N',N'-tetramethylenediamine, N.N.N',N'-tetra The halogenation is advantageously performed in the pres ethylenediamine, quinoxaline, N-propyldiisopropylamine, ence of diluents. N-ethyl-diisopropylamine, N,N'-dimethylcyclohexylamine, The diluents are advantageously used in Such an amount 2.6-lutidine, 2.4-lutidine or triethyldiamine. Preferred basic 65 that the reaction mixture remains efficiently stirrable over the auxiliaries are lithium bis(trimethylsilyl)amide or potassium entire process. Suitable diluents are all organic solvents bis(trimethylsilyl)-amide. which are inert under the reaction conditions. Preferred dilu US 8,343,893 B2 17 18 ents are nitriles Such as acetonitrile, propionitrile, butyroni Academic Press; G. W. H. Cheeseman, E. S. G. Werstiuk in trile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; Advances in Heterocyclic Chemistry, vol. 22, p. 390-392, particularly preferred diluents are acetonitrile, propionitrile 1978, A. R. Katritzky, A.J. Boulton, (Eds.), Academic Press. or butyronitrile. The inventive compounds, given good plant tolerance, Suitable halogenating agents are known to those skilled in favourable homeotherm toxicity and good environmental the art. Preference is given to using N-halo compounds (e.g. compatibility, are Suitable for protecting plants and plant N-haloamines such as 1-chloromethyl-4-fluorodiazoniabicy organs, for increasing harvest yields, for improving the qual clo2.2.2]octane bis(tetrafluoroborate) (Selectfluor R), N.N- ity of the harvested material and for controlling animal pests, dihaloamines, N-halocarboxamides, N-halo-carbamic esters, especially insects, arachnids, helminths, nematodes and mol N-halourea, N-halosulphonylamides, N-halodisulphonyla 10 luscs, which are encountered in agriculture, in horticulture, in mides, N-halosulphonylimides such as N-fluorobis(trifluo animal husbandry, in forests, in gardens and leisure facilities, romethyl)sulphonyl)imide and N-halodicarboximides such in the protection of stored products and of materials, and in as N-chlorophthalimide, N-bromophthalimide, N-iodoph the hygiene sector. They may be preferably employed as plant thalimide, N-chlorosuccinimide (NCS), N-bromosuccinim protection agents. They are active against normally sensitive ide (NBS), N-bromosaccharin or N-iodosuccinimide). Par 15 and resistant species and against all or Some stages of devel ticular preference is given to N-halocarboxamides or opment. The abovementioned pests include: 1-chloromethyl-4-fluorodiazoniabicyclo[2.2.2]octane bis From the order of the Anoplura (Phthiraptera), for (tetrafluoroborate)) (Selectfluor R). example, Damalinia spp., Haematopinus spp., Linognathus The reaction time in this process is generally 10 minutes to spp., Pediculus spp., Trichodectes spp. 48 hours. From the class of the Arachnida, for example, Acarus siro, The reaction is effected at temperatures between -10°C. Aceria Sheldoni, Aculops spp., Aculus spp., Amblyomma spp., and +100° C., preferably between 0° C. and 60° C., more Argas spp., Boophilus spp., Brevipalpus spp., Bryobia pra preferably between 10° C. and room temperature. etiosa, Chorioptes spp., Dermanyssus gallinae, Eotetrany After the reaction has ended, the entire reaction mixture is chus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes concentrated. The products obtained after workup can be 25 spp., Hemitarisonemus spp., Hyalomma spp., Ixodes spp., purified in a customary manner by recrystallization, vacuum Latrodectus mactans, Metatetranychus spp., Oligonychus distillation or column chromatography. spp., Ornithodoros spp., Panonychus spp., Phylocoptruta Here too, the halogenated geometric (for example the E or oleivora, Polyphagotarisonemus latus, Psoroptes spp., Rhipi Z isomers) and/or optically active isomers or corresponding cephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio isomer mixtures of the formula (I) can of course be separated 30 maurus, Stenotarisonemus spp., Tarsonemus spp., Tetrany by a suitable separation process, for example by means of chus spp., Vasates lycopersici. column chromatography, optionally on a chiral phase, or by From the class of the Bivalva, for example, Dreissena spp. means of extraction processes (e.g. Craig partition). From the order of the Chilopoda, for example, Geophilus Salts of the inventive compounds are prepared by standard spp., Scutigera spp. methods. Representative acid addition salts are, for example, 35 From the order of the Coleoptera, for example, Acan those which are formed by reaction with inorganic acids, for thoscelides Obtectus, Adoretus spp., Agelastica alni, Agriotes example Sulphuric acid, hydrochloric acid, hydrobromic spp., Amphimallon solstitialis, Anobium punctatum, Anoplo acid, phosphoric acid, or organic carboxylic acids Such as phora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., acetic acid, trifluoroacetic acid, citric acid. Succinic acid, Atomaria spp., Attagenus spp., Bruchidius Obtectus, Bruchus butyric acid, lactic acid, formic acid, fumaric acid, maleic 40 spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus acid, malonic acid, camphoric acid, oxalic acid, phthalic acid, spp., Cosmopolites spp., Costelytra zealandica, Curculio propionic acid, glycolic acid, glutaric acid, Stearic acid, sali spp., Cryptorhynchus lapathi, Deiniestes spp., Diabrotica cylic acid, Sorbic acid, tartaric acid, cinnamic acid, Valeric spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, acid, picric acid, benzoic acid, or organic Sulphonic acids Heteronychus arator, Hylamorpha elegans, Hylotrupes baju Such as methaneSulphonic acid and 4-toluenesulphonic acid. 45 lus, Hypera postica, Hypothenemus spp., Lachnosterna Con Other representatives are salts of inventive compounds sanguinea, Leptinotarsa decemlineata, Lissorhoptrus Oryzo which are formed from organic bases, for example pyridine or philus, Lixus spp., Lyctus spp., Melligethes aeneus, triethylamine, or those which are formed from inorganic Melolontha melolontha, Migdolus spp., Monochamus spp., bases, for example hydrides, hydroxides or carbonates of Naupactus xanthographus, Niptus hololeucus, Oryctes rhi Sodium, potassium, lithium, calcium, magnesium or barium, 50 noceros, Oryzaephilus Surinamensis, Otiorrhynchus sulca when the compounds of the general formula (I) have a struc tus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga tural element capable of this salt formation. spp., Popillia japonica, Premnotrypes spp., Psylliodes Synthesis methods for preparation of heterocyclic N-ox chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha ides and tert-amines are known. They can be obtained with dominica, Sitophilus spp., Sphenophorus spp., Sternechus peroxy acids (e.g. peracetic acid and meta-chloroperbenzoic 55 spp., Symphyletes spp., Tenebrio molitor; Tribolium spp., Tro acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides goderma spp., Tichius spp., Xylotrechus spp., Zabrus spp. (e.g. tert-butyl hydroperoxide), sodium perborate and diox From the order of the Collembola, for example, Onychi iranes (e.g. dimethyldioxirane). These methods are lirtiS drinatti.S. described, for example, by T. L. Gilchrist, in Comprehensive From the order of the Dermaptera, for example, Forficula Organic Synthesis, vol. 7, p. 748-750, 1992, S.V. Ley, (Ed.), 60 auricularia. Pergamon Press; M. Tisler, B. Stanovnik, in Comprehensive From the order of the Diplopoda, for example, Blaniulus Heterocyclic Chemistry, Vol. 3, p. 18-20, 1984, A.J. Boulton, guttulatus. A. McKillop, (Eds.), Pergamon Press: M. R. Grimmett, B. R. From the order of the Diptera, for example, Aedes spp., T. Keene in Advances in Heterocyclic Chemistry, vol.43, p. Anopheles spp., Bibio hortulanus, Caliphora erythro 149-163, 1988, A. R. Katritzky, (Ed.), Academic Press: M. 65 cephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia Tisler, B. Stanovnik, in Advances in Heterocyclic Chemistry, spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., vol. 9, p. 285-291, 1968, A. R. Katritzky, A.J. Boulton (Eds.), Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia US 8,343,893 B2 19 20 spp., Gastrophilus spp., Hyllemyia spp., Hyppobosca spp., spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., spp., Saissetia spp., Scaphoides titanus, Schizaphis grani Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyos num, Selenaspidus articulatus, Sogata spp., Sogatella fur cyani, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia cifera, Sogatodes spp., Stictocephala festina, Tenalaphara spp., Tipula paludosa, Wohlfahrtia spp. malayensis, Tinocallis caryaefoliae, Tomaspis spp., Tox From the class of the Gastropoda, for example, Arion spp., optera spp., Trialeurodes vaporariorum, Trioza spp., Typhlo Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., cyba spp., Unaspis spp., Viteus vitifolii. Lynnaea spp., Oncomelania spp., Succinea spp. From the order of the Hymenoptera, for example, Diprion From the class of the helminths, for example, Ancylostoma spp., Hoplocampa spp., Lasius spp., Monomorium phara duodenale, Ancylostoma ceylanicum, Acylostoma brazilien 10 Onis, Vespa spp. sis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Bru From the order of the Isopoda, for example, Armadillidium gia malayi, Brugia timori, Bunostomum spp., Chabertia spp., vulgare, Oniscus asellus, Porcellio scaber. Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyo From the order of the Isoptera, for example, Reticulitermes caulus filaria, Diphyllobothrium latum, Dracunculus medin spp., Odontotermes spp. ensis, Echinococcus granulosus, Echinococcus multilocu 15 From the order of the Lepidoptera, for example, Acronicta laris, Enterobius vermicularis, Faciola spp., Haemonchus major; Aedia leucomelas, Agrotis spp., Alabama argillacea, spp., Heterakis spp., Hymenolepis nana, Hvostrongulus spp., Anticarsia spp., Barathra brassicae, Bucculatrix thurberi Loa Loa, Nematodirus spp., Oesophagostomum spp., ella, Bupalus piniarius, Cacoeciapodana, Capua reticulana, Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Paragonimus spp., Schistosomen spp., Strongyloides fielle Choristoneura filmiferana, Clysia ambiguella, Cnaphalo borni, Strongyloides Stercoralis, Stronyloides spp., Taenia cerus spp., Earias insulana, Ephestia kuehniella, Euproctis saginata, Taenia solium, Trichinella spiralis, Trichinella chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, nativa, Trichinella britovi, Trichinella nelsoni, Trichinella Helicoverpa spp., Heliothis spp., Hofinannophila pseu pseudopsiralis, Tricho strongulus spp., Trichuris trichuria, dospretella, Homona magnanima, Hyponomeuta padella, Wuchereria bancrofti. 25 Laphygma spp., Lithocolletis blancardella, Lithophane It is additionally possible to control protozoa, such as antennata, Loxagrotis albicosta, Lymantria spp., Malaco Eineria. Soma neustria, Mamestra brassicae, Mocis repanda, From the order of the Heteroptera, for example, Anasa Mythinna separata, Oria spp., Oulema Oryzae, Panolis flam tristis, Antestiopsis spp., Blissus spp., Calocoris spp., mea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris Campylomma livida, Cavelerius spp., Cimex spp., Creontia 30 spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., des dilutus, Dasynus piperis, Dichelops fircatus, Dicono Pseudoplusia includens, Pyrausta nubilalis, Spodoptera coris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Thermesia gemmatalis, Tinea pellionella, Tineola bis spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., selliella, Tortrix viridana, Trichoplusia spp. Leptoglossus phyllopus, Lygus spp., Macropes excavatus, From the order of the Orthoptera, for example, Acheta Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma 35 domesticus, Blatta Orientalis, Blattella germanica, Gryllo quadrata, Piezodorus spp., Psalus seriatus, Pseudacy.sta talpa spp., Leucophaea maderae, Locusta spp., Melanoplus persea, Rhodnius spp., Sahlbergella singularis, Scotino spp., Periplaneta americana, Schistocerca gregaria. phora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. From the order of the Siphonaptera, for example, Cerato From the order of the Homoptera, for example, Acyrtho phyllus spp., Xenopsylla cheopis. Sipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes 40 From the order of the Symphyla, for example, Scutigerella spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca immaculata. spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, From the order of the Thysanoptera, for example, Balio Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus thrips biformis, Enneothrips flavens, Frankliniella spp., spp., Atanus spp., Aulacorthum Solani, Bemisia spp., Brachy Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., caudus helichrysii, Brachycolus spp., Brevicoryne brassicae, 45 Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips Calligypona marginata, Carneocephalafiulgida, Ceratova cardamomi, Thrips spp. cuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon From the order of the Thysanura, for example, Lepisma fragaefolii, Chionaspis tegalensis, Chlorita Onuki, Chroma saccharina. phis juglandicola, Chrysomphalus ficus, Cicadulina mbila, The phytoparasitic nematodes include, for example, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbu 50 Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bur lus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Saphelenchus spp., Dity lenchus dipsaci, Globodera spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus Heliocotylenchus spp., Heterodera spp., Longidorus spp., spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Eus Meloidogyne spp., Pratylenchus spp., Radopholus similis, celis bilobatus, Geococcus coffeae, Homalodisca coagulata, Rotylenchus spp., Trichodorus spp., Tilenchorhynchus spp., Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idiosco 55 Tvlenchulus spp., Tilenchulus semipenetrans, Xiphinema pus spp., Laodelphax striatellus, Lecanium spp., Lepi spp. dosaphes spp., Lipaphis erysimi, Macrosiphum spp., Maha If appropriate, the inventive compounds can, at certain marva fimbriolata, Melanaphis sacchari, Metcalfiella spp., concentrations or application rates, also be used as herbi Metopolophium dirhodium, Monellia Costalis, Monelliopsis cides, safeners, growth regulators or agents to improve plant pecanis, Myzus spp., Nasonovia ribismigri, Nephotettix spp., 60 properties, or as microbicides, for example as fungicides, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, antimycotics, bactericides, viricides (including agents Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pem against Viroids) or as agents against MLO (Mycoplasma-like phigus spp., Peregrinus maidis, Phenacoccus spp., Phlo organisms) and RLO (Rickettsia-like organisms). If appro eomyzus passerinii, Phorodon humuli, Phylloxera spp., Pin priate, they can also be employed as intermediates or precur naspis aspidistrae, Planococcus spp., Protopulvinaria 65 sors for the synthesis of other active ingredients. pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., The active ingredients can be converted to the customary Psylla spp., Pteromalus spp., Pyrilla spp., Ouadraspidiotus formulations, such as solutions, emulsions, wettable pow US 8,343,893 B2 21 22 ders, water- and oil-based Suspensions, powders, dusts, employ lignin and its Sulphonic acid derivatives, unmodified pastes, soluble powders, soluble granules, granules for broad and modified celluloses, aromatic and/or aliphatic Sulphonic casting, Suspension-emulsion concentrates, natural materials acids and their adducts with formaldehyde. impregnated with active ingredient, synthetic materials Tackifiers such as carboxymethylcellulose and natural and impregnated with active ingredient, fertilizers and microen synthetic polymers in the form of powders, granules or lati capsulations in polymeric Substances. ces, such as gum arabic, polyvinyl alcohol and polyvinyl These formulations are produced in a known manner, for acetate, as well as natural phospholipids such as cephalins example by mixing the active ingredients with extenders, that and lecithins, and synthetic phospholipids, can be used in the is liquid solvents and/or Solid carriers, optionally with the use formulations. of Surfactants, that is emulsifiers and/or dispersants and/or 10 It is possible to use dyes such as inorganic pigments, for foam-formers. The formulations are prepared either in suit example iron oxide, titanium oxide and Prussian Blue, and able plants or else before or during the application. organic dyes, such as alizarin dyes, azo dyes and metal phtha Suitable for use as auxiliaries are substances which are locyanine dyes, and trace nutrients such as salts of iron, Suitable for imparting to the composition itself and/or to manganese, boron, copper, cobalt, molybdenum and zinc. preparations derived therefrom (for example spray liquors, 15 Further possible additives are perfumes, mineral or veg seed dressings) particular properties such as certain technical etable, optionally modified oils, waxes and nutrients (includ properties and/or also particular biological properties. Typi ing trace nutrients). Such as salts of iron, manganese, boron, cal suitable auxiliaries are: extenders, solvents and carriers. copper, cobalt, molybdenum and zinc. Suitable extenders are, for example, water, polar and non Stabilizers such as low-temperature stabilizers, preserva polar organic chemical liquids, for example from the classes tives, antioxidants, light stabilizers or other agents which of the aromatic and nonaromatic hydrocarbons (such as par improve chemical and/or physical stability may also be affins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), present. the alcohols and polyols (which may optionally also be Sub The formulations generally comprise between 0.01 and stituted, etherified and/or esterified), the ketones (such as 98% by weight of active ingredient, preferably between 0.5 acetone, cyclohexanone), esters (including fats and oils) and 25 and 90%. (poly)ethers, the unsubstituted and Substituted amines, The inventive active ingredient can be used in its commer amides, lactams (such as N-alkylpyrrolidones) and lactones, cially available formulations and in the use forms, prepared the Sulphones and Sulphoxides (such as dimethyl SulphoX from these formulations, as a mixture with other active ingre ide). dients, such as insecticides, attractants, sterilizing agents, If the extender used is water, it is also possible to employ, 30 bactericides, acaricides, nematicides, fungicides, growth for example, organic solvents as auxiliary solvents. Essen regulating Substances, herbicides, Safeners, fertilizers