USOO8629084B2

(12) United States Patent (10) Patent No.: US 8,629,084 B2 Fischer et al. (45) Date of Patent: Jan. 14, 2014

(54) IODINE-PHENYL-SUBSTITUTED CYCLIC 4,256,657 A 3, 1981 Wheeler CETOENOLS 4,256,658 A 3, 1981 Wheeler 4,256,659 A 3, 1981 Wheeler (75) Inventors: Reiner Fischer, Monheim (DE); 4,257,858 A 3, 1981 Wheeler Thomas Bretschneider, Lohmar (DE); 4,283,348 A 8, 1981 Wheeler Kerstin Ilg, Köln (DE); Stefan Lehr, 35.26 A SE: SSR, Liederbach (DE): Dieter Feucht, 4.338,122 A 7, 1982. Wheeler Eschborn (DE); Olga Malsam, Rösrath 4,351,666 A 9, 1982 Koerwer (DE); Udo Reckmann, Köln (DE); 4,409,153 A 10/1983 Hodakowski Guido Bojack, Wiesbaden (DE); SS A 3. 3. While tal ChristianO O Arnold, Langenfeld (DE): 4,551,547 A 1 1/1985 Wheeler ea. Thomas Auler, Leichlingen (DE), 4,613,617 A 9, 1986 Sousa Martin Jeffrey Hills, Idstein (DE); 4,623,727 A 11/1986 Hibele Heinz Kehne, Hofheim (DE); Waltraud 4,632,698 A l 1986 E. 1 4,639,266 A 1, 1987 Heubach et al. E. tsh (DE); Erich 4,659,372 A 4, 1987 Wheeler (73) Assignee: Bayer CropScience AG, Monheim (DE) (Continued) (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 AU T26090 B2 4, 1998 U.S.C. 154(b) by 1169 days. CA 2298 033 A1 3/1999 (21) Appl. No.: 11/663,029 (Continued) OTHER PUBLICATIONS (22) PCT Filed: Sep. 13, 2005 Baciocchi, E., et al., “Dimethyl Arylmalonates from Cerium(IV) (86). PCT No.: PCT/EP2005/009807 Ammonium Nitrate Promoted Reactions of Dimethyl Malonate with Aromatic Compounds in Methanol.” Tetrahedron Lett. 27:2763 S371 (c)(1), 2766, Pergamon Journals Ltd. (1986). (2), (4) Date: Jun. 10, 2009 Balthazor, T.M., et al., "Synthesis and Structure of Benziodazoles.”.J. Org. Chem. 44:1447-1449, American Chemical Society (1979). (87) PCT Pub. No.: WO2006/029799 Bhattacharya, B., “Isoquinoline Derivatives: PartXVIII—Formation of I-Alkyl-(or alkaryl or aryl)-3-methyl-7-chloro-(or 5-chloro)- PCT Pub. Date: Mar. 23, 2006 isoquinolines.” Indian J. Chem. 6:341-345, Council of Scientific and Industrial Research (1968). (65) Prior Publication Data Breslow, R., et al., “Selective Halogenation of Steroids. Using Attached Aryl Iodide Templates.” J. Am. Chem. Soc. 99:905-915, US 201O/OOO985O A1 Jan. 14, 2010 American Chemical Society (1977). Campbell, A.C., et al., “Synthesis of (E)- and (Z)-Pulvinones,” J. (30) Foreign Application Priority Data Chem. Soc. Perkin Trans. 1:1567-1576, The Chemical Society (1985). Sep. 16, 2004 (DE) ...... 10 2004 O44,827 (Continued) (51) Int. Cl. Primary Examiner — Noble Jarrell AOIN 43/36 (2006.01) Assistant Examiner — Valerie Rodriguez-Garcia C07D 491/107 (2006.01) (74) Attorney, Agent, or Firm — Sterne, Kessler, Goldstein C07D 209/54 (2006.01) & Fox PL.L.C. C07D 207/273 (2006.01) (57) ABSTRACT (52) AOINU.S. Cl 43/38 (2006.01) The invention relates to novel iodophenyl-substituted cyclic USPC ...... s04/283.s04/284.514,409:514.425. ketenols of the formula () 548/410: 548/513; 548/544 (58) Field of Classification Search (I) USPC ...... 504/283, 248: 514/409, 425, 456: J 548/410, 513, 544 s yx See application file for complete search history. CKE \, f^y/, (56) References Cited U.S. PATENT DOCUMENTS in which CKE, J, X and Y are as defined above, to a plurality 3,542,809 A 11, 1970 Nakanishi of processes and intermediates for their preparation and to 4,021,224. A 5, 1977 Palos et al. their use as pesticides and/or herbicides, and also to selective 4,091,006 A 5/1978. Durden, Jr. et al. herbicidal compositions comprising firstly iodophenyl-Sub 4,175,135 A 11, 1979 Haines stituted cyclicketonols of the formula (I) and secondly at least 4,186,130 A 1, 1980 Teach one crop plant compatibility-improving compound. 4,209,432 A 6, 1980 Roth 4,209,532 A 6, 1980 Wheeler 11 Claims, No Drawings US 8,629,084 B2 Page 2

(56) References Cited 2007/0129252 A1 6/2007 Fischer et al. 2007/0225.167 A1 9, 2007 Fischer et al. U.S. PATENT DOCUMENTS 2007/022517O A1 9, 2007 Fischer et al. 2007/0244007 A1* 10, 2007 Fischer et al...... 504,104 4,881,966 11, 1989 Nyffeler et al. 2007/0254949 A1 11/2007 Bretschneider et al. 4,891,057 1, 1990 Sohn et al. 2007,0265266 A1 11/2007 Fischer et al. 4.902.340 2, 1990 Hubele 2007/0270416 A1 11/2007 Funke et al. 4,925,868 5, 1990 Terao et al. 2007/0276023 A1 11/2007 Fischer et al. 4,985,063 1, 1991 Fischer et al. 2007/0298.968 A1 12/2007 Bretschneider et al. 5,045,560 9, 1991 Fischer et al. 2007,0298969 A1 12/2007 Fischer et al. 5,094,681 3, 1992 Krämer et al. 5,116,836 5, 1992 Fischer et al. FOREIGN PATENT DOCUMENTS 5,138,563 8, 1992 Debitsch et al. 5,225,434 7, 1993 Bertram et al. CA 2382 432 A1 3, 2001 5,258,527 11, 1993 Krauskopfet al. CA 2382 491 A1 3, 2001 5,262,383 11, 1993 Fischer et al. CA 2492 O96 A1 1, 2004 5,314,863 5, 1994 Löher et al. CA 2497 O74 A1 3, 2004 5,332,720 T. 1994 Kriger et al. CA 2513 51.0 A1 8, 2004 5,350,861 9, 1994 Fischer et al...... 548,544 CA 2518 620 A1 9, 2004 5,380,852 1, 1995 Schlitze et al. CA 2535 512 A1 2, 2005 5,393,729 2, 1995 Fischer et al. CA 2544 537 A1 5, 2005 5,401,700 3, 1995 Sohn et al. CA 2544548 A1 5, 2005 5,407,897 4, 1995 Cary et al. CA 2546 815 A1 6, 2005 5,494,890 2, 1996 Cederbaum et al. CA 2546 817 A1 6, 2005 5,504,057 4, 1996 Fischer et al. EP O 346 620 A1 12, 1989 5,516,750 5, 1996 Willms et al. EP O 442 077 B1 8, 1991 5,565.450 10, 1996 Fischer et al. GB 2266 888 A 11, 1993 5,567,671 10, 1996 Fischer et al. JP 2000-53670 A 2, 2000 5,589.469 12, 1996 Fischer et al. WO WO94,29268 A1 12, 1994 5,610,122 3, 1997 Fischer et al. WO WO 96.O2539 A1 2, 1996 5,622,917 4, 1997 Fischer et al...... 504,283 WO WO96, 11574 A1 4f1996 5,677.449 10, 1997 Fischer et al. WO WO96/21652 A1 T 1996 5,683,965 11, 1997 Bachmann et al. WO WO99/11605 A1 3, 1999 5,700,758 12, 1997 Rösch et al. WO WOOOf 47585 A1 8, 2000 5,739,079 4, 1998 Holdgrin WO WOO4/OOO152 A2 12/2003 5,808, 135 9, 1998 Fischer et al. WO WO 2004/048314 A1 6, 2004 5,830,825 11, 1998 Fischer et al. WO WO 2004/065.366 A1 8/2004 5,830,826 11, 1998 Fischer et al. 5,840,661 11, 1998 Fischer et al. OTHER PUBLICATIONS 5,945,444 8, 1999 Fischer et al. CAPLUS Database. Accession No. 1975:453382, Deckart, H., et al., 5,960,443 9, 1999 Young et al. "Pharmacokinetics of new radioiodine-labeled aromatic acids.” 5,977,029 11, 1999 Fischer et al. Radiobiol. Radiother: 15:27-38, Verlag Volk Und Gesundheit (1974). 6,071,937 6, 2000 Bretschneider et al. Carson, J.R., et al., “2-Ethynylbenzenealkanamines. A New Class of 6,114,374 9, 2000 Lieb et al. 6,133,296 10, 2000 Lieb et al. Calcium Entry Blockers,” J. Med Chem. 31:630-636, American 6,140,358 10, 2000 Lieb et al. Chemical Society (1988). 6,200,932 3, 2001 Fischer et al. Chambers, M.S., et al., “An Asymmetric Synthesis of Thiotetronic 6,235,680 5, 2001 Ziemer et al. Acids using Chirality Transfer via an Allyl Xanthate-to 6,251,827 6, 2001 Ziemer et al. Dithiocarbonate Rearrangement. X-Ray Crystal Structure of (5R)- 6,251,833 6, 2001 Erdelen et al. 2,5-Dihydro-4-hydroxy-5-methyl-3-phenyl-5-prop-1'-enyl-2- 6,316,486 11, 2001 Lieb et al...... 514,411 oXothiophene.” J. Chem. Soc., Chem. Commun., pp. 1228-1230. The 6,410,480 6, 2002 Mühlebach et al. Chemical Society (1987). 6,472.419 10, 2002 Fischer et al. Compagnon, P.L., and Miocque, M., "Addition des Réactifs 6,515, 184 2, 2003 Fischer et al. Nucleophiles Sur la Triple Liaison Nitrile.” Ann. Chim. 5:11-22, 6,555.499 4, 2003 Glock et al. 6,589,976 T/2003 Fischer et al. Masson (1970). 6,642,180 11, 2003 Fischer et al. Edward, J.T., and JitrangSri. C., “Stereochemistry of the Bucherer 6,861,391 3, 2005 Fischer et al. Bergs and Strecker Reactions of 4-tert-Butylcyclohexanone.” CanJ. 6,894,005 5/2005 Maetzke et al. Chem, 53:3339-3350, NRC Research Press (1975). 2002/0022575 2, 2002 Fischer et al. Edwards, R.L., et al., “Constituents of the Higher Fungi. Part IV. 2002fOO726.17 6, 2002 Hagemann et al. Involutin, a Diphenyl-cyclopenteneone from Paxillus involutus 2002fO188136 12, 2002 Lieb et al. (Oeder ex Fries).” J. Chem. Soc. (C), pp. 405-409, Chemical Society 2003/0045432 3, 2003 Fischer et al. (1967). 2003/OO73851 4, 2003 Lieb et al. Harrison, H.R., et al., “Use of molecular sieves in the methyl 2003/0096806 5/2003 Lieb et al. esterification of carboxylic acids.” Chem. Ind., p. 1568, Society of 2003/01712.19 9, 2003 Lieb et al. Chemical Industry (1968). 2003/0171220 9, 2003 Ziemer et al. 2003/O1995.72 10, 2003 Lieb et al. Ketcham, R., et al., “Synthesis of Heterocycles. 174 (1.2) Substituted 2003/0216260 11, 2003 Ruther et al. Thiazines and Bisthiazinyls from Dithiooxamide and 2003/0228984 12, 2003 Hagemann et al. Trichlorophenyl Malonates.”.J. Heterocycl. Chem. 10:223-224, Jour 2004/026.6624 12, 2004 Hofer nal of Heterocyclic Chemistry (1973). 2005.0054535 3, 2005 Fischer et al. Larock, R.C., and Yum, E.K., “Palladium-catalyzed Annulation of 2005/0090399 4, 2005 Friedmann et al. Vinylic Cyclopropanes and Cyclobutanes.” Tetrahedron 52:2743 2005, 0164886 7/2005 Glock 2758, Elsevier Science Ltd., (1996). 2006.0160847 T/2006 Fischer et al. Micklefield, J., et al., “Alkylation and Acylation of 2006, O166829 T/2006 Fischer et al. 5-Phenylsulphonyl- and 5-Cyanobutyrolactones.” Tetrahedron 2007, OO15825 1/2007 Fischer et al. 48:7519-7526, Pergamon Press Ltd. (1992). 2007/0066488 3, 2007 Fischer et al. Munday, L., “Amino-acids of the Cyclohexane Series. Part I.” J. 2007/0093391 4, 2007 Fischer et al. Chem. Soc., pp. 4372-4379, American Chemical Society (1961). US 8,629,084 B2 Page 3

(56) References Cited Aidhen, I. S., and Ahuja, J. R. “A novel synthesis of benzocyclobutenones.” Tetrahedron Letters 33 (37):5431-5432, OTHER PUBLICATIONS Pergamon Press Ltd., Great Britain (Sep. 1992). Carson, J. R. et al., “2-Ethynylbenzenealkanamines. A new class of Nakanishi, S., and Butler, K., “Synthesis of Chlorocarbonyl Ketenes.” Org. Prep. Procedures Int. 7:155-158, Organic Prepara calcium entry blockers,” J. Med Chem. 31(3):630-636, American tions and Procedures, Inc. (1975). Chemical Society, United States (Mar. 1988). Schmierer, R., and Mildenberger, H., “Cyclisierung von Ishibashi, H., et al., “Stereoselective radical cascade approach to N-ACylalanin-und N-Acylglycinestern.” Liebigs Ann. Chem., pp. benzooquinolizidines.” Tetrahedron Letters 40(6): 1149-1152, 1095-1098, VCH Verlagsgesellschaft mbH (1985). Elsevier Science Ltd., Great Britain (Feb. 1999). Sonntag, N.O.V., “The Reactions of Aliphatic Acid Chlorides.” Office Action mailed Sep. 28, 1998, in U.S. Appl. No. 08/945,664, Chem. Rev. 52:237-416, American Chemical Society (1953). Lieb et al., S. 371(c) date Oct. 31, 1997 (issued as U.S. Patent No. Sousa, A.A., et al., “Esters of 3-Hydroxy-2-Arylindones, a New 6,316.486). Class of Acaricide.” J. Econ. Entomol. 66:584-586, Entomological Office Action mailed Apr. 23, 1999, in U.S. Appl. No. 08/945,664, Society of America (1973). Lieb et al., S. 371(c) date Oct. 31, 1997 (issued as U.S. Patent No. Suzuki, S., et al., “Studies on Antiviral Agents. Biological Activity of 6,316.486). TenuaZonic Acid Derivatives.” Chem. Pharm. Bull. 15:1120-1122, Pharmaceutical Society of Japan (1967). Advisory Action mailed Jan. 13, 2000, in U.S. Appl. No. 08/945,664. Tsuzuki, K., and Omura, S., “Syntheses and Biological Activities of Lieb et al., S. 371(c) date Oct. 31, 1997 (issued as U.S. Patent No. Thiotetromycin Analogs,” J. Antibiotics XXXVI: 1589-1591, Japan 6,316.486). Antibiotics Research Association (1983). Office Action mailed Apr. 12, 2000, in U.S. Appl. No. 08/945,664. Wheeler, T.N., “Novel Photochemical Synthesis of 2-Aryl-1,3- Lieb et al., S. 371(c) date Oct. 31, 1997 (issued as U.S. Patent No. cyclohexanediones.”.J. Org. Chem. 44:4906-4912, American Chemi 6,316.486). cal Society (1979). Office Action mailed Aug. 25, 2000, in U.S. Appl. No. 08/945,664. International Search Report for International Application No. PCT/ Lieb et al., S. 371(c) date Oct. 31, 1997 (issued as U.S. Patent No. EP2005/009807, European Patent Office, Netherlands, mailed on 6,316.486). Feb. 1, 2006. Advisory Action mailed Jan. 11, 2001, in U.S. Appl. No. 08/945,664. Dialog File 351. Accession No. 4963457, English language abstract Lieb et al., S. 371(c) date Oct. 31, 1997 (issued as U.S. Patent No. for EP 0346 620 A1, (1989). 6,316.486). Dialog File 351. Accession No. 5637204, English language abstract Office Action mailed Aug. 15, 2011, in U.S. Appl. No. 12,083,691. for EP 0442077 B1, (1995). Fischer et al., S. 371(c) date May 4, 2009. Patent Abstracts of Japan, English language abstract for JP 2000 53670 A, (2000). * cited by examiner US 8,629,084 B2 1. 2 ODINE-PHENYL-SUBSTITUTED CYCLC have herbicidal, acaricidal and insecticidal properties are CETOENOLS described in EP-A-588 137, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/16436, WO 97/19 The present invention relates to novel iodophenyl-substi 941, WO 97/36 868, WO 98/05638, WO 99/43649, WO tuted cyclic ketoenols, to a plurality of processes for their 5 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO preparation and for their use as pesticides and/or herbicides. 03/013249, WO 04/080962, WO 04/111042. The invention also provides selective herbicidal composi Certain 5-phenyl-1,3-thiazine derivatives which are unsub tions comprising firstly iodophenyl-Substituted cyclic stituted in the phenyl ring are already known (cf. E. Ziegler ketoenols and secondly a crop plant compatibility-improving and E. Steiner, Monatsh. 95, 147 (1964), R. Ketcham, T. compound. 10 Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 (1973)); Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones however, a possible use of these compounds as pesticides is are described in the prior art (S. Suzuki et al. Chem. Pharm. not stated. 5-Phenyl-1,3-thiazine derivatives which are sub Bull. 15 1120 (1967)). Furthermore, R. Schmierer and H. stituted in the phenyl ring and have herbicidal, acaricidal and Mildenberger (Liebigs Ann. Chem. 1985, 1095) synthesized insecticidal action are described in WO94/14785, WO 96/02 N-phenylpyrrolidine-2,4-diones. A biological activity of 15 539, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO these compounds has not been described. 97/02243, WO 97/36868, WO 99/05638, WO99/43649, WO EP-A-0262399 and GB-A-2266888 disclose compounds 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO of a similar structure (3-arylpyrrolidine-2,4-diones); how 03/013249, WO 04/080962, WO 04/111042. ever, a herbicidal, insecticidal or acaricidal action of these It is known that certain Substituted 2-arylcyclopentanedi compounds is not known. Known to have a herbicidal, insec ones have herbicidal, insecticidal and acaricidal properties ticidal or acaricidal action are unsubstituted, bicyclic (cf., for example, U.S. Pat. Nos. 4.283.348; 4.338,122; 4,436, 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355.599, EP 666; 4,526,723; 4,551,547; 4,632,698; WO 96/01798: WO A415 211 and JP-A-12-053 670), and also substituted mono 96/03 366, WO 97/14 667 and also WO 98/39281, WO cyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 893 and EP-A-442 077). 25 01/74770, WO 03/013249, WO 04/080 962, WO 04/111 Also known are polycyclic 3-arylpyrrolidine-2,4-dione 042). Also known are compounds Substituted in a similar derivatives (EP-A-442 073), and also 1H-arylpyrrolidinedi manner, 3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-ene one derivatives (EP-A456 063, EP-A-521 334, EP-A-596 1-one from the publication Micklefield et al., Tetrahedron, 298, EP-A-613 884, EP-A-613 885, WO95/01 997, WO (1992), 7519-26 and the natural compound involutin (-)-cis 95/26954, WO95/20572, EP-A-0 668 267, WO 96/25395, 30 5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphe WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 nyl)cyclopent-2-enone from the publication Edwards et al., J. 868, WO 97/43275, WO 98/05638, WO 98/06721, WO Chem. Soc. S. (1967), 405-9. An insecticidal or acaricidal 98/25928, WO 99/16748, WO 99/24437, WO 99/43649, WO action is not described. Also known is 2-(2,4,6-trimethylphe 99/48869 and WO99/55673, WO 01/17972, WO 01/23354, nyl)-1,3-indanedione from the publication J. Economic Ento WO 01/74770, WO 03/013249, WO 04/007448, WO 35 mology, 66, (1973), 584 and the laid-open publication DE-A 04/024688, WO 04/065366, WO 04/080962, WO 04/111042, 2361084, with herbicidal and acaricidal actions being stated. WO 05/044791, WO 05/044796, WO 05/048710, WO It is known that certain substituted 2-arylcyclohexanedi 05/049596, DE-A-04 001 433. ones have herbicidal, insecticidal and acaricidal properties It is known that certain substituted A-dihydrofuran-2-one (U.S. Pat. Nos. 4,175,135, 4,209,432, 4,256,657, 4.256,658, derivatives have herbicidal properties (cf. DE-A-4 014.420). 40 4,256,659, 4,257,858, 4,283,348, 4,303,669, 4,351,666, The synthesis of the tetronic acid derivatives (such as, for 4,409,153, 4,436,666, 4,526,723, 4,613,617, 4,659,372, example, 3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophe DE-A2 813 341, and also Wheeler, T. N., J. Org. Chem. 44, nyl)-A-dihydrofuran-2-one) used as starting materials is also 4906 (1979)), WO 99/43649, WO 99/48869, WO 99/55673, described in DE-A-4014.420. Compounds of a similar struc WO 01/17972, WO 01/74770, WO 03/013249, WO 04/080 ture with no stated insecticidal and/or acaricidal activity are 45 962, WO 04/111042). known from the publication Campbell et al., J. Chem. Soc., It is known that certain substituted 4-arylpyrazolidine-3,5- Perkin Trans. 1, 1985, (8) 1567-76. Furthermore, 3-aryl-A- diones have acaricidal, insecticidal and herbicidal properties dihydrofuranone derivatives having herbicidal, acaricidal and (cf., for example, WO92/16510, EP-A-508 126, WO 96/11 insecticidal properties are known from EP-A-528 156, EP 574, WO 96/21 652, WO 99/47525, WO 01/17 351, WO A-0 647 637, WO95/26345, WO 96/20 196, WO 96/25395, 50 01/17 352, WO 01/17 353, WO 01/17 972, WO 01/17973, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 WO 03/028 466, WO 03/062 244, WO 04/080 962, WO 868, WO 98/05638, WO 98/25928, WO 99/16748, WO 04/111042, WO 05/005428, WO 05/016873). 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO However, the efficacy and activity spectrum of these com 01/23354 and WO 01/74770, WO 03/013 249, WO 04/024 pounds, in particular at low application rates and concentra 688, WO 04/080 962, WO 04/11 1 042. Also known are 55 tions, are not always satisfactory. Furthermore, the compat 3-aryl-A-dihydrothiphenone derivatives (WO 95/26 345, ibility of these compounds with crops is not always sufficient. 96/25 395, WO 97/01 535, WO 97/02 243, WO 97/36 868, This invention now provides novel compounds of the for WO 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, mula WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO 03/013249, WO 04/080962, WO 04/111 60 042). (I) Certain phenylpyrone derivatives unsubstituted in the phe J nyl ring are already known (cf. A. M. Chirazi, T. Kappe and E. s yx Ziegler, Arch. Pharm. 309,558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem. Ber. 91,2849); however, a possible 65 use of these compounds as pesticides is not stated. Phenylpy rone derivatives which are substituted in the phenyl ring and US 8,629,084 B2 4 in which -continued J represents iodine, (8) X represents hydrogen, alkyl, halogen, haloalkyl, alkoxy or haloalkoxy, Y represents hydrogen, alkyl, halogen or alkoxy, with the proviso that at least one of the radicals J. X orY is located in the 2-position of the phenyl radical and is not hydrogen, 10 CKE represents one of the groups in which A represents hydrogen, in each case optionally halogen substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, (1) G Saturated or unsaturated, optionally substituted o1 15 cycloalkyl in which optionally at least one ring atom is replaced by a heteroatom, or in each case optionally A halogen-, alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, - N . cyano- or nitro-substituted aryl, arylalkyl or hetaryl, D1 N B represents hydrogen, alkyl or alkoxyalkyl, or O A and B together with the carbon atom to which they are

(2) attached represent a saturated or unsaturated, unsubsti tuted or substituted cycle which optionally contains at least one heteroatom, 25 D represents hydrogen or an optionally Substituted radical from the group consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl, Saturated or unsaturated cycloalkyl in which optionally one or more ring members are replaced by heteroatoms, arylalkyl, aryl, hetarylalkyl or hetaryl or (3) 30 A and D together with the atoms to which they are attached represent a saturated or unsaturated cycle which is unsubstituted or substituted in the A.D moiety and optionally contains at least one (in the case of CKE=8 one further) heteroatom, or 35 A and Q' together represent alkanediyl or alkenediyl. optionally Substituted by hydroxyl, in each case option (4) ally substituted alkyl, alkoxy, alkylthio, cycloalkyl, ben Zyloxy or aryl or 40 Q" represents hydrogen or alkyl, Q, Q, Q and Q independently of one another represent hydrogen or alkyl, Q represents hydrogen, represents optionally substituted (5) alkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted 45 cycloalkyl (in which optionally one methylene group is replaced by oxygen or Sulfur) or optionally substituted phenyl, or Q and Q together with the carbonatom to which they are 50 attached represent a saturated or unsaturated, unsubsti tuted or Substituted cycle which optionally contains a (6) heteroatom, G represents hydrogen (a) or represents one of the groups

55 (b)

(7) 60 (c)

(d) 65 SO-R3, US 8,629,084 B2 5 6 -continued -continued

(I-2)

(f) (g)

10 (I-3)

in which E represents a metalion equivalent oran ammonium ion, 15 L represents oxygen or Sulfur, M represents oxygen or Sulfur, R" represents in each case optionally halogen-substi tuted alkyl, alkenyl, alkoxyalkyl, alylthioalkyl, poly alkoxyalkyl or optionally halogen-, alkyl- or alkoxy (I-4) substituted cycloalkyl which may be interrupted by at least one heteroatom, in each case optionally Substi tuted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, 25 R represents in each case optionally halogen-substi tuted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each case optionally Substituted (I-5) cycloalkyl, phenyl or benzyl, R. RandR independently of one another represent in 30 each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alk enylthio, cycloalkylthio or represent in each case optionally Substituted phenyl, benzyl, phenoxy or phenylthio. 35 (I-6) RandR independently of one another represent hydro gen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, repre sent optionally Substituted phenyl, represent option 40 ally substituted benzyl, or together with the Natom to which they are attached represent a cycle which is optionally interrupted by oxygen or Sulfur. (I-7) Depending also on the nature of the Substituents, the com pounds of the formula (I) can be present as geometrical and/or 45 optical isomers or isomer mixtures of varying composition which, if appropriate, may be separated in a customary man ner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use, and composi tions comprising them. However, for the sake of simplicity, 50 hereinbelow only compounds of the formula (I) are referred to, although what is meant are both the pure compounds and, (I-8) if appropriate, also mixtures having varying proportions of isomeric compounds. Including the meanings (1) to (8) of group CKE, the fol 55 lowing principal structures (I-1) to (I-8) result:

(I-1) 60 in which A, B, D, G, J, Q, Q, Q, Q, Q, Q, XandY areas defined above. 65 Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following principal structures (I-1-a) to (I-1-g) result if CKE represents group (1) US 8,629,084 B2 7 8 -continued

5

10 J

X Y 15 (I-1-g):

2O L

R7-N V 25 R Y Y

in which (I-1-c): 30 A, B, D, E, J, L, M, X, Y, R. R. R. R. R. Rand R7 are as defined above. Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following principal structures (I-2-a) as to (I-2-g) result if CKE represents group (2)

(I-2-a):

Y 40

(I-1-d):

45

50

(I-1-e): 55

60

65 US 8,629,084 B2 9 10 -continued -continued

in which A, B, E, J, L, M, X,Y, R', R,R,R,R, R and R7 are as 50 defined above. Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following principal structures (I-3-a) to (I-3-g) result if CKE represents group (3) 55

60

in which A, B, E, J, L, M, X, Y, R. R. R. R. R. Rand R7 are as defined above. 65 Depending on the position of the Substituent G, the com pounds of the formula (I4) can be present in the two isomeric forms of the formulae (I4-A) and (I-4-B) US 8,629,084 B2 11 12 -continued (I-4-A) (I-4-c):

A O 5

/O Y (s\ > y R4-M2 A O 10 X-d L

(I-4-B) A O J (I-4-d): D / Oyx 15 / \ }

which is meant to be indicated by the dashed line in the formula (I-4). 25 The compounds of the formulae (I-4-A) and (I-4-B) can be present both as mixtures and in the form of their pure isomers. (I-4-e): If appropriate, mixtures of the compounds of the formulae (I-4-A) and (I-4-B) can be separated in a manner known perse by physical methods, for example by chromatographic meth 30 ods. For reasons of clarity, hereinbelow in each case only one of the possible isomers is shown. This does not preclude that, if appropriate, the compounds may be present in the form of the isomer mixtures or the respective other isomeric forms. Including the different meanings (a), (b), (c), (d), (e), (f) 35 and (g) of group G, the following principal structures (I-4-a) to (I-4-g) result if CKE represents group (4)

40

45

(I-4-g):

50

55 X-d

60 in which A, D, E, J, L, M, X,Y, R', R. R. R. R. RandR are as defined above. 65 Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following principal structures (I-5-a) to (I-5-g) result if CKE represents group (5) US 8,629,084 B2 13 14 -continued (I-5-a): (I-5-g): A A