or tially, suitable liquid solvents are: aromatics such as xylene, semiochemicals. toluene or alkylnaphthalenes, chlorinated aromatics and Particularly favourable mixing components are, for chlorinated aliphatic hydrocarbons such as chlorobenzenes, example, the following compounds: chloroethylenes or methylene chloride, aliphatic hydrocar 35 Fungicides: bons such as cyclohexane or paraffins, for example petroleum (1) Nucleic acid synthesis inhibitors, for example benalaxyl, fractions, mineral and vegetable oils, alcohols such as butanol benalaxyl-M, bupirimate, cloZylacon, dimethirimol, or glycol and also their ethers and esters, ketones Such as ethirimol, furalaxyl, hymexaZol, metalaxyl, metalaxyl-M, acetone, methyl ethyl ketone, methyl isobutyl ketone or ofurace, oxadixyl and oxolinic acid. cyclohexanone, strongly polar solvents such as dimethyl Sul 40 (2) Mitosis and cell division inhibitors, for example benomyl, phoxide, and also water. carbendazim, chlorfenazole, diethofencarb, ethaboxam, Useful solid carriers are: fuberidazole, pencycuron, thiabendazole, thiophanate, for example, ammonium salts and ground natural minerals thiophanate-methyl and Zoxamide. Such as kaolins, clays, talc, chalk, quartz, attapulgite, mont (3) Respiration inhibitors (inhibitors of the respiratory chain), morillonite ordiatomaceous earth, and ground synthetic min 45 for example diflumetorim as inhibitor which acts on com erals, such as finely divided silica, alumina and silicates; plex I of the respiratory chain; biXafen, boscalid, carboxin, Suitable Solid carriers for granules are: for example, crushed fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, and fractionated natural rocks such as calcite, marble, pum isopyrazam (mixture of the Syn-epimeric racemate 1RS, ice, Sepiolite and dolomite, and also synthetic granules of 4SR.9RS and the anti-epimeric racemate 1RS.4SR.9SR), inorganic and organic meals, and granules of organic material 50 isopyrazam (syn-epimeric racemate 1RS.4SR.9RS), Such as paper, sawdust, coconut shells, maize cobs and isopyrazam (Syn-epimeric enantiomer 1R,4S.9R), isopy tobacco stalks; suitable emulsifiers and/or foam-formers are: razam (Syn-epimeric enantiomer 1S.4R.9S), isopyrazam for example, nonionic and anionic emulsifiers, such as poly (anti-epimeric racemate 1RS.4SR.9SR), isopyrazam (anti oxyethylene fatty acid esters, polyoxyethylene fatty alcohol epimeric enantiomer 1 R,4S.9S), isopyrazam (anti ethers, for example alkylaryl polyglycol ethers, alkylsulpho 55 epimeric enantiomer 1S.4R.9R), nates, alkyl Sulphates, arylsulphonates and also protein mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, hydrolysates; Suitable dispersants are nonionic and/or ionic thifluzamid as inhibitors which act on complex II of the substances, for example from the classes of the alcohol POE respiratory chain; amisulbrom, azoxystrobin, cyaZofamid, and/or POP ethers, acid and/or POP-POE esters, alkyl aryl dimoxystrobin, enestroburin, famoxadone, fenamidone, and/or POP-POE ethers, fat and/or POP-POE adducts, POE 60 fuoxastrobin, kresoxim-methyl, metominostrobin, orysas and/or POP-polyol derivatives, POE- and/or POP-sorbitan trobin, picoxystrobin, pyraclostrobin, pyraoxystrobin, or -Sugar adducts, alkyl or aryl Sulphates, alkyl- or arylsul pyrametostrobin, pyribencarb, trifloxystrobin as inhibitors phonates and alkyl or aryl phosphates or the corresponding which act on complex III of the respiratory chain. PO-ether adducts. In addition, suitable oligo- or polymers, for (4) Decouplers, for example binapacryl, dinocap, fluazinam example those derived from vinylic monomers, from acrylic 65 and meptylidinocap. acid, from EO and/or PO alone or in combination with, for (5) ATP production inhibitors, for example fentin acetate, example, (poly)alcohols or (poly)amines. It is also possible to fentin chloride, fentin hydroxide and silthiofam. US 8,343,893 B2 23 24 (6) Amino acid and protein biosynthesis inhibitors, for ethylideneamino)oxymethylphenyl)ethanamide, (2E)- example andoprim, blasticidin-S, cyprodinil, kasugamy 2-(methoxyimino)-N-methyl-2-2-(E)-(1-3- cin, kasugamycin hydrochloride hydrate, mepanipyrim (trifluoromethyl)phenylethoxy)imino)methyl and pyrimethanil. phenylethanamide, (2E)-2-2-({(1E)-1-(3-(E)-1- (7) Signal transduction inhibitors, for example fenpiclonil, fluoro-2-phenylethenyloxyphenyl)ethylidene fludioxonil and quinoxyfen. amino oxy)methylphenyl)-2-(methoxyimino)-N- (8) Lipid and membrane synthesis inhibitors, for example methylethanamide, 1-(4-chlorophenyl)-2-(1H-1,2,4- biphenyl, chloZolinate, edifenphos, etridiazole, iodocarb, triazol-1-yl)cycloheptanol, methyl 1-(2,2-dimethyl-2,3- iprobenfos, iprodione, isoprothiolane, procymidone, pro dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate, pamocarb, propamocarb hydrochloride, pyrazophos, tol 10 N-ethyl-N-methyl-N'-(2-methyl-5-(trifluoromethyl)-4- clofos-methyl and Vinclozolin. 3-(trimethylsilyl)propoxyphenyl)imidoformamide, (9) Ergosterol biosynthesis inhibitors, for example N'-(5-(difluoromethyl)-2-methyl-4-3-(trimethylsilyl) aldimorph, azaconazole, bitertanol, bromuconazole, propoxyphenyl-N-ethyl-N-methylimidoformamide, cyproconazole, diclobutrazole, difenoconazole, dinicona O-1-(4-methoxyphenoxy)methyl-2.2- Zole, diniconazole-M, dodemorph, dodemorph acetate, 15 dimethylpropyl-1H-imidazole-1-carbothioate, N-(2-(4- epoxiconazole, etaconazole, fenarimol, fenbuconazole, 3-(4-chlorophenyl)prop-2-yn-1-yl)oxy-3-methoxyphe fenhexamid, fenpropidin, fempropimorph, fluguincona nyl)ethyl-N'-(methylsulphonyl)valinamide, 5-chloro-7- zole, flurprimidol, flusilazole, flutriafol, furconazole, fur (4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)12.4 conazole-cis, hexaconazole, imazalil, imazalil Sulphate, triazolo 1.5-alpyrimidine, 5-amino-1,3,4-thiadiazole-2- imibenconazole, ipconazole, metconazole, myclobutanil, thiole, propamocarb-fosetyl, 1-(4-methoxyphenoxy) naftifine, nuarimol, Oxpoconazole, paclobutraZol, pefura methyl-2,2-dimethylpropyl 1H-imidazole-1-carboxylate, Zoate, penconazole, piperalin, prochloraz, propiconazole, 1-methyl-N-2-(1,1,2,2-tetrafluoroethoxy)phenyl)-3-(trif prothioconazole, pyributicarb, pyrifenox, quinconazole, luoromethyl)-1H-pyrazole-4-carboxamide, 2,3,5,6-tetra simeconazole, spiroxamine, tebuconazole, terbinafine, tet chloro-4-(methylsulphonyl)pyridine, 2-butoxy-6-iodo-3- raconazole, triadimefon, triadimenol, tridemorph, triflu 25 propyl-4H-chromen-4-one, 2-phenylphenol and its salts, mizole, triforine, triticonazole, uniconazole, Viniconazole 3-(difluoromethyl)-1-methyl-N-2-(1,1,2,2-tetrafluoroet and Voriconazole. hoxy)phenyl)-1H-pyrazole-4-carboxamide, 3,4,5-trichlo (10) Cell wall synthesis inhibitors, for example benthiavali ropyridine-2,6-dicarbonitrile, 3-5-(4-chlorophenyl)-2,3- carb, dimethomorph, flumorph, iprovalicarb, mandipropa dimethylisoxazolidin-3-ylpyridine, 3-chloro-5-(4- mid, polyoxins, polyoxorim, prothiocarb, validamycin A 30 chlorophenyl)-4-(2,6-difluorophenyl)-6- and Valefenalate. methylpyridazine, 4-(4-chlorophenyl)-5-(2,6- (11) Melanin biosynthesis inhibitors, for example carpropa difluorophenyl)-3,6-dimethylpyridazine, mid, diclocymet, fenoxanil, phthalide, pyroquilon and tri 8-hydroxyquinoline, 8-hydroxyquinoline Sulphate, tebu cyclazole. floquin, 5-methyl-6-octyl-3,7-dihydro 1.2.4 triazolo 1.5- (12) Resistance inductors, for example acibenzolar-S-me 35 apyrimidine-7-amine, 5-ethyl-6-octyl-3,7-dihydro 12.4 thyl, probenazole and tiadinil. triazolo 1.5-alpyrimidine-7-amine, ametoctradin, (13) Compounds with multi-site activity, for example Bor benthiazol, bethoxazin, capsimycin, carvone, chinome deaux mixture, captafol, captan, chlorothalonil, copper thionat, chloroneb, cufraneb, cyflufenamide, cymoxaniil, naphthenate, copper oxide, copper oxychloride, copper cyprosulfamide, dazomet, debacarb, dichlorophen, preparations such as, for example, copper hydroxide, cop 40 diclomeZine, dicloran, difenZoquat, difenZoquat methyl per Sulphate, dichlofluanid, dithianon, dodine and its free Sulphate, diphenylamine, ecomat, ferimZone, flumetover, base, ferbam, fluorofolpet, folpet, guaZatine, guaZatine fluopicolide, fluoromide, flusulfamide, flutianil, fosetyl acetate, iminoctadine, iminoctadine albesilate, iminocta aluminium, fosetyl-calcium, fosetyl-Sodium, hexachlo dine triacetate, mancopper, mancoZeb, maneb, metiram, robenzene, irumamycin, isotianil, methasulfocarb, methyl metiram Zinc, oxine-copper, propamidine, propineb, Sul 45 (2E)-2-2-(cyclopropyl (4-methoxyphenyl)iminol phur and Sulphur preparations such as, for example, cal methylthio)methylphenyl-3-methoxyacrylate, methyl cium polysulphide, thiram, tolylfluanid, Zineb and Ziram. isothiocyanate, metrafenone, (5-chloro-2-methoxy-4-me (14) Further compounds, for example 2,3-dibutyl-6-chlo thylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl) rothieno 2,3-dipyrimidin-4(3H)-one, ethyl (2Z)-3-amino methanone, mildiomycin, tolnifanide, N-(4-chloroben 2-cyano-3-phenylprop-2-enoate, N-2-(1,3-dimethylbu 50 Zyl)-3-3-methoxy-4-(prop-2-yn-1-yloxy)phenyl tyl)phenyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4- propanamide, N-(4-chlorophenyl)(cyano)methyl-3-3- carboxamide, 3-(difluoromethyl)-1-methyl-N-(3',4',5'- methoxy-4-(prop-2-yn-1-yloxy)phenylpropanamide, trifluorobiphenyl-2-yl)-1H-pyrazole-4-carboxamide, N-(5-bromo-3-chloropyridin-2-yl)methyl-2,4-dichloro 