S)-N O 5 S)-N O HO 21 A. X-d 21 A. N y--X 10 R7-NV SXj-X Y R6 Y (I-5-b): A in which )=x A. E. J. L. M, X, Y. R. R. R. R. R. R. and R7 are as S O defined above. Depending on the position of the Substituent G, the com RI o J pounds of the formula (I-6) can be present in the two isomeric X-d 21 A. 2O forms of the formulae (I-6-A) and (I-6-B) -HX O NxJ Y G (I-6-A) (I-5-c): A 25 A O J )-N B y X S O 2 2 o \ > y R4-M J O 21 7. 30 Q Q2 O HX (I-6-B) L N x A. O J Y B FIFVX (I-5-d): 35 S A \ }^y )=x Q Q? O S O

o J 40 R3-SO- 21 ily which is meant to be indicated by the dashed line in the N x formula (I). Y The compounds of the formulae (I-6-A) and (I-6-B) can be (I-5-e): 45 present both as mixtures and in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulae A (I-6-A) and (I-6-B) can be separated by physical methods, for )-N example by chromatographic methods. S O For reasons of clarity, hereinbelow in each case only one of o 50 the possible isomers is shown. This does not preclude that, if R J appropriate, the compounds may be present in the form of the )p-d 21 A. isomer mixtures or the respective other isomeric forms. R5 | j-X Including the different meanings (a), (b), (c), (d), (e), (f) N X and (g) of group G, the following principal structures (I-6-a) Y to (I-6-g) result: (I-5-f): A ) N (I-6-a): S O 60 A OH J o J B VX E-O 21 7. / X1Q j-X w Y NX 65 Q US 8,629,084 B2 15 16 -continued in which A, B, J, Q, Q, E, L, M, X,Y, R. R. R. R. R. Rand R' are as defined above. Depending on the position of the Substituent G, the com pounds of the formula (I-7) can be present in the two isomeric forms of the formulae (I-7-A) and (I-7-B), which is meant to be indicated by the dashed line in the formula (I-7):

10 (I-7-A)

L 15

A O-C-M-Rl, J B / x (I-7-B)

Q Q? O (I-6-d): 25

A O-SO-R J B 30 The compounds of the formulae (I-7-A) and (I-7-B) can be /ixx present both as mixtures and in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulae Q Q? O (I-7-A) and (I-7-B) can be separated by physical methods, for example by chromatographic methods. (I-6-e): 35 For reasons of clarity, hereinbelow in each case only one of L the possible isomers is shown. This does not preclude that, if O-P - R' appropriate, the compound in question may be present in the A NR5 form of the isomer mixtures or the respective other isomeric J form. B 40 Including the different meanings (a), (b), (c), (d), (e), (f) / and (g) of group G, the following principal structures (I-7-a) to (I-7-g) result: Q Q? O 45 (I-6-f): (I-7-a):

A O-E J B / x 50

Q Q? O (I-6-g): 55 L

us Y R6 A O S. 60 B / x Q 65 US 8,629,084 B2 17 18 -continued Depending on the position of the Substituent G, the com (I-7-c): pounds of the formula (I-8) can be present in the two isomeric formulae (I-8-A) and (I-8-B)

(I-8-A) O J

10 Da VX SC 1N X-(' v Y O (I-7-d): / 15 G

(I-8-B) G V O J DS VX Y / SXs. 1N v Y

25 O

which is meant to be indicated by the dashed line in the formula (I-8). 30 The compounds of the formulae (I-8-A) and (I-8-B) can be present both as mixtures and in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulae (I-8-A) and (I-8-B) can be separated in a manner known perse by physical methods, for example by chromatographic meth 35 ods. For reasons of clarity, hereinbelow in each case only one of the possible isomers is shown. This does not preclude that, if appropriate, the compounds may be present in the form of the 40 isomer mixtures or the respective other isomeric forms. Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following principal structures (I-8-a) to (I-8-g) result if Het represents the group (8)

45

O J 50 Da MX

1N X-('Sv SS Y OH 55 (I-8-b) O J Da MX 60 SS 1N X-(' v Y O in which 65 A, B, J, E, L, M, Q, Q, Q, Q, X, Y, R', R,R,R,R, o={R1 RandR are as defined above. US 8,629,084 B2 19 20 -continued (I-8-c): (I-1-a) O J A1DS ( o/ s YX 10 1={M-R2

(I-8-d): in which O J A, B, D, J, X and Y are as defined above, 15 are obtained when Da MX N-acylamino acid esters of the formula (II) N 1)/ ( 'sSC A1 w Y (II) O COR / SO Y: A-HN J D1 21 A. 25 --x O O N x J Y

in which s 30 A1Da o/ A, B, D, J, X and Y are as defined above and y/ R represents alkyl (preferably C-C-alkyl) are condensed intramolecularly in the presence of a diluent and in the presence of a base. 35 (B) Furthermore, it has been found that substituted 3-phe nyl-4-hydroxy-A-dihydrofuranone derivatives of the formula (I-2-a) O J

40

(I-2-a) A1Da / o/ s YX

45

O Y

in which o/ s YX 50 A, B, J, X and Y are as defined above A1DS are obtained when ( carboxylic esters of the formula (III)

55 (III) S. COR

in which 4. 21 7. A, D, E, J, L, M, X,Y, R', R. R. R. R. Rand Rare as 60 defined above. rC Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes in which described below: 65 A, B, J, X, Y and Rare as defined above (A) substituted 3-phenylpyrrolidine-2,4-diones or their are condensed intramolecularly in the presence of a diluent enols of the formula (I-1-a) and in the presence of a base. US 8,629,084 B2 21 22 (C) Furthermore, it has been found that substituted 3-phe nyl-4-hydroxy-A-dihydrothiophenone derivatives of (Va) the formula (I-3-a) CHA D-C-OSi(R)1-nero

(I-3-a) in which A, D and Rare as defined above 10 are reacted with ketene acid halides of the formula (VI)

(VI) COHall in which 15 A, B, J, X and Y are as defined above {M ==o are obtained when yX / B-ketocarboxylic esters of the formula (IV) in which (IV) J, X and Y are as defined above and A B Hal represents halogen (preferably chlorine or bromine), O S if appropriate in the presence of a diluent and if appropriate N 25 in the presence of an acid acceptor. Furthermore, it has been found A 4-0 4/ J (E) that the novel substituted phenyl-1,3-thiazine deriva -HX tives of the formula (I-5-a) 8 Ny 30 Y (I-5-a) J in which MX A, B, J, X, Y and Rare as defined above and 35 V represents hydrogen, halogen, alkyl (preferably C-C- ul-(' alkyl) or alkoxy (preferably C-C-alkoxy) A US OH are cyclized intramolecularly, if appropriate in the pres ence of a diluent and in the presence of an acid. (D) Furthermore, it has been found that the novel substi 40 in which tuted 3-phenylpyrone derivatives of the formula (I-4-a) A, J, X and Y are as defined above are obtained when thioamides of the formula (VII) (I-4-a) O J 45 (VII) D O -: i \ A \ X. HN-C-A 50 A OH in which A is as defined above in which are reacted with ketene acid halides of the formula (VI) A, D, J, X and Y are as defined above 55 are obtained when (VI) carbonyl compounds of the formula (V) J COHall

(V) XYM "l. O 60 yX / D-C-CH-A in which in which 65 Hal, J, X and Y are as defined above, A and Dare as defined above if appropriate in the presence of a diluent and if appropriate or silylenol ethers thereof of the formula (Va) in the presence of an acid acceptor. US 8,629,084 B2 23 24 Furthermore, it has been found and (F) that compounds of the formula (I-6-a) R represents alkyl (preferably C-C-alkyl) are condensed intramolecularly in the presence of a diluent (I-6-a) 5 and in the presence of a base. A OH J (H) Furthermore, it has been found that the compounds of B -: the formula (I-8-a) \ }

25 HX (X) in which 30 A, B, Q', Q, J, X and Y are as defined above and R represents alkyl (in particular C-C-alkyl) in which are cyclized intramolecularly, if appropriate in the pres A and Dare as defined above ence of a diluent and in the presence of a base. C.) are reacted with compounds of the formula (VI) Moreover, it has been found 35 (G) that compounds of the formula (I-7-a) (VI) COHall

(I-7-a) 40 y’XYM / " .

in which 45 Hal, X, Y and Jare as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, or B) are reacted with compounds of the formula (XI) 50 in which (XI) A, B, J, Q, Q, Q, Q, X and Y are as defined above J O are obtained when X-7- U 6-aryl-5-ketohexanoic esters of the formula (IX) 55 \ Y\- U (IX) A B Q Q O J 60 ROC Sé,HX in which 2é J, X and Y are as defined above Y and U represents NH or O R, where R is as defined 65 above, in which if appropriate in the presence of a diluent and if appropriate A, B, J, Q, Q, Q, Q, X and Y are as defined above in the presence of a base, or US 8,629,084 B2 25 26 Y) are reacted with compounds of the formula (XII) (XVI) C M-R2

A (XII) r J 5 S X/,? \ NC1 n cor in which {o M and Rare as defined above, O if appropriate in the presence of a diluent and if appropriate 10 in the presence of an acid binder, in which and A, D, J, X, Y and Rare as defined above, (L) that compounds of the formulae (I-1-d) to (I-8-d) if appropriate in the presence of a diluent and if appropriate shown above in which A, B, D, J, Q', Q, Q, Q', Q, Q, in the presence of a base. 15 R, X and Y are as defined above are obtained when Moreover, it has been found compounds of the formulae (I-1-a) to (I-8-a) shown (I) that the compounds of the formulae (I-1-b) to (I-8-b) above in which A, B, D, J, Q, Q, Q, Q, Q, Q, Xand shown above in which A, B, D, J, Q, Q, Q, Q, Q, Q, Y are as defined above are in each case R', X and Y are as defined above are obtained when reacted with sulfonyl chlorides of the formula (XVII) compounds of the formulae (I-1-a) to (I-8-a) shown 20 R SO Cl (XVII) above in which A, B, D, J, Q, Q, Q, Q, Q, Q, Xand in which Y are as defined above are in each case R is as defined above, (C.) reacted with acid halides of the formula (XIII) if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, (XIII) 25 (M) that compounds of the formulae (I-1-e) to (I-8-e) Hal RI shown above in which A, B, D, J, L. Q', Q, Q, Q, Q, Q, R. R. X and Y are as defined above are obtained when compounds of the formulae (I-1-a) to (I-8-a) O 30 shown above in which A, B, D, J, Q, Q, Q, Q, Q, Q, X and Y are as defined above are in each case reacted in which with phosphorus compounds of the formula (XVIII) R" is as defined above and Hal represents halogen (in particular chlorine or bromine) (XVIII) O 35 R4 (B) with carboxylic anhydrides of the formula (XIV) Hall-P R CO. O. CO R' (XIV) LNRs in which 40 R" is as defined above, in which if appropriate in the presence of a diluent and if appropriate L. R* and Rare as defined above and in the presence of an acid binder, Hal represents halogen (in particular chlorine or bromine), (J) that the compounds of the formulae (I-1-c) to (I-8-c) if appropriate in the presence of a diluent and if appropriate shown above in which A, B, D, J, Q', Q, Q, Q, Q, Q", is in the presence of an acid binder, R. M, X and Y are as defined above and L represents (N) that compounds of the formulae (I-1-f) to (I-8-f) shown oxygen are obtained when compounds of the formulae above in which A, B, D, E, J, Q', Q, Q, Q, Q, Q°, X (I-1-a) to (I-8-a) shown above in which A, B, D, J, Q, and Y are as defined above are obtained when com Q, Q, Q, Q, Q, X and Y are as defined above are in pounds of the formulae (I-1-a) to (I-8-a) in which A, B, each case 50 D, J, Q, Q, Q, Q, Q, Q, X and Y are as defined reacted with chloroformicesters or chloroformic thioesters above are in each case of the formula (XV) reacted with metal compounds or amines of the formulae (XIX) or (XX) R°-M-CO Cl (XV) in which 55 R and Mare as defined above Me(OR 10) (XIX) if appropriate in the presence of a diluent and if appropriate (XX) in the presence of an acid binder, RR - R' (K) that compounds of the formulae (I-1-c) to (I-8-c) N shown above in which A, B, D, J, Q, Q, Q, Q, Q, Q, 60 2 R. M. X and Y are as defined above and L represents R sulfur are obtained when compounds of the formulae (I-1-a) to (I-8-a) shown above in which A, B, D, J, Q, in which Q, Q, Q, Q, Q, X and Y are as defined above are in Me represents a mono- or divalent metal (preferably an each case 65 alkali metal or alkaline earth metal. Such as lithium, reacted with chloromonothioformic esters or chlorodithio- Sodium, potassium, magnesium or calcium), or repre formic esters of the formula (XVI) sents an ammonium ion US 8,629,084 B2 27 28 -continued R'S GR'

NS R11A Y: trepresents the number 1 or 2 and R', R', R' independently of one another represent hydrogen or alkyl (preferably C-C-alkyl). if appropriate in the presence of a diluent, 10 (O) that compounds of the formulae (I-1-g) to (I-8-g) shown above in which A, B, D, J, L. Q', Q, Q, Q, Q, Q, R. R. X and Y are as defined above are obtained when compounds of the formulae (I-1-a) to (I-8-a) shown above in which A, B, D, J, Q, Q, Q, Q, Q, Q, 15 X and Y are as defined above are in each case (C) reacted with isocyanates or isothiocyanates of the for mula (XXI) in which Rand L are as defined above, if appropriate in the presence of a diluent and if appropriate 25 in the presence of a catalyst, or (B) reacted with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XXII) 30 (XXII) L R6 ls SN C 35 R7 in which

L. Rand Rare as defined above, 40 if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, (P) that compounds of the formulae (I-1-a) to (I-8-a) shown above in which A, B, D, J, Q, Q, Q, Q, Q, Q, Xand Y areas defined above are obtained when compounds of 45 the formulae (I-1-a') to (I-8-a') in which A, B, D, Q', Q, Q, Q, Q, Q, X and Y are as defined above and W. preferably represents bromine

50 C.) are reacted with metal iodides (for example sodium iodide or potassium iodide), if appropriate in the pres ence of a diluent, a Cu(I) salt (for example CuBr, Cul) 55 and a base (for example N,N-dimethylethylenedi amine), or B) Subjected to a halogen/metal exchange with metal orga nyls (for example n, S-, -butyllithium) and the anion formed is quenched with iodinating agents (for example 60 iodine, iodine monochloride). Furthermore, it has been found that the novel compounds of the formula (I) have good activity as pesticides, preferably as insecticides, acaricides and/or herbicides. Surprisingly, it has now also been found that certain Sub 65 stituted cyclic ketoenols, when employed together with the crop plant compatibility-improving compounds (safenerS/an tidotes) described later on, are extremely good at preventing US 8,629,084 B2 29 30 damage to the crop plants and can be used with particular y15-chloroquinoline-8-oxyacetate, 4-allyloxybutyl 5-chloro advantage as broad-spectrum combination products for the quinoline-8-oxyacetate, 1-allyloxyprop-2-yl 5-chloroquino selective control of unwanted plants in crops of useful plants, line-8-oxyacetate, methyl 5-chloroquinoxaline-8- Such as, for example, in cereals, but also in corn, Soya beans oxyacetate, ethyl 5-chloroquinoline-8-oxyacetate, allyl and rice. 5-chloroquinoxaline-8-oxyacetate, 2-oxoprop-1-yl 5-chloro The invention also provides selective herbicidal composi quinoline-8-oxyacetate, diethyl 5-chloroquinoline-8-oxyma tions comprising an effective amount of an active compound lonate, diallyl 5-chloroquinoxaline-8-oxymalonate, diethyl combination comprising, as components, 5-chloroquinoline-8-oxymalonate (cf. also related com (a) at least one substituted cyclic ketoenol of the formula pounds in EP-A-582198), 4-carboxychroman-4-ylacetic acid (I) in which CKE, J, X and Y are as defined above 10 and (AC-304415, cf. EP-A-613618), 4-chlorophenoxyacetic (b") at least one crop plant compatibility-improving com acid, 3,3'-dimethyl-4-methoxybenzophenone, 1-bromo-4- pound from the following group of compounds: chloromethylsulfonylbenzene, 1-4-(N-2-methoxybenzoyl 4-dichloroacetyl-1-oxa-4-azaspiro4.5 decane (AD-67, sulfamoyl)-phenyl-3-methylurea (also known as N-(2-meth MON4660), 1-dichloroacetylhexahydro-3,3,8a-trimeth 15 oxybenzoyl)-4-(methylaminocarbonyl)-amino ylpyrrolo 1,2-alpyrimidin-6(2H)-one (dicyclonon, BAS benzenesulfonamide), 1-4-(N-2- 145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4- methoxybenzoylsulfamoyl)phenyl-3,3-dimethylurea, 1-4- benzoxazine(benoxacor), 1-methylhexyl 5-chloroquinoline (N-4,5-dimethylbenzoylsulfamoyl)phenyl-3-methylurea, 8-oxy-acetate (cloquintocet-mexyl-cf. also related 1-4-(N-naphthylsulfamoyl)phenyl)-3,3-dimethylurea, compounds in EP-A-86750, EP-A-94349, EP-A-191736, N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylaminocar EP-A-492366), 3-(2-chlorobenzyl)-1-(1-methyl-1-phenyl bonyl)-benzenesulfonamide, ethyl)urea (cumyluron), C.-(cyanomethoximino)phenylac and/or one of the following compounds, defined by general etonitrile(cyometrinil), 2,4-dichlorophenoxyacetic acid (2,4- formulae, D), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), 1-(1- of the general formula (IIa) methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron, 25 dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba), S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate (IIa) (dimepiperate), 2.2-dichloro-N-(2-oxo-2-(2-propenylamino) ethyl)-N-(2-propenyl)acetamide (DKA-24), 2,2-dichloro-N. (X) + 30 2 N-di-2-propenylacetamide (dichlormid), 4,6-dichloro-2- CluAl R 14 phenylpyrimidine(fenclorim), ethyl 1-(2,4-dichlorophenyl)- 5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (fenchlorazole-ethyl-cf. also related compounds in EP-A- or of the general formula (IIb) 174562 and EP-A-346620), phenylmethyl 2-chloro-4- trifluoromethylthiazole-5-carboxylate(flurazole), 4-chloro 35 N-(1,3-dioxolan-2-ylmethoxy)-O-trifluoroacetophenone (IIb) oxime(fluxofenim), 3-dichloroacetyl-5-(2-furanyl)-2,2-dim X3 X2 ethyloxazolidine(furilazole, MON-13900), ethyl 4,5-dihy f N1S/S dro-5,5-diphenyl-3-isoxazolecarboxylate(isoxadifen ethyl-cf. also related compounds in WO-A-95/07897), 40 % 21 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor), (4-chloro-o-tolyloxy)acetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), diethyl 1-(2,4-dichorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole 3,5-dicarboxylate (mefenpyrdiethyl cf. also related com 45 or of the formula (Ic) pounds in WO-A-91/07874), 2-dichloromethyl-2-methyl-1, 3-dioxolane (MG-191), 2-propenyl-1-oxa-4-azaspiro4.5 decane-4-carbodithioate (MG-838), 1.8-naphthalic (IIc) anhydride, C.-(1,3-dioxolan-2-ylmethoximino)phenylaceto O nitrile(oxabetrinil), 2,2-dichloro-N-(1,3-dioxolan-2-ylm 50 R17 ethyl)-N-(2-propenyl)acetamide (PPG-1292), 3-dichloro acetyl-2,2-dimethyloxazolidine (R-28725), . 3-dichloroacetyl-2.2.5-trimethyloxazolidine (R-29148), R18 4-(4-chloro-o-tolyl)butyric acid, 4-(4-chlorophenoxy)bu tyric acid, diphenylmethoxyacetic acid, methyl diphenyl 55 where methoxyacetate, ethyl diphenylmethoxyacetate, methyl 1-(2- m represents a number 0, 1, 2, 3, 4 or 5, chlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl A represents one of the divalent heterocyclic groupings 1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3-carboxy shown below late, ethyl 1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole 3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimeth 60 ylethyl)-1H-pyrazole-3-carboxylate, ethyl 1-(2,4- N N N dichlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate (cf. NY N NY N NY Y also related compounds in EP-A-269806 and EP-A-333131), o )=N ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, R19 OR20 R19 R19 ethyl 5-phenyl-2-isoxazoline-3-carboxylate, ethyl 5-(4-fluo 65 rophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also O related compounds in WO-A-91/08202), 1,3-dimethylbut-1- US 8,629,084 B2 31 32 -continued of the general formula (IId) 1. (CH2) 3ry (IId) O-N R23 (X) in represents a number 0, 1, 2, 3, 4 or 5, ON N SAS R22 21 A represents optionally C1-C4-alkyl- and/or C-C- R24 l -H(X'), alkoxy-carbonyl- and/or C-C-alkenyloxy-carbonyl 21 SO, S Substituted alkanediyl having 1 or 2 carbon atoms, 10 R'' represents hydroxyl, mercapto, amino, C1-Co-alkoxy, O C-C-alkylthio, C-C-alkylamino or di(C-C-alkyl)- amino, or of the general formula (IIe) R" represents hydroxyl, mercapto, amino, C-C-alkoxy, 15 C-C-alkenyloxy, C-C-alkenyloxy-C-C-alkoxy, C-C-alkylthio, C-C-alkylamino or di(C-C-alkyl)- (IIe) amino, O R' represents in each case optionally fluorine-, chlorine R2S (X), and/or bromine-substituted C-C-alkyl, n N S/S R22 21 R7 represents hydrogen, in each case optionally fluorine-, k l -H(X'), chlorine- and/or bromine-substituted C-C-alkyl, 2 SO, N C-C-alkenyl or C-C-alkynyl, C-C-alkoxy-C-C- alkyl, dioxolanyl-C-C-alkyl, furyl, furyl-C-C-alkyl, 25 O thienyl, thiazolyl, piperidinyl, or optionally fluorine-, chlorine- and/or bromine- or C-C-alkyl-substituted where phenyl, trepresents a number 0, 1, 2, 3, 4 or 5, V represents a number 0, 1, 2, 3, 4 or 5, R" represents hydrogen, in each case optionally fluorine-, 30 R represents hydrogen or C-C-alkyl, chlorine- and/or bromine-substituted C-C-alkyl, R’ represents hydrogen or C-C-alkyl, C-C-alkenyl or C-C-alkynyl, C-C-alkoxy-C-C- R" represents hydrogen, in each case optionally cyano-, alkyl, dioxolanyl-C-C-alkyl, furyl, furyl-C-C-alkyl, halogen- or C-C-alkoxy-substituted C-C-alkyl, thienyl, thiazolyl, piperidinyl, or optionally fluorine-, C-C-alkoxy, C-C-alkylthio, C-C-alkylamino or chlorine- and/or bromine- or C-C-alkyl-substituted 35 di(C-C-alkyl)-amino, or in each case optionally phenyl, cyano-, halogen- or C-C-alkyl-substituted C-C-cy cloalkyl, C-C-cycloalkyloxy, C-C-cycloalkylthio or R7 and R' also together represent C-C-alkanediyl or C-C-cycloalkylamino, C-Cs-Oxaalkanediyl, each of which is optionally Sub R represents hydrogen, optionally cyano-, hydroxyl-, stituted by C-C-alkyl, phenyl, furyl, a fused benzene 40 halogen- or C-C-alkoxy-substituted C-C-alkyl, in ring or by two substituents which, together with the C each case optionally cyano- or halogen-substituted atom to which they are attached, form a 5- or 6-mem C-C-alkenyl or C-C-alkynyl, or optionally cyano-, bered carbocycle, halogen- or C-C-alkyl-substituted C-C-cycloalkyl, R" represents hydrogen, cyano, halogen, or represents in R" represents hydrogen, optionally cyano-, hydroxyl-, each case optionally fluorine-, chlorine- and/or bro 45 halogen- or C-C-alkoxy-Substituted C-C-alkyl, in mine-substituted C-C-alkyl, C-C-cycloalkyl orphe each case optionally cyano- or halogen-substituted nyl, C-C-alkenyl or C-C-alkynyl, optionally cyano-, halogen- or C-C-alkyl-substituted C-C-cycloalkyl, R" represents hydrogen, optionally hydroxyl-, cyano-, or optionally nitro-, cyano-, halogen-, C-C-alkyl-, halogen- or C-C-alkoxy-Substituted C-C-alkyl, 50 C-Ca-haloalkyl-, C-C-alkoxy- or C-C-haloalkoxy C-C-cycloalkyl or tri-(C-C-alkyl)-silyl, substituted phenyl, or together with R represents in R" represents hydrogen, cyano, halogen, or represents in each case optionally C-C-alkyl-substituted C-C-al each case optionally fluorine-, chlorine- and/or bro kanediyl or C-Cs-Oxaalkanediyl. mine-substituted C-C-alkyl, C-C-cycloalkyl orphe X' represents nitro, cyano, carboxyl, carbamoyl, formyl, nyl, 55 Sulphamoyl, hydroxyl, amino, halogen, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, X' represents nitro, cyano, halogen, C-C-alkyl, C-C- and haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, X represents nitro, cyano, carboxyl, carbamoyl, formyl, X represents hydrogen, cyano, nitro, halogen, C-C- Sulfamoyl, hydroxyl, amino, halogen, C-C-alkyl, alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-ha 60 C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy. loalkoxy, The formula (I) provides a general definition of the com X represents hydrogen, cyano, nitro, halogen, C-C- pounds according to the invention. Preferred substituents or alkyl, C-C-haloalkyl, C-C-alkoxy or C-C-ha ranges of the radicals listed in the formulae given above and loalkoxy, below are illustrated below: 65 J preferably represents iodine, and/or the following compounds, defined by general for X preferably represents hydrogen, halogen, C-C-alkyl, mulae, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, US 8,629,084 B2 33 34 Ypreferably represents hydrogen, C-C-alkyl, halogen or -continued C-C-alkoxy, (8) with the proviso that at least one of the radicals J. X orY is located in the 2-position of the phenyl radical and is not hydrogen, CKE preferably represents one of the groups

10 G (1) A preferably represents hydrogen or in each case option o1 ally halogen-substituted C-C2-alkyl, C-Cs-alkenyl, A C-Co-alkoxy-C-C-alkyl, C-Co-alkylthio-C-C- - \ , alkyl, optionally halogen-, C-C-alkyl- or C-C- N 15 alkoxy-Substituted C-Cs-cycloalkyl in which option D1 ally one or two not directly adjacent ring members are O replaced by oxygen and/or Sulfur or represents in each case optionally halogen-, C-C-alkyl-, C-C-ha loalkyl-, C-C-alkoxy-, C-C-haloalkoxy-, cyano- or (2) nitro-substituted phenyl, naphthyl, hetaryl having 5 to 6 ring atoms (for example furanyl, pyridyl, imidazolyl, triazolyl pyrazolyl, pyrimidyl, thiazolyl or thienyl), phenyl-C-C-alkyl or naphthyl-C-C-alkyl, B preferably represents hydrogen, C-C2-alkyl or C-Cs 25 alkoxy-C-C-alkyl, or A, B and the carbon atom to which they are attached preferably represent saturated C-Co-cycloalkyl or unsaturated Cs-Co-cycloalkyl in which optionally one (3) ring member is replaced by oxygen or Sulfur and which 30 are optionally mono- or disubstituted by C-C-alkyl, Cs-Co-cycloalkyl, C-Cs-haloalkyl, C-C-alkoxy, C-C-alkoxy-C-C-alkoxy, C-Cs-alkylthio, halogen or phenyl or A, B and the carbon atom to which they are attached 35 preferably represent C-C-cycloalkyl which is substi tuted by an alkylenedithioyl group or by an alkylene dioxyl group or by an alkylenediyl group which option (4) ally contains one or two not directly adjacent oxygen and/or sulfur atoms and which is optionally substituted 40 by C-C-alkyl, which group, together with the carbon atom to which it is attached, forms a further five- to eight-membered ring, or A, B and the carbon atom to which they are attached (5) preferably represent C-Cs-cycloalkyl or Cs-Cs-cy 45 cloalkenyl in which two substituents together with the carbon atoms to which they are attached represent in each case optionally C-C-alkyl-, C-C-alkoxy- or halogen-substituted C-C-alkanediyl, C-C-alkene diyl or C-C-alkanedienediyl in which optionally one 50 methylene group is replaced by oxygen or Sulfur, D preferably represents hydrogen, in each case optionally (6) halogen-substituted C-C2-alkyl, C-Cs-alkenyl, C-Cs-alkynyl, C-Co-alkoxy-C-C-alkyl, optionally halogen-, C-C-alkyl-, C-C-alkoxy- or C-C-ha 55 loalkyl-substituted C-Cs-cycloalkyl in which option ally one ring member is replaced by oxygen or Sulfur or in each case optionally halogen-, C-C-alkyl-, C-C- haloalkyl-, C-C-alkoxy-, C-C-haloalkoxy-, cyano (7) or nitro-Substituted phenyl, hetaryl having 5 or 6 ring 60 atoms atoms (for example furanyl, imidazolyl pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or or triazolyl), phenyl-C-C-alkyl or hetaryl-C-C-alkyl having 5 or 6 ring atoms (for example furanyl, imida Zolyl, pyridyl, thiazolyl pyrazolyl, pyrimidyl, pyrrolyl, 65 thienyl or or triazolyl) or A and D together preferably represent in each case option ally Substituted C-C-alkanediyl or C-C-alkenediyl US 8,629,084 B2 35 36 in which optionally one methylene group is replaced by -continued a carbonyl group, oxygen or Sulfur, S R15a possible Substituents being in each case: halogen, hydroxyl, mercapto or in each case optionally D.( D.( v. Rita halogen-substituted C-Co-alkyl, C-C-alkoxy, Yoro,s \R,s S R18a;s C-C-alkylthio, C-C-7-cycloalkyl, phenyl or benzy O loxy, or a further C-C-alkanediyl grouping, C-C- O R17a us alkenediyl grouping or abutadienyl grouping which is optionally substituted by C-C-alkyl or in which X. )- R19 optionally two adjacent Substituents together with the 10 carbon atoms to which they are attached form a fur ther saturated or unsaturated cycle having 5 or 6 ring Oul R19a atoms (in the case of the compound of the formula (I-1) A and D in this case together with the atoms to which they are attached represent, for example, the 15 groups AD-1 to AD-10 mentioned further below) that O R20a may contain oxygen or Sulfur or which optionally contains one of the following groups O

or is bridged by a C-C-alkanediyl group or by an oxygen atOn Or Q' preferably represents hydrogen or C-Ca-alkyl,

25 Q’, Q, Q and Qindependently of one another preferably C represent hydrogen or C-C-alkyl, 1. Q preferably represents hydrogen, C-C-alkyl, C-C- OR 15a SR 15a alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, N/ N/ O R17a optionally C-C-alkyl- or C-C-alkoxy-Substituted 1. 1. X 30 C-Cs-cycloalkyl in which optionally one methylene OR 16a, SR 16a; O R18a; group is replaced by oxygen or Sulfur or optionally halo O gen-, C-C-alkyl-, C-C-alkoxy-, C-C-haloalkyl-, S R17a us C-C-haloalkoxy-, cyano- or nitro-substituted phenyl, O X. )—o R19 or 35 Q and Q together with the carbonatom to which they are O attached preferably represent an optionally C-C- alkyl-, C-C-alkoxy- or C-C-haloalkyl-substituted -l R19a C-C-ring in which optionally one ring member is replaced by oxygen or Sulfur, 40 G preferably represents hydrogen (a) or represents one of "S R20a or the groups O (b) 45 A and Q' together preferably represent Cs-Co-alkanediyl or C-C-alkenediyl, each of which is optionally mono or disubstituted by identical or different substituents from the group consisting of halogen; hydroxyl: C-Co alkyl, C-C-alkoxy, C-C-alkylthio, C-C-7-cy 50 cloalkyl, each of which is optionally mono- to trisubsti tuted by identical or different halogen substituents; and (d) benzyloxy or phenyl, each of which is optionally mono to trisubstituted by identical or different substituents from the group consisting of halogen, C-C-alkyl and 55 (e) C-C-alkoxy, which C-C-alkanediyl or C-C-alk enediyl furthermore optionally contains one of the groups below (f) 60 (g)

65 in particular (a), (b), (c) or (g) US 8,629,084 B2 37 38 in which or C-Cs-alkoxy, preferably represents optionally halo E represents a metal ion equivalent or an ammonium ion, gen-, C-C-alkyl- or C-C-alkoxy-substituted C-C- L represents oxygen or Sulfur and cycloalkyl in which optionally one methylene group is M represents oxygen or Sulfur. replaced by oxygen or Sulfur, or preferably represents in R" preferably represents in each case optionally halogen each case optionally halogen-, C-C-alkyl-, C-C- Substituted C-Co-alkyl, C-Co-alkenyl, C-Cs alkoxy-, C-Ca-haloalkyl-, C-Ca-haloalkoxy-, nitro- or alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, cyano-Substituted phenyl, phenyl-C-C-alkyl or phe poly-C-C-alkoxy-C-C-alkyl or optionally halogen nyl-C-C-alkoxy, C-C-alkyl- or C-C-alkoxy-substituted C-C-cy R'" preferably represents hydrogen or C-Cs-alkyl, or cloalkyl in which optionally one or more (preferably not 10 more than two) not directly adjacent ring members are R" and R'" together preferably represent Ca-Ca-al replaced by oxygen and/or Sulfur, kanediyl. preferably represents optionally halogen-, cyano-, R'' and R'' are identical or different and preferably rep nitro-, C-C-alkyl-, C-C-alkoxy-, C-C-ha resent C-C-alkyl, or loalkyl-, C-C-haloalkoxy-, C-C-alkylthio- or 15 R'' and R'' together preferably represent a C-C-al C-C-alkylsulfonyl-substituted phenyl, kanediyl radical which is optionally substituted by preferably represents optionally halogen-, nitro-, C-C-alkyl, C-C-haloalkyl or by optionally halogen cyano-, C-C-alkyl-, C-C-alkoxy-, C-C-ha C-C-alkyl-, C-C-haloalkyl-, C-C-alkoxy-, C-C- loalkyl- or C-C-haloalkoxy-Substituted phenyl-C- haloalkoxy-, nitro- or cyano-Substituted phenyl, Co-alkyl, R'' and R'' independently of one another preferably preferably represents optionally halogen- or C-C- represent hydrogen, represent optionally halogen-Sub alkyl-substituted 5- or 6-membered hetaryl (for stituted C-C-alkyl or represent optionally halogen example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, C-C-alkyl-, C-C-alkoxy-, C-Ca-haloalkyl-, C-C- furanyl or thienyl), haloalkoxy-, nitro- or cyano-Substituted phenyl, or preferably represents optionally halogen- or C-C- 25 R'' and R'' together with the carbonatom to which they alkyl-substituted phenoxy-C-C-alkyl or are attached preferably represent a carbonyl group or preferably represents optionally halogen-, amino- or represent optionally halogen-, C-C-alkyl- or C-C- C-C-alkyl-substituted 5- or 6-membered hetary alkoxy-Substituted Cs-C7-cycloalkyl in which option loxy-C-C-alkyl (for example pyridyloxy-C-C- ally one methylene group is replaced by oxygen or Sul alkyl, pyrimidyloxy-C-C-alkyl or thiazolyloxy-C- 30 Co-alkyl). fur, R preferably represents in each case optionally halogen R'' and R' independently of one another preferably Substituted C-Co-alkyl, C-Co-alkenyl, C-C- represent C-Co-alkyl, C-Co-alkenyl, C-Co-alkoxy, alkoxy-C-C-alkyl, poly-C-C-alkoxy-C-C-alkyl, C-Co-alkylamino, C-Co-alkenylamino, di-(C-Co preferably represents optionally halogen-, C-C-alkyl 35 alkyl)amino or di-(C-Co-alkenyl)amino. or C-C-alkoxy-Substituted C-Cs-cycloalkyl or In the radical definitions mentioned as being preferred, preferably represents in each case optionally halogen halogen represents fluorine, chlorine, bromine and iodine, cyano-, nitro-, C-C-alkyl-, C-C-alkoxy-, C-C- and in particular fluorine, chlorine and bromine. haloalkyl- or C-C-haloalkoxy-Substituted phenyl or J particularly preferably represents iodine, benzyl, 40 X particularly preferably represents hydrogen, fluorine, R preferably represents optionally halogen-substituted chlorine, bromine, iodine, C-C-alkyl, trifluoromethyl, C-C-alkyl or represents in each case optionally halo C-C-alkoxy, difluoromethoxy or trifluoromethoxy, gen-, C-C-alkyl-, C-C-alkoxy-, C-Ca-haloalkyl-, Y particularly preferably represents hydrogen, fluorine, C-Ca-haloalkoxy-, cyano- or nitro-Substituted phenyl chlorine, bromine, iodine, C-C-alkyl or C-C-alkoxy, or benzyl, 45 with the proviso that at least one of the radicals J. X orY is R" and Rindependently of one another preferably repre located in the 2-position of the phenyl radical and is not sent in each case optionally halogen-substituted C-C- hydrogen. alkyl, C-C-alkoxy, C-C-alkylamino, di-(C-C- Here, the radicals J. X and Y. having their particularly alkyl)amino, C-C-alkylthio. C-C-alkenylthio. preferred meanings, are particularly preferably present in the C-C7-cycloalkylthio or represent in each case option 50 following phenyl Substitution patterns ally halogen-, nitro-, cyano-, C-C-alkoxy-, C-Ca-ha loalkoxy-, C-C-alkylthio-, C-Ca-haloalkylthio-, C-C-alkyl- or C-C-haloalkyl-substituted phenyl, (A) phenoxy or phenylthio. RandR independently of one another preferably repre 55 sent hydrogen, represent in each case optionally halo gen-substituted C-Cs-alkyl, C-Cs-cycloalkyl, C-C- alkoxy, C-C-alkenyl, C-Cs-alkoxy-C-C-alkyl, represent optionally halogen-C-C-haloalkyl-C-C- alkyl- or C-Cs-alkoxy-Substituted phenyl, optionally 60 (B) halogen-, C-C-alkyl-, C-C-haloalkyl- or C-C- alkoxy-Substituted benzyl or together represent an optionally C-C-alkyl-substituted C-C-alkylene radi cal in which optionally one carbon atom is replaced by oxygen or Sulfur, 65 R" preferably represents hydrogen, preferably represents in each case optionally halogen-substituted C-Cs-alkyl US 8,629,084 B2 39 40 -continued -continued (C) (5) X

/ V-YX

J (6) (D) 10 X

J

15 Y (7) (E) X

J

Y (8) (G) 25 J

X

30 where only in the phenyl substitution patterns (A) and (G) X may also represent hydrogen. A particularly preferably represents hydrogen, represents CKE particularly preferably represents one of the groups C-C-alkyl or C-C-alkoxy-C-C-alkyl, each of 35 which is optionally mono- to trisubstituted by fluorine or chlorine, represents C-C-cycloalkyl which is option (1) ally mono- to disubstituted by C-C-alkyl or C-C- o1 G alkoxy or (but not in the case of the compounds of the A formulae (I-3). (I-4), (I-6) and (I-7)) represents phenyl or 40 benzyl, each of which is optionally mono- to disubsti - \ . tuted by fluorine, chlorine, bromine, C-C-alkyl, D1 N C-C-haloalkyl, C-C-alkoxy, C-C-haloalkoxy, O cyano or nitro, (2) 45 B particularly preferably represents hydrogen, C-C-alkyl or C-C-alkoxyl-C-C-alkyl, or A, B and the carbon atom to which they are attached particularly preferably represent Saturated or unsatur ated Cs-C7-cycloalkyl in which optionally one ring 50 member is replaced by oxygen or Sulfur and which is optionally mono- to disubstituted by C-C-alkyl, trif luoromethyl, C-C-alkoxy or C-C-alkoxy-C-C- (3) alkoxy, with the proviso that in this case Q particularly preferably represents hydrogen or methyl, or 55 A, B and the carbon atom to which they are attached particularly preferably represent Cs-C-cycloalkyl which is substituted by an alkylenedithiol group or by an alkylenedioxyl group or by an alkylenediyl group which optionally contains one or two not directly adjacent oxy 60 gen or Sulfur atoms and which is optionally substituted (4) by methyl or ethyl, which group together with the carbon atom to which it is attached forms a further five- or six-membered ring, with the proviso that Q in this case particularly preferably represents hydrogen or methyl, 65 A, B and the carbon atom to which they are attached particularly preferably represent C-C-cycloalkyl or Cs-C-cycloalkenyl in which two Substituents together US 8,629,084 B2 41 42 with the carbon atoms to which they are attached repre -continued sent in each case optionally C-C-alkyl- or C-C- AD-7 alkoxy-Substituted C-C-alkanediyl, C-C-alkenediyl or butadienediyl, with the proviso that Q in this case represents hydrogen or methyl, N N D particularly preferably represents hydrogen, particularly preferably represents C-C-alkyl, C-C-alkenyl, AD-8 C-C-alkoxy-C-C-alkyl, each of which is optionally mono- to trisubstituted by fluorine, particularly prefer 10 ably represents C-C-cycloalkyl which is optionally N N mono- to disubstituted by C-C-alkyl, C-C-alkoxy or C-C-haloalkyl and in which optionally one methylene group is replaced by oxygen or (but not in the case of the AD-9 compounds of the formulae (I-1)) represents phenyl or 15 pyridyl, each of which is optionally mono- to disubsti tuted by fluorine, chlorine, bromine, C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, or Ol O A and D together particularly preferably represent option AD-10 ally mono- to disubstituted C-C-alkanediyl in which one methylene group may be replaced by a carbonyl group (but not in the case of the compounds of the formula (I-1)), oxgen or Sulfur, possible Substituents being C-C2-alkyl or C-C2-alkoxy, or 25 A and D (in the case of the compounds of the formula (I-1)) together with the atoms to which they are attached rep A and Q' together particularly preferably represent Ca-Ca resent one of the groups AD-1 to AD-10: alkanediyl which is in each case optionally mono- or disubstituted by identical or different substituents 30 selected from the group consisting of C-C-alkyl and C-C2-alkoxy, or AD-1 Q' particularly preferably represents hydrogen, Q particularly preferably represents hydrogen, Q, Q and Q independently of one another particularly N W 35 preferably represent hydrogen or C-C-alkyl, Q particularly preferably represents hydrogen, C-C- AD-2 alkyl, or C-C-cycloalkyl which is optionally mono- to disubstituted by methyl or methoxy, or Q and Q together with the carbon to which they are 40 attached particularly preferably represent an optionally C-C-alkyl- or C-C-alkoxy-substituted saturated Cs-Ca-ring in which optionally one ring member is replaced by oxygen or sulfur, with the proviso that in this AD-3 case A particularly preferably represents hydrogen or 45 methyl, G particularly preferably represents hydrogen (a) or repre

N w sents one of the groups

AD-4 50 (b)

N N AD-5 55

N (d)

60 AD-6 (e)

N 65 (f) US 8,629,084 B2 43 44 -continued J very particularly preferably represents iodine, (g) X very particularly preferably represents hydrogen, fluo rine, chlorine, bromine, methyl, ethyl, propyl, methoxy or ethoxy, Y very particularly preferably represents hydrogen, chlo rine, bromine, methyl, ethyl, propyl, methoxy or ethoxy, in particular (a), (b), or (c), with the proviso that at least one of the radicals J. X orY is in which located in the 2-position of the phenyl radical and is not E represents a metalion equivalent oran ammonium ion, 10 hydrogen. L represents oxygen or Sulfur and M represents oxygen or Sulfur, Here, the radicals J, X and Y, having their very particularly R" particularly preferably represents C-Cs-alkyl, Ca-Cs preferred meanings, are very particularly preferably present alkenyl, C-C-alkoxy-C-C-alkyl, C-C-alkylthio in the following phenyl Substitution patterns C-C-alkyl, each of which is optionally mono- to 15 trisubstituted by fluorine or chlorine, or C-C-cy (F) cloalkyl which is optionally mono- to disubstituted by J fluorine, chlorine, C-C-alkyl or C-C-alkoxy and in which optionally one or two not directly adjacent ring members are replaced by oxygen, particularly preferably represents phenyl which is optionally mono- to disubstituted by fluorine, chlo X rine, bromine, cyano, nitro, C-C-alkyl, C-C- (G) alkoxy, C-C-haloalkyl or C-C-haloalkoxy, J R particularly preferably represents C-Cs-alkyl, Ca-Cs 25 alkenyl or C-C-alkoxy-C-C-alkyl, each of which is optionally mono- to trisubstituted by fluorine, X particularly preferably represents C-C-cycloalkyl (H) which is optionally monosubstituted by C-C-alkyl 30 J or C-C2-alkoxy or particularly preferably represents phenyl or benzyl, each of which is optionally mono- to disubstituted by fluo rine, chlorine, bromine, cyano, nitro, C-C-alkyl, C-C-alkoxy, trifluoromethyl or trifluoromethoxy, 35 R particularly preferably represents C-C-alkyl which is X optionally mono- to trisubstituted by fluorine or repre (I) sents phenyl which is optionally monosubstituted by X fluorine, chlorine, bromine, C-C-alkyl, C-C-alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, 40 R" particularly preferably represents C-C-alkyl, C-C- Y alkoxy, C-C-alkylamino, di-(C-C-alkyl)amino, C-C-alkylthio, C-C-alkenylthio, C-C-cycloalky X lthio or represents phenyl, phenoxy or phenylthio, each (J) of which is optionally monosubstituted by fluorine, 45 J chlorine, bromine, nitro, cyano, C-C-alkoxy, C-C- haloalkoxy, C-C-alkylthio, C-C-haloalkylthio. C-C-alkyl or trifluoromethyl, X R particularly preferably represents C-C-alkoxy or C-C-alkylthio. 50 R particularly preferably represents hydrogen, C1-Co J alkyl, C-C-cycloalkyl, C-C-alkoxy, C-C-alkenyl, Yi H C-C-alkoxy-C-C-alkyl, represents phenyl which is (K) optionally monosubstituted by fluorine, chlorine, bro J mine, trifluoromethyl, C-C-alkyl or C-C-alkoxy, 55 represents benzyl which is optionally monosubstituted Y by fluorine, chlorine, bromine, C-C-alkyl, trifluorom ethyl or C-C-alkoxy, R" particularly preferably represents C1-Co-alkyl, Ca-Ca X alkenyl or C-C-alkoxy-C-C-alkyl, 60 R and R7 together particularly preferably represent an Yi H optionally methyl- or ethyl-substituted C-C-alkylene (L) radical in which optionally one methylene group is replaced by oxygen or Sulfur. In the radical definitions mentioned as being particularly 65 preferred, halogen represents fluorine, chlorine and bromine, in particular fluorine and chlorine. US 8,629,084 B2 45 46 -continued -continued (M) (5) X

J

Y (6) Yi H 10 (N) X

J 15 (7) Y Yi H (O) X

(8) 25 Y J Yi H

where only in the phenyl substitution pattern (G) X may 30 also represent hydrogen. CKE very particularly preferably represents one of the A very particularly preferably represents hydrogen, repre groups sents C-C-alkyl or C-C-alkoxy-C-C-alkyl, each of 35 which is optionally mono- to trisubstituted by fluorine, represents cyclopropyl, cyclopentyl or cyclohexyl and, (1) G only in the case of the compounds of the formula (I-5), o1 represents phenyl which is optionally mono- to disub A stituted by fluorine, chlorine, bromine, methyl, ethyl, 40 n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, - N trifluoromethoxy, cyano or nitro, D1 N B very particularly preferably represents hydrogen, methyl O or ethyl, or G (2) 45 A, B and the carbon atom to which they are attached very o1 particularly preferably represent saturated C-C-cy cloalkyl in which optionally one ring member is A replaced by oxygen or Sulfur and which is optionally - \ . monosubstituted by methyl, ethyl, propyl, isopropyl, tri O 50 fluoromethyl, methoxy, ethoxy, propoxy, methoxy ethoxy, butoxy or ethoxyethoxy, with the proviso that in O this case Q very particularly preferably represents G (3) hydrogen, or o1 A, B and the carbon atom to which they are attached very A 55 particularly preferably represent C-cycloalkyl which is optionally substituted by alkylenedioxyl group which - \ . contains with S two not directly adjacent oxygen atoms, with the proviso O that in this case Q very particularly preferably repre 60 sents hydrogen, or (4) A, B and the carbon atom to which they are attached very particularly preferably represent Cs-C-cycloalkyl or Cs-C-cycloalkenyl in which two substituents together with the carbon atoms to which they are attached repre 65 sent C-C-alkanediyl or C-C-alkenediyl or butadi enyl, with the proviso that in this case Q very particu larly preferably represents hydrogen, US 8,629,084 B2 47 48 D very particularly preferably represents hydrogen, repre X especially preferably represents hydrogen, chlorine, sents C-C-alkyl, C-C-alkenyl, C-C-alkoxy-C- methyl or ethyl, C-alkyl, each of which is optionally mono- to trisubsti Y especially preferably represents hydrogen, chlorine, tuted by fluorine, represents cyclopropyl, cyclopentylor methyl or ethyl, cyclohexyl or (but not in the case of the compounds of 5 the formulae (I-1)) represents phenyl or pyridyl, each of with the proviso that at least one of the radicals J. X orY is which is optionally monosubstituted by fluorine, chlo located in the 2-position of the phenyl radical and is not rine, methyl, ethyl, n-propyl, isopropyl, methoxy, hydrogen. ethoxy or trifluoromethyl, 10 Here, the radicals J. X and Y, having their especially pre ferred meanings, are especially preferably present in the fol A and D together very particularly preferably represent lowing phenyl Substitution patterns C-C-alkanediyl which is optionally monosubstituted by methyl or methoxy and in which optionally one car bonatom is replaced by oxygen or Sulfur or represent the 15 (F) group AD-1, J A and Q' together very particularly preferably represent C-C-alkanediyl which is optionally mono- or disub stituted by methyl or methoxy, or Q' very particularly preferably represents hydrogen, Q very particularly preferably represents hydrogen, X Q, Q and Q independently of one another very particu (G) larly preferably represent hydrogen or methyl, J Q very particularly preferably represents hydrogen, methyl, ethyl or propyl, or 25 X Q and Q together with the carbon to which they are attached very particularly preferably represent a Satu (I) rated C-C-ring which is optionally monosubstituted X by methyl or methoxy, with the proviso that in this case A very particularly preferably represents hydrogen, 30 G very particularly preferably represents hydrogen (a) or Y represents one of the groups

J (b) 35 (J) J

X (c) 40 Y Y it H (d) (M) (f) 45 in which y-()-X L represents oxygen or Sulfur, M represents oxygen or Sulfur and 50 E represents an ammonium ion, Y it H R" very particularly preferably represents C-C-alkyl, C-C7-alkenyl, C-C2-alkoxy-C-alkyl, C-C2-alky lthio-C-alkyl, each of which is optionally monosubsti where only in the phenyl substitution pattern (G) X may tuted by chlorine, or represents cyclopropyl or cyclo 55 also represent hydrogen, hexyl, each of which is optionally monosubstituted by CKE especially preferably represents one of the groups fluorine, chlorine, methyl or methoxy, very particularly preferably represents phenyl which is optionally monosubstituted by fluorine, chlorine, bro (1) mine, cyano, nitro, methyl, methoxy, trifluoromethyl 60 G or trifluoromethoxy, o1 R very particularly preferably represents C-Cs-alkyl, A C-C-alkenyl or C-C-alkoxy-C-C-alkyl, each of - N which is optionally monosubstituted by fluorine, or rep N resents phenyl or benzyl, 65 D1 R very particularly preferably represents C-Cs-alkyl. O Jespecially preferably represents iodine, US 8,629,084 B2 49 50 -continued Saturated or unsaturated hydrocarbon radicals, such as G (2) alkyl, alkanediyl or alkenyl, can in each case be straight-chain o1 or branched as far as this is possible, including in combination A with heteroatoms, such as, for example, in alkoxy. Unless indicated otherwise, optionally substituted radicals B N O can be mono- or poly Substituted, where in the case of O polysubstitution the substituents can be identical or different. In addition to the compounds mentioned in the preparation O examples, particular mention may be made of the following (8) 10

15

A especially preferably represents C-C-alkyl or cyclo propyl. B especially preferably represents hydrogen or methyl, A, B and the carbon atom to which they are attached especially preferably represent saturated C-C-cy cloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monoSub stituted by methyl, methoxy or propoxy, Despecially preferably represents hydrogen, or 25 A and D together especially preferably represent the group AD-1, in the case of CKE-group (8) A and D together especially preferably represent C-C-alkanediyl. G especially preferably represents hydrogen (a) or repre 30 sents one of the groups (b) 1s, 35 (c) O R2, --- 40 R" especially preferably represents C-C-alkyl, C-C- alkoxy-C-alkyl, cyclopropyl, each of which is option ally monosubstituted by chlorine, or represents phenyl which is optionally monosubstituted by chlorine, 45 Respecially preferably represents C-Cs-alkyl, Ca-Ca alkenyl or benzyl. The general or preferred radical definitions or illustrations given above can be combined with one another as desired, i.e. including combinations between respective ranges and pre 50 ferred ranges. They apply both to the end products and, cor respondingly, to precursors and intermediates. Preference according to the invention is given to the com pounds of the formula (I) which contain a combination of the meanings given above as being preferred (preferable). 55 Particular preference according to the invention is given to the compounds of the formula (I) which contain a combina tion of the meanings given above as being particularly pre ferred. Very particular preference according to the invention is 60 given to the compounds of the formula (I) which contain a combination of the meanings given above as being very par ticularly preferred. Special preference according to the invention is given to the compounds of the formula (I) which contain a combina 65 tion of the meanings given above as being especially pre ferred.

US 8,629,084 B2 53 54 TABLE 23-continued Table 25: A and B as stated in table 23 2-I; X=6-CH:Y=H. Table 26: A and B as stated in table 23 2-I; X=6-CHs;Y=H. Table 27: A and B as stated in table 23 X=2-CH: Y=H: 5-I. Table 28: A and B as stated in table 23 X=2-CH: Y=4-CH: 5-I. Table 29: A and B as stated in table 23 10 2-I; X=4-CH:Y=6-CH. Table 30: A and B as Stated in table 23 2-I; X=6-CHs:Y=4-CH. Table 31: A and B as stated in table 23 2-I; X=6-CH:Y=4-C1. 15 Table 32: A and B as stated in table 23 2-I; X=6-CHs;Y=4-C1. Table 33: A and B as Stated in table 23 2-I; X=6-Cl; Y=4-CH. Table 34: A and B as stated in table 23 2-I; X=5-CH:Y=4-CH. Table 35: A and B as Stated in table 23 X=2-CH: 4-I:Y=H. Table 36: A and B as stated in table 23 X=2-CHs: 4-I:Y=H. 25 Table 37: A and B as Stated in table 23 X=2-CH: 4-I:Y=6-CH. Table 38: A and B as Stated in table 23 X=2-CHs: 4-I;Y=6-CH. Table 39: A and B as Stated in table 23 30 X=2-CHs: 4-I;Y=6-CHs. Table 40: A and B as stated in table 23 X=2-Cl: 4-I;Y=6-CH. —CH2—CHOCHs (CH2)3 - Table 41: A and B as stated in table 23 —CH2—CHOCH7 -(CH2) - X=2-Cl: 4-I:Y=6-CHs. —CH2—CHOCHg (CH2)3 - 35 Table 42: A and B as stated in table 23 X=2-CH: 4-I;Y=5-CH. Table 43: A and B as stated in table 23 X=2-CH: 3-I:Y=6-CH. Table 44: A and B as stated in table 23 40 2-I; X=5-CHY-H. Preferred definitions of the groups listed above in connec tion with the crop plant compatibility-improving compounds (“herbicide safeners') of the formulae (IIa), (IIb), (IIc), (IId) and (IIe) are defined below. 45 m preferably represents the numbers 0, 1, 2, 3 or 4. -CH-CH-(CH)-CH A preferably represents one of the divalent heterocyclic N/CH groupings shown below -CH-CH CH-CH Yen./ 50 N/N NYN NY -CH-CH s yr )= / R19 OR20 R19 R19 Yen. 55 O 1 (Cy

60 in preferably represents the numbers 0, 1, 2, 3 or 4. A preferably represents in each case optionally methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl-substi tuted methylene or ethylene. 65 R'' preferably represents hydroxyl, mercapto, amino, Table 24: A and B as stated in table 23 methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, 2-I; X=4-CH:Y=H methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or US 8,629,084 B2 55 56 t-butylthio, methylamino, ethylamino, n- or i-propy ethyl, trichloromethyl, chlorodifluoromethyl, fluorod lamino, n-, i-, s- or t-butylamino, dimethylamino or ichloromethyl, methoxy, ethoxy, n- ori-propoxy, difluo diethylamino. romethoxy or trifluoromethoxy. R" preferably represents hydroxyl, mercapto, amino, t preferably represents the numbers 0, 1, 2, 3 or 4. methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, 1-methylhexyloxy, allyloxy, 1-allyloxymethylethoxy, V preferably represents the numbers 0, 1, 2, or 3. methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or R’ preferably represents hydrogen, methyl, ethyl, n- or t-butylthio, methylamino, ethylamino, n- or i-propy i-propyl. lamino, n-, i-, s- or t-butylamino, dimethylamino or R’ preferably represents hydrogen, methyl, ethyl, n- or diethylamino. 10 i-propyl. R" preferably represents in each case optionally fluorine R" preferably represents hydrogen, in each case option chlorine- and/or bromine-substituted methyl, ethyl, n- or ally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n i-propyl. ori-propoxy-Substituted methyl, ethyl, n- ori-propyl. n-, R'' preferably represents hydrogen, in each case option 15 i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, ally fluorine- and/or chlorine-substituted methyl, ethyl, S- or t-butoxy, methylthio, ethylthio, n- or i-propylthio. n- or i-propyl. n-, i-, s- or t-butyl, propenyl, butenyl, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or propynyl or butynyl, methoxymethyl, ethoxymethyl, i-propylamino, n-, i-, s- ort-butylamino, dimethylamino methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, or diethylamino, or in each case optionally cyano-, fluo furyl-methyl, thienyl, thiazolyl, piperidinyl, or option rine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-pro ally fluorine-, chlorine-, methyl-, ethyl-, m- or i-propyl-, pyl-Substituted cyclopropyl, cyclobutyl, cyclopentyl, n-, i-, s- or t-butyl-substituted phenyl. cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopen R" preferably represents hydrogen, in each case option tyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio. cyclopentylthio, cyclohexylthio, cyclopropylamino, ally fluorine- and/or chlorine-substituted methyl, ethyl, 25 n- or i-propyl. n-, i-, s- or t-butyl, propenyl, butenyl, cyclobutylamino, cyclopentylamino or cyclohexy propynyl or butynyl, methoxymethyl, ethoxymethyl, lamino. methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, R’ preferably represents hydrogen, in each case option furyl-methyl, thienyl, thiazolyl, piperidinyl, or option ally cyano-, hydroxyl-, fluorine-, chlorine-, methoxy-, ally fluorine-, chlorine-, methyl-, ethyl-, m- or i-propyl-, 30 ethoxy-, n- or i-propoxy-Substituted methyl, ethyl, n- or n-, i-, s- or t-butyl-substituted phenyl, or together with i-propyl. n-, i- or S-butyl, in each case optionally cyano-, R7 represents one of the radicals —CH O CH fluorine-, chlorine- or bromine-substituted propenyl, CH2— and —CH2—CH2—O—CH2—CH2— which butenyl, propynyl or butynyl, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, are optionally substituted by methyl, ethyl, furyl, phe 35 nyl, a fused benzene ring or by two Substituents which, n- or i-propyl-substituted cyclopropyl, cyclobutyl, together with the C atom to which they are attached, cyclopentyl or cyclohexyl. form a 5- or 6-membered carbocycle. R’ preferably represents hydrogen, in each case option R" preferably represents hydrogen, cyano, fluorine, chlo ally cyano-, hydroxyl-, fluorine-, chlorine-, methoxy-, rine, bromine, or represents in each case optionally fluo 40 ethoxy-, n- or i-propoxy-Substituted methyl, ethyl, n- or rine-, chlorine- and/or bromine-substituted methyl, i-propyl. n-, i- or S-butyl, in each case optionally cyano-, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopen fluorine-, chlorine- or bromine-substituted propenyl, tyl, cyclohexyl or phenyl. butenyl, propynyl or butynyl, in each case optionally R" preferably represents hydrogen, optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or 45 n- or i-propyl-substituted cyclopropyl, cyclobutyl, i-propoxy-Substituted methyl, ethyl, n- ori-propyl. n-, i-, cyclopentyl or cyclohexyl, or optionally nitro-, cyano-, s- or t-butyl. fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or R" preferably represents hydrogen, cyano, fluorine, chlo i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, meth rine, bromine, or represents in each case optionally fluo oxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy- or rine-, chlorine- and/or bromine-substituted methyl, 50 trifluoromethoxy-substituted phenyl, or together with ethyl, n- or i-propyl. n-, i-, s- or t-butyl, cyclopropyl. R represents in each case optionally methyl- or ethyl cyclobutyl, cyclopentyl, cyclohexyl or phenyl. substituted butane-1,4-diyl(trimethylene), pentane-1,5- X' preferably represents nitro, cyano, fluorine, chlorine, diyl, 1-oxabutane-1,4-diyl or 3-oxapentane-1,5-diyl. bromine, methyl, ethyl, n- ori-propyl. n-, i-, s- ort-butyl, X' preferably represents nitro, cyano, carboxyl, carbam difluoromethyl, dichloromethyl, trifluoromethyl, 55 trichloromethyl, chlorodifluoromethyl, fluorodichlo oyl, formyl, Sulfamoyl, hydroxyl, amino, fluorine, chlo romethyl, methoxy, ethoxy, n- or i-propoxy, difluo rine, bromine, methyl, ethyl, n- or i-propyl. n-, i-, s- or romethoxy or trifluoromethoxy. t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-pro X preferably represents hydrogen, nitro, cyano, fluorine, poxy, difluoromethoxy or trifluoromethoxy. chlorine, bromine, methyl, ethyl, n- or i-propyl. n-, i-, S 60 X preferably represents nitro, cyano, carboxyl, carbam or t-butyl, difluoromethyl, dichloromethyl, trifluorom oyl, formyl, Sulphamoyl, hydroxyl, amino, fluorine, ethyl, trichloromethyl, chlorodifluoromethyl, fluorod chlorine, bromine, methyl, ethyl, n- or i-propyl. n-, i-, S ichloromethyl, methoxy, ethoxy, n- ori-propoxy, difluo or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-pro romethoxy or trifluoromethoxy. poxy, difluoromethoxy or trifluoromethoxy. X preferably represents hydrogen, nitro, cyano, fluorine, 65 Examples of the compounds of the formula (IIa) which are chlorine, bromine, methyl, ethyl, n- or i-propyl. n-, i-, S very particularly preferred as herbicide Safeners according to or t-butyl, difluoromethyl, dichloromethyl, trifluorom the invention are listed in the table below. US 8,629,084 B2 57 58 Table Examples of the Compounds of the Formula (IIa) -continued (IIa) 3 4 N 2 O (IIa) 5 (X'), H- ls O 21 Al R 14 (X), Example (Positions) .. No. (X"), A. R 14 10 IIa-8 (2) F N OCH Example (Positions) NY N 3 No. (X'), A. R 14 IIa-1 (2) Cl, (4) Cl N OCH N1S 15 C H3C OCH IIa-9 O (2) Cl, (4) Cl N YN OCHs 2O Y IIa-2 (2) Cl, (4) Cl N OCH NY N )=. ClC

HC IIa-10 25 (2) Cl, (4) CF NN -Y- OCH O OCH5 )= IIa-3 (2) Cl, (4) Cl N OCHs N-1N N 30 HC IIa-11 (2) Cl N OCH OCH NY N O 35 IIa-4 (2) Cl, (4) Cl N YN OCHs N F H3C OCH5 40 IIa-12 OCHs O O-N IIa-5 (2) Cl N OCH N1 N Cr o 45 IIa-13 (2) Cl, (4) Cl N r OCHs

HC o

50 IIa-6 (2) Cl, (4) Cl N1 NN OCH, IIa-14 (2) Cl, (4) Cl N YN OCHs

C3H7-i o 55

IIa-15 (2) Cl, (4) Cl N yr OCHs IIa-7 (2) F N OCH N-1N1 N 3 60 C4H9-t IIa-16 (2) Cl, (4) Cl -CH2ry- OCHs 65 O-N US 8,629,084 B2 59 60 -continued -continued

(IIa) (Posi 3 5 Example tion) (Position) 4 N 2 O No. X2 X3 A2 R15 (X), H ls 4N R 14 IIb-12 (5) CH2 CH C 10 -CH Example (Positions) HC No. (X'), Al R 14 HC1 O IIa-17 (2) Cl, (4) Cl Y- OCHs 15 N1nCH3C O-N IIb-13 (5) ": OCH-CH=CH C IIa-18 OH CH \ 2O HC1 O/ N ON O C 25 1, IN Examples of the compounds of the formula (IIb) which are very particularly preferred as herbicide Safeners according to IIb-14 (5) CH5 OCHs the invention are listed in the table below. C O h 30 N (IIb) 1inC X3 4 5 X2 X^n-1SS IIb-15 (5) th OCH C 2 2 7 35 N a s' suln A2 R15 1 C N.