3-(difluoromethyl)-N-4-fluoro-2-(1,1,2,3,3,3-hexafluo pyridine-3-carboxamide, N-1-(5-bromo-3-chloropyridin ropropoxy)-phenyl-1-methyl-1H-pyrazole-4-carboxam 55 2-yl)ethyl-2,4-dichloropyridine-3-carboxamide, N-1-(5- ide, (2E)-2-(2-6-(3-chloro-2-methylphenoxy)-5-fluoro bromo-3-chloropyridin-2-yl)ethyl)-2-fluoro-4- pyrimidin-4-yl)oxyphenyl)-2-(methoxyimino)-N- iodopyridine-3-carboxamide, N-(Z)- methylethanamide, (2E)-2-2-((2E.3E)-4-(2,6- (cyclopropylmethoxy)imino 6-(difluoromethoxy)-2,3- dichlorophenyl)but-3-en-2-ylidenelaminooxy)methyl difluorophenyl)methyl)-2-phenylacetamide, N-(E)- phenyl)-2-(methoxyimino)-N-methylethanamide, 60 (cyclopropylmethoxy)imino 6-(difluoromethoxy)-2,3- 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl) difluorophenyl)methyl)-2-phenylacetamide, natamycin, pyridine-3-carboxamide, N-(3-ethyl-3,5,5-trimethylcy nickel dimethyldithiocarbamate, nitrothal-isopropyl. clohexyl)-3-(formylamino)-2-hydroxybenzamide, octhillinone, oxamocarb, oxyfenthiin, pentachlorophenol 5-methoxy-2-methyl-4-(2-({(1E)-1-3-(trifluorom and its salts, phenazine-1-carboxylic acid, phenothrin, ethyl)phenylethylideneamino)oxymethylphenyl)-2,4- 65 phosphoric acid and its salts, propamocarb fosetylate, pro dihydro-3H-1,2,4-triazol-3-one, (2E)-2-(methoxyimino)- panosine-Sodium, produinazid, pyrrolnitrin, quintoZene, N-methyl-2-(2-({(1E)-1-3-(trifluoromethyl)phenyl S-prop-2-en-1-yl 5-amino-2-(1-methylethyl)-4-(2-meth US 8,343,893 B2 25 26 ylphenyl)-3-oxo-2,3-dihydro-1H-pyrazole-1-carbothio RU 15525, silafluofen, tefluthrin, tetramethrin (1R)-iso ate, tecloftalam, tecnaZene, triazoxide, trichlamide, mers, tralomethrin, transfluthrin and ZXI 8901; or DDT. 5-chloro-N'-phenyl-N'-prop-2-yn-1-ylthiophene-2-sul or methoxychlor. phonohydrazide, Zarilamide, N-methyl-2-(1-5-methyl (4) Nicotinergic acetylcholine receptoragonists, for example 3-(trifluoromethyl)-1H-pyrazol-1-yl)acetylpiperidin-4- neonicotinoids, for example acetamiprid, clothianidin, yl)-N-(1R)-1,2,3,4-tetrahydronaphthalen-1-yl-1,3- dinotefuran, imidacloprid, nitenpyram, thiacloprid, thia thiazole-4-carboxamide, N-methyl-2-(1-5-methyl-3- methoxam, AKD-1022, imidaclothiz: or nicotine. (trifluoromethyl)-1H-pyrazol-1-yl)acetylpiperidin-4- (5) Allosteric acetylcholine receptor modulators (agonists), yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4- for example spinosyns, for example spinetoram and Spi carboxamide, 3-(difluoromethyl)-N-4-fluoro-2-(1,1,2,3, 10 nosad. (6) Chloride channel activators, for example avermectins/ 3.3-hexafluoropropoxy)phenyl-1-methyl-1H-pyrazole milbemycins, for example abamectin, emamectin ben 4-carboxamide and pentyl {6-({(1-methyl-1H-tetrazol Zoate, lepimectin and milbemectin. 5-yl)(phenyl)methylidenelaminooxy)methylpyridin-2- (7) Juvenile hormone analogues, for example hydroprene, yl)carbamate. 15 kinoprene, methoprene; or fenoxycarb: pyriproxyfen. Bactericides: (8) Active ingredients with unknown or non-specific mecha bronopol, dichlorophen, nitrapyrin, nickel dimethyldithio nisms of action, for example fumigants, for example carbamate, kasugamycin, octhillinone, furancarboxylic acid, methyl bromide and other alkyl halides; or chloropicrin; oxytetracycline, probenazole, Streptomycin, tecloftalam, sulphuryl fluoride; borax: tartar emetic. copper Sulphate and other copper preparations. (9) Selective antifeedants, for example pymetrozine; or floni Insecticides/Acaricides/Nematicides: camid. The active ingredients specified in this description by their (10) Mite growth inhibitors, for example clofentezine, diflov “common name are known, for example, from “The Pesti idazin, hexythiazox, etoxazole. cide Manual, 14th Ed., British Crop Protection Council (11) Microbial disruptors of the insect gut membrane, for 2006, and from the Web page http://www.alanwood.net/pes 25 example Bacillus thuringiensis Subsp. israelensis, Bacillus ticides/. sphaericus, Bacillus thuringiensis Subsp. aizawai, Bacillus (1) Acetylcholinesterase (AChE) inhibitors, for example car thuringiensis subsp. kurstaki, Bacillus thuringiensis Subsp. bamates, for example alanycarb, aldicarb, bendiocarb, tenebrionis, and BT plant proteins, for example Cry1Ab, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, Cry1Ac, Cry1 Fa, Cry2Ab, mCry3A, Cry3 Ab, Cry3Bb, carbofuran, carbosulfan, ethiofencarb, fenobucarb, 30 Cry34/35Ab1. formetanate, furathiocarb, isoprocarb, methiocarb, meth (12) Oxidative phosphorylation inhibitors, ATP disruptors, omyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodi for example diafenthiuron; or organotin compounds, for carb, thiofanox, triazamate, trimethacarb. XMC and xylyl example azocyclotin, cyhexatin, fenbutatin oxide; or pro carb; or pargite; tetradifon. organophosphates, for example acephate, azamethiphos, 35 (13) Oxidative phoshorylation decouplers acting by inter azinphos (-methyl, -ethyl), cadusafos, chlorethoxyfos, rupting the H proton gradient, for example chlorfenapyr chlorfenvinphos, chlormephos, chlorpyrifos (-methyl), and DNOC. coumaphos, cyanophos, demeton-S-methyl, diazinon, (14) Nicotinergic acetylcholine receptor antagonists, for dichlorvos/DDVP. dicrotophos, dimethoate, dimethylvin example benSultap, cartap (hydrochloride), thiocylam, and phos, disulfoton, EPN, ethion, ethoprophos, famphur, 40 thiosultap (sodium). fenamiphos, fenitrothion, fenthion, fosthiazate, hepteno (15) Chitin biosynthesis inhibitors, type 0, for example ben phos, isofenphos, isopropyl O-(methoxyaminothiophos Zoylureas, for example bistrifluron, chlorfluaZuron, phoryl)salicylate, isoxathion, malathion, mecarbam, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumu methamidophos, methidathion, mevinphos, monocroto ron, lufenuron, novaluron, noviflumuron, teflubenZuron phos, naled, omethoate, oxydemeton-methyl, parathion 45 and triflumuron. (-methyl), phenthoate, phorate, phosalone, phosmet, phos (16) Chitin biosynthesis inhibitors, type 1, for example phamidon, phoxim, pirimiphos (-methyl), profenofos, pro buprofezin. petamphos, prothiofos, pyraclofos, pyridaphenthion, (17) Moulting disruptors, for example cyromazine. quinalphos, Sulfotep, tebupirimfos, temephos, terbufos. (18) Ecdysone agonists/disruptors, for example diacylhydra tetrachlorvinphos, thiometon, triaZophos, triaZamate, tri 50 Zines, for example chromafenozide, halofenozide, meth clorfon and vamidothion. oxyfenozide and tebufenozide. (2) GABA-gated chloride channel antagonists, for example (19) Octopaminergic agonists, for example amitraz. organochlorines, for example chlordane and endosulfan (20) Site III electron transport inhibitors/site II electron trans (alpha-); or fiproles (phenylpyrazoles), for example port inhibitors, for example hydramethylnone; ace ethiprole, fipronil, pyrafluprole and pyriprole. 55 quinocyl; fluacrypyrim, or cyflumetofen and cyenopy (3) Sodium channel modulators/voltage-dependent sodium rafen. channel blockers, for example pyrethroids, for example (21) Electron transport inhibitors, for example site I electron acrinathrin, allethrin (d-cis-trans, d-trans), bifenthrin, bio transport inhibitors, from the group of the METI acari allethrin, bioallethrin-S-cyclopentenyl, bioresmethrin, cides, for example fenaZaquin, fenpyroximate, pyrimid cycloprothrin, cyfluthrin (beta-), cyhalothrin (gamma-, 60 ifen, pyridaben, tebufenpyrad, tolfenpyrad; or rotenone lambda-), cypermethrin (alpha-, beta-, theta-, Zeta-), (Derris). cyphenothrin (1R)-trans-isomers, deltamethrin, dime (22) Voltage-dependent sodium channel blockers, for fluthrin, empenthrin (EZ)-(1R)-isomeres, esfenvalerate, example indoxacarb; metaflumizone. etofemprox, fempropathrin, fenvalerate, flucythrinate, flu (23) Inhibitors of acetyl-CoA carboxylase, for example methrin, fluvalinate (tau-), halfenproX, imiprothrin, metof 65 tetronic acid derivatives, for example spirodiclofen and luthrin, permethrin, phenothrin (1R)-trans-isomer, pral spiromesi?en; or tetramic acid derivatives, for example lethrin, profluthrin, pyrethrins (pyrethrum), resmethrin, spirotetramat. US 8,343,893 B2 27 28 (24) Site IV electron transport inhibitors, for example phos which increase the action of the active ingredients, without it phines, for example aluminium phosphide, calcium phos being necessary for the synergist added to be active itself. phide, phosphine, Zinc phosphide; or cyanide. When used as insecticides, the inventive active ingredients (25) Ryanodine receptor effectors, for example diamides, for can also be present in their commercially available formula example chlorantraniliprole (Rynaxypyr), cyantraniliprole tions and in the use forms, prepared from these formulations, (Cyazypyr) and flubendiamide. as a mixture with inhibitors which reduce degradation of the Further active ingredients with unknown mechanism of active ingredient after use in the environment of the plant, on action, for example azadirachtin, amidoflumet, benzoximate, the Surface of parts of plants or in plant tissues. bifenazate, chinomethionat, cryolite, dicofol, flufenerim, The active ingredient content of the use forms prepared 10 from the commercially available formulations can vary pyridalyl and pyrifluquinazon; or the known active com within wide limits. The active ingredient concentration of the pounds below use forms can be from 0.00000001 to 95% by weight of active 