40 Table Examples of the Compounds of the Formula (IIb) Examples of the compounds of the formula (Ic) which are very particularly preferred as herbicide Safeners according to the invention are listed in the table below. (Posi- 45 Example tion) (Position) No. X2 X3 A2 R15 (IIc) O b-1 (5) CH, OH C ls R17 b-2 (5) CH2 OCH R 16 N1 C 50 b-3 (5) CH2 OCHs R18 C b-4 (5) CH2 OCH7-n C b-S (5) CH2 OCH7-i Table Examples of the Compounds of the Formula (IIc) C 55 b-6 (5) CH2 OCHg-n C b-7 (5) CH2 OCH(CH)CH-n Example C No R 16 N(R7R 18) b-8 (5) (2) CH, OH C F 60 IIc-1 CHCl, N(CH-CH=CH-), b-9 (5) (2) CH2 OH C C IIc-2 CHCl, H3C CH3 IIb-10 (5) CH2 OCH-CH=CH C N N O IIb-11 (5)C CH 2 OCH4-lig 65 W f US 8,629,084 B2 61 62 -continued -continued Example (Positions) (Positions) R 16 R24 (X), (X), IIc-3 CHCl, IId-5 (2) OCH

10 IId-6 (2) OCH (5) CH IIc-4 CHCl, I-7 (2) OCH (5) CH IId-8 (2) OCH 15 (5) CH, IId-9 (2) OCH (5) CH IId-10 (2) OCH IIc-5 CHCl, (5) CH

OCH OCHs 25 IIc-6 CHCl, OCH7-i SCH, SC2H5 30 SCH7-i NHCH,

IIc-7 NHCH CHCl, 35 NHCH7-i

NH 40

IId-21 (2) OCH Examples of the compounds of the formula (IId) which are IId-22 (2) OCH, very particularly preferred as herbicide Safeners according to 45 IId-23 (2) OCH the invention are listed in the table below. IId-24 (3) CH (4) CH (IId) IId-25 H H (2) OCH

R23 50 (X), SAS R22 21 Examples of the compounds of the formula (IIe) which are s --(X'), very particularly preferred as herbicide Safeners according to R24 N N 2 SO 1. the invention are listed in the table below. 55 O Table Examples of the Compounds of the Formula (IId) (IIe) (X), 60 S/S R22 Example (Positions) (Positions) (X), (X), N 21 SO 1. IId-1 (2) OCH, IId-2 (2) OCH IId-3 (2) OCH 65 IId-4 (2) OCH US 8,629,084 B2

Table Examples of the Compounds of the Formula (IIe) TABLE-continued Examples of the combinations according to the invention Example (Positions) (Positions) No. R22 R25 R26 (X), (X), Active compounds 5 of the formula (I) Safeners IIe-1 H H CH (2) OCH — IIe-2 H H C2H5 (2) OCH -1 isoxadi?en-ethyl IIe-3 H H C3H7-n (2) OCH -1 mefenpyr-diethyl IIe-4 H H C3H7-i (2) OCH -1 furiazole -1 enclorim IIe-5 H H (2) OCH 10 -1 cumyluron -1 daimuron dymron -1 dimepiperate -1 Ie-11 -1 Ie-5 IIe-6 H CH CH (2) OCH, -2 cloquintocet-mexyl IIe-7 H H CH (2) OCH 15 -2 fenchlorazole-ethyl (5) CH -2 isoxadifen-ethyl IIe-8 H H C2H5 (2) OCH — -2 mefenpyr-diethyl (5) CH -2 Furilazole IIe-9 H H C3H7-n (2) OCH — -2 Fenclorim (5) CH -2 Cumyluron IIe-10 H H CH7-i (2) OCH — 2O -2 daimuron/dymron (5) CH -2 dimepiperate 3 -2 Ie-11 IIe-11 H H (2) OCH — -2 Ie-5 (5) CH -3 cloquintocet-mexyl 3 -3 enchlorazole-ethyl -3 isoxadifen-ethyl 25 -3 mefenpyr-diethyl IIe-12 H CH, CH (2) OCH — -3 firilazole (5) CH -3 enclorim 3 -3 cumyluron -3 daimuron dymron Most preferred as crop plant compatibility-improving------30 -3 dimepiperateIe-5 compound component (b") are cloquintocet-mexyl, fenchlo- -3 Ie-11 razole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole, -4 cloquintocet-mexyl fenclorim, cumyluron, dymron, dimepiperate and the com- -4 fenchlorazole-ethyl poundsds IIe-5Ile-s and IIe-11Ile-I, and particuicul ar emphas1shasis is1s gigiven to -4 mefenpyr-diethylisoxadifen-ethyl cloquintocet-mexyl and mefenpyrdiethyl. 35 -4 furiazole The compounds of the general formula (IIa) to be used as -4 enclorim safeners according to the invention are known and/or can be -4 cumyluron preprepared byy pprocesses known pper se (cf. WO-A-91/07874 s -4 dimepiperatedaimuron dymron WO-A-95/07897). -4 Ie-11 The compounds of the general formula (IIb) to be used as -4 Ie-5 safeners according to the invention are known and/or can be -S cloquintocet-mexyl prepareddb by processes knknown perse (cf.f. EPA-191736EP-A- ). -S isoxadifen-ethylenchlorazole-ethyl The compounds of the general formula (Ic) to be used as -S mefenpyr-diethyl safeners according to the invention are known and/or can be -S furiazole pp. 56. presses known per se (cf. DE-A-2218097, 45 -S cumyluronenclorim ). -S daimuron dymron The compounds of the general formula (IId) to be used as -S dimepiperate safeners according to the invention are known and/or can be -S Ie-5 prepared by processes known per se (cf. DE-A-1962 1522/ -S le-11 U.S. Pat No. 6,235 680) -6 cloquintocet-mexyl M • as s 50 -6 enchlorazole-ethyl The compounds of the general formula (IIe) to be used as -6 isoxadifen-ethyl safeners according to the invention are known and can be -6 mefenpyr-diethyl prepared by processes known per se (cf. WO-A-99/66795/ (CIOrole U.S. Pat No. 6.251.827). -6 cumyluron Examples of the selective herbicidal combinations accord- 55 -6 daimuron dymron ing to the invention comprising in each case one active com- -6 dimepiperate pound of the formula (I) and one of the safeners defined above E.e are listed in the table below. -7 cloquintocet-mexyl -7 enchlorazole-ethyl TABLE -7 isoxadifen-ethyl 60 -7 mefenpyr-diethyl Examples of the combinations according to the invention -7 firilazole -7 enclorim Active compounds -7 cumylurOil of the formula (I) Safeners -7 daimuron/dymron -7 dimepiperate I-1 cloquintocet-mexyl 65 -7 Ie-5 I-1 fenchlorazole-ethyl -7 Ie-11 US 8,629,084 B2 65 TABLE-continued CO2C2H5 Examples of the combinations according to the invention HC H3C

Active compounds 5 H3C 1. base of the formula (I) Safeners O I 2. H+ I-8 cloquintocet-mexyl I-8 fenchlorazole-ethyl O CH3 I-8 isoxadifen-ethyl I-8 mefenpyr-diethyl H3C I 10 HO I-8 furiazole I-8 fenclorim I-8 cumyluron H3C N I-8 daimuron dymron HC I-8 dimepiperate O CH3 I-8 IIe-5 15 O I-8 IIe-11 Using, for example, according to process (C) ethyl 2-(2,6- It has now surprisingly been found that the above-defined dimethyl-4-iodophenyl)-4-(4-methoxy)benzylmercapto-4- active-compound combinations of iodophenyl-substituted methyl-3-oxovalerate, the course of the process according to the invention can be represented by the reaction scheme cyclic ketoenols of the general formula (I) and safeners (anti below: dotes) from the group (b") set out above combine very good useful plant tolerance with a high herbicidal activity and can be used in various crops, in particular in cereals (especially wheat), but also in Soya beans, potatoes, corn and rice, for 25 selective weed control. In this context it is considered Surprising that, from a mul tiplicity of known safeners orantidotes capable of antagoniz H3C CH3 CH ing the damaging effect of a herbicide on the crop plants, it is S O acid specifically the compounds of group (b") set out above which 30 --- are Suitable for compensating—almost completely—the damaging effect of Substituted cyclic ketoenols on the crop O I plants, without at the same time having any critical adverse H.C.1 O CH effect on the herbicidal activity against the weeds. 35 Emphasis may be given here to the particularly advanta CH3 I geous effect of the particularly preferred and most preferred HO combination partners from group (b'), particularly with H3C N regard to the gentle treatment of cereal plants, such as wheat, HC barley and rye, for example, but also corn and rice, as crop 40 S CH3 plants. O Using, for example, according to process (A) ethyl N-(2, 6-dimethyl-4-iodophenylacetyl)-1-amino-cyclohexanecar Using, for example, according to process (D) chlorocarbo boxylate as starting material, the course of the process nyl 2-(2,6-dimethyl-4-iodophenyl)ketene and acetone as according to the invention can be represented by the reaction 45 starting materials, the course of the process according to the scheme below: invention can be represented by the reaction scheme below:

CH I I CH3 O O 1. base 50 -- 2. H+ ls base H C=O + HC CH, -- N HSCOC CH CH3 COC 55 I CH3 OH CH3 OH

N I 21

60 CH3 O CH O O CH Using, for example, according to process (E) chlorocarbo Using, for example, according to process. (B) ethyl O-(2, nyl 2-(2,6-dimethyl-4-iodophenyl)ketene and thiobenzamide 6-dimethyl-4-iodophenylacetyl)-2-hydroxyisobutyrate, the 65 as starting materials, the course of the process according to course of the process according to the invention can be rep the invention can be represented by the reaction scheme resented by the reaction scheme below: below: US 8,629,084 B2

I CH3 CH S H EO base N1 C CFO + -- 5 21 -- I Her NH2 Nin CH3 COC H COC CH OH CH I CH 10 OH N / N /)-( ) O-K)- CH N 15 O HC O Using, for example, according to process (HB) hexahydro Using, for example, according to process (F) ethyl 5-(2,6- pyridazine and dimethyl 2-(2,6-dimethyl-4-iodo)phenylma dimethyl-4-iodophenyl)-2,3-trimethylene-4-oxovalerate, the 20 lonate as starting materials, the course of the process accord course of the process according to the invention can be rep ing to the invention can be represented by the reaction scheme resented by the reaction scheme below: below:

CH 25 CH3 O N -H COCH I 1. base -- I He He 2. H N NH COCH3 30 COCHs HC CH3 OH CH3 OH CH3 CO) ( ) I 35 N N I N O HC O HC 40 Using, for example, according to process (G) ethyl 5-(2, 6-dimethyl-4-iodo)phenyl)-2-methyl-5-oxohexanoate, the Using, for example, according to process (HY) 1-ethoxy course of the process according to the invention can be rep carbonyl-2-(2,6-dimethyl-4-iodo)phenyl-acetylhexahy resented by the reaction scheme below: dropyridazine as starting material, the course of the reaction 45 can be represented by the scheme below:

H3C CH CO2C2H5 H3C base COCHs I - 50 M N I --- H V base N O CH3 HC O CH CH3 HO 55 OH HC ( ) I N N I H \ CH O 60 O CH3

Using, for example, according to process (HC) hexahydro- Using, for example, according to process (IC) 3-(2-methyl pyridazine and chlorocarbonyl 2-(2,6-dimethyl-4-iodo)phe- 4-iodo-6-ethylphenyl)-5,5-dimethylpyrrolidine-2,4-dione nylketene as starting materials, the course of the reaction of 65 and pivaloyl chloride as starting materials, the course of the the process according to the invention can be represented by process according to the invention can be represented by the the reaction scheme below: reaction scheme below: US 8,629,084 B2 70 -continued CH I HC --coa CH3 He base

10

Using, for example, according to process (K) 3-(2,6-dim 15 ethyl-4-iodophenyl)-4-hydroxy-5-methyl-6-(3-pyridyl)py rone and methyl chloromonothioformate as starting materi als, the course of the reaction can be represented as follows:

O CH5 OH CH3 S Using, for example, according to process (IB) 3-(2,6-dim ethyl-4-iodophenyl)-5,5-dimethylpyrrolidine-2,4-dione and " y M \, -s. acetic anhydride as starting materials, the course of the pro 25 O FN base cess according to the invention can be represented by the O reaction scheme below:

HC-CO 30 CH3 I 3 V OH ? H3C HC-CO H3C N Hessbase 35 HN CH O O ls CH3 I HC O 40 Using, for example, according to process (L) 3-(2,6-dim HC ethyl-4-iodophenyl)-5,5-penta-methylenepyrrolidine-2,4- H3C N dione and methanesulfonyl chloride as starting material, the HN CH course of the reaction can be represented by the reaction O 45 scheme below:

Using, for example, according to process (J) 8-(2,6-dim ethyl-4-iodo)phenyl-1-azabicyclo-(4.3.0')-nonane-7,9-di OH CH3 one and ethyl chloroformate as starting materials, the course 50 of the process according to the invention can be represented \ I --+ CI-SO-CH by the reaction scheme below: base HN

O CH 55 O-SOCH

HCO-C-Cl Her 60 base

65 Using, for example, according to process (M) 3-(2,6-dim ethyl-4-iodophenyl)-4-hydroxy-5,5-dimethylpyrrolidine-2, 4-dione and 2.2.2-trifluoroethyl methanethiophosphonyl US 8,629,084 B2 71 72 chlorideas starting materials, the course of the reaction can be -continued represented by the reaction scheme below:

SOCHCF CH3 OH CH3 In rers + C1-P

H3C \ Yh3 --- I base HN 10 O CH Using, for example, according to process (O) variant B SOCH2CF, 3-(2-methyl-4-iodo-6-ethylphenyl)-5-methylpyrrolidine-2, |/ 15 O-P 4-dione and dimethylcarbamoyl chloride as starting materi als, the course of the reaction can be represented by the CH CH Y-H, scheme below: H3C \ I HN O OH CH C us-ch Using, for example, according to process (N) 3-(2-ethyl 25 HC

4-iodo-6-methylphenyl-5-cyclopropyl-5-methylpyrroli N I HeCH3 dine-2,4-dione and NaOH as components, the course of the HN -HCI process according to the invention can be represented by the O CH6 reaction scheme below: 30

CH OH C2H5 O N 35 NaOH N YCH, H3C N I e O CH3 HN N I O CH 40 Na(+) O CHs

Using, for example, according to process (P) 3-(4-bromo 45 2,6-dimethylphenyl)-5,5-dimethylpyrrolidine-2,4-dione and Sodium methoxide as starting materials, the course of the reaction can be represented by the scheme below:

50 OH CH3 H3C Using, for example, according to process (O) variant a N n-butyllithium 3-(2,6-dimethyl-4-iodophenyl)-4-hydroxy-5,5-tetramethyl H3C B - - ene-A-dihydrofuran-2-one and ethyl isocyanate as starting HN 2 materials, the course of the reaction can be represented by the 55 reaction scheme below: O CH OH. His H3C

OH CH 60 H3C N I HN

65 The compounds, required as starting materials for the pro cess (a) according to the invention, of the formula (II) US 8,629,084 B2 73 74 The compounds of the formula (XXV) (II) > (XXV) D1B N sas%J 5 A>1 CO2H alHX D1 N 4y, Y 10 E l' itchecker: Above, please change J to Ii in which in which A, B, D, J, X, Y and Rare as defined above A, B, D, J, X and Y are as defined above are novel. is are novel. The acylamino acid esters of the formula (II) are obtained, The compounds of the formula (XXV) are obtained when for example, when amino acid derivatives of the formula amino acids of the formula (XXVI) (XXIII)

2O A CO2H (XXVI) A COR (XXIII) Dr Dr D1 NH NH 1. D 25 in which A, B and Dare as defined above in which are acylated with substituted phenylacetic acid derivatives A, B, Rand D are as defined above of the formula (XXIV) are acylated with Substituted phenylacetic acid derivatives 30 formula (XXIV) J (XXIV) (XXIV) XC |= g J \ 35 & / COZ X1 Y VE COZ in which J, X and Y are as defined above and 40 Z is as defined above, in which for example according to Schotten-Baumann (Organikum, J, X and Y are as defined above and VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. Z represents a leaving group introduced by reagents, such 505). as carbonyldiimidazole, carbonyldiimides (such as, for The compounds of the formula (XXIV) are novel. They can example, dicyclohexylcarbondiimide), phosphorylating 45 be prepared by processes known in principle and as illustrated agents (such as, for example, POCl, BOP-Cl), haloge- in the examples (see, for example, H. Henecka, Houben nating agents, for example thionyl chloride, oxalyl chlo- Weyl, Methoden der Organischen Chemie Methods of Organic Chemistry, Vol. 8, pp. 467-469 (1952)). this or chloroformic esters, for activating car The compounds of the formula (XXIV) are obtained, for - 50 example, by reacting Substituted phenylacetic acids of the (Chem. Reviews 52,237-416 (1953); Bhattacharya, Indian formula (XXVII) J. Chem. 6,341-5, 1968) or when acylamino acids of the formula (XXV) (XXVII)

55 A CO2H (XXV) XC

B J D --X 60 in which ric withJ, X andhalogenating Y are as defined agents above (for example thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide orphosphorus pentachlo in which 65 ride), phosphonylating agents, such as (for example POCl, A, B, D, J, X and Y are as defined above BOP-Cl), carbonyidiimidazole, carbonyldiimides (for are esterified (Chem. Ind. (London) 1568 (1968)). example dicyclohexylcarbonyldiimide), if appropriate in the US 8,629,084 B2 75 76 presence of a diluent (for example optionally chlorinated aliphatic or aromatic hydrocarbons, such as toluene or meth (XXIV) ylene chloride, or ethers, for example tetrahydrofuran, diox J ane, methyl tert-butyl ether) attemperatures of from -20°C. to 150° C., preferably from -10° C. to 100° C. sXM Some of the compounds of the formulae (XXIII) and y1A / COZ (XXVI) are known, and/or they can be prepared by known processes (see, for example, Compagnon, Miocque Ann. in which Chim. (Paris) 145, pp. 11-22, 23-27 (1970)). 10 The substituted cyclic aminocarboxylic acids of the for J, X, Y and Z are as defined above mula (XXVI) in which A and B form a ring are generally to give compounds of the formula (XXIX) obtainable by the Bucherer-Bergs synthesis or by the Strecker synthesis, where they are obtained in different isomeric forms. Thus, the conditions of the Bucherer-Bergs synthesis 15 afford predominantly the isomers (hereinbelow for the sake (XXIX) of simplicity referred to as B) in which the radicals R and the carboxyl group are in equatorial positions, whereas the con XSW ditions of the Strecker synthesis afford predominantly the ?y isomers (hereinbelow for the sake of simplicity referred to as Y* / ) - C.) in which the amino group and the radicals R are in equa CEN torial positions. O X B A

H NH H CO2H 25 R R COH NH in which R 2' R 2 A, B, D, J, X and Y are as defined above and then Subjecting these to an acidic alcoholysis. H H Bucherer-Bergs synthesis Strecker synthesis 30 The compounds of the formula (XXIX) are likewise novel. (f isomer) (C. isomer) The compounds, required as starting materials in the pro cess (B) according to the invention, of the formula (III) (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can. J. Chem. 53,3339 (1975). 35 The starting materials, used in the above process (A), of the (III) formula (II) A COR Dr J (II) 40 A COR "N114 Dr J D1 N Sé, 45 in which A, B, J, X, Y and Rare as defined above, are novel. in which 50 They can be prepared by methods known in principle. A, B, D, J, X, Y and Rare as defined above Thus, the compounds of the formula (III) are obtained, for can furthermore be prepared by reacting aminonitriles of example, when 2-hydroxycarboxylic esters of the formula the formula (XXVIII) (XXX-A) 55 (XXVIII) (XXX-A) X A COR H- EN 60 D1 D OH

in which in which

A, B and Dare as defined above 65 A, B and Rare as defined above with substituted phenylacetic acid derivatives of the for are acylated with substituted phenylacetic acid derivatives mula (XXIV) of the formula (XXIV) US 8,629,084 B2 77 78 are hydrolyzed in the presence of acids or bases, in the (XXIV) presence of a solvent under generally known standard condi tions. Some of the compounds of the formula (XXXI) are com 5 mercially available, some are known, for example from WO Y COZ 01/17973; however, some are also novel. The compounds of the formula (XXXI) in which J, X, Y and Z are as defined above 10 (Chem. Reviews 52,237-416 (1953)). (XXXI) Furthermore, compounds of the formula (III) are obtained when substituted phenylacetic acids of the formula (XXVII) COR 15

(XXVII) in which CO2H J, X, Y and Rare as defined above are furthermore obtained by the process (Q) described in the examples in which when phenylacetic esters of the formula (XXXI-a) J, X and Y are as defined above 25 are alkylated with C-halocarboxylic esters of the formula (XXXI-a) (XXX-B)

XXX-B A COR ( ) 30

B Hal in which R, X and Y are as defined above in which 35 are reacted in the presence of iodides (preferably sodium A, B and Rare as defined above and iodide or potassium iodide) in the presence of a base and, if Hal represents chlorine or bromine. appropriate, in the presence of a catalyst (preferably copper Some of the compounds of the formula (XXVII) are com mercially available. Some are known; however, Some are also salts, such as, for example, copper(I) iodide). novel. 40 The phenylacetic esters of the formula (XXXI-a) are The compounds of the formula (XXX-B) are commercially known in principle, for example from the applications WO available. 96/35664, WO 97/02243, WO 97/01535, WO 98/05638 and The compounds of the formula (XXVII) DE-A-10301 804, and they can be prepared by the processes described in these publications. 45 The compounds, required as starting materials for the pro (XXVII) cess (C) above, of the formula (IV) COH

50 (IV) S / \ S in which v ( / B J J, X and Y are as defined above are obtained, for example, when phenylacetic esters of the 55 s1” Sé, formula (XXXI) O 2 HX Y (XXXI) 60 in which COR A, B, J. V. X, Y and Rare as defined above Y VE are novel.