4-(6-bromopyrid-3-yl)methyl(2-fluoroethyl) ingredient, preferably between 0.00001 and 1% by weight. aminofuran-2(5H)-one (known from WO 2007/115644), The compounds are employed in a customary manner 4-(6-fluoropyrid-3-yl)methyl(2,2-difluoroethyl) 15 appropriate for the use forms. aminofuran-2(5H)-one (known from WO 2007/115644), All plants and plant parts can be treated in accordance with 4-(2-chloro-1,3-thiazol-5-yl)methyl(2-fluoroethyl)amino the invention. Plants are to be understood as meaning in the furan-2(5H)-one (known from WO 2007/115644), 4-(6- present context all plants and plant populations such as chloropyrid-3-yl)methyl(2-fluoroethyl)amino furan-2(5H)- desired and undesired wild plants or crop plants (including one (known from WO 2007/115644), 4-(6-chloropyrid-3- naturally occurring crop plants). Crop plants can be plants yl)methyl(2,2-difluoroethyl)aminofuran-2(5H)-one which can be obtained by conventional plant breeding and (known from WO 2007/115644), 4-(6-chloro-5-fluoropy optimization methods or by biotechnological and genetic rid-3-yl)methyl(methyl)aminofuran-2(5H)-one (known engineering methods or by combinations of these methods, from WO 2007/115643), 4-(5,6-dichloropyrid-3-yl)me including the transgenic plants and including the plant culti thyl(2-fluoroethyl)aminofuran-2(5H)-one (known from 25 vars protectable or not protectable by plant breeders’ rights. WO 2007/115646), 4-(6-chloro-5-fluoropyrid-3-yl)me Plant parts are to be understood as meaning all parts and thyl (cyclopropyl)aminofuran-2(5H)-one (known from WO organs of plants above and below the ground, such as shoot, 2007/115643), 4-(6-chloropyrid-3-yl)methyl(cyclopro leaf flower and root, examples which may be mentioned pyl)aminofuran-2(5H)-one (known from EP-A-0539.588), being leaves, needles, stalks, stems, flowers, fruit bodies, 4-(6-chloropyrid-3-yl)methyl(methyl)aminofuran-2 30 fruits, seeds, roots, tubers and rhizomes. The plant parts also (5H)-one (known from EP-A-0539.588), (6-chloropyridin include harvested material, and vegetative and generative 3-yl)methyl(methyl)oxido- '-sulphanylidenecyanamide propagation material, for example cuttings, tubers, rhizomes, (known from WO 2007/149134), 1-(6-chloropyridin-3-yl) offshoots and seeds. ethyl(methyl)oxido-N-Sulphanylidenecyanamide (known Treatment according to the invention of the plants and plant from WO 2007/149134) and its diastereomers (A) and (B) 35 parts with the active ingredients is carried out directly or by allowing the compounds to act on the Surroundings, habitator storage space by the customary treatment methods, for (A) example by immersion, spraying, evaporation, fogging, scat CH3 tering, painting on, injection and, in the case of propagation N -CH 40 material, in particular in the case of seeds, also by applying M \, One Or more COatS. 2 O N Treatment according to the invention of the plants and plant C N parts with the active ingredient combinations is carried out CN directly or by allowing the compounds to act on the Surround (B) 45 ings, habitat or storage space by the customary treatment CH3 methods, for example by immersion, spraying, evaporation, N -CH fogging, Scattering, painting on, and, in the case of propaga / \ tion material, in particular in the case of seeds, also by apply 2 O N ing one or more coats. C N 50 The inventive mixtures are particularly suitable for treating CN seed. Here, the combinations according to the invention men tioned above as preferred or particularly preferred may be (likewise known from WO 2007/149134), (6-trifluorometh mentioned as being preferred. Thus, a large part of the dam ylpyridin-3-yl)methyl(methyl)oxido- '-sulphanylidenecy age to crop plants which is caused by pests occurs as early as anamide (known from WO 2007/095229), sulfoxaflor 55 when the seed is attacked during storage and after the seed is (likewise known from WO 2007/149134), 11-(4-chloro-2, introduced into the soil, and also during and immediately 6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro after germination of the plants. This phase is particularly 4.2.4.2 tetradec-11-en-10-one (known from WO 2006/ critical since the roots and shoots of the growing plant are 089633), 3-(4-fluoro-2,4-dimethylbiphenyl-3-yl)-4- particularly sensitive and even minor damage can lead to the hydroxy-8-Oxa-1-azaspiro4.5 dec-3-en-2-one (known from 60 death of the whole plant. Protecting the seed and the germi WO 2008/067911) and 1-2,4-dimethyl-5-[(2.2.2-trifluoro nating plant by the use of Suitable compositions is therefore of ethyl)sulphinylphenyl-3-(trifluoromethyl)-1H-1,2,4-triaz particularly great interest. ole (known from WO 1999/55668). The control of pests by treating the seeds of plants has been When used as insecticides, the inventive active ingredients known for a long time and is the Subject of continuous can also be present in their commercially available formula 65 improvements. However, the treatment of seedentails a series tions and in the use forms, prepared from these formulations, of problems which cannot always be solved in a satisfactory as a mixture with Synergists. Synergists are compounds manner. Thus, it is desirable to develop methods for protect US 8,343,893 B2 29 30 ing the seed and the germinating plant which dispense with Clavibacter, Glomus or Gliocladium. The present invention is the additional application of crop protection agents after Sow particularly Suitable for the treatment of transgenic seed ing or after the emergence of the plants. It is also desirable to which comprises at least one heterologous gene originating optimize the amount of active ingredient employed in Such a from Bacillus sp. and whose gene product shows activity way as to provide maximum protection for the seed and the against the European corn borer and/or the corn root worm. It germinating plant from attack by pests, but without damaging is particularly preferably a heterologous gene derived from the plant itself by the active ingredient employed. In particu Bacillus thuringiensis. lar, methods for the treatment of seed should also take into In the context of the present invention, the inventive com consideration the intrinsic insecticidal properties of trans position is applied to the seed either alone or in a Suitable genic plants in order to achieve optimum protection of the 10 formulation. Preferably, the seed is treated in a state which is seed and the geiiiiinating plant with a minimum of crop stable enough to avoid damage during treatment. In general, protection agents being employed. the seed may be treated at any point in time between harvest The present invention therefore in particular also relates to and sowing. The seed usually used has been separated from a method for the protection of seed and germinating plants the plant and freed from cobs, shells, stalks, coats, hairs or the from attack by pests, by treating the seed with an inventive 15 flesh of the fruits. composition. The invention likewise relates to the use of the When treating the seed, care must generally be taken that inventive compositions for the treatment of seed for protect the amount of the inventive composition applied to the seed ing the seed and the resultant plant from pests. The invention and/or the amount of further additives is chosen in Such away further relates to seed which has been treated with an inven that the germination of the seed is not adversely affected, or tive composition so as to afford protection from pests. that the resulting plant is not damaged. This must be borne in One of the advantages of the present invention is that the mind in particular in the case of active ingredients which may particular systemic properties of the inventive compositions have phytotoxic effects at certain application rates. mean that treatment of the seed with these compositions not As already mentioned above, it is possible to treat all plants only protects the seed itself, but also the resulting plants after and their parts according to the invention. In a preferred emergence, from pests. In this manner, the immediate treat 25 embodiment, wild plant species and plant cultivars, or those ment of the crop at the time of sowing or shortly thereafter can obtained by conventional biological breeding methods. Such be dispensed with. as crossing or protoplast fusion, and parts thereof, are treated. A further advantage is the synergistically increased insec In a further preferred embodiment, transgenic plants and ticidal activity of the inventive compositions in comparison plant cultivars obtained by genetic engineering methods, if with the individual insecticidal active ingredient, which 30 appropriate in combination with conventional methods (Ge exceeds the anticipated activity of the two active ingredients netically Modified Organisms), and parts thereof are treated. when applied individually. Also advantageous is the syner The terms “parts”, “parts of plants” and “plant parts” have gistically increased fungicidal activity of the inventive com been explained above. positions in comparison with the individual fungicidal active Particularly preferably, plants of the plant cultivars which ingredient, which exceeds the anticipated activity of the 35 are in each case commercially available or in use are treated active ingredient when applied individually. This makes pos according to the