65 They can be prepared by methods known in principle. in which The compounds of the formula (IV) are obtained, for J, X, Y and Rare as defined above example, when US 8,629,084 B2 79 80 substituted phenylacetic esters of the formula (XXXI) in the presence of catalysts, such as, for example, dimethyl formamide, methylsterylformamide or triphenylphosphine, and, if appropriate, in the presence of bases, such as, for (XXXI) example, pyridine or triethylamine. Some of the substituted phenylmalonic acids of the for X mula (XXXIII) are known or commercially available; how COR ever, Some are also novel. They can be prepared in a simple Y manner by known processes (cf., for example, Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. in which 10 517 ff. EP-A-528 156, WO 96/35 664, WO 97/02 243, WO J, X, Y and Rare as defined above 97/01535, WO 97/36868 and WO 98/05638). are acylated with 2-benzylthiocarbonylhalides of the for Thus, phenylmalonic acids of the formula (XXXIII) mula (XXXII) 15 J (XXXIII) (XXXII) XM \ CO2H (y-r X. Y 1S CO2H Hal in which in which J, X and Y are as defined above A, B and V are as defined above and are obtained when phenylmalonic esters of the formula Hal represents halogen (in particular chlorine or bromine) 25 (XI) in the presence of strong bases (see, for example, M. S. Chambers, E.J. Thomas, D.J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228). (XI) Some of the benzylthiocarbonyl halides of the formula 30 (XXXII) are known, and/or they can be prepared by known XM \ COU processes (J. Antibiotics (1983), 26, 1589). The halocarbonyl ketenes of the formula (VI) required as Y( - COU starting materials for the above processes (D), (E) and (H-C.) are novel. They can be prepared by methods known in prin 35 in which ciple (cf., for example, Org. Prep. Proced. Int., 7, (4), 155 J, X and Y are as defined above 158, 1975 and DE 1945 703). Thus, for example, the com and U represents OR or NH, pounds of the formula (VI) where R is as defined above, 40 are initially hydrolyzed in the presence of a base and of a solvent and then carefully acidified (see, for example, EP-A- CO (VI) 528 156, WO 96/35664, WO 97/02243). J y N COHal The malonic esters of the formula (XI) X 45 y 21 (XI) Y XM \ COU in which J, X and Y are as defined above and 50 Y( - COU Hal represents chlorine or bromine are obtained when substituted phenylmalonic acids of the formula (XXXIII) in which J, X and Y are as defined above 55 and U represents OR or NH, J (XXXIII) where R is as defined above, are known (for example WO 01/017973, Larock et al., s o Tetrahedron 522743 ff. (1996); however, some are also novel. 60 They can be prepared by generally known methods of X / YooH organic chemistry (cf., for example, Tetrahedron Lett. 27. 2763 (1986), Organikum VEB Deutscher Verlag der Wissen in which schaften, Berlin 1977, p. 587 ff., WO 96/35664, WO J, X and Y are as defined above 97/02243, WO 97/01535, WO 97/36868, WO 98/05638 and are reacted with acid halides. Such as, for example, thionyl 65 WO 99/47525). chloride, phosphorus(V) chloride, phosphorus(III) chloride, The carbonyl compounds, required as starting materials for oxalyl chloride, phosgene or thionyl bromide, if appropriate the process (D) according to the invention, of the formula (V) US 8,629,084 B2 81 82

(V) (XXXIV) O Q Q? XW SC/ \ CO2H -- X Y VE A B

in which in which A and Dare as defined above 10 J, X, Y, A, B, Q' and Q are as defined above or silylenol ethers thereof of the formula (Va) are esterified (cf., for example, Organikum, 15th edition, Berlin, 1977, page 499) or alkylated (see Preparation Example). The 5-aryl-4-ketocarboxylic acids of the formula (Va) CHA 15 (XXXIV) D-C-OSi(R)1-nero (XXXIV) in which A, D and Rare as defined above CO2H are commercially available compounds, generally known compounds or compounds which can be obtained by known processes. 25 in which The preparation of the ketene acid chlorides of the formula A, B, J, Q, Q , X and Y are as defined above (VI) required as starting materials for carrying out the process are novel; however, they can be prepared by methods (E) according to the invention have already been described known in principle (WO 96/01 798, WO 97/14667, WO above. The thioamides, required for carrying out the process 98/39281). (E) according to the invention, of the formula (VII) 30 The 5-aryl-4-ketocarboxylic acids of the formula (XXXIV) are obtained, for example, when 2-phenyl-3-oxoa dipicesters of the formula (XXXV) (VII)

35 (XXXV)

in which 40 A is as defined above are compounds which are generally known in organic chemistry. in which The compounds, required as starting materials in the above A, B, J, Q, Q, X and Y are as defined above and 45 RandR represent alkyl (in particular C-Cs-alkyl) and, process (F), of the formula (VIII) when the compound of the formula (XXXVII-a) is used, R represents hydrogen, are decarboxylated, if appropriate in the presence of a (VIII) diluent and if appropriate in the presence of a base or acid (cf. 50 for example, Organikum, 15th edition, Berlin, 1977, page 519 to 521, WO 96/01798, WO 97/14667, WO 98/39281). The compounds of the formula (XXXV)

55 (XXXV)

in which 60 A, B, J, Q, Q, X, Y and Rare as defined above are novel. in which They can be prepared by methods known in principle. A, B, J, Q, Q, X, Y. R. Rare as defined above and, The 5-aryl-4-ketocarboxylic esters of the formula (VIII) 65 when the compound of the formula (XXXVII-a) is used, R are obtained, for example, when 5-aryl-4-ketocarboxylic represents hydrogen acids of the formula (XXXIV) are novel. US 8,629,084 B2 83 84 The compounds of the formula (XXXV) are obtained, for example, Q3 Q Qs (IX) when dicarboxylic monoester chlorides of the formula 6 (XXXVI), ROC Q CO A. B J (XXXVI) Q? A Q B 10 S Xj-X Y ORC COR V Hal in which A, B, J, Q, Q, Q, Q, X, Y and Rare as defined above 15 are novel. They can be prepared by methods known in principle. The 6-aryl-5-ketocarboxylic esters of the formula (IX) are in which obtained, for example, when 6-aryl-5-ketocarboxylic acids of A, B, Q, Q and Rare as defined above and the formula (XXXVIII) Hal represents chlorine or bromine

or carboxylic anhydrides of the formula (XXXVII-a) (XXXVIII)

25 O (XXXVII-a) A

B O 30 in which 2 Q Q A, B, J, Q, Q, Q, Q, X and Y are as defined above O are esterified (cf., for example, Organikum, 15th edition, Berlin, 1977, page 499, WO 99/43649, WO 99/48869). The 6-aryl-5-ketocarboxylic acids of the formula (XXX 35 VIII)

in which

(XXXVIII) A, B, Q and Q are as defined above are acylated with a phenylacetic ester of the formula 40 (XXXI)

(XXXI) 45 in which A, B, J, Q, Q, Q, Q, X and Y are as defined above OR8 are novel. They can be prepared by methods known in principle (WO99/43649, WO 99/48869), for example when 50 substituted 2-phenyl-3-oxoheptanedioic esters of the for mula (XXXIX)

(XXXIX) in which 55 J, X, Y and Rare as defined above in the presence of a diluent and in the presence of a base (cf., for example, M. S. Chambers, E. J. Thomas, D. J. Will iams, J. Chem. Soc. Chem. Commun., (1987), 1228, cf. also the Preparation Examples). 60 Some of the compounds of the formulae (XXXVI) and (XXXVII-a) are known compounds of organic chemistry, in which and/or they can be prepared in a simple manner by methods A, B, J, Q, Q, Q, Q, X and Y are as defined above and known in principle. 65 RandR represent alkyl (preferably C-C-alkyl) and, The compounds, required as starting materials in the above when the compound of the formula (XXXVII-b) is used, process (G), of the formula (IX) R represents hydrogen, US 8,629,084 B2 85 86 are hydrolyzed and decarboxylated, if appropriate in the are known, and/or they can be prepared by methods known presence of a diluent and if appropriate in the presence of a from the literature (cf., for example, Liebigs Ann. Chem. 585, base or acid (cf., for example, Organikum, 15th edition, Ber 6 (1954); Reaktionen der organischen Synthese Reactions of lin, 1977, pages 519 to 521, WO99/43649, WO 99/48869). Organic Synthesis, C. Ferri, pages 212, 513; Georg Thieme The compounds of the formula (XXXIX) Verlag Stuttgart, 1978; Liebigs Ann. Chem. 443,242 (1925); Chem. Ber. 98, 2551 (1965), EP-A-508 126, WO 92/16510, (XXXIX) WO 99/47525, WO 01/17972). The compounds, required for the process (H-Y) according to the invention, of the formula (XII) 10

(XII) J ^4 \ N -CO2R in which 15 s A, B, J, Q, Q, Q, Q, X,Y, RandR areas defined above Y VE O A are novel and can be obtained when dicarboxylic esters of the formula (XL) in which ' A, D, J, X, Y and Rare as defined above 3 (XL) are novel. Q Q. A B The acylcarbazates of the formula (XII) are obtained, for Qs example, when carbazates of the formula (XLI) COR 25 Q6 COR 8 (XLI) n -CO2R in which NH A, B, Q, Q, Q, Q and Rare as defined above 30 D1 or carboxylic anhydrides of the formula (XXXVII-b) in which O (XXXVII-b) A. Rand D are as defined above are acylated with substituted phenylacetic acid derivatives A of the formula (XXIV) O B XXIV Q4 O 40 ( ) Qs Q6 X ?'M \ in which A, B, Q,3. Q,4 Q,5 Q 6 are as defined above Y X1VE COZ are condensed with a substituted phenylacetic ester of the as formula (XXXI) in which J, X, Y and Z are as defined above (XXXI) (Chem. Reviews 52,237-416 (1953); Bhattacharya, Indian 50 J. Chem. 6,341-5, 1968). OR8 Some of the carbazates of the formula (XLI) are commer cially available compounds and some are known compounds, or they can be prepared by processes of organic chemistry known in principle. 55 The compounds of the formula (XXIV) have already been in which described in connection with the intermediates for the process J, X, Y and Rare as defined above (A) and (B). in the presence of a diluent and in the presence of a base. The acid halides of the formula (XIII), carboxylic anhy Some of the compounds of the formula (XL) are known, and/or they can be prepared by known processes. drides of the formula (XIV), chloroformic esters or chloro 60 formic thioesters of the formula (XV), chloromonothiofor Some of the hydrazines, required as starting materials for micesters or chlorodithioformic esters of the formula (XVI), the process (H-C) and (H-B) according to the invention, of the sulfonyl chlorides of the formula (XVII), phosphorus com formula (X) pounds of the formula (XVIII) and metal hydroxides, metal alkoxides or amines of the formulae (XIX) and (XX) and A-NH NH-D (X) is isocyanates of the formula (XXI) and carbamoyl chlorides of in which the formula (XXII) furthermore required as starting materials A and Dare as defined above for carrying out the processes (I), (J), (K), (L), (M), (N) and US 8,629,084 B2 87 88 (O) according to the invention are generally known com alkaline earth metal oxides, hydroxides and carbonates, such pounds of organic or inorganic chemistry. as sodium hydroxide, potassium hydroxide, magnesium In addition, the compounds of the formulae (V), (VII), oxide, calcium oxide, Sodium carbonate, potassium carbon (XIII) to (XXII), (XXIII), (XXVI), (XXVIII), (XXX-A), ate and calcium carbonate, which can also be used in the (XXX-B), (XXXII), (XXXVI), (XXXVII-a), (XXXVII-b), presence of phase-transfer catalysts, such as, for example, (XL) and (XLI) are furthermore known from the patent appli triethylbenzylammonium chloride, tetrabutylammonium cations cited at the outset, and/or they can be prepared by the bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium methods stated in these publications. chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is The process (A) is characterized in that compounds of the furthermore possible to use alkali metals, such as sodium or formula (II) in which A, B, D, J, X, Y and Rare as defined 10 potassium. It is also possible to employ alkali metal and above are subjected to an intramolecular condensation in the alkaline earth metal amides and hydrides, such as Sodium presence of a base. amide, sodium hydride and calcium hydride, and additionally Suitable for use as diluents in the process (A) according to also alkali metal alkoxides, such as sodium methoxide, the invention are all inert organic solvents. Preference is given Sodium ethoxide and potassium tert-butoxide. to using hydrocarbons, such as toluene and Xylene, further 15 When carrying out the process (B) according to the inven more ethers, such as dibutyl ether, tetrahydrofuran, dioxane, tion, the reaction temperatures can be varied within a rela glycol dimethyl ether and diglycol dimethyl ether, moreover tively wide range. In general, the process is carried out at polar solvents. Such as dimethyl Sulfoxide, Sulfolane, dimeth temperatures between 0° C. and 250° C., preferably between ylformamide and N-methylpyrrolidone, and also alcohols, 50° C. and 150° C. Such as methanol, ethanol, propanol, isopropanol, butanol, The process (B) according to the invention is generally isobutanol and tert-butanol. carried out under atmospheric pressure. Suitable bases (deprotonating agents) for carrying out the When carrying out the process (B) according to the inven process (A) according to the invention are all customary tion, the reaction components of the formula (II) and the proton acceptors. Preference is given to using alkali metaland deprotonating bases are generally employed in approxi alkaline earth metal oxides, hydroxides and carbonates, such 25 mately equimolaramounts. However, it is also possible to use as sodium hydroxide, potassium hydroxide, magnesium a relatively large excess (up to 3 mol) of one or the other oxide, calcium oxide, Sodium carbonate, potassium carbon component. ate and calcium carbonate, which can also be used in the The process (C) is characterized in that compounds of the presence of phase-transfer catalysts, such as, for example, formula (IV) in which A, B, V. J, X, Y and Rare as defined triethylbenzylammonium chloride, tetrabutylammonium 30 above are cyclized intramolecularly in the presence of an acid bromide, Adogen 464 (methyltrialkyl (Cs-Co)ammonium and, if appropriate, in the presence of a diluent. chloride) or TDA 1 (tris(methoxyethoxyethyl)amine). It is Suitable diluents for the process (C) according to the inven furthermore possible to use alkali metals, such as sodium or tion are all inert organic solvents. Preference is given to using potassium. It is also possible to employ alkali metal and hydrocarbons, such as toluene and Xylene, furthermore halo alkaline earth metal amides and hydrides, such as sodium 35 genated hydrocarbons, such as dichloromethane, chloroform, amide, sodium hydride and calcium hydride, and additionally ethylene chloride, chlorobenzene, dichlorobenzene, more also alkali metal alkoxides, such as sodium methoxide, over polar solvents, such as dimethyl sulfoxide, Sulfolane, Sodium ethoxide and potassium tert-butoxide. dimethylformamide and N-methylpyrrolidone. It is further When carrying out the process (A) according to the inven more possible to use alcohols, such as methanol, ethanol, tion, the reaction temperatures can be varied within a rela 40 propanol, isopropanol, butanol, isobutanol, tert-butanol. tively wide range. In general, the process is carried out at If appropriate, the acid used may also serve as diluent. temperatures between 0° C. and 250° C., preferably between Suitable for use as acid in the process (C) according to the 50° C. and 150° C. invention are all customary inorganic and organic acids. Such The process (A) according to the invention is generally as, for example, hydrohalic acids, Sulfuric acid, alkyl-, aryl carried out under atmospheric pressure. 45 and haloalkylsulfonic acids, in particular halogenated alkyl When carrying out the process (A) according to the inven carboxylic acids, Such as, for example, trifluoroacetic acid. tion, the reaction components of the formula (II) and the When carrying out the process (C) according to the inven deprotonating bases are generally employed in approxi tion, the reaction temperatures can be varied within a rela mately doubly equimolar amounts. However, it is also pos tively wide range. In general, the process is carried out at sible to use a relatively large excess (up to 3 mol) of one or the 50 temperatures between 0° C. and 250° C., preferably between other component. 50° C. and 150° C. The process (B) is characterized in that compounds of the The process (C) according to the invention is generally formula (III) in which A, B, J, X, Y and Rare as defined carried out under atmospheric pressure. above are subjected to an intramolecular condensation in the When carrying out the process (C) according to the inven presence of a diluent and in the presence of a base. 55 tion, the reaction components of the formula (IV) and the acid Suitable for use as diluents in the process (B) according to are, for example, employed in equimolar amounts. However, the invention are all inert organic solvents. Preference is given it is also possible, if appropriate, to use the acid as solvent or to using hydrocarbons, such as toluene and Xylene, further as catalyst. more ethers, such as dibutyl ether, tetrahydrofuran, dioxane, The process (D) according to the invention is characterized glycol dimethyl ether and diglycol dimethyl ether, moreover 60 in that carbonyl compounds of the formula (V) or their enole polar solvents. Such as dimethyl Sulfoxide, Sulfolane, dimeth ethers of the formula (V-a) are reacted with ketene acid ylformamide and N-methylpyrrolidone, and also alcohols, halides of the formula (VI) in the presence of a diluent and, if Such as methanol, ethanol, propanol, isopropanol, butanol, appropriate, in the presence of an acid acceptor. isobutanol and tert-butanol. Suitable diluents for use in the process (D) according to the Suitable bases (deprotonating agents) for carrying out the 65 invention are all inert organic Solvents. Preference is given to process (B) according to the invention are all customary pro using optionally halogenated hydrocarbons, such as toluene, ton acceptors. Preference is given to using alkali metal and Xylene, mesitylene, chlorobenzene and dichlorobenzene, fur US 8,629,084 B2 89 90 thermore ethers, such as dibutyl ether, glycol dimethyl ether dimethyl sulfoxide, sulfolane, dimethylformamide and diglycol dimethyl ether and diphenyl ether, moreover polar N-methylpyrrolidone. It is furthermore possible to use alco solvents, such as dimethyl sulfoxide, sulfolane, dimethylfor hols, such as methanol, ethanol, propanol, isopropanol, mamide or N-methylpyrrolidone. butanol, isobutanol, tert-butanol. Suitable acid acceptors for carrying out the process variant Suitable bases (deprotonating agents) for carrying out the (D) according to the invention are all customary acid accep process (F) according to the invention are all customary pro tOrS. ton acceptors. Preference is given to using alkali metal and Preference is given to using tertiary amines, such as tri alkaline earth metal oxides, hydroxides and carbonates, such ethylamine, pyridine, diazabicyclooctane (DABCO), diaz as sodium hydroxide, potassium hydroxide, magnesium abicycloundecane (DBU), diazabicyclononene (DBN), 10 oxide, calcium oxide, Sodium carbonate, potassium carbon Hünig base and N,N-dimethylaniline. ate and calcium carbonate, which can also be used in the When carrying out the process variant (D) according to the presence of phase-transfer catalysts, such as, for example, invention, the reaction temperatures can be varied within a triethylbenzylammonium chloride, tetrabutylammonium relatively wide range. Expediently, the process is carried out bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium at temperatures between 0° C. and 250° C., preferably 15 chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is between 50° C. and 220° C. furthermore possible to use alkali metals, such as sodium or The process (D) according to the invention is expediently potassium. It is also possible to employ alkali metal and carried out under atmospheric pressure. alkaline earth metal amides and hydrides, such as Sodium When carrying out the process (D) according to the inven amide, sodium hydride and calcium hydride, and additionally tion, the reaction components of the formulae (V) and (VI), in also alkali metal alkoxides, such as sodium methoxide, which A, D, J, X and Y are as defined above and Hal repre Sodium ethoxide and potassium tert-butoxide. sents halogen, and, if appropriate, the acid acceptors are When carrying out the process (F) according to the inven generally employed in approximately equimolar amounts. tion, the reaction temperatures can be varied within a rela However, it is also possible to use a relatively large excess (up tively wide range. In general, the process is carried out at to 5 mol) of one component or the other. 25 temperatures between -75° C. and 250° C., preferably The process (E) according to the invention is characterized between -50° C. and 150° C. in that thioamides of the formula (VII) are reacted with ketene The process (F) according to the invention is generally acid halides of the formula (VI) in the presence of a diluent carried out under atmospheric pressure. and, if appropriate, in the presence of an acid acceptor. When carrying out the process (F) according to the inven Suitable for use as diluents for the process variant (E) 30 tion, the reaction components of the formula (VIII) and the according to the invention are all inert organic solvents. Pref deprotonating bases are generally employed in approxi erence is given to using hydrocarbons, such as toluene and mately equimolaramounts. However, it is also possible to use Xylene, furthermore ethers, such as dibutyl ether, glycol dim a relatively large excess (up to 3 mol) of one or the other ethyl ether and diglycol dimethyl ether, moreover polar sol component. vents, such as dimethylsulfoxide, Sulfolane, dimethylforma 35 The process (G) is characterized in that compounds of the mide and N-methylpyrrolidone. formula (IX) in which A, B, Q, Q, Q, Q, J, X,Y and Rare Suitable for use as acid acceptors for carrying out the as defined above are subjected to an intramolecular conden process (E) according to the invention are all customary acid sation in the presence of bases. acceptors. Suitable diluents for use in the process (G) according to the Preference is given to using tertiary amines, such as tri 40 invention are all organic solvents which are inert toward the ethylamine, pyridine, diazabicyclooctane (DABCO), diaz reaction participants. Preference is given to using hydrocar abicycloundecane (DBU), diazabicyclononene (DBN), bons, such as toluene and Xylene, furthermore ethers, such as Hünig base and N,N-dimethylaniline. dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether When carrying out the process (E) according to the inven and diglycol dimethyl ether, moreoverpolar solvents, such as tion, the reaction temperatures can be varied within a rela 45 dimethyl sulfoxide, sulfolane, dimethylformamide and tively wide range. Expediently, the process is carried out at N-methylpyrrolidone. It is furthermore possible to use alco temperatures between 0° C. and 250° C., preferably between hols, such as methanol, ethanol, propanol, isopropanol, 20° C. and 220° C. butanol, isobutanol, tert-butanol. The process (E) according to the invention is expediently Suitable bases (deprotonating agents) for carrying out the carried out under atmospheric pressure. 50 process (G) according to the invention are all customary When carrying out the process (E) according to the inven proton acceptors. tion, the reaction components of the formulae (VII) and (VI), Preference is given to using alkali metal and alkaline earth in which A.J., X and Y areas defined above and Hal represents metal oxides, hydroxides and carbonates, such as Sodium halogen, and, if appropriate, the acid acceptors are generally hydroxide, potassium hydroxide, magnesium oxide, calcium employed in approximately equimolar amounts. However, it 55 oxide, Sodium carbonate, potassium carbonate and calcium is also possible to use a relatively large excess (up to 5 mol) of carbonate, which can also be used in the presence of phase one component or the other. transfer catalysts, such as, for example, triethylbenzylammo The process (F) is characterized in that compounds of the nium chloride, tetrabutylammonium bromide, Adogen 464 formula (VIII) in which A, B, J, Q, Q, X, Y and Rare as (-methyltrialkyl (Cs-Co)ammonium chloride) or TDA 1 defined above are Subjected to an intramolecular condensa 60 (tris(methoxyethoxyethyl)amine). It is furthermore pos tion in the presence of a base. sible to use alkali metals, such as Sodium or potassium. It is Suitable diluents for use in the process (F) according to the also possible to employ alkali metal and alkaline earth metal invention are all organic solvents which are inert toward the amides and hydrides, such as sodium amide, Sodium hydride reaction participants. Preference is given to using hydrocar and calcium hydride, and additionally also alkali metal alkox bons, such as toluene and Xylene, furthermore ethers, such as 65 ides, such as sodium methoxide, Sodium ethoxide and potas dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether sium tert-butoxide. When carrying out the process (G) and diglycol dimethyl ether, moreoverpolar solvents, such as according to the invention, the reaction temperatures can be US 8,629,084 B2 91 92 varied within a relatively wide range. In general, the process ate and calcium carbonate, which can also be used in the is carried out at temperatures between 0° C. and 250° C. presence of phase-transfer catalysts, such as, for example, preferably between 50° C. and 150° C. triethylbenzylammonium chloride, tetrabutylammonium The process (G) according to the invention is generally bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium carried out under atmospheric pressure. chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is When carrying out the process (G) according to the inven furthermore possible to use alkali metals, such as sodium or tion, the reaction components of the formula (IX) and the potassium. It is also possible to employ alkali metal and deprotonating bases are generally employed in approxi alkaline earth metal amides and hydrides, such as Sodium mately equimolar amounts. However, it is also possible to use amide, sodium hydride and calcium hydride, and additionally a relatively large excess (up to 3 mol) of one or the other 10 also alkali metal alkoxides, such as sodium methoxide, component. Sodium ethoxide and potassium tert-butoxide. The process (H-C) according to the invention is character It is also possible to use tertiary amines. Such as triethy ized in that hydrazines of the formula (X) or salts of these lamine, pyridine, diazabicyclooctane (DABCO), diazabicy compounds are reacted with ketene acid halides of the for cloundecane (DBU), diazabicyclononene (DBN), Hünig base mula (VI) in the presence of a diluent and, if appropriate, in 15 and N,N-dimethylaniline. the presence of an acid acceptor. When carrying out the process (H-B) according to the Suitable diluents for use in the process (H-C.) according to invention, the reaction temperatures can be varied within a the invention are all inert organic solvents. Preference is given relatively wide range. In general, the process is carried out at to using optionally chlorinated hydrocarbons, such as, for temperatures between 0° C. and 280°C., preferably between example, mesitylene, chlorobenzene and dichlorobenzene, 50° C. and 180° C. toluene, xylene, furthermore ethers, such as dibutyl ether, The process (H-B) according to the invention is generally glycol dimethyl ether, diglycol dimethyl ether and diphenyle carried out under atmospheric pressure. thane, moreover polar solvents, such as dimethyl Sulfoxide, When carrying out the process (H-B) according to the sulfolane, dimethylformamide or N-methylpyrrolidone. invention, the reaction components of the formulae (XI) and Suitable acid acceptors for carrying out the process variant 25 (X) are generally employed in approximately equimolar (H-C) according to the invention are all customary acid amounts. However, it is also possible to use a relatively large acceptors. excess (up to 3 mol) of one component or the other. Preference is given to using tertiary amines, such as tri The process (H-Y) is characterized in that compounds of the ethylamine, pyridine, diazabicyclooctane (DABCO), diaz formula (XII) in which A, D, J, X, Y and Rare as defined abicycloundecane (DBU), diazabicyclononene (DBN), 30 above are Subjected to an intramolecular condensation in the Hünig base and N,N-dimethylaniline. presence of a base. When carrying out the process variant (H-C) according to Suitable for use as diluents in the process (H-Y) according the invention, the reaction temperatures can be varied within to the invention are all inert organic solvents. Preference is a relatively wide range. Expediently, the process is carried out given to using hydrocarbons, such as toluene and Xylene, at temperatures between 0° C. and 250° C., preferably 35 furthermore ethers, such as dibutyl ether, tetrahydrofuran, between 50° C. and 220° C. dioxane, glycol dimethyl ether and diglycol dimethyl ether, The process (H-C) according to the invention is expedi moreover polar solvents, such as dimethyl Sulfoxide, Sul ently carried out under atmospheric pressure. folane, dimethylformamide and N-methylpyrrolidone, and When carrying out the process (H-C) according to the also alcohols, such as methanol, ethanol, propanol, isopro invention, the reaction components of the formulae (VI) and 40 panol, butanol, isobutanol and tert-butanol. (X), in which A, D, J, X and Y are as defined above and Hal Suitable bases (deprotonating agents) for carrying out the represents halogen, and, if appropriate, the acid acceptors are process (H-Y) according to the invention are all customary generally employed in approximately equimolar amounts. proton acceptors. Preference is given to using alkali metaland However, it is also possible to use a relatively large excess (up alkaline earth metal oxides, hydroxides and carbonates, such to 5 mol) of one component or the other. 45 as sodium hydroxide, potassium hydroxide, magnesium The process (H-B) is characterized in that hydrazines of the oxide, calcium oxide, Sodium carbonate, potassium carbon formula (X) or salts of this compound, in which A and Dare ate and calcium carbonate, which can also be used in the as defined above, are subjected to a condensation with mal presence of phase-transfer catalysts, such as, for example, onic esters or malonamides of the formula (XI) in which U.J. triethylbenzylammonium chloride, tetrabutylammonium X, Y and Rare as defined above, in the presence of a base. 50 bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium Suitable diluents for use in the process (H-B) according to chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is the invention are all inert organic solvents. Preference is given furthermore possible to use alkali metals, such as sodium or to using optionally halogenated hydrocarbons, such as tolu potassium. It is also possible to employ alkali metal and ene, Xylene, mesitylene, chlorobenzene and dichloroben alkaline earth metal amides and hydrides, such as Sodium Zene, furthermore ethers, such as dibutyl ether, tetrahydrofu 55 amide, sodium hydride and calcium hydride, and additionally ran, dioxane, diphenyl ether, glycol dimethyl ether and also alkali metal alkoxides, such as sodium methoxide, diglycol dimethyl ether, moreover polar solvents, such as Sodium ethoxide and potassium tert-butoxide. dimethylsulfoxide, sulfolane, dimethylformamide, dimethy When carrying out the process (H-Y) according to the lacetamide and N-methylpyrrolidone, and also alcohols, such invention, the reaction temperatures can be varied within a as methanol, ethanol, propanol, isopropanol, butanol, isobu 60 relatively wide range. In general, the process is carried out at tanol and tert-butanol. temperatures between 0° C. and 250° C., preferably between Suitable bases (deprotonating agents) for carrying out the 50° C. and 150° C. process (H-B) according to the invention are all customary The process (H-Y) according to the invention is generally proton acceptors. Preference is given to using alkali metaland carried out under atmospheric pressure. alkaline earth metal oxides, hydroxides and carbonates, such 65 When carrying out the process (H-Y) according to the as sodium hydroxide, potassium hydroxide, magnesium invention, the reaction components of the formula (XII) and oxide, calcium oxide, Sodium carbonate, potassium carbon the deprotonating bases are generally employed in approxi US 8,629,084 B2 93 94 mately doubly equimolar amounts. However, it is also pos In general, diluent and excess carboxylic anhydride and the sible to use a relatively large excess (up to 3 mol) of one or the carboxylic acid formed are removed by distillation or by other component. washing with an organic Solvent or with water. The process (I-C.) is characterized in that compounds of the The process (J) is characterized in that compounds of the formulae (I-1-a) to (I-8-a) are in each case reacted with car formulae (I-1-a) to (I-a) are in each case reacted with chloro bonyl halides of the formula (XIII), if appropriate in the formic esters or chloroformic thioesters of the formula (XV), presence of a diluent and if appropriate in the presence of an if appropriate in the presence of a diluent and if appropriate in acid binder. the presence of an acid binder. Suitable diluents for use in the process (I-C) according to Suitable acid binders for the reaction according to process the invention are all solvents which are inert toward the acid 10 (J) according to the invention are all customary acid accep halides. Preference is given to using hydrocarbons, such as tors. Preference is given to using tertiary amines. Such as benzine, benzene, toluene, Xylene and tetralin, furthermore triethylamine, pyridine, DABCO, DBU, DBA, Hünig base halogenated hydrocarbons, such as methylene chloride, chlo and N,N-dimethylaniline, furthermore alkaline earth metal roform, carbon tetrachloride, chlorobenzene and o-dichlo 15 oxides, such as magnesium oxide and calcium oxide, more robenzene, moreover ketones, such as acetone and methyl over alkali metal and alkaline earth metal carbonates, such as isopropyl ketone, furthermore ethers, such as diethyl ether, Sodium carbonate, potassium carbonate and calcium carbon tetrahydrofuran and dioxane, additionally carboxylic esters, ate, and also alkali metal hydroxides, such as Sodium hydrox Such as ethyl acetate, and also strongly polar solvents, such as ide and potassium hydroxide. dimethylsulfoxide and sulfolane. The hydrolytic stability of Suitable diluents for use in the process (J) according to the the acid halide permitting, the reaction can also be carried out invention are all solvents which are inert toward the chloro in the presence of water. formic esters or chloroformic thioesters. Preference is given Suitable acid binders for the reaction according to the to using hydrocarbons, such as benzine, benzene, toluene, process (I-C) according to the invention are all customary Xylene and tetralin, furthermore halogenated hydrocarbons, acid acceptors. Preference is given to using tertiary amines, 25 such as methylene chloride, chloroform, carbon tetrachlo Such as triethylamine, pyridine, diazabicyclooctane ride, chlorobenzene and o-dichlorobenzene, moreover (DABCO), diazabicycloundecene (DBU), diazabicyclonon ketones, such as acetone and methyl isopropyl ketone, fur ene (DBN), Hünig base and N,N-dimethylaniline, further thermore ethers, such as diethyl ether, tetrahydrofuran and more alkaline earth metal oxides, such as magnesium oxide dioxane, additionally carboxylic esters, such as ethyl acetate, and calcium oxide, moreover alkali metal and alkaline earth 30 and also strongly polar solvents, such as dimethyl Sulfoxide metal carbonates, such as sodium carbonate, potassium car and Sulfolane. bonate and calcium carbonate, and also alkali metal hydrox ides, such as Sodium hydroxide and potassium hydroxide. When carrying out the process (J) according to the inven The reaction temperatures in the process (I-C) according to tion, the reaction temperatures can be varied within a rela the invention may be varied within a relatively wide range. In 35 tively wide range. If the reaction is carried out in the presence general, the process is carried out at temperatures between of a diluent and an acid binder, reaction temperatures are –20° C. and +150° C., preferably between 0° C. and 100° C. generally between -20°C. and +100°C., preferably between When carrying out the process (I-C) according to the inven O° C. and 50° C. tion, the starting materials of the formulae (I-1-a) to (I-8-a) The process (J) according to the invention is generally and the carbonyl halide of the formula (XIII) are generally 40 carried out under atmospheric pressure. each employed in approximately equivalent amounts. How When carrying out the process (J) according to the inven ever, it is also possible to use a relatively large excess (up to 5 tion, the starting materials of the formulae (I-1-a) to (I-8-a) mol) of the carbonyl halide. Work-up is carried out by cus and the appropriate chloroformic ester or chloroformic tomary methods. thioester of the formula (XIII) are generally each employed in The process (I-B) is characterized in that compounds of the 45 approximately equivalent amounts. However, it is also pos formulae (I-1-a) to (I-8-a) are reacted with carboxylic anhy sible to use a relatively large excess (up to 2 mol) of one drides of the formula (XIV), if appropriate in the presence of component or the other. Work-up is carried out by customary a diluent and if appropriate in the presence of an acid binder. methods. In general, precipitated salts are removed and the Suitable for use as diluents in the process (I-B) according to reaction mixture that remains is concentrated by removing the invention are, preferably, those diluents which are also 50 the diluent under reduced pressure. preferred when acid halides are used. Besides, it is also pos The process (K) according to the invention is characterized sible for excess carboxylic anhydride to act simultaneously as in that compounds of the formulae (I-1-a) to (I-8-a) are in diluent. each case reacted with compounds of the formula (XVI) in the Suitable acid binders for process (I-B), which are added, if presence of a diluent and, if appropriate, in the presence of an appropriate, are preferably those acid binders which are also 55 acid binder. preferred when acid halides are used. In preparation process (K), about 1 mol of chloromono The reaction temperatures in the process (I-B) according to thioformic ester or chlorodithioformic ester of the formula the invention can be varied within a relatively wide range. In (XVI) is reacted per mole of the starting material of the general, the process is carried out at temperatures between formulae (I-1-a) to (I-8-a) at from 0 to 120° C., preferably –20° C. and +150° C., preferably between 0° C. and 100° C. 60 from 20 to 60° C. When carrying out the process (I-B) according to the inven Suitable diluents, which are added, if appropriate, are all tion, the starting materials of the formulae (I-1-a) to (I-8-a) inert polar organic solvents, such as ethers, amides, Sulfones, and the carboxylic anhydride of the formula (XIV) are gen Sulfoxides, and also halogenated alkanes. erally each employed in approximately equivalent amounts. Preference is given to using dimethyl sulfoxide, tetrahy However, it is also possible to use a relatively large excess (up 65 drofuran, dimethylformamide or methylene chloride. to 5 mol) of the carboxylic anhydride. Work-up is carried out If, in a preferred embodiment, the enolate salt of the com by customary methods. pounds (I-1-a) to (I-8-a) is prepared by addition of strong US 8,629,084 B2 95 96 deprotonating agents, such as, for example, Sodium hydride fication or by so-called “incipient distillation’, i.e. removal of or potassium tert-butoxide, the further addition of acid bind the Volatile components under reduced pressure. ers may be dispensed with. The process (N) is characterized in that compounds of the If acid binders are used, customary inorganic or organic formulae (I-1-a) to (I-8-a) are reacted with metal hydroxides bases are suitable, by way of example sodium hydroxide, or metal alkoxides of the formula (XIX) or amines of the Sodium carbonate, potassium carbonate, pyridine, triethy formula (XX), if appropriate in the presence of a diluent. lamine. Suitable for use as diluents in the process (N) according to The reaction can be carried out at atmospheric pressure or the invention are, preferably, ethers, such as tetrahydrofuran, under elevated pressure and is preferably carried out at atmo dioxane, diethyl ether, or else alcohols, such as methanol, 10 ethanol, isopropanol, but also water. spheric pressure. Work-up is carried out by customary meth The process (N) according to the invention is generally ods. carried out under atmospheric pressure. The process (L) according to the invention is characterized The reaction temperatures are generally between -20°C. in that compounds of the formulae (I-1-a) to (I-8-a) are in and 100° C., preferably between 0° C. and 50° C. each case reacted with sulfonyl chlorides of the formula The process (O) according to the invention is characterized (XVII), if appropriate in the presence of a diluent and if in that compounds of the formulae (I-1-a) to (I-8-a) are in appropriate in the presence of an acid binder. each case reacted with (O-O.) compounds of the formula In preparation process (L), about 1 mol of sulfonyl chloride (XXI), if appropriate in the presence of a diluent and if appro of the formula (XVII) is reacted per mole of starting material priate in the presence of a catalyst, or (O-3) with compounds of the formula (I-1-a to I-8-a), at from -20 to 150°C., pref of the formula (XXII), if appropriate in the presence of a erably from 20 to 70° C. diluent and if appropriate in the presence of an acid binder. Suitable diluents, which are added, if appropriate, are all In preparation process (O-O.), about 1 mol of isocyanate of inert polar organic solvents, such as ethers, amides, nitrites, the formula (XXI) is employed per mole of starting material Sulfones, Sulfoxides or halogenated hydrocarbons, such as of the formulae (I-1-a) to (I-8-a), at from 0 to 100°C., pref methylene chloride. 25 erably from 20 to 50° C. Preference is given to using dimethyl sulfoxide, tetrahy Suitable diluents, which are added, if appropriate, are all drofuran, dimethylformamide, methylene chloride. inert organic solvents, such as ethers, amides, nitriles, Sul If, in a preferred embodiment, the enolate salt of the com fones, Sulfoxides. pounds (I-1-a) to (I-8-a) is prepared by addition of strong If appropriate, catalysts may be added to accelerate the deprotonating agents (such as, for example, sodium hydride 30 reaction. Suitable for use as catalysts are, very advanta or potassium tert-butoxide), the further addition of acid bind geously, organotin compounds. Such as, for example, dibu ers may be dispensed with. tyltin dilaurate. The reaction is preferably carried out at atmo If acid binders are used, customary inorganic or organic spheric pressure. bases are suitable, by way of example sodium hydroxide, In preparation process (O-3), about 1 mol of carbamoyl Sodium carbonate, potassium carbonate, pyridine, triethy 35 chloride of the formula (XXII) is employed per mole of lamine. starting material of the formulae (I-1-a) to (I-8-a) at from -20 The reaction can be carried out at atmospheric pressure or to 150° C., preferably from 0 to 70° C. under elevated pressure and is preferably carried out at atmo Suitable diluents, which are added, if appropriate, are all spheric pressure. Work-up is carried out by customary meth inert polar organic solvents, such as ethers, amides, Sulfones, ods. 40 Sulfoxides or halogenated hydrocarbons. The process (M) according to the invention is characterized Preference is given to using dimethyl sulfoxide, tetrahy in that compounds of the formulae (I-1-a) to (I-8-a) are in drofuran, dimethylformamide or methylene chloride. each case reacted with phosphorus compounds of the formula If, in a preferred embodiment, the enolate salt of the com (XVIII), if appropriate in the presence of a diluent and if pound (I-1-a) to (I-8-a) is prepared by addition of strong appropriate in the presence of an acid binder. 45 deprotonating agents (such as, for example, Sodium hydride In preparation process (M), to obtain compounds of the or potassium tert-butoxide), the further addition of acid bind formulae (I-1-e) to (I-8-e) 1 to 2, preferably 1 to 1.3, mol of ers may be dispensed with. the phosphorus compound of the formula (XVIII) are If acid binders are used, customary inorganic or organic employed per mole of the compounds (I-1-e) to (I-8-e), at bases are suitable, by way of example sodium hydroxide, temperatures between -40° C. and 150° C., preferably 50 Sodium carbonate, potassium carbonate, triethylamine or between -10 and 110° C. pyridine. Suitable diluents which are added, if appropriate, are all The reaction may be carried out at atmospheric pressure or inert polar organic solvents, such as ethers, amides, nitriles, under elevated pressure and is preferably carried out at atmo alcohols, Sulfides, Sulfones, Sulfoxides, etc. spheric pressure. Work-up is carried out by customary meth Preference is given to using acetonitrile, dimethyl sulfox 55 ods. ide, tetrahydrofuran, dimethylformamide, methylene chlo The process (PC) is characterized in that compounds of the ride. formulae (I-1-a') to (I-8-a') in which A, B, D, Q', Q, Q, Q, Suitable acid binders, which are added, if appropriate, are Q, Q, X and Y are as defined above and W" preferably customary inorganic or organic bases, such as hydroxides, represents bromine are reacted with metal iodides (for carbonates or amines. Sodium hydroxide, sodium carbonate, 60 example sodium iodide, potassium iodide), if appropriate in potassium carbonate, pyridine, triethylamine may be men the presence of a base and a Cu(I) salt (for example CuBr or tioned by way of example. CuI). The reaction can be carried out at atmospheric pressure or Suitable for use as diluents in the process (PC) according to under elevated pressure and is preferably carried out at atmo the invention are all organic Solvents which are inert toward spheric pressure. Work-up is carried out by customary meth 65 the reaction participants. Preference is given to using hydro ods of organic chemistry. The end products obtained are carbons, such as toluene and Xylene, furthermore ethers. Such preferably purified by crystallization, chromatographic puri as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl US 8,629,084 B2 97 98 ether and diglycol dimethyl ether, moreover polar solvents, employed as plant protection agents. They are active against such as dimethyl sulfoxide, sulfolane, dimethylformamide, normally sensitive and resistant species and against all or dimethylacetamide and N-methylpyrrolidone, esters, such as Some stages of development. The abovementioned pests methyl acetate, ethyl acetate, propyl acetate, and also alco include: hols, such as, for example, methanol, ethanol, propanol, iso 5 From the order of the Anoplura (Phthiraptera), for propanol, butanol and isobutanol. example, Damalinia spp., Haematopinus spp., Linognathus Suitable bases for carrying out the process (PC) according spp., Pediculus spp., Trichodectes spp. to the invention are especially organic bases. Preference is From the class of the Arachnida, for example, Acarus siro, given to using amines, such as, for example, N,N-dimethyl Aceria Sheldoni, Aculops spp., Aculus spp., Amblyomma spp., ethylenediamine, 1,2-diaminocyclohexane. 10 Argas spp., Boophilus spp., Brevipalpus spp., Bryobia pra When carrying out the process (PC) according to the inven etiosa, Chorioptes spp., Dermanyssus gallinae, Eotetrany tion, the reaction temperature can be varied within a relatively chus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes wide range. In general, the process is carried out attempera spp., Hemitarisonemus spp., Hyalomma spp., Ixodes spp., tures between 0° C. and 250° C., preferably between 50° C. Latrodectus mactans, Metatetranychus spp., Oligonychus and 150° C. 15 spp., Ornithodoros spp., Panonychus spp., Phylocoptruta The process (PC) according to the invention is generally oleivora, Polyphagotarisonemus latus, Psoroptes spp., Rhipi carried out under atmospheric pressure. cephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio When carrying out the process (PC) according to the inven maurus, Stenotarisonemus spp., Tarsonemus spp., Tetrany tion, the reaction component of the formula (I-1-a') to (I-8-a') chus spp., Vasates lycopersici. is generally reacted with excesses of the metal iodides of up to From the class of the Bivalva, for example, Dreissena spp. 20 mol, preferably from 1.1 to 5 mol. The copper(I) salts are From the order of the Chilopoda, for example, Geophilus generally employed in catalytic amounts; from 0.001 to 0.5 spp., Scutigera spp. mol, preferably from 0.01 to 0.2 mol. However, they can also From the order of the Coleoptera, for example, Acan be employed in equimolar amounts. thoscelides Obtectus, Adoretus spp., Agelastica alni, Agriotes The process (PB) is characterized in that compounds of the 25 spp., Amphimallon solstitialis, Anobium punctatum, Anoplo formulae (I-1-a') to (I-8-a') in which A, B, D, Q, Q, Q, Q, phora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Q, Q, X and Y are as defined above and W" preferably Atomaria spp., Attagenus spp., Bruchidius Obtectus, Bruchus represents bromine are Subjected to a halogen/metal spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus exchange with metal organyls and the anion formed is reacted spp., Cosmopolites spp., Costelytra zealandica, Curculio with iodinating agents. 30 spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica Suitable diluents for use in the process (PB) according to spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, the invention are all organic solvents which are inert toward Heteronychus arator, Hylamorpha elegans, Hylotrupes baiu the reaction participants. Preference is given to using hydro lus, Hypera postica, Hypothenemus spp., Lachnosterna Con carbons, such as toluene and Xylene, furthermore ethers. Such sanguinea, Leptinotarsa decemlineata, Lissorhoptrus Oryzo as diethyl ether, methyl tert-butyl ether, dibutyl ether, tetrahy 35 philus, Lixus spp., Lyctus spp., Melligethes aeneus, drofuran, dioxane, glycol dimethyl ether and diglycol dim Melolontha melolontha, Migdolus spp., Monochamus spp., ethyl ether. Naupactus xanthographus, Niptus hololeucus, Oryctes rhi Suitable for use as iodinating agents for carrying out the noceros, Oryzaephilus Surinamensis, Otiorrhynchus sulca process (PB) are customary reagents, such as iodine, iodine tus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga monochloride, iodine monobromide. 40 spp., Popillia japonica, Premnotrypes spp., Psylliodes When carrying out the process (PB) according to the inven chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha tion, all customary metal organyls can be used for the halo dominica, Sitophilus spp., Sphenophorus spp., Sternechus gen/metal exchange. Preference is given to using n-butyl spp., Symphyletes spp., Tenebrio molitor; Tribolium spp., Tro lithium, sec-butyllithium, tert-butyllithium, phenyllithium. goderma spp., Tichius spp., Xylotrechus spp., Zabrus spp. When carrying out the process (PB) according to the inven 45 From the order of the Collembola, for example, Onychi tion, the reaction temperature can be varied within a relatively lirtiS drinatti.S. wide range. In general, the process is carried out attempera From the order of the Dermaptera, for example, Forficula tures between -120° C. and 50° C., preferably between -78° auricularia. C. and 30° C. From the order of the Diplopoda, for example, Blaniulus The process (PB) according to the invention is generally 50 guttulatus. carried out under atmospheric pressure. From the order of the Diptera, for example, Aedes spp., When carrying out the process (PB) according to the inven Anopheles spp., Bibio hortulanus, Caliphora erythro tion, the reaction component of the formula (I-1-a') to (I-8-a') cephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia is generally reacted with excesses of the metal organyls and spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., the iodinating agents of up to 20 mol, preferably from 1.2 to 55 Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia 5 mol. spp., Gastrophilus spp., Hyllemyia spp., Hyppobosca spp., The inventive active compounds/active compound combi Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., nations, in combination with good plant tolerance and favour Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyos able toxicity to warm-blooded animals and being tolerated cyani, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia well by the environment, are Suitable for protecting plants and 60 spp., Tipula paludosa. plant organs, for increasing the harvest yields, for improving From the class of the Gastropoda, for example, Arion spp., the quality of the harvested material and for controlling ani Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., mal pests, in particular insects, arachnids, helminths, nema Lynnaea spp., Oncomelania spp., Succinea spp. todes and molluscs, which are encountered in agriculture, in From the class of the helminths, for example, Ancylostoma horticulture, in animal husbandry, in forests, in gardens and 65 duodenale, Ancylostoma ceylanicum, Acylostoma brazilien leisure facilities, in the protection of stored products and of sis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Bru materials, and in the hygiene sector. They may be preferably gia malayi, Brugia timori, Bunostomum spp., Chabertia spp., US 8,629,084 B2 99 100 Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyo From the order of the Isoptera, for example, Reticulitermes caulus filaria, Diphyllobothrium latum, Dracunculus medin spp. ensis, Echinococcus granulosus, Echinococcus multilocu 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., 5 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 10 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. It is furthermore possible to control Protozoa, such as Laphygma spp., Lithocolletis blancardella, Lithophane Eineria. 15 antennata, Loxagrotis albicosta, Lymantria spp., Malaco From the order of the Heteroptera, for example, Anasa Soma neustria, Mamestra brassicae, Mocis repanda, tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Mythinna separata, Oria spp., Oulema Oryzae, Panolis flam Campylomma livida, Cavelerius spp., Cimex spp., Creontia mea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris des dilutus, Dasynus piperis, Dichelops fircatus, Dicono spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., coris hewetti, Dysdercus spp., Euschistus spp., Eurygaster Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., spp., Thermesia gemmatalis, Tinea pellionella, Tineola bis Leptoglossus phyllopus, Lygus spp., Macropes excavatus, selliella, Tortrix viridana, Trichoplusia spp. Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma From the order of the Orthoptera, for example, Acheta quadrata, Piezodorus spp., Psalus seriatus, Pseudacy.sta domesticus, Blatta Orientalis, Blattella germanica, Gryllo persea, Rhodnius spp., Sahlbergella singularis, Scotino 25 talpa spp., Leucophaea maderae, Locusta spp., Melanoplus phora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. spp., Periplaneta americana, Schistocerca gregaria. From the order of the Homoptera, for example, Acyrtho From the order of the Siphonaptera, for example, Cerato Sipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes phyllus spp., Xenopsylla cheopis. spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca From the order of the Symphyla, for example, Scutigerella spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, 30 immaculata. Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus From the order of the Thysanoptera, for example, Balio spp., Atanus spp., Aulacorthum Solani, Bemisia spp., Brachy thrips biformis, Enneothrips flavens, Frankliniella spp., caudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips Calligypona marginata, Carneocephalafiulgida, Ceratova cruentatus, Scirtothrips spp., Taeniothrips cardanoni, Thrips cuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon 35 spp. fragaefolii, Chionaspis tegalensis, Chlorita Onuki, Chroma From the order of the Thysanura, for example, Lepisma phis juglandicola, Chrysomphalus ficus, Cicadulina mbila, saccharina. Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbu The phytoparasitic nematodes include, for example, Aph lus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., elen.choides spp., Bursaphelenchus spp., Dity lenchus dipsaci, Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca 40 Globodera spp., Heterodera spp., Longidorus spp., Meloid spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, ogyne spp., Pratylenchus spp., Radopholus similis, Tri Geococcus coffeae, Homalodisca coagulata, Hvalopterus chodorus spp., Tilenchulus semipenetrans, Xiphinema spp. arundinis, Icerya spp., Idiocerus spp., IdioScopus spp., Lao If appropriate, the compounds/active compound combina delphax striatellus, Lecanium spp., Lepidosaphes spp., Lipa tions according to the invention can, at certain concentrations phis erysimi, Macrosiphum spp., Mahanarva fimbriolata, 45 or application rates, also be used as herbicides, safeners, Melanaphis sacchari, Metcalfiella spp., Metopolophium growth regulators or agents to improve plant properties, or as dirhodium, Monelia Costalis, Monelliopsis pecanis, Myzus microbicides, for example as fungicides, antimycotics, bac spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata tericides, viricides (including agents against Viroids) or as lugens, Oncometopia spp., Orthezia praelonga, Parabemisia agents against MLO (Mycoplasma-like organisms) and RLO myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., 50 (Rickettsia-like organisms). If appropriate, they can also be Peregrinus maidis, Phenacoccus spp., Phloeomyzus passeri employed as intermediates or precursors for the synthesis of nii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidis other active compounds. trae, Planococcus spp., Protopulvinaria pyriformis, Pseu All plants and plant parts can be treated in accordance with daulacaspis pentagona, Pseudococcus spp., Psylla spp., the invention. Plants are to be understood as meaning in the Pteromalus spp., Pyrilla spp., Ouadraspidiotus spp., Oue 55 present context all plants and plant populations such as Sada gigas, RastroCOccus spp., Rhopalosiphum spp., Saisse desired and undesired wild plants or crop plants (including tia spp., Scaphoides titanus, Schizaphis graminum, Selena naturally occurring crop plants). Crop plants can be plants spidus articulatus, Sogata spp., Sogatella fircifera, which can be obtained by conventional plant breeding and Sogatodes spp., Stictocephala festina, Tenalaphara malayen optimization methods or by biotechnological and genetic sis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., 60 engineering methods or by combinations of these methods, Trialeurodes vaporariorum, Trioza spp., Tiphlocyba spp., including the transgenic plants and including the plant culti Unaspis spp., Viteus vitifolii. vars protectable or not protectable by plant breeders’ rights. From the order of the Hymenoptera, for example, Diprion Plant parts are to be understood as meaning all parts and spp., Hoplocampa spp., Lasius spp., Monomorium phara organs of plants above and below the ground, such as shoot, Onis, Vespa spp. 65 leaf flower and root, examples which may be mentioned From the order of the Isopoda, for example, Armadillidium being leaves, needles, stalks, stems, flowers, fruit bodies, vulgare, Oniscus asellus, Porcellio scaber. fruits, seeds, roots, tubers and rhizomes. The plant parts also US 8,629,084 B2 101 102 include harvested material, and vegetative and generative The formulations generally comprise between 0.1 and 95% propagation material, for example cuttings, tubers, rhizomes, by weight of active compound, preferably between 0.5 and offshoots and seeds. 90%. Treatment according to the invention of the plants and plant The active compound/active compound combinations parts with the active compounds/active compound combina according to the invention can be present in their commer tions is carried out directly or by allowing the compounds to cially available formulations, as well as in the use forms act on their Surroundings, habitat or storage space by the prepared from these formulations, in a mixture with other customary treatment methods, for example by immersion, active compounds such as insecticides, attractants, sterilizers, spraying, evaporation, fogging, Scattering, painting on, injec bactericides, acaricides, nematicides, fungicides, growth 10 regulating Substances, herbicides, Safeners, fertilizers or tion and, in the case of propagation material, in particular in semiochemicals. the case of seeds, also by applying one or more coats. Compounds which are Suitable as mixing partners are, for The active compounds/active compound combinations can example, the following: be converted to the customary formulations, such as solu Fungicides: tions, emulsions, wettable powders, water- and oil-based Sus 15 2-phenylphenol; 8-hydroxyquinoline Sulfate; acilbenzolar pensions, powders, dusts, pastes, soluble powders, soluble S-methyl; aldimorph; amidoflumet, ampropylfos; ampropy granules, granules for broadcasting, Suspension-emulsion lfos-potassium; andoprim; anilazine; azaconazole; aZOX concentrates, natural materials impregnated with active com ystrobin; benalaxyl; benodanil; benomyl; benthiavalicarb pound, synthetic materials impregnated with active com isopropyl; benzamacril; benZamacril-isobutyl; bilanafos; pound, fertilizers and microencapsulations in polymeric Sub binapacryl; biphenyl; bitertanol; blasticidin-S; bromucona Stances. Zole; bupirimate; buthiobate; butylamine; calcium polysul These formulations are produced in a known manner, for fide; capsimycin; captafol; captan; carbendazim; carboxin; example by mixing the active compounds/active compound carpropamid; carvone; chinomethionat, chlobenthiaZone; combinations with extenders, that is liquid solvents and/or chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Solid carriers, optionally with the use of Surfactants, that is 25 cloZylacon; cyaZofamid; cyflufenamid; cymoxanil; cypro emulsifiers and/or dispersants and/or foam-formers. conazole; cyprodinil; cyprofuram; Dagger G; debacarb; If the extender used is water, it is also possible to use dichlofluanid; dichlone; dichlorophen; diclocymet; diclom organic solvents, for example, as auxiliary solvents. Suitable eZine; dicloran; diethofencarb; difenoconazole; diflume liquid solvents are essentially aromatics, such as Xylene, tolu torim; dimethirimol; dimethomorph; dimoxystrobin; dini ene or alkylnaphthalenes, chlorinated aromatics and chlori 30 conazole; diniconazole-M; dinocap: diphenylamine; nated aliphatic hydrocarbons, such as chlorobenzenes, chlo dipyrithione; ditalimfos; dithianon; dodine; draZOXolon; roethylenes or methylene chloride, aliphatic hydrocarbons, edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiaz Such as cyclohexane or paraffins, for example petroleum frac ole; famoxadone; fenamidone; fenapanil; fenarimol; fen tions, mineral and vegetable oils, alcohols, such as butanol or buconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; glycol, as well as their ethers and esters, ketones, such as 35 fenpiclonil; fempropidin; fempropimorph, ferbam; fluaZinam, acetone, methyl ethyl ketone, methyl isobutyl ketone or flubenzimine; fludioxonil; flumetover; flumorph; fluoromide: cyclohexanone, strongly polar solvents, such as dimethyl Sul fluoxastrobin: fluguinconazole; flurprimidol; flusilazole; foxide, and also water. flusulfamide; flutolanil; flutriafol; folpet; fosetyl-A1; fosetyl Suitable solid carriers are: sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; fur for example ammonium salts and ground natural minerals 40 mecyclox, guaZatine; hexachlorobenzene: hexaconazole; Such as kaolins, clays, talc, chalk, quartz, attapulgite, mont hymexazole; imazalil; imibenconazole; iminoctadine triac morillonite ordiatomaceous earth, and ground synthetic min etate; iminoctadine tris(albesilate); iodocarb; ipconazole; erals such as highly disperse silica, alumina and silicates; iprobenfos: iprodione; iprovalicarb; irumamycin; isoprothi Suitable solid carriers for granules are: for example crushed olane; isovaledione; kasugamycin; kresoxim-methyl; manco and fractionated natural rocks such as calcite, marble, pum 45 Zeb; maneb, meferimZone; mepanipyrim, mepronil; metal ice, Sepiolite and dolomite, or else synthetic granules of inor axyl; metalaxyl-M; metconazole; methasulfocarb; ganic and organic meals, and granules of organic material methfuroxam; metiram; metominostrobin: metSulfovax, mil Such as sawdust, coconut shells, maize cobs and tobacco diomycin; myclobutanil; mycloZolin; natamycin; nicobifen; stalks; suitable emulsifiers and/or foam formers are: for nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; example nonionic and anionic emulsifiers such as polyoxy 50 orysastrobin, oxadixyl; oXolinic acid; Oxpoconazole; oxycar ethylene fatty acid esters, polyoxyethylene fatty alcohol boxin; oxyfenthiin, paclobutrazole; pefurazoate; pencona ethers, for example alkylaryl polyglycol ethers, alkylsulpho Zole; pencycuron; phosdiphen; phthalide, picoxystrobin; pip nates, alkylsulfates, arylsulfonates, or else protein hydrolyZ eralin, polyoxins; polyoxorim, probenazole; prochloraZ; ates; Suitable dispersants are: for example lignoSulfite waste procymidone; propamocarb; propanosine-sodium; propi liquors and methylcellulose. 