invention. Plant cultivars are to be under sible an optimization of the amount of active ingredient stood as meaning plants having novel properties (“traits”) employed. which have been obtained by conventional breeding, by Furthermore, it must be considered as advantageous that mutagenesis or by recombinant DNA techniques. These can the inventive mixtures can also be employed in particular in 40 be cultivars, bio- or genotypes. transgenic seed, the plants arising from this seed being Depending on the plant species or plant cultivars, their capable of expressing a protein directed against pests. By location and growth conditions (soils, climate, vegetation treating Such seed with the inventive compositions, certain period, diet), the treatment according to the invention may pests can be controlled merely by the expression of the, for also result in superadditive (“synergistic) effects. Thus, for example, insecticidal protein, and additionally be protected 45 example, reduced application rates and/or a widening of the by the inventive compositions against damage. activity spectrum and/or an increase in the activity of the The inventive compositions are Suitable for protecting seed Substances and compositions which can be used according to of any plant variety as already mentioned above which is the invention, better plant growth, increased tolerance to high employed in agriculture, in the greenhouse, in forests or in or low temperatures, increased tolerance to drought or to horticulture. In particular, this takes the form of seed of 50 water or soil salt content, increased flowering performance, maize, peanut, canola, oilseed rape, poppy, Soya beans, cot easier harvesting, accelerated maturation, higher harvest ton, beet (for example Sugar beet and fodder beet), rice, Sor yields, higher quality and/or a higher nutritional value of the ghum and millet, wheat, barley, oats, rye, Sunflower, tobacco, harvested products, better storage stability and/or processi potatoes or vegetables (for example tomatoes, cabbage bility of the harvested products are possible, which exceed the plants). The inventive compositions are likewise suitable for 55 effects which were actually to be expected. treating the seed of fruit plants and vegetables as already The transgenic plants or plant cultivars (obtained by mentioned above. The treatment of the seed of maize, soya genetic engineering) which are preferably to be treated beans, cotton, wheat and canola or oilseed rape is of particular according to the invention include all plants which, by virtue importance. of the genetic modification, received genetic material which As already mentioned above, the treatment of transgenic 60 imparted particularly advantageous, useful traits to these seed with an inventive composition is also of particular plants. Examples of Such traits are better plant growth, importance. This takes the form of seed of plants which, as a increased tolerance to high or low temperatures, increased rule, comprise at least one heterologous gene which governs tolerance to drought or to water or soil salt content, increased the expression of a polypeptide with in particular insecticidal flowering performance, easier harvesting, accelerated matu properties. In this context, the heterologous genes in trans 65 ration, higher harvest yields, higher quality and/or a higher genic seed may be derived from microorganisms such as nutritional value of the harvested products, better storage Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, stability and/or processibility of the harvested products. Fur US 8,343,893 B2 31 32 ther and particularly emphasized examples of such traits area From the order of the Mallophagida and the suborders better defence of the plants against animal and microbial Amblycerina and Ischnocerina, for example, Trimenopon pests, such as against insects, mites, phytopathogenic fungi, spp., Menopon spp., Trinoton spp., Bovicola spp., Werneck bacteria and/or viruses, and also increased tolerance of the iella spp., Lepikentron spp., Damalina spp., Trichodectes plants to certain herbicidally active ingredients. Examples of 5 spp., Felicola spp. transgenic plants which may be mentioned are the important From the order of the Diptera and the suborders Nemato crop plants. Such as cereals (wheat, rice), maize, Soya beans, cerina and Brachycerina, for example, Aedes spp., Anopheles potatoes, Sugar beet, tomatoes, peas and other vegetable vari spp., Culex spp., Simulium spp., Eusimulium spp., Phleboto eties, cotton, tobacco, oilseed rape and also fruit plants (with mus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., the fruits apples, pears, citrus fruits and grapes), and particu 10 Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota lar emphasis is given to maize, soya beans, potatoes, cotton, spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea tobacco and oilseed rape. Traits that are emphasized are in spp., Stomoxys spp., Haematobia spp., Morelia spp., Fannia particular increased defence of the plants against insects, spp., Glossina spp., Caliphora spp., Lucilia spp., Chry arachnids, nematodes and slugs and Snails by virtue of toxins somyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus formed in the plants, in particular those formed in the plants 15 spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., by the genetic material from Bacillus thuringiensis (for Lipoptena spp., Mellophagus spp. example by the genes CryIA(a), CryIA(b), CryIA(c), Cry IIA, From the order of the Siphonapterida, for example, Pulex CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus also combinations thereof) (referred to hereinbelow as “Bt spp. plants'). Traits that are also particularly emphasized are the From the order of the Heteropterida, for example, Cimex increased defence of the plants against fungi, bacteria and spp., Triatoma spp., Rhodnius spp., Panstrongylus spp. viruses by Systemic acquired resistance (SAR), systemin, From the order of the Blattarida, for example, Blatta ori phytoalexins, elicitors and resistance genes and correspond entalis, Periplaneta americana, Blattela germanica, Supella ingly expressed proteins and toxins. spp. Traits that are also particularly emphasized are the 25 From the subclass of the Acari (Acarina) and the orders of increased tolerance of the plants to certain herbicidally active the Meta- and Mesostigmata, for example, Argas spp., Orni ingredients, for example imidazolinones, Sulphonylureas, thodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., glyphosate orphosphinotricin (for example the "PAT gene). Boophilus spp., Dermacentor spp., Haemophysalis spp., The genes which impart the desired traits in question can also Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., be present in combination with one another in the transgenic 30 Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa plants. Examples of “Bt plants' which may be mentioned are spp. maize varieties, cotton varieties, soya bean varieties and From the order of the Actinedida (Prostigmata) and Acari potato varieties which are sold under the trade names YIELD dida (Astigmata), for example, Acarapis spp., Cheyletiella GARDR) (for example maize, cotton, soya beans), Knock spp., OrnithOcheyletia spp., Myobia spp., Psorergates spp., Out(R) (for example maize), StarLink R. (for example maize), 35 Demodex spp., Trombicula spp., Listrophorus spp., Acarus Bollgard(R) (cotton), Nucotnir (cotton) and NewLeaf R (po spp., Trophagus spp., Caloglyphus spp., Hypodectes spp., tato). Examples of herbicide-tolerant plants which may be Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes mentioned are maize varieties, cotton varieties and Soya bean spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., varieties which are sold under the trade names Roundup Cytodites spp., Laminosioptes spp. Ready R (tolerance to glyphosate, for example maize, cotton, 40 The inventive active ingredients of the formula (I) are also soya bean), Liberty Link. R (tolerance to phosphinotricin, for suitable for controlling arthropods which infest agricultural example oilseed rape), IMIR (tolerance to imidazolinones) productive livestock, for example cattle, sheep,goats, horses, and STS(R) (tolerance to sulphonylureas, for example maize). pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, Herbicide-resistant plants (plants bred in a conventional man ducks, geese and bees, other pets, for example dogs, cats, ner for herbicide tolerance) which may be mentioned include 45 caged birds and aquarium fish, and also so-called test ani the varieties sold under the name Clearfield(R) (for example mals, for example hamsters, guinea pigs, rats and mice. By maize). Of course, these statements also apply to plant culti controlling these arthropods, cases of death and reduction in vars having these genetic traits or genetic traits still to be productivity (for meat, milk, wool, hides, eggs, honey etc.) developed, which plant cultivars will be developed and/or should be diminished, so that more economic and easier marketed in the future. 