55 conazole; propineb; produinazid; prothioconazole; pyraclos Tackifiers such as carboxymethylcellulose and natural and trobin; pyrazophos; pyrifenox, pyrimethanil; pyroquilon; synthetic polymers in the form of powders, granules or lati pyroxyfur, pyrrollenitrine; quinconazole; quinoxyfen, quin ces, such as gum arabic, polyvinyl alcohol and polyvinyl toZene; Simeconazole; spiroxamine; Sulfur, tebuconazole; acetate, or else natural phospholipids such as cephalins and tecloftalam, tecnaZene; tetcyclacis; tetraconazole; thiabenda lecithins and synthetic phospholipids can be used in the for 60 Zole; thicyofen; thifluzamide; thiophanate-methyl; thiram; mulations. Other additives can be mineral and vegetable oils. tioxymid; tolclofos-methyl; tolylfluanid; triadimefon: triadi It is possible to use colorants such as inorganic pigments, menol; triazbutil; triazoxide; tricyclamide: tricyclazole; tri for example iron oxide, titanium oxide and Prussian blue, and demorph; trifloxystrobin; triflumizole; triforine; triticona organic colorants such as alizarin colorants, azo colorants and Zole; uniconazole; validamycin A; VincloZolin; Zineb., Ziram; metal phthalocyanine colorants, and trace nutrients such as 65 Zoxamide; (2S)-N-2-4-3-(4-chlorophenyl)-2-propynyl salts of iron, manganese, boron, copper, cobalt, molybdenum oxy-3-methoxyphenylethyl-3-methyl-2-(methylsulfo and zinc. nyl)aminobutanamide: 1-(1-naphthalenyl)-1H-pyrrole-2,5- US 8,629,084 B2 103 104 dione; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine: propathrin, fenpyrithrin, fenvalerate, flubrocythrinate, 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide: flucythrinate, flufenprox, flumethrin, fluvalinate, 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3- fubfenproX, gamma-cyhalothrin, imiprothrin, kade pyridinecarboxamide: 3,4,5-trichloro-2,6-pyridinedicarbo thrin, lambda-cyhalothrin, metofluthrin, permethrin nitrile; actinovate; cis-1-(4-chlorophenyl)-2-(1H-1,2,4-tria (cis-, trans-), phenothrin (1R trans-isomer), prallethrin, Zol-1-yl)cycloheptanol: methyl 1-(2,3-dihydro-2,2- profluthrin, protrifenbute, pyresmethrin, resmethrin, RU dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate: 15525, silafluofen, tau-fluvalinate, tefluthrin, teral monopotassium carbonate, N-(6-methoxy-3-pyridinyl)cy lethrin, tetramethrin (1R isomer), tralomethrin, trans clopropanecarboxamide: N-butyl-8-(1,1-dimethylethyl)-1- fluthrin, ZXI 8901, pyrethrins (pyrethrum) oxaspiro4.5 decane-3-amine; sodium tetrathiocarbonate; 10 DDT and copper salts and preparations, such as Bordeaux mixture; 2.2 Oxadiazines, copper hydroxide; copper naphthenate; copper oxychloride; for example indoxacarb copper Sulfate; cufraneb, cuprous oxide; mancopper, OXine Acetylcholine receptor agonists/antagonists copper. 3.1 Chloronicotinyls, Bactericides: 15 for example acetamiprid, clothianidin, dinotefuran, imida bronopol, dichlorophen, nitrapyrin, nickel dimethyldithio cloprid, nitenpyram, nithiazine, thiacloprid, thia carbamate, kasugamycin, octhillinone, furancarboxylic acid, methoxam oxytetracyclin, probenazole, streptomycin, tecloftalam, cop 3.2 Nicotine, bensultap, cartap per Sulfate and other copper preparations. Acetylcholine receptor modulators Insecticides/Acaricides/Nematicides: 4.1 Spinosyns, 1. Acetylcholine esterase(AChE) inhibitors for example spinosad 1.1 Carbamates, GABA-gated chloride channel antagonists for example alanycarb, aldicarb, aldoxycarb, allyxycarb, 5.1 Cyclodiene organochlorines, aminocarb, bendiocarb, benfuracarb, bufencarb, butac for example camphechlor, chlordane, endosulfan, gamma arb, butocarboxim, butoxycarboxim, carbaryl, carbofu 25 HCH, HCH, heptachlor, lindane, methoxychlor ran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, 5.2 Fiproles, fenobucarb, fenothiocarb, formetanate, furathiocarb, for example acetoprole, ethiprole, fipronil, pyrafluprole, isoprocarb, metam-Sodium, methiocarb, methomyl, pyripole, Vaniliprole metolcarb, oxamyl, pirimicarb, promecarb, propoXur, Chloride channel activators thiodicarb, thiofanox, trimethacarb. XMC, xylylcarb, 30 6.1 Mectins, triazamate for example avermectin, emamectin, emamectin benzoate, 1.2 Organophosphates, ivermectin, milbemycin for example acephate, azamethiphos, azinphos (-methyl, Juvenile hormone mimetics, -ethyl), bromophos-ethyl, brom-fenvinfos (-methyl), for example diofenolan, epolfenonane, fenoxycarb, hydro butathiofos, cadusafos, carbophenothion, chlorethoxy 35 prene, kinoprene, methoprene, pyriproxifen, triprene fos, chlorfenvinphos, chlormephos, chlorpyrifos (-me Ecdyson agonists/disruptors thyl/-ethyl), coumaphos, cyanofenphos, cyanophos, 8.1 Diacylhydrazines, chlorfenvinphos, demeton-S-methyl, demeton-S-me for example chromafenozide, halofenozide, methoxy thyl sulfone, dialifos, diazinon, dichlofenthion, dichlo fenozide, tebufenozide rvos/DDVP. dicrotophos, dimethoate, dimethylvinphos, 40 Chitin biosynthesis inhibitors dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, 9.1 Benzoylureas, etrimfos, famphur, fenamiphos, fenitrothion, fensul for example bistrifluron, chlofluaZuron, diflubenzuron, fothion, fenthion, flupyrazofos, fonofos, formothion, fluaZuron, flucycloXuron, flufenoXuron, hexaflumuron, foSmethilan, fosthiazate, heptenophos, iodofenphos, lufenuron, novaluron, noviflumuron, penfluron, iprobenfos, isazofos, isofenphos, isopropyl O-Salicy 45 teflubenzuron, triflumuron late, isoxathion, malathion, mecarbam, methacrifos, 9.2 Buprofezin methamidophos, methi-dathion, mevinphos, monocro 9.3 Cyromazine tophos, naled, omethoate, oxydemeton-methyl, par Oxidative phosphorylation inhibitors, ATP disruptors athion (-methyl/-ethyl), phenthoate, phorate, phosalone, 10.1 Diafenthiuron phosmet, phosphamidon, phosphocarb, phoxim, pirimi 50 10.2 Organotins, phos (-methyl/-ethyl), profenofos, propaphos, pro for example azocyclotin, cyhexatin, fenbutatin oxide petamphos, prothiofos, prothoate, pyraclofos, Oxidative phosphorylation decouplers acting by interrupt pyridaphenthion, pyridathion, quinalphos, Sebufos, Sul ing the H-proton gradient fotep, Sulprofos, tebupirimfos, temephos, terbufos, tet 11.1 Pyrroles, rachlorvinphos, thiometon, triazophos, triclorfon, Vami 55 for example chlorfenapyr dothion 11.2 Dinitrophenols, 2. Sodium channel modulators/voltage-gated Sodium for example binapacyrl, dinobuton, dinocap, DNOC channel blockers Page-I electron transport inhibitors 2.1 Pyrethroids, 12.1 METIs, for example acrinathrin, allethrin (d-cis-trans, d-trans), 60 for example fenaZaquin, fenpyroximate, pyrimidifen, beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S pyridaben, tebufenpyrad, tolfenpyrad cyclopentyl isomer, bioethanomethrin, biopermethrin, 12.2 Hydramethylnone bioresmethrin, chlovaporthrin, cis-cypermethrin, cis 12.3 Dicofol resmethrin, cis-permethrin, clocythrin, cycloprothrin, Page-II electron transport inhibitors cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, 65 Rotenone theta-, Zeta-), cyphenothrin, deltamethrin, empenthrin Page-III electron transport inhibitors (IR isomer), esfenvalerate, etofemprox, fenfluthrin, fen Acequinocyl, fluacrypyrim US 8,629,084 B2 105 106 Microbial disruptors of the insect gut membrane the use forms can be from 0.00000001 up to 95% by weight of Bacillus thuringiensis strains active compound and is preferably between 0.00001 and 1% Fat synthesis inhibitors by weight. tetronic acids, Application is in a customary manner adapted to Suit the for example spirodiclofen, spiromesi?en use forms. tetramic acids, As already mentioned above, it is possible to treat all plants for example spirotetramat (CAS Reg. No.: 203313-25-1) and their parts inaccordance with the invention. In a preferred and 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-aza embodiment, wild plant species or plant varieties and plant spiro4.5 dec-3-en-4-yl ethyl carbonate (also known as: cultivars which have been obtained by traditional biological carbonic acid, 3-(2,5-dimethylphenyl)-8-methoxy-2- 10 breeding methods, such as hybridization or protoplast fusion, and the parts of these varieties and cultivars are treated. In a oxo-1-azaspiro4.5 dec-3-en-4-yl ethyl ester, CAS Reg. further preferred embodiment, transgenic plants and plant No.: 382608-10-8) cultivars which have been obtained by recombinant methods, carboxamides, if appropriate in combination with conventional methods (ge for example flonicamid 15 netically modified organisms), and their parts are treated. The Octopaminergic agonists, term “parts” or “parts of plants' or “plant parts” has been for example amitraz explained above. Inhibitors of magnesium-stimulated ATPase, Plants which are treated particularly preferably in accor propargite dance with the invention are those of the plant cultivars which benzoic acid dicarboxamides, are in each case commercially available or in use. Plant cul for example flubendiamides tivars are understood as meaning plants with new traits which nereistoxin analogs have been bred either by conventional breeding, by mutagen for example thiocyclam hydrogen oxalate, thiosultap-so esis or by recombinant DNA techniques. They may take the dium form of cultivars, biotypes and genotypes. Biologicals, hormones or pheromones 25 Depending on the plant species or plant cultivars, their azadirachtin, Bacillus spec. Beauveria spec., codilemone, location and growth conditions (soils, climate, vegetation Metarrhizium spec. period, nutrition), the treatment according to the invention Paecilomyces spec., thuringiensin, Verticillium spec. may also result in superadditive (“synergistic) effects. Thus, Active compounds with unknown or unspecific mecha for example, reduced application rates and/or a widened nisms of action 30 activity spectrum and/or an increase in the activity of the 23.1 Fumigants, Substances and compositions which can be used in accor for example aluminum phosphide, methyl bromide, sulfu dance with the invention, better plant growth, increased tol ryl fluoride erance to high or low temperatures, increased tolerance to 23.2 Antifeedants, drought or to Salinity in the water or soil, increased flowering for example cryolite, flonicamid, pymetrozine 35 performance, facilitated harvesting, accelerated maturation, 23.3 Mite growth inhibitors, higher yields, higher quality and/or better nutritional value of for example clofentezine, etoxazole, hexythiazox the harvested products, better storage characteristics and/or 23.4 Amidoflumet, benclothiaz, benzoximate, bifenazate, processability of the harvested products are possible which bromopropylate, buprofezin, chinomethionat, chlo exceed the effects which were actually to be expected. rdimeform, chlorobenzilate, chloropicrin, clothiazoben, 40 The preferred transgenic plants or plant cultivars (those cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fen obtained by recombinant methods) to be treated in accor trifanil, flubenzimine, flufenerim, flutenZin, gossyplure, dance with the invention include all those plants which, hydramethylnone, japonilure, metoxadiaZone, petro owing to the process of recombinant modification, were given leum, piperonyl butoxide, potassium oleate, pyridalyl, genetic material which confers particular, advantageous, sulfluramid, tetradifon, tetrasul, triarathene, verbutin 45 valuable traits to these plants. Examples of Such properties A mixture with other known active compounds, Such as are better plant growth, increased tolerance to high or low herbicides, fertilizers, growth regulators, Safeners, semio temperatures, increased tolerance to drought or to Salinity in chemicals, or else with agents which improve plant properties the water or soil, increased flowering performance, facilitated is also possible. harvesting, accelerated maturation, higher harvest yields, When used as insecticides in their commercially available 50 higher quality and/or higher nutritional value of the harvested formulations and in the use forms prepared from these for products, better storage characteristics and/or better process mulations, the active compounds/active compound combina ability of the harvested products. Further examples of such tions according to the invention can furthermore be present in traits, examples which must be mentioned especially, are the form of a mixture with Synergists. Synergists are com better defense of the plants against animal and microbial pounds by which the activity of the active compounds is 55 pests, such as against insects, mites, phytopathogenic fungi, increased without it being necessary for the synergist added to bacteria and/or viruses and an increased tolerance of the be active itself. plants to certain herbicidal active compounds. Examples of When used as insecticides in their commercially available transgenic plants which may be mentioned are the important formulations and in the use forms prepared from these for crop plants, such as cereals (wheat, rice), maize, soybeans, mulations, the active compounds/active compound combina 60 potato, Sugar beet, tomatoes, peas and other vegetable variet tions according to the invention can furthermore be present in ies, cotton, tobacco, oilseed rape and fruit plants (with the the form of mixtures with inhibitors which reduce the degra fruits apples, pears, citrus fruits and grapes), with particular dation of the active compound after application in the habitat emphasis on maize, soybeans, potatoes, cotton, tobacco, and of the plant, on the Surface of parts of plants or in plant tissues. oilseed rape. Traits which are especially emphasized are the The active compound content of the use forms prepared 65 increased defense of the plants against insects, arachnids, from the commercially available formulations can vary nematodes and slugs and Snails, owing to toxins being formed within wide ranges. The active compound concentration of in the plants, in particular toxins which are generated in the US 8,629,084 B2 107 108 plants by the genetic material of Bacillus thuringiensis (for somyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus example by the genes CryIA(a), CryIA(b), CryIA(c), Cry IIA, spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and Lipoptena spp. and Mellophagus spp. their combinations (hereinbelow “Bt plants'). Other traits From the order of the Siphonapterida, for example, Pulex which are particularly emphasized are the increased defense spp., Ctenocephalides spp., Xenopyslla spp. and Ceratophyl of plants against fungi, bacteria and viruses by the systemic lus spp. acquired resistance (SAR), systemins, phytoalexins, elicitors From the order of the Heteropterida, for example, Cimex and resistance genes and correspondingly expressed proteins spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp. and toxins. Other traits which are especially emphasized are From the order of the Blattarida, for example, Blatta ori the increased tolerance of the plants to certain herbicidal 10 active compounds, for example imidazolinones, Sulfony entalis, Periplaneta americana, Blattela germanica and lureas, glyphosate or phosphinotricin (for example “PAT” Supella spp. gene). The genes which confer the desired traits in each case From the sub-class of the Acari (Acarina) and the orders of may also be present in the transgenic plants in combination the Meta- and Mesostigmata, for example, Argas spp., Orni with one another. Examples of “Bt plants' which may be 15 thodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., mentioned are maize cultivars, cotton cultivars, soybean cul Boophilus spp., Dermacentor spp., Haemophysalis spp., tivars and potato cultivars which are commercially available Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., under the trade names YIELD GARDR) (for example maize, Raillietia spp., Pneumonyssus spp., Sternostoma spp. and cotton, soybeans), KnockCut(R) (for example maize), Star Varroa spp. Link R. (for example maize), Boligard(R) (cotton), Nucotnr) From the order of the Actinedida (Prostigmata) and Acari (cotton) and New LeafR (potato). Examples of herbicide dida (Astigmata), for example, Acarapis spp., Cheyletiella tolerant plants which may be mentioned are maize cultivars, spp., OrnithOcheyletia spp., Myobia spp., Psorergates spp., cotton cultivars and Soybean cultivars which are commer Demodex spp., Trombicula spp., Listrophorus spp., Acarus cially available under the trade names Roundup Ready(R) (tol spp., Trophagus spp., Caloglyphus spp., Hypodectes spp., erance to glyphosate, for example maize, cotton, Soybeans), 25 Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes Liberty LinkR) (tolerance to phosphinotricin, for example spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., oilseed rape), IMIR (tolerance to imidazolinones) and STS(R) Cytodites spp. and Laminosioptes spp. (tolerance to sulfonylureas, for example maize). Herbicide The active compounds/active compound combinations of resistant plants (plants bred in a conventional manner for the formula (I) according to the invention are also suitable for herbicide tolerance) which may be mentioned also include 30 controlling arthropods which attack agricultural livestock, the varieties commercially available under the name Such as, for example, cattle, sheep, goats, horses, pigs, don Clearfield(R) (for example maize). Naturally, these statements keys, camels, buffaloes, rabbits, chickens, turkeys, ducks, also apply to plant cultivars having these genetic traits or geese, honeybees, other domestic animals, such as, for genetic traits still to be developed, which plant cultivars will example, dogs, cats, cage birds, aquarium fish, and so-called be developed and/or marketed in the future. 35 experimental animals, such as, for example, hamsters, The plants listed can be treated particularly advanta guinea-pigs, rats and mice. By combating these arthropods, it geously according to the invention with the compounds of the is intended to reduce deaths and decreased performances (in general formula I or the active compound mixtures according meat, milk, wool, hides, eggs, honey and the like), so that to the invention. The preferred ranges stated above for the more economical and simpler animal keeping is made pos active compounds and mixtures also apply to the treatment of 40 sible by using the active compounds according to the inven these plants. Particular emphasis may be given to the treat tion. ment of plants with the compounds or mixtures specifically In the Veterinary sector, the active compounds/active com mentioned in the present text. pound combinations according to the invention are used in a The active compounds/active compound combinations known manner by enteral administration, for example in the according to the invention are not only active against plant, 45 form of tablets, capsules, drinks, drenches, granules, pastes, hygiene and stored-product pests, but also, in the veterinary boli, the feed-through method, Suppositories, by parenteral medicine sector, against animal parasites (ectoparasites and administration, Such as, for example, by means of injections endoparasites). Such as ixodid ticks, argasid ticks, scab mites, (intramuscular, Subcutaneous, intravenous, intraperitoneal trombiculid mites, flies (stinging and Sucking), parasitic fly and the like), implants, by nasal application, by dermal larvae, lice, hair lice, bird lice and fleas. These parasites 50 administration, for example in the form of dipping or bathing, include: spraying, pouring-on and spotting-on, Washing, dusting, and From the order of the Anoplurida, for example, Hae with the aid of shaped articles which comprise active com matopinus spp., Linognathus spp., Pediculus spp., Phtirus pound, Such as collars, ear tags, tail marks, limb bands, hal spp., Solenopotes spp. ters, marking devices and the like. From the order of the Mallophagida and the sub-orders 55 When administered to livestock, poultry, domestic animals Amblycerina and Ischnocerina, for example, Trimenopon and the like, the active compounds of the formula (D can be spp., Menopon spp., Trinoton spp., Bovicola spp., Werneck used as formulations (for example powders, emulsions, flow iella spp., Lepikentron spp., Damalina spp., Trichodectes ables) which comprise the active compounds in an amount of spp., Felicola spp. 1 to 80% by weight, either directly or after dilution by a factor From the order of the Diptera and the sub-orders Nemato 60 of 100 to 10000, or they may be used in the form of a chemical cerina and Brachycerina, for example, Aedes spp., Anopheles bath. spp., Culex spp., Simulium spp., Eusimulium spp., Phleboto Furthermore, it has been found that the compounds/active mus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., compound combinations according to the invention have a Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota potent insecticidal action against insects which destroy indus spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea 65 trial materials. spp., Stomoxys spp., Haematobia spp., Morelia spp., Fannia The following insects may be mentioned by way of spp., Glossina spp., Caliphora spp., Lucilia spp., Chry example and as being preferred, but without any limitation: US 8,629,084 B2 109 110 Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Substances which are advantageously used are mineral oils Anobium punctatum, Xestobium rufovillosum, Ptilinus pecti with a boiling range of 170 to 220° C., white spirit with a cornis, Dendrobium pertinex, Ernobius mollis, Priobium car boiling range of 170 to 220° C., spindle oil with a boiling pini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, range of 250 to 350° C., petroleum or aromatics of boiling Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Mint range 160 to 280°C., essence of turpentine and the like. hes rugicollis, Xvleborus spec. Tryptodendron spec. Apate In a preferred embodiment, liquid aliphatic hydrocarbons monachus, Bostrychus capucins, Heterobostrychus brun with a boiling range of 180 to 210°C. or high-boiling mix neus, Sinoxylon spec. Dinoderus minutus, tures of aromatic and aliphatic hydrocarbons with a boiling Dermapterans, such as Sirex juvencus, Urocerus gigas, range of 180 to 220° C. and/or spindle oil and/or monochlo Urocerus gigas taignus, Urocerus augur, 10 ronaphthalene, preferably o-monochloronaphthalene, are Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reti used. culitermes Santonensis, Reticulitermes lucifigus, Mastoter The organic oily or oil-type solvents of low volatility hav mes darwiniensis, Zootermopsis nevadensis, Coptotermes ing an evaporation number of above 35 and a flash point of formosanus, 15 above 30° C., preferably above 45° C. can be partially Bristletails, such as Lepisma saccharina. replaced by organochemical Solvents of high or medium Vola Industrial materials are to be understood as meaning, in the tility, with the proviso that the solvent mixture also has an present context, non-live materials, such as, preferably, Syn evaporation number of above 35 and a flashpoint of above 30° thetic materials, glues, sizes, paper and board, leather, wood C., preferably above 45°C., and that the insecticide/fungicide and timber products, and paint. mixture is soluble or emulsifiable in this solvent mixture. The materials to be very particularly preferably protected In a preferred embodiment, part of the organochemical against attack by insects are wood and timber products. Solvent or solvent mixture oran aliphatic polar organochemi Wood and timber products which can be protected by the cal solvent or solvent mixture is replaced. Substances which composition according to the invention or mixtures compris are preferably used are aliphatic organochemical solvents ing Such a composition are to be understood as meaning, for 25 having hydroxyl and/or ester and/or ether groups, such as, for example: example, glycol ethers, esters and the like. construction timber, wooden beams, railway sleepers, The organochemical binders used within the scope of the bridge components, jetties, wooden vehicles, boxes, pallets, present invention are the synthetic resins and/or binding dry containers, telephone poles, wood cladding, windows and ing oils which are known perse and can be diluted with water doors made of wood, plywood, particle board, joiner's 30 and/or are soluble or dispersible or emulsifiable in the orga articles, or wood products which, quite generally, are used in nochemical solvents employed, in particular binders com the construction of houses or in joinery. posed of, or comprising, an acrylate resin, a vinyl resin, for The active compounds can be used as such, in the form of example polyvinyl acetate, polyester resin, polycondensation concentrates or generally customary formulations, such as or polyaddition resin, polyurethane resin, alkyd resin or powders, granules, Solutions, Suspensions, emulsions or 35 modified alkyd resin, phenol resin, hydrocarbon resin, Such as pastes. indene/cumarone resin, silicone resin, drying vegetable and/ The formulations mentioned can be prepared in a manner or drying oils and/or physically drying binders based on a known per se, for example by mixing the active compounds natural and/or synthetic resin. with at least one solvent or diluent, emulsifier, dispersant The synthetic resin used as the binder can be employed in and/or binder or fixative, water repellent, if appropriate des 40 the form of an emulsion, dispersion or solution. Up to 10% by iccants and UV stabilizers and, if appropriate, colorants and weight of bitumen orbituminous Substances can also be used pigments and other processing auxiliaries. as binders. In addition, colorants, pigments, water repellents, The insecticidal compositions or concentrates used for the odor-masking Substances and inhibitors or anticorrosives protection of wood and wooden materials comprise the active known perse and the like can also be employed. compound according to the invention in a concentration of 45 The composition or the concentrate preferably comprises, 0.0001 to 95% by weight, in particular 0.001 to 60% by in accordance with the invention, at least one alkyd resin or weight. modified alkyd resin and/or a drying vegetable oil as the The amount of the compositions or concentrates employed organochemical binder. Preferably used according to the depends on the species and the occurrence of the insects and invention are alkyd resins with an oil content of over 45% by on the medium. The optimum rate of application can be 50 weight, preferably 50 to 68% by weight. determined upon use in each case by a test series. However, in All or some of the abovementioned binder can be replaced general, it suffices to employ 0.0001 to 20% by weight, pref by a fixative (mixture) or a plasticizer (mixture). These addi erably 0.001 to 10% by weight, of the active compound, based tives are intended to prevent volatilization of the active com on the material to be protected. pounds and crystallization or precipitation. They preferably The solvent and/or diluent used is an organochemical Sol 55 replace 0.01 to 30% of the binder (based on 100% of binder vent or solvent mixture and/or an oily or oil-type orga employed). nochemical solvent or solvent mixture of low volatility and/or The plasticizers are from the chemical classes of the a polar organochemical solvent or solvent mixture and/or phthalic esters, such as dibutyl phthalate, dioctyl phthalate or water and, if appropriate, an emulsifier and/or wetting agent. benzylbutyl phthalate, the phosphoric esters, such as tributyl Organochemical solvents which are preferably employed 60 phosphate, the adipicesters, such as di(2-ethylhexyl) adipate, are oily or oil-type solvents having an evaporation number of the Stearates. Such as butyl Stearate or amyl Stearate, the above 35 and a flash point of above 30°C., preferably above oleates, such as butyl oleate, the glycerol ethers or relatively 45° C. Substances which are used as such oily and oil-type high molecular weight glycol ethers, glycerol esters and solvents which have low volatility and are insoluble in water p-toluenesulfonic esters. are Suitable mineral oils or their aromatic fractions, or min 65 Fixatives are chemically based on polyvinyl alkyl ethers, eral-oil-containing solvent mixtures, preferably white spirit, Such as, for example, polyvinyl methyl ether, or ketones. Such petroleum and/or alkylbenzene. as benzophenone or ethylenebenZophenone. US 8,629,084 B2 111 112 Particularly suitable as a solvent or diluent is also water, if algicides such as appropriate as a mixture with one or more of the abovemen 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1.3, tioned organochemical solvents or diluents, emulsifiers and 5-triazine, dichlorophen, diuron, endothal, fentinacetate, iso dispersants. proturon, methabenzthiaZuron, oxyfluorfen, quinoclamine and terbutryn; Particularly effective protection of wood is achieved by fungicides Such as large-scale industrial impregnation processes, for example benzobthiophenecarboxylic acid cyclohexylamide S.S.- vacuum, double-vacuum or pressure processes. dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynylbutyl If appropriate, the ready-to-use compositions can addition carbamate, tolylfluanid and azoles Such as ally comprise other insecticides and, if appropriate, addition aZaconazole, cyproconazole, epoxyconazole, hexacona ally one or more fungicides. 10 Zole, metconazole, propiconazole and tebuconazole; Suitable additional components which may be admixed molluscicides Such as are, preferably, the insecticides and fungicides mentioned in fentin acetate, metaldehyde, methiocarb, niclosamid, WO 94/29268. The compounds mentioned in that document thiodicarb and trimethacarb, Fechelates; are expressly part of the present application. or conventional antifouling active compounds such as 15 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodometh Very particularly preferred components which may be ylparatryl sulfone, 2-(N,N-dimethyl-thiocarbamoylthio)-5- admixed are insecticides, such as chlorpyriphos, phoxim, nitrothiaZyl, potassium, copper, Sodium and Zinc salts of Silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta 2-pyridinethiol methrin, permethrin, imidacloprid, NI-25, flufenoxuron, 1-oxide, pyridine-triphenylborane, tetrabutyldistannox hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxid, ane, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine, 2.4.5, triflumuron, chlothianidin, spinosad, tefluthrin, 6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and fungicides, such as epoxyconazole, hexaconazole, and 2,4,6-trichlorophenylmaleimide. aZaconazole, propiconazole, tebuconazole, cyproconazole, The antifouling compositions used comprise the active metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2- compound according to the invention of the compounds propynyl butylcarbamate, N-octyl-isothiazolin-3-one and 25 according to the invention in a concentration of 0.001 to 50% 4,5-dichloro-N-octylisothiazolin-3-one. by weight, in particular 0.01 to 20% by weight. The compounds according to the invention can at the same Moreover, the antifouling compositions according to the time be employed for protecting objects which come into invention comprise the customary components such as, for contact with saltwater or brackish water, in particular hulls, example, those described in Ungerer, Chem. Ind. 1985, 37, Screens, nets, buildings, moorings and signaling Systems, 30 730–732 and Williams, Antifouling Marine Coatings, Noyes, against fouling. Park Ridge, 1973. Fouling by sessile Oligochaeta, such as Serpulidae, and by Besides the algicidal, fungicidal, molluscicidal active shells and species from the Ledamorpha group (goose bar compounds and insecticidal active compounds according to nacles). Such as various Lepas and Scalpellum species, or by the invention, antifouling paints comprise, in particular, bind species from the Balanomorpha group (acorn barnacles), 35 CS. Such as Balanus or Policipes species, increases the frictional Examples of recognized binders are polyvinyl chloride in a drag of ships and, as a consequence, leads to a marked Solvent system, chlorinated rubber in a solvent system, increase in operation costs owing to higher energy consump acrylic resins in a solvent system, in particular in an aqueous tion and additionally frequent residence in the dry dock. system, vinyl chloride/vinyl acetate copolymer systems in the Apart from fouling by algae, for example Ectocarpus sp. 40 form of aqueous dispersions or in the form of organic solvent and Ceramium sp., fouling by sessile Entomostraka groups, systems, butadiene/styrenefacrylonitrile rubbers, drying oils which come under the generic term Cirripedia (cirriped crus Such as linseed oil, resin esters or modified hardened resins in taceans), is of particular importance. combination with tar or bitumens, asphalt and epoxy com Surprisingly, it has now been found that the compounds pounds, Small amounts of chlorine rubber, chlorinated according to the invention, alone or in combination with other 45 polypropylene and vinyl resins. active compounds, have an outstanding antifouling action. If appropriate, paints also comprise inorganic pigments, Using the compounds according to the invention, alone or organic pigments or colorants which are preferably insoluble in combination with other active compounds, allows the use in saltwater. Paints may furthermore comprise materials such of heavy metals such as, for example, in bis(trialkyltin) Sul as rosin to allow controlled release of the active compounds. fides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) 50 Furthermore, the paints may comprise plasticizers, modifiers oxide, triethyltin chloride, tri-n-butyl-(2-phenyl-4-chlo which affect the rheological properties and other conven rophenoxy)tin, tributyltin oxide, molybdenum disulfide, anti tional constituents. The compounds according to the inven mony oxide, polymeric butyl titanate, phenyl(bispyridine) tion or the abovementioned mixtures may also be incorpo bismuth chloride, tri-n-butyltin fluoride, manganese rated into self-polishing antifouling systems. ethylenebisthiocarbamate, Zinc dimethyldithiocarbamate, 55 The active compounds are also Suitable for controlling Zinc ethylenebisthiocarbamate, Zinc salts and copper salts of animal pests, in particular insects, arachnids and mites, which 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc are found in enclosed spaces such as, for example, dwellings, ethylenebisthiocarbamate, zinc oxide, copper(I) ethylenebi factory halls, offices, vehicle cabins and the like. They can be Sdithiocarbamate, copper thiocyanate, copper naphthenate employed in domestic insecticide products for controlling and tributyltinhalides to be dispensed with, or the concentra 60 these pests alone or in combination with other active com tion of these compounds to be substantially reduced. pounds and auxiliaries. They are active against sensitive and If appropriate, the ready-to-use antifouling paints can addi resistant species and against all development stages. These tionally comprise other active compounds, preferably algi pests include: cides, fungicides, herbicides, molluscicides, or other anti From the order of the Scorpionidea, for example, Buthus fouling active compounds. 65 OCCitanus. Preferably suitable components in combination with the From the order of the Acarina, for example, Argas persicus, antifouling compositions according to the invention are: Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyci US 8,629,084 B2 113 114 phagus domesticus, Ornithodorus moubat, Rhipicephalus gel and membrane evaporators, propeller-driven evaporators, sanguineus, Trombicula alfreddugesi, Neutrombicula autum energy-free, or passive, evaporation systems, moth papers, nalis, Dermatophagoides pteronissimus, Dermatophagoides moth bags and moth gels, as granules or dusts, in baits for forinae. spreading or in bait stations. From the order of the Araneae, for example, Aviculariidae, The active compounds/active compound combinations Araneidae. according to the invention can also be used as defoliants, From the order of the Opiliones, for example, Pseudoscor desiccants, haulm killers and, in particular, as weed killers. piones chelifer, Pseudoscorpiones cheiridium, Opiliones Weeds in the broadest sense are understood as meaning all phalangium. plants which grow at locations where they are undesired. From the order of the Isopoda, for example, Oniscus asel 10 lus, Porcellio Scaber: Whether the substances according to the invention act as From the order of the Diplopoda, for example, Blaniulus nonselective or selective herbicides depends essentially on guttulatus, Polydesmus spp. the application rate. From the order of the Chilopoda, for example, Geophilus The active compounds/active compound combinations spp. 15 according to the invention can be used, for example, in the From the order of the Zygentoma, for example, Ctenolepi following plants: Sma spp., Lepisma Saccharina, Lepismodes inquilinus. Dicotyledonous weeds of the genera: Abutilon, Amaran From the order of the Blattaria, for example, Blatta orien thus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, tallies, Blattella germanica, Blattella asahinai, Leucophaea Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopo maderae, Panchlora spp., Parcoblatta spp., Periplaneta aus dium, Cirsium, Convolvulus, Datura, Desmodium, Emex, tralasiae, Periplaneta americana, Periplaneta brunnea, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibis Periplaneta fuliginosa, Supella longipalpa. cus, Ipomoea, Kochia, Lamium, Lepidium, Lindemia, Matri From the order of the Saltatoria, for example, Acheta caria, Mentha, Mercurialis, Mulugo, Myosotis, Papaver, domesticus. Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, From the order of the Dermaptera, for example, Forficula 25 Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesba auricularia. nia, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, From the order of the Isoptera, for example, Kalotermes Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, spp., Reticulitermes spp. Xanthium. From the order of the Psocoptera, for example, Lepinatus Dicotyledonous crops of the genera: Arachis, Beta, Bras spp., LipOscelis spp. 30 Sica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, From the order of the Coleptera, for example, Anthrenus Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicoti spp., Attagenus spp., Dermestes spp., Latheticus Oryzae, ana, Phaseolus, Pisum, Solanum, Vicia. Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus Monocotyledonous weeds of the genera: Aegilops, Agro granarius, Sitophilus Oryzae, Sitophilus zeanais, Stegobium pyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bro paniceum. 35 mus, Cenchrus, Commelina, Cynodon, Cyperus, Dactylocte From the order of the Diptera, for example, Aedes aegypti, nium, Digitaria, Echinochloa, Eleocharis, Eleusine, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Caliphora erythrocephala, Chrysozona pluvialis, Culex Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboelia, spp., Fannia canicularis, Musca domestica, Phlebotomus 40 Sagittaria, Scirpus, Setaria, Sorghum. spp., Sarcophaga camaria, Simulium spp., Stomoxys calci Monocotyledonous crops of the genera: Allium, Ananas, trans, Tipula paludosa. Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, From the order of the Lepidoptera, for example, Achroia Secale, Sorghum, Triticale, Triticum, Zea. grisella, Galleria mellonella, Plodia interpunctella, Tinea However, the use of the active compounds/active com cloacella, Tinea pellionella, Tineola bisselliella. 45 pound combinations according to the invention is in no way From the order of the Siphonaptera, for example, Cteno restricted to these genera, but extends in the same manner to cephalides canis, Ctenocephalides felis, Pulex irritans, other plants. Tunga penetrans, Xenopsylla cheopis. Depending on the concentration, the active compounds/ From the order of the Hymenoptera, for example, Cam active compound combinations according to the invention are ponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius 50 suitable for the nonselective weed control on, for example, umbratus, Monomorium pharaonis, Paravespula spp., Tet industrial terrains and railway tracks and on paths and loca ramorium caespitum. tions with and without trees. Likewise the active compounds From the order of the Anoplura, for example, Pediculus according to the invention can be employed for controlling humanus capitis, Pediculus humanus corporis, Phthirus weeds in perennial crops, for example forests, ornamental pubis. 55 tree plantings, orchards, Vineyards, citrus groves, nut From the order of the Heteroptera, for example, Cimex orchards, banana plantations, coffee plantations, tea planta hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma tions, rubber plantations, oil palm plantations, cocoa planta infestans. tions, soft fruit plantations and hop fields, on lawns, turf and They are used in the household insecticides sector alone or pastureland, and for the selective control of weeds in annual in combination with other Suitable active compounds such as 60 CropS. phosphoric esters, carbamates, pyrethroids, neonicotinoids, The compounds of the formula (I)/active compound com growth regulators or active compounds from other known binations according to the invention have strong herbicidal classes of insecticides. activity and a broad activity spectrum when used on the soil They are used in aerosols, pressure-free spray products, for and on aerial plant parts. To a certain extent, they are also example pump and atomizer sprays, automatic fogging sys 65 suitable for the selective control of monocotyledonous and tems, foggers, foams, gels, evaporator products with evapo dicotyledonous weeds in monocotyledonous and dicotyle rator tablets made of cellulose or polymer, liquid evaporators, donous crops, both pre- and post-emergence. US 8,629,084 B2 115 116 At certain concentrations or application rates, the active possible. Mixtures with herbicide products which contain one compounds/active compound combinations according to the or more known herbicides and a safener are hence also pos invention can also be employed for controlling animal pests sible. and fungal or bacterial plant diseases. If appropriate, they can Herbicides which are suitable for the mixtures are known also be used as intermediates or precursors for the synthesis of 5 herbicides, for example other active compounds. acetochlor, acifluorfen (-Sodium), aclonifen, alachlor, The active compounds/active compound combinations can alloxydim (-Sodium), ametryne, amicarbazone, amidochlor, be converted into the customary formulations, such as solu amidosulfuron, aminopyralid, anilofos, asulam, atrazine, tions, emulsions, wettable powders, Suspensions, powders, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), dusting agents, pastes, Soluble powders, granules, Suspo 10 benfuresate, bensulfuron (-methyl), bentazone, bencarba emulsion concentrates, natural and synthetic materials Zone, benzfendizone, benzobicyclon, benzofenap, benzoyl impregnated with active compound, and very fine capsules in prop (-ethyl), bialaphos, bifenox, bispyribac (-Sodium), bro polymeric Substances. mobutide, bromofenoxim, bromoxynil, butachlor, These formulations are produced in a known manner, for butafenacil (-allyl), butroxydim, butylate, cafenstrole, example by mixing the active compounds with extenders, that 15 caloxydim, carbetamide, carfentraZone (-ethyl), chlom is liquid solvents and/or Solid carriers, optionally with the use ethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), of Surfactants, that is emulsifiers and/or dispersants and/or chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), foam-formers. cinmethylin, cinosulfuron, clefoxydim, clethodim, clodin If the extender used is water, it is also possible to use, for afop (-propargyl), clomaZone, clomeprop, clopyralid, clopy example, organic solvents as auxiliary solvents. Suitable liq rasulfuron (-methyl), cloranSulam (-methyl), cumyluron, uid solvents are essentially: aromatics, such as Xylene, tolu cyanazine, cybutryne, cycloate, cycloSulfamuron, cycloxy ene or alkylnaphthalenes, chlorinated aromatics and chlori dim, cyhalofop (-butyl), 2,4-D, 2.4-DB, desmedipham, dial nated aliphatic hydrocarbons, such as chlorobenzenes, late, dicamba, dichlorprop (-P), diclofop (-methyl), diclosu chloroethylenes or methylene chloride, aliphatic hydrocar lam, diethatyl (-ethyl), difenZoquat, diflufenican, bons, such as cyclohexane or paraffins, for example petro 25 diflufenZopyr, dimefuron, dimepiperate, dimethachlor, leum fractions, mineral and vegetable oils, alcohols, such as dimethametryn, dimethenamid, dimexyflam, dinitramine, butanol or glycol, and also their ethers and esters, ketones, diphenamid, diduat, dithiopyr, diuron, dymron, epropodan, Such as acetone, methyl ethyl ketone, methyl isobutyl ketone EPTC, esprocarb, ethal fluralin, ethametsulfuron (-methyl), or cyclohexanone, strongly polar solvents, such as dimethyl ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, formamide and dimethyl sulfoxide, and also water. 30 fenoxaprop (-P-ethyl), fentraZamide, flamprop (-isopropyl. Suitable solid carriers are: for example ammonium salts -isopropyl-L, -methyl), flaZaSulfuron, florasulam, fluazifop and ground natural minerals, such as kaolins, clays, talc. (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flu chalk, quartz, attapulgite, montmorillonite or diatomaceous metSulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, earth, and ground synthetic minerals, such as finely divided flumetSulam, fluometuron, fluorochloridone, fluoroglycofen silica, alumina and silicates, Suitable solid carriers for gran 35 (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -so ules are: for example crushed and fractionated natural rocks dium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypro Such as calcite, marble, pumice, Sepiolite and dolomite, and pyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), also synthetic granules of inorganic and organic meals, and fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammo granules of organic material Such as sawdust, coconut shells, nium), glyphosate (-isopropylammonium), halosafen, maize cobs and tobacco stalks; suitable emulsifiers and/or 40 haloxyfop (-ethoxyethyl, -P-methyl), hexazinone. HOK-201, foam-formers are: for example nonionic and anionic emulsi imazamethabenZ (-methyl), imazamethapyr, imaZamox, fiers. Such as polyoxyethylene fatty acid esters, polyoxyeth imazapic, imazapyr, imaZaquin, imazethapyr, imaZosulfuron, ylene fatty alcohol ethers, for example alkylaryl polyglycol iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, iso ethers, alkylsulfonates, alkyl Sulfates, arylsulfonates and pro proturon, isouron, isoxaben, isoxachlortole, isoxaflutole, tein hydrolyzates; Suitable dispersants are: for example ligno 45 isoxapyrifop, KIH 485, lactofen, lenacil, linuron, MCPA, Sulfite waste liquors and methylcellulose. mecoprop, mefenacet, mesosulfuron, mesotrione, metami Tackifiers such as carboxymethylcellulose and natural and fop, metamitron, metaZachlor, methabenzthiazuron, meto synthetic polymers in the form of powders, granules or lati benZuron, metobromuron, (alpha-) metolachlor, metoSulam, ces, such as gum arabic, polyvinyl alcohol and polyvinyl metoxuron, metribuzin, metSulfuron (-methyl), molinate, acetate, and also natural phospholipids, such as cephalins and 50 monolinuron, naproanilide, napropamide, neburon, nicosul lecithins, and synthetic phospholipids, can be used in the furon, norflurazon, orbencarb, orthosulfamuron, oryzalin, formulations. Other possible additives are mineral and veg oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxy etable oils. fluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, It is possible to use colorants such as inorganic pigments, penoXSulam, pentoxaZone, phenmedipham, picolinafen, for example iron oxide, titanium oxide and Prussian blue, and 55 pinoxaden, piperophos, pretilachlor, primisulfuron (-me organic colorants, such as alizarin colorants, azo colorants thyl), profluaZol, prometryn, propachlor, propanil, pro and metal phthalocyanine colorants, and trace nutrients such paquizafop, propisochlor, propoxycarbazone (-Sodium), pro as salts of iron, manganese, boron, copper, cobalt, molybde pyZamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), num and zinc. pyrasulfotole, pyrazogyl, pyrazolate, pyrazosulfuron The formulations generally comprise between 0.1 and 95 60 (-ethyl), pyrazoxyfen, pyribenZoxim, pyributicarb, pyridate, per cent by weight of active compound, preferably between pyridatol, pyriftalide, pyriminobac (-methyl), pyrimisulfan, 0.5 and 90%. pyrithiobac (-Sodium), quinchlorac, quinmerac, quinoc The active compounds/active compound combinations lamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron, set according to the invention, as Such or in their formulations, hoxydim, simazine, simetryn, Sulcotrione, SulfentraZone, Sul can also be used for weed control purposes as a mixture with 65 fometuron (-methyl), Sulfosate, Sulfosulfuron, tebutam, known herbicides and/or with substances which improve crop tebuthiuron, tembotrione, tepraloxydim, terbuthylazine, ter plant tolerance ('safeners'), ready mixes or tank mixes being butryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, US 8,629,084 B2 117 118 thifensulfuron (-methyl), thiobencarb, tiocarbazil, topram range; they depend, inter alia, on the weather and on Soil eZone, tralkoxydim, triallate, triasulfuron, tribenuron (-me factors. In general, the application rates are between 0.001 thyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, tri and 5 kg perha, preferably between 0.005 and 2 kg perha, flusulfuron (-methyl), tritosulfuron and particularly preferably between 0.01 and 0.5 kg per ha. The active compound combinations according to the invention can be applied before and after emergence of the plants, that is to say by the pre-emergence and post-emer No F F gence method. F. Depending on their properties, the Safeners to be used 4 Y-N S 10 y-N11. according to the invention can be used for pretreating the seed N S. O of the crop plant (seed dressing) or can be introduced into the O N N N seed furrows prior to sowing or be used separately prior to the O N herbicide or together with the herbicide, before or after emer CH gence of the plants. CH 15 Preparation and use of the active compounds according to the invention are illustrated in the examples below. A mixture with other known active compounds, Such as fungicides, insectides, acaricides, nematicides, bird repel PREPARATION EXAMPLES lents, plant nutrients and soil conditioners, is also possible. The active compounds/active compound combinations can Example I-1-a-1 be applied as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready to-use Solutions, Suspensions, emulsions, powders, pastes and granules. They are applied in the customary manner, for 25 example by pouring, spraying, atomizing, spreading. The active compounds/active compound combinations according to the invention can be applied both before and 2 after plant emergence. They can also be incorporated into the soil prior to planting. 30 The application rate of active compound can vary within a substantial range. Essentially, it depends on the nature of the f isomer desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of Soil area, Under argon, 5.24 g of potassium tert-butoxide-95% pure preferably between 5g and 5 kg per ha. 35 (44.4 mmol) are initially charged in 10 ml of dimethylaceta The advantageous effect of the compatibility with crop mide in a 100 ml three-necked flask fitted with thermometer plants of the active compound combinations according to the and reflux condenser. invention is particularly pronounced at certain concentration At 40 to 50° C., 8.7 g of the compound according to ratios. However, the weight ratios of the active compounds in Example II-1 (20.2 mmol) in 10 ml of dimethylacetamide are the active compound combinations can be varied within rela 40 added dropwise. The mixture is stirred at 60° C. for 1 h and tively wide ranges. In general, from 0.001 to 1000 parts by monitored by thin-layer chromatography during this time. weight, preferably from 0.01 to 100 parts by weight, particu The reaction solution is then stirred into 100 ml of ice larly preferably 0.05 to 20 parts by weight, of one of the water, the pH is adjusted to 2 using conc. HCl and the pre compounds which improves crop plant compatibility (anti cipitate is filtered off with suction. The product is then puri dotes/safeners) mentioned above under (b") are present per 45 fied by column chromatography on silica gel part by weight of active compound of the formula (I). (dichloromethane:ethyl acetate 5:3). The active compound combinations according to the Yield 7.8 g (94% of theory), m.p. 225.6°C. invention are generally applied in the form offinished formu lations. However, the active compounds contained in the Example I-1-a-3 active compound combinations can, as individual formula 50 tions, also be mixed during use, i.e. be applied in the form of tank mixes. For certain applications, in particular by the post-emer Process P-B gence method, it may furthermore be advantageous to O include, as further additives in the formulations, mineral or 55 J vegetable oils which are compatible with plants (for example the commercial preparation “Rako Binol), or ammonium HC 2 salts, such as, for example, ammonium Sulfate or ammonium thiocyanate. OH The novel active compound combinations can be used as 60 CH CH such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use f isomer Solutions, Suspensions, emulsions, powders, pastes and gran ules. Application is in the customary manner, for example by Under argon, 1.413 g (3 mmol) of example I-1-c-4 from watering, spraying, atomizing, dusting or scattering. 65 WO 97/02243 are initially charged in 30 ml of anhydrous The application rates of the active compound combinations tetrahydrofuran in a 100 ml three-necked flask. At -78°C., according to the invention can be varied within a certain 2.64 ml of n-butyllithium (2.5 m in n-hexane) are added