50 animal husbandry is possible by use of the inventive active The plants listed can be treated according to the invention ingredients. in a particularly advantageous manner with the compounds of The inventive active ingredients are used in the veterinary the general formula I and/or the active ingredient inventive sector and in animal husbandry in a known manner by enteral mixtures. The preferred ranges stated above for the active administration in the form of, for example, tablets, capsules, ingredients or mixtures also apply to the treatment of these 55 potions, drenches, granules, pastes, boluses, the feed-through plants. Particular emphasis is given to the treatment of plants process and Suppositories, by parenteral administration, for with the compounds or mixtures specifically mentioned in the example by injection (intramuscular, Subcutaneous, intrave present text. nous, intraperitoneal and the like), implants, by nasal admin The inventive active ingredients act not only against plant, istration, by dermal use in the form, for example, of dipping hygiene and stored product pests, but also in the veterinary 60 or bathing, spraying, pouring on and spotting on, Washing and medicine sector against animal parasites (ecto- and endopara powdering, and also with the aid of moulded articles contain sites). Such as hard ticks, soft ticks, mange mites, leaf mites, ing the active ingredient, such as collars, ear marks, tail flies (biting and licking), parasitic fly larvae, lice, hair lice, marks, limb bands, halters, marking devices and the like. feather lice and fleas. These parasites include: When used for cattle, poultry, pets and the like, the active From the order of the Anoplurida, for example, Hae 65 ingredients of the formula (I) can be used as formulations (for matopinus spp., Linognathus spp., Pediculus spp., Phtirus example powders, emulsions, free-flowing compositions), spp., Solenopotes spp. which comprise the active ingredients in an amount of 1 to US 8,343,893 B2 33 34 80% by weight, directly or after 100 to 10 000-fold dilution, From the order of the Diplopoda, for example, Blaniulus or they can be used as a chemical bath. guttulatus, Polydesmus spp. It has also been found that the inventive compounds also From the order of the Chilopoda, for example, Geophilus have a strong insecticidal action against insects which destroy spp. industrial materials. 5 The following insects may be mentioned as examples and From the order of the Zygentoma, for example, Ctenolepi as preferred—but without any limitation: Sma spp., Lepisma Saccharina, Lepismodes inquilinus. Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, From the order of the Blattaria, for example, Blatta Orien Anobium punctatum, Xestobium rufovillosum, Ptilinus pecti tallies, Blattella germanica, Blattella asahinai, Leucophaea cornis, Dendrobium pertinex, Ernobius mollis, Priobium car 10 maderae, Panchlora spp., Parcoblatta spp., Periplaneta aus pini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, tralasiae, Periplaneta americana, Periplaneta brunnea, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Mint Periplaneta fuliginosa, Supella longipalpa. hes rugicollis, Xvleborus spec. Tryptodendron spec. Apate From the order of the Saltatoria, for example, Acheta monachus, Bostrychus capucins, Heterobostrychus brun 15 domesticus. neus, Sinoxylon spec. Dinoderus minutus, From the order of the Dermaptera, for example, Forficula Hymenopterons, such as Sirex juvencus, Urocerus gigas, auricularia. Urocerus gigas taignus, Urocerus augur, Termites, such as Kalotermes flavicollis, Cryptotermes From the order of the Isoptera, for example, Kalotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reti spp., Reticulitermes spp. culitermes Santonensis, Reticulitermes lucifigus, Mastoter From the order of the Psocoptera, for example, Lepinatus mes darwiniensis, Zootermopsis nevadensis, Coptotermes spp., LipOscelis spp. formosanus, From the order of the Coleoptera, for example, Anthrenus Bristletails, such as Lepisma saccharina. spp., Attagenus spp., Dermestes spp., Latheticus Oryzae, Industrial materials in the present connection are to be 25 understood as meaning non-living materials, such as, prefer Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus ably, plastics, adhesives, sizes, papers and cardboards, granarius, Sitophilus Oryzae, Sitophilus zeanais, Stegobium leather, wood and processed wood products and coating com paniceum. positions. From the order of the Diptera, for example, Aedes aegypti, The ready-to-use compositions may, if appropriate, com 30 Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., prise further insecticides and, if appropriate, one or more Caliphora erythrocephala, Chrysozona pluvialis, Culex fungicides. quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila With respect to possible additional additives, reference spp., Fannia canicularis, Musca domestica, Phlebotomus may be made to the insecticides and fungicides mentioned spp., Sarcophaga carnaria, Simulium spp., Stomoxys calci above. 35 trans, Tipula paludosa. The inventive compounds can likewise be employed for protecting objects which come into contact with seawater or From the order of the Lepidoptera, for example, Achroia brackish water, Such as hulls, screens, nets, buildings, moor grisella, Galleria mellonella, Plodia interpunctella, Tinea ings and signalling Systems, against fouling. cloacella, Tinea pellionella, Tineola bisselliella. Furthermore, the inventive compounds, alone or in combi 40 From the order of the Siphonaptera, for example, Cteno nations with other active ingredients, may be employed as cephalides canis, Ctenocephalides felis, Pulex irritans, antifouling agents. Tunga penetrans, Xenopsylla cheopis. In domestic, hygiene and stored-product protection, the From the order of the Hymenoptera, for example, Cam active ingredients are also suitable for controlling animal ponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius pests, in particular insects, arachnids and mites, which are 45 found in enclosed spaces such as, for example, dwellings, umbratus, Monomorium pharaonis, Paravespula spp., Tet factory halls, offices, vehicle cabins and the like. They can be ramorium caespitum. used to control these pests alone or in combination with other From the order of the Anoplura, for example, Pediculus active ingredients and auxiliaries in domestic insecticide humanus capitis, Pediculus humanus corporis, Pemphigus products. They are active against sensitive and resistant spe 50 spp., Phylloera vastatrix, Phthirus pubis. cies and against all developmental stages. These pests include: From the order of the Heteroptera, for example, Cimex From the order of the Scorpionidea, for example, Buthus hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma OCCitanus. infestans. From the order of the Acarina, for example, Argas persi 55 In the field of household insecticides, they are used alone or cus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Gly in combination with other Suitable active ingredients, such as ciphagus domesticus, Ornithodorus moubat, Rhipicephalus phosphoric esters, carbamates, pyrethroids, neonicotinoids, sanguineus, Trombicula alfreddugesi, Neutrombicula autum growth regulators or active ingredients from other known nalis, Dermatophagoides pteronissimus, Dermatophagoides classes of insecticides. forinae. 60 They are used in aerosols, pressure-free spray products, for From the order of the Araneae, for example, Aviculariidae, example pump and atomizer sprays, automatic fogging sys Araneidae. tems, foggers, foams, gels, evaporator products with evapo From the order of the Opiliones, for example, Pseudoscor rator tablets made of cellulose or polymer, liquid evaporators, piones chelifer, Pseudoscorpiones cheiridium, Opiliones gel and membrane evaporators, propeller-driven evaporators, phalangium. 65 energy-free, or passive, evaporation systems, moth papers, From the order of the Isopoda, for example, Oniscus asel moth bags and moth gels, as granules or dusts, in baits for lus, Porcellio Scaber: spreading or in bait stations.

US 8,343,893 B2 39 40 Preparation of Starting Compounds A solution of 355 mg (2.5 mmol) of methyl 4-hydroxyhex Compounds of the Formula (IV) 2-ynecarboxylate (cf. J. Kunes et al., Coll. Czech. Chem. IV-1 Comm. 66, 1809-1830, 2001) and 243 ul(3 mmol) of pyridine iso-Propyl 4-acetoxybut-2-ynecarboxylate (cf. also analo in 25 ml of dichloromethane is slowly admixed at 0°C. with gous synthesis: R. Tayama, R. Hashimoto Tetrahedron Lett. 5 48,7950-7952, 2007) 196 ul (3 mmol) of acetyl chloride. After 16 hat room tem perature, the mixture is washed successively with dilute aque ous Sulphuric acid and sodium hydrogencarbonate solution. Drying over magnesium Sulphate and concentrating the 10 organic phase affords 410 mg (89% of theory) of methyl 4-acetoxyhex-2-ynecarboxylate. 'HNMR (CDCN, 8, ppm)=5.27 (t, 1H), 3.77 (s.3H), 3.75 (s, 3H), 1.88 (m, 2H), 1.01 (t, 3H), To an initial charge of 2.45 g (25 mmol) of prop-2-yn-1-yl Table 2 below lists further compounds of the general for acetate in 250 ml of anhydrous tetrahydrofuran (THF) are mula (IV). TABLE 2 Compounds of the formula (IV) O D