US 8,629,084 B2 123 124 -continued

(I-1-b)

I-1-b-17 6-CH i-CH7 217 I-1-b-18 6-CH CH CH i-CH7 137 I-1-b-19 6-CH -(CH2)5- t-CHg 2O6 I-1-b-20 6-CH i-CH7 CH HC-O-CH2— *4.05 (dd, 2H, OCH) 3.20 (s, 3H, OCH) 1.50 (d, 3H, CH) I-1-b-21 6-CH CH CH HC-O-CH2— 16S I-1-b-22 6-CH t i-CH7 CH i-CH7 130 *H-NMR (300 MHz/400 MHz, CDC13): shifts & in ppm. **H-NMR (400 MHz, d-DMSO): shifts & in ppm

Example I-1-c-1 Under argon, 0.66 g (1.5 mmol) of example I-1-a-2 is 25 initially charged in 20 ml of anhydrous methylene chloride in O a 100 ml three-necked flask, 0.21 ml (1.5 mmol) of triethy f isomer lamine is added and 0.14 ml (1.5 mmol) of ethyl chlorofor mate is added dropwise at 20°C. The mixture is stirred for 4 HCO hours, the Solvent is evaporated under reduced pressure and 30 the residue is chromatographed on silica gel using the mobile phase methylene chloride/ethyl acetate 10:1. Yield: 0.4 g ( 43% of theory) m.p. 198°C. The following compounds of the formula (I-1-c) are obtained analogously to example (I-1-c-1) and in accordance with the general statements on the preparation

(I-1-c)

D B M R2 m.p. C. Isomer

O CHS CH2— 152 B 6-CH O C2H5 186 B O C2H5 Wax B O C2H5 *4.11 (q, 2H, O CH), 4.03, (m, 2H, OCH) 2.20 (s.3H, Ar CH) O C2H5 *4.11 (q, 2H, O CH), B 3.39, (s, 3H, OCH) 2.61 (q, 2H, Ar CH) -1-c-7 O C2H5 Wax B -1-c-8 6-CH O C2H5 208 B -1-c-9 6-CI O C2H5 214 -1-c-10 6-CH CH O C2H5 *4.02 (m, 2H, OCH), 2.21 (d. 3H, ArCH) 1.46 (s, 3H, CH)

US 8,629,084 B2 129 130 Example XXIX-1 1.31 g (5 mmol) of 2-lodophenylacetylchloride and 0.66 g (5 mmol) of ethyl 2-methyl-2-hydroxy-propionate are heated H3C at 140° C. for 10 h, after cooling, 10 ml of dimethylforma O CH3 mide are added, and 6 ml of 1M potassium t-butoxide solution (6 mmol) are added dropwise. The mixture is stirred at room N temperature for 10 h and concentrated using a rotary evapo H rator, and the residue is partitioned between water and ethyl acetate. The aqueous phase is acidifed with 2N HCl and the product is extracted with ethyl acetate, the organic phase is 10 dried and concentrated using a rotary evaporator. Yield: 1.11 g (68% of theory) J 1.7 g (5.59 mmol) of 4-iodo-2-ethyl-6-methylphenylacetic log P 1.80 acid are initially charged in 25 ml of tetrahydrofuran, 2 ml of The following compounds of the formula (I-2-a) are triethylamine and 0.627 g (5.59 mmol) of 2-amino-2-meth 15 obtained analogously to example (I-2-a-1) and in accordance ylisobutyronitrile are added, the mixture is stirred at room with the general statements on the preparation temperature for 15 minutes, 1 ml of triethylamine is added followed by the dropwise addition of 0.6 ml of phosphorus oxychloride such that the mixture boils gently. The mixture is (I-2-a) stirred under reflux for 30 minutes, concentrated on a rotary evaporator and worked up with ethyl acetate/water, and the organic phase is dried with sodium sulfate, stirred with silica gel, filtered off and concentrated using a rotary evaporator. Yield: 1.82 g (74% of theory), m.p. 186° C. The following compounds of the formula (XXIX) are obtained analogously to example (XXIX-1) and in accor 25 dance with the general statements on the preparation Ex. No. J X Y A. B logP I-2-a-2 2-J H H -(CH2). CHOCH -(CH2)2 - 1.92 (XXIX) I-2-a-3 2-J 5-CH H —(CH2)— 2.51 30 I-2-a-4 2-J 5-CH H —(CH2)2–CHOCH-(CH2)2- 2.19 I-2-a-5 4-J 2-C2H 6- —(CH2)2—O—(CH2)2 2.63 CH, I-2-a-6 4-J 2-C2H5. 6- —(CH2)2—CHOCH -(CH2)2— 2.92 CH I-2-a-7 4-J 2-C2H 6- CH CH 2.81 35 CH H-NMR (300 MHz I-2-a-8 4-J 2-C2H 6- —(CH2)— 3.00 (CDC1) Shift 8 in CH Ex. No. J X Y A. B ppm I-2-a-9 4-J 2-CH 6- —(CH2)2–CHOCH-(CH2)2- 2.94 XXIX-2 4-J 2-C2H 6-CH n-CH, CH 0.90 (tr., 3H, CH (CH2)2 CH3) 1.60 (s.3H, 40 xt Example I-2-b-1 3.6 (s, 2H, CH Ar CH-CO) 45 O XXIX-3 4-J 2-C2Hs ch CH 0.60-0.7 (m, 2H, CH P H 50 1.70 (s, 3H, N-C-CH3)

3.60 (s, 2H, 55 Ar CH-CO) 0.25 g (0.757 mmol) of the compound of example I-2-a-1 and 0.092 g (0.909 mmol) of triethylamine are initially Example I-2-a-1 charged in 10 ml of dichloromethane, 0.097 g (0.909 mmol) 60 of isobutyryl chloride is added dropwise and the mixture is stirred at room temperature overnight, washed with 10% HO strength citric acid and 10% strength aqueous Sodium hydroxide Solution, dried and concentrated using a rotary H3C s evaporator. The crude product is purified by column chroma tography O silica gel (gradient H3C J 65 O O dichloromethane-dichloromethane/ethyl acetate 95:5). Yield: 0.23 g (74% of theory), log P3.53

US 8,629,084 B2 133 134 Example I-8-a-1 Example No. (I-8-b-2) is obtained analogously to example (I-8-b-1)

CH3 O

J 10 /

O CH3 O CH3 CH 15 CH3 HC 'H-NMR (300 MHz, CDC1): 8–7.40 (s. 2H, Ar H), 3.90 (m,2H, N CH), 3.40 (m, 2H, N CH), 2.60-2.40 (m, 2H, Ar CH) ppm. Example I-8-c-1 0.566 g of potassium tert-butoxide is initially charged in 5 ml of N,N-dimethylacetamide at 50° C. 1 g of the compound of example (XII-1) in 5 ml of N,N-dimethylacetamide is 25 added and the mixture is stirred at 60° C. for 2 h. The cooled reaction solution is then added dropwise to ice-water/concen ( ) trated HC1. The crystals are filtered off with suction. N-N O Yield: 0.54 g (86% of theory), m.p. 229°C. 30 O 2s-s-s CH CH Example I-8-b-1 HC 35

0.07 ml of ethyl chloroformate is added to 0.25 g (0.001 40 mol) of the compound of example I-8-a-1 and 0.11 ml of N-N CH3 triethylamine and 15 ml of toluene, and the mixture is stirred at room temperature for 1 hour. The reaction solution is O 2 O CH extracted with water and the organic phase is dried. Purifica tion is carried out by HPLC. 45 Yield: 0.09 g (29% of theory) 'H-NMR (300 MHz, CDC1): 8–7.40 (s.2H, Ar H), 4.15 (q,2H, O CH), 3.80 (tr. 2H, N CH), 3.45 (tr. 2H, Ar C H), 2.50 (m,2H, Ar CH), 2.00- 1.80 (m, 4H,2xCH cycle) ppm. 50 Example XII-1

0.25 g (0.001 mol) of the compound of example I-8-a-1 and 0.074 g of 2-methylpropionyl chloride are initially charged in 55 15 ml of toluene at room temperature, 0.11 ml of triethy lamine is added dropwise, the mixture is stirred for 2 h, water is added and the mixture is extracted. The organic phase is dried and concentrated using a rotary evaporator, and the residue is crystallized using n-heptane and a little ethyl 60 acetate. Yield: 0.1 g (32% of theory) H-NMR (300 MHz, CDC1): 8–7.40 ppm (s. 2H, Ar H), 3.80 ppm (m, 2H, N CH), 3.40 ppm (m. 2H, N CH), 65 2.40 ppm (sept, 1H, CHC(CH)), 2.00-1.80 ppm (m, 4H. J 2xCH2 cycle). US 8,629,084 B2 135 136 1.83 ml of triethylamine are added to 2 g of 4-iodo-2-ethyl temperature for 18 h. The mixture is then evaporated to dry 6-methylphenylacetic acid in 40 ml of tetrahydrofuran, and ness using a rotary evaporator, and in each case 50 ml of ethyl the mixture is stirred for 15 minutes. 1.095g of ethylhexahy acetate and water are added to the residue. The phases are dropyridazine carbamate are then added, the mixture is stirred separated and the ethyl acetate phase is washed with water. for 10 minutes and 1.92 ml of triethylamine are added. Imme The combined aqueous phases are adjusted to pH-1 using diately afterward, 0.55 ml of phosphoryl chloride is slowly HCl, and the precipitated solid is filtered off with suction, added dropwise. The mixture is stirred under reflux for 30 washed with water and dried under reduced pressure. Yield of minutes. (2-ethyl-4-iodo-6-methylphenyl)acetic acid: 6 g., 78%. After cooling, the mixture is concentrated using a rotary 'H-NMR (300 MHz, d-DMSO): 8=12.5 (s(br), 1H), 7.40 evaporator, the residue is worked up with ethyl acetate/water 10 (d. 1H), 7.38 (d. 1H), 3.57 (s. 2H), 2.56 (q, 2H), 1.09 (t, 3H) and the organic phase is separated off, dried with sodium ppm. Sulfate, filtered off and concentrated using a rotary evapora tOr. Example XXXI-2 Yield: 2.5 g (85% of theory) 'H-NMR (400 MHz, CDC1): 8=1.15, 1.30 (2 t, 6H, OCH, 15 CH, Ar CHCH), 2.20 (s.3H, Ar CH), 2.50 (q, 2H, Ar— CHCH), 3.60.3.70 (2d,2H, NCH), 7.40 (s. 2H, Ar H) ppm. Process Q CH Example XXXI-1 HC

O 25 CH Under argon, a solution of 20 g of methyl(5-bromo-2- o1 3 methylphenyl)acetate, 24.663g of sodium iodide, 15.668g of H3C copper(I) iodide and 7.075 g of N,N'-dimethylethylenedi CH3 amine in 500 ml of dioxane is heated at 110° C. for 3 days. 30 Another 8 g of sodium, 5.5g of copper(I) iodide and 3.3 g of N,N'-dimethylethylenediamine are then added. After a fur ther 3 days of heating at 110° C., the reaction mixture is filtered and the mother liquor is diluted with 300 ml of water 35 and extracted twice with 200 ml of dichloromethane. The Under argon, a solution of 10 g of methyl(4-bromo-2- organic phase is washed with 25% strength ammonia Solu methyl-6-ethylphenyl)acetate, 11.056 g of sodium iodide, tion, dried over NaSO and freed from the solvent. Yield of 7.023 g of copper(I) iodide and 3.172g of N,N'-dimethyleth methyl(5-iodo-2-methylphenyl)acetate: 11.6 g., 30%. ylenediamine in 250 ml of dioxane is heated at 110°C. for 18 'H-NMR (300 MHz, d-DMSO): 8–7.56 (d. 1H), 7.51 (d. h. After the reaction has ended, the reaction mixture is filtered 40 1H), 6.99 (d. 1H), 3.62 (s. 2H), 3.57 (s.3H), 2.16 (s.3H) ppm. and the mother liquor is diluted with 300 ml of water and extracted twice with 200 ml of dichloromethane. The organic Example XXVII-2 phase is washed with 25% strength ammonia Solution, dried over sodium sulfate and freed from the solvent. Yield of methyl(2-ethyl-4-iodo-6-methylphenyl)acetate: 7.8 g. 65%. 45 'H-NMR (300 MHz, d-DMSO): 8–7.42 (d. 1H), 7.39 (d. 1H), 3.68 (s. 2H), 3.61 (s.3H), 2.55 (q, 2H), 219 (s.3H), 1.10 (t, 3H) ppm. OH HC Example XXVII-1 50

55 A solution of 1.048g of LiOH in 75 ml of water is added to OH a solution of 10.7 g of methyl(5-iodo-2-methylphenyl)acetate in 75 ml of THF, and the mixture is stirred at room tempera ture for 18 h. The mixture is then concentrated to dryness CH3 using a rotary evaporator, and in each case 75 ml of ethyl 60 acetate and water are added to the residue. The phases are separated and the organic phase is washed with water. The combined aqueous phases are adjusted to pH-1 using HCl and the precipitated solid is triturated successively with dichloromethane and ethyl acetate, filtered off with suction A solution of 0.696 g of LiOH in 50 ml of water is added to 65 and dried under reduced pressure. For further purification, it a solution of 7.7 g of methyl(2-ethyl-4-iodo-6-methylphenyl) is triturated with diethyl ether and filtered off. Yield of acetate in 50 ml of THF, and the mixture is stirred at room (5-iodo-2-methylphenyl)acetic acid: 5.5 g. 44%.

US 8,629,084 B2 140 -continued Structure Ex. No. "H-NMR (400 MHz, d, DMSO) O XXVII-5 8 = 12.46 (s (br), 1H), 7.75 (d. 1H), 7.33 (d. 1H), 3.80 (s, 2H), 2.31 (s, 3H), ppm. OH

J CH3

C O XXXI-6 8 = 12.47 (s (br), 1H), 7.76 (d. 1H), 7.31 (d. 1H), 3.81 (s, 2H), 2.64 (q, 2H), 1.11 (t,3H) ppm. OH

J CH3

C O XXVII-7 8 = 12.50 (s (br), 1H), 7.65 (d. 1H), 7.58 (d. 1H), 3.71 (s, 2H), 2.25 (s, 3H), ppm. OH C CH

O XXVII-8 8 = 12.41 (s (br), 1H), 7.66 (d. 1H), 7.55 (d. 1H), 3.72 (s, 2H), 2.63 (q, 2H), 1.11 (t,3H)

The logP values given in the Tables and Preparation The lambda max values were determined in the maxima of Examples above are determined in accordance with the chromatographic signals using the UV spectra from 200 EEC Directive 79/831 Annex V.A8 by HPLC (High Per- 50 nm to 400 nm. formance Liquid Chromatography) on a reversed-phase column (C18). Temperature: 43°C. Use Examples The determination is carried out in the acidic range at pH 2.3 using the mobile phases 0.1% aqueous phosphoric acid Example A and acetonitrile; linear gradient from 10% acetonitrile to 95% acetonitrile. 55 Phaedon Test (Spray Treatment) The LC-MS determination in the acidic range is carried out Solvents: 78 parts by weight of acetone at pH 2.7 using the mobile phases 0.1% aqueous formic acid 1.5 parts by weight of dimethylformamide and acetonitrile (contains 0.1% formic acid); linear gradient Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether from 10% acetonitrile to 95% acetonitrile. To produce a suitable preparation of active compound, 1 The LC-MS determination in the neutral range is carried 60 part by weight of active compound is mixed with the stated out at pH 7.8 using the mobile phases 0.001 molar aqueous amounts of solvents and emulsifier, and the concentrate is ammonium bicarbonate solution and acetonitrile; linear gra diluted with emulsifier-containing water to the desired con dient from 10% acetonitrile to 95% acetonitrile. centration. Calibration is carried out using unbranched alkan-2-ones Discs of Chinese cabbage (Brassica pekinensis) are (having 3 to 16 carbon atoms) with known logP values (deter 65 sprayed with an active compound preparation of the desired mination of the logP values by the retention times using linear concentration and, after drying, populated with larvae of the interpolation between two Successive alkanones). mustard beetle (Phaedon cochleariae). US 8,629,084 B2 141 142 After the desired period of time, the effect in % is deter Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether mined. 100% means that all beetle larvae have been killed; To produce a suitable preparation of active compound, 1 0% means that none of the beetle larvae have been killed. part by weight of active compound is mixed with the stated In this test, for example, the following compounds of the amounts of solvents and emulsifier, and the concentrate is Preparation Examples show, at an application rate of 500 diluted with emulsifier-containing water to the desired con g/ha, an efficacy of 80%. centration. Discs of bean leaves (Phaseolus vulgaris) which are I-1-a-1, I-1-a-2, I-1-a-3, I-1-a-4, I-1-a-5, I-1-a-11, I-1-a- heavily infested by all stages of the greenhouse red spider 12, I-1-a-13, I-1-a-14, I-1-a-18, I-1-a-19, I-1-a-21, I-1-a-23, mite (Tetranychus urticae) are sprayed with an active com I-1-b-1, I-1-b-7, I-1-b-11, I-1-b-18, I-1-c-4, I-1-c-7, I-1-c-8, pound preparation of the desired concentration. I-1-c-9, I-1-c-10, I-1-c-11, I-1-c-17, I-1-c-20, I-2-a-6, I-2-b- 10 After the desired period of time, the effect in % is deter 10, I-2-b-11. mined. 100% means that all spidermites have been killed: 0% means that none of the spider mites have been killed. Example B In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 