B R3 Physical data: Ex. No. B R3 D "H NMR, 8 ppm, known literature IV-3 OCH, H O—CO-CH(CH), 4.64 (s, 2H), 3.59 (s.3H), 2.44 (sept., 1H), 0.99 (d, 6H) IV-4 OCH H O CO-Cypr 4.64 (s, 2H), 3.58 (s.3H), 1.48 (m, 1H), 0.78 (m, 4H) IV-5 OCHCH H O CO-CH 4.78 (s, 2H), 4.22 (s, 2H), 2.06 (s, 3H), 1.27 (t,3H) IV-6 OCH2CHCCH)2 H O CH 4.62 (s, 2H), 3.79 (d. 2H), 1.88 (s, 3H), 1.76 (m, 1H), 0.78 (d. 6H) IV-7 OCH H O CO CHCH 4.64 (s, 2H), 3.59 (s.3H), 2.21 (q, 2H), 0.95 (t,3H) IV-8 OCH H O CH, DMP 7.22 (m, 1H), 6.53 (m, 2H), 4.50 (s, 2H), 4.27 (s, 2H), 3.81 (s.3H), 3.78 (s, 3H), 3.74 (s, 3H) IV-9 OCH CHCH. O. CH, DMP 5.27 (t, 1H), 3.77 (s.3H), 3.75 (s, 3H), 1.88 (m, 2H), 1.01 (t, 3H) CDCN; Cypr = cyclopropyl; DMP = 2,4-dimethoxyphenyl added dropwise, at -75° C., 27.5 ml (27.5 mmol) of a 1 M Compounds of the Formula (V) lithium bis-(trimethylsilyl)amide solution in THF. After stir V-1 ring at -75° C. for 30 min, 3.68 g (30 mmol) of iso-propyl 45 chloroformate are slowly added dropwise at -75° C. After stirring at -75° C. for 30 min, the reaction mixture is warmed N-(6-Chloropyridin-3-yl)methyl-2,2-difluoroethan to room temperature within 1 h. It is partitioned between 1-amine water and dichloromethane, and the organic phase is washed Successively with dilute aqueous Sulphuric acid and sodium 50 At 45° C., 41.57 g (256.6 mmol) of 2-chloro-5-chlorom hydrogencarbonate Solution. After drying over magnesium ethylpyridine, 20.80 g (256.6 mmol) of 2,2-difluoroethan-1- Sulphate and concentrating the organic phase under reduced amine and 35.8 ml (256.6 mmol) of triethylamine are stirred pressure, the residue is distilled. This gives 160 mg (3.5% of theory) of iso-propyl 4-acetoxybut-2-ynecarboxylate. in 500 ml of acetonitrile for 21 hours. After concentrating the "H NMR (CDCN, 8, ppm)—4.88 (sept., 1H), 4.61 (s. 2H), 55 reaction mixture under reduced pressure, it is taken up with 1 1.91 (s, 3H), 1.10 (d. 6H). Naqueous hydrochloric acid and washed with ethyl acetate. IV-2 The aqueous phase is alkalized with 2.5 N aqueous Sodium hydroxide solution and extracted repeatedly with ethyl Methyl 4-acetoxyhex-2-ynecarboxylate 60 acetate. Concentrating the organic phase under reduced pres sure affords 28.6 g (53% of theory) of N-(6-chloropyridin HC-O CH3 3-yl)methyl-2,2-difluoroethan-1-amine. )-( CH H NMR (CDCN, 8, ppm)=2.93 (td, 2H), 3.80 (s. 2H), O O 65 5.85 (tt, 1H), 7.33 (d. 1H), 7.71 (dd. 1H), 8.30 (d. 1H). O In an Analogous Manner, it is Possible to Prepare: V-2 US 8,343,893 B2 41 42 N-(6-Chloropyridin-3-yl)methyl-3-fluoropropan-1- are filled with sand, active ingredient Solution, Meloidogyne amine incognita egg/larvae Suspension and lettuce seeds. The let tuce seeds germinate and the plants develop. On the roots, LC-MS (m/z, %)=203 (MH, 100). galls develop. After 14 days, the nematicidal efficacy is deter V-3 mined by the gall formation in %. 100% means that no galls were found: 0% means that the number of galls on the treated N-(6-Chloropyridin-3-yl)methyl-2-chloro-2-fluoro plants corresponds to that of the untreated controls. In this test, compound 10 exhibits an efficacy of 90% at an ethan-1-amine application rate of 20 ppm. The invention claimed is: LC-MS (m/z, %)=223 (MH, 100). 10 1. A compound of formula (I) Biological Examples Example A (I) 15 Lucilia Cuprina Test (LUCICU) Solvent: dimethyl sulphoxide To prepare an active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of dimethylsulphox ide and the concentrate is diluted to the desired concentration with water. Vessels containing horsemeat, which has been treated with the active ingredient formulation of the desired or a salt thereof, concentration, are populated with Lucilia cuprina larvae. wherein After 2 days, the kill in % is determined. 100% means that A is a substituted heterocycle of the following formula all larvae have been killed; 0% means that no larvae have been 25 killed. In this test, the following compounds show an efficacy of 100% at an application rate of 100 ppm. Ex. No.: 6, 10, 14 30 Example B

Myzus Test (MYZUPE Spray Treatment) wherein Solvent: 78 parts by weight of acetone and 1.5 parts by weight X is halogen, C-C-alkyl or halo-C-C-alkyl, and of dimethylformamide 35 Y is halogen, C-C-alkyl, halo-C-C-alkoxy, azido or Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether cyano; or To prepare an active ingredient formulation, 1 part by A is pyrid-2-yl; pyrid-4-yl; or pyrid-3-yl which is option weight of active ingredient is mixed with the specified ally 6-substituted by fluorine, chlorine, bromine, iodine, amounts of solvent and emulsifier, and the concentrate is methyl, difluoromethyl, trifluoromethyl or trifluo diluted to the desired concentration with emulsifier-contain 40 romethoxy; pyridazin-3-yl which is optionally 6-substi ing water. tuted by chlorine or methyl pyrazin-3-yl: 2-chloropy Discs of Chinese cabbage (Brassica pekinensis) infested razin -5-yl: 1,3-thiazol-5-yl which is optionally with all stages of the greenpeach aphid (Myzus persicae) are 2-substituted by chlorine or methyl; tetrahydrofuryl; sprayed with an active ingredient formulation of the desired pyrimidinyl; pyrazolyl; thiophenyl, oxazolyl; isox concentration. 45 azolyl: 1,2,4-oxadiazolyl; isothiazolyl: 1,2,4-triazolyl, After the desired time, the efficacy in % is determined. 1,2,5-thiadiazolyl which is optionally substituted by 100% means that all aphids have been killed; 0% means that fluorine, chlorine, bromine, cyano, nitro, or is Substi no aphids have been killed. tuted by in each case optionally fluoro- and/or chlorine After 5 days and at an application rate of 500 g/ha, the -Substituted C-C-alkyl, C-C-alkylthio, or C-C- following compounds exhibit the efficacy specified: 50 alkylsulphonyl: Compound 1 exhibits an efficacy of 80%; compounds 8 B is a Z-R radical in which Z is oxygen or Sulphur, and and 14 exhibit an efficacy of 90% at an application rate of 500 R" is hydrogen, C1-Co-alkyl, C1-C4-alkoxy-C-C- g/ha; compounds 2, 3, 5, 6, 7, 9, 10, 11, 12 and 13 exhibit an alkyl, C-C-alkylthio -C-C-alkyl, halo-C-C- efficacy of 100%. alkyl, cyano-C-C-alkyl, C-C-alkenyl, C-C- After 6 days and at an application rate of 500 g/ha, com 55 alkynyl, C-C-cycloalkyl, di-C-C-cycloalkyl-C- pound 19 exhibits an efficacy of 100%. C2-alkyl, tri-C-C-alkylsilyl, tri-C-C-alkylsilyl Example C C-C-alkyl, hetaryl, hetaryl-C-C-alkyl, aryl-C- C2-alkyl, aryl-C-C-alkyloxy-C-C-alkyl, phenyl Meloidogyne Incognita Test (MELGIN) or a nitro-, halogen-, C-C-alkoxy-, C-C-alky 60 lthio-, C-C-alkylsulphinyl- or C-C-alkylsulpho Solvent: 78.0 parts by weight of acetone and 1.5 parts by nyl-substituted phenyl: weight of dimethylformamide D is a T-R radical in which Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether T is oxygen and To prepare an active ingredient formulation, 1 part by R is hydrogen, formyl, C1-Co-alkyl, C-Ca-alkoxy-C- weight of active ingredient is mixed with the specified 65 Co-alkyl, halo-C-C-alkoxy-C-C-alkyl, C-C- amounts of solvent and emulsifier, and the concentrate is alkoxy-C-C-alkoxy-C-C-alkyl, C-C-alkylthio diluted to the desired concentration with water. Containers C-C-alkyl, C-C-alkenyl, C-C-cycloalkyl,

US 8,343,893 B2 45 46 6. A compound according to claim 1, wherein with a compound of formula (III) A is 6-fluoropyrid-3-yl, 6-chloropyrid-3-yl, 6-bromopy rid-3-yl, 6-methylpyrid-3-yl, 6-trifluoromethylpyrid-3- (III) y1, 6-trifluoromethoxypyrid-3-yl, 6-chloro-1,4-py O ridazin-3-yl, 6-methyl-1,4-pyridazin-3-yl 2-chloro-1, 3-thiazol-5-yl or 2-methyl-1,3-thiazol-5-yl. X-ra 7. A compound according to claim 1, wherein B A is 6-fluoropyrid-3-yl, 6-chloropyrid-3-yl, 6-bromopy rid-3-yl, 6-chloro-1,4-pyridazin-3-yl or 2-chloro-1,3- in which thiazol-5-yl. B, D and Rare each as defined in claim 2; and 8. A compound according to claim 1, wherein 10 LG is halo-C-C-alkoxy, C-Cs-alkanoyloxy, mercapto, A is 6-chloropyrid-3-yl, 6-bromopyrid-3-yl, or 6-chloro-1, C-Cs-alkylthio, halo-C-C-alkylthio or halogen, 4-pyridazin-3-yl; B is OCH, OCHCH, or OCH(CH): optionally in the presence of a diluent and optionally in the D is a T-R radical in which presence of a basic auxiliary to give a compound of T is oxygen and 15 formula (IV); and R is methylcarbonyl, ethylcarbonyl, tert-butylcarbonyl or methoxycarbonyl: (b) reacting the compound of formula (IV) R" is methyl, cyclopropyl or 2,2-difluoroethyl; and R and Rare each hydrogen. (IV) 9. A compound according to claim 8, wherein A is 6-chlo O D ropyrid-3-yl. 10. A compound according to claim 9, wherein B is OCH or OCH(CH). B R3 11. A compound according to claim 8, wherein B is OCH (CH). 25 12. A compound according to claim 8, wherein B is OCH: with a compound of formula (V) and R' is methyl or 2,2-difluoroethyl. 13. A compound according to claim8, wherein R is meth HN(R)-CH-A (V) ylcarbonyl. 14. A compound according to claim 7, wherein A is 6-chlo in which B, D, A and R', and Rare each as defined in claim ropyrid-3-yl; B is OCH(CH); and R is hydrogen. 30 2, optionally in the presence of a diluent. 15. A composition for controlling animal pests, comprising at least one compound according to claim 1. 17. A method for controlling animal pests in an agrochemi 16. A process for preparing a compound according to claim cal sector, in an animal health sector or a combination thereof, 1, comprising: comprising contacting said pests, their habitat or a combina (a) reacting a compound of formula (II) 35 tion thereof with a pest-controlling effective amount of a compound according to claim 1. 18. A method for controlling plant pests, characterized in (II) that a compound according to claim 1 or a composition according to claim 11 is applied to the plant pests, their 40 habitat or a combination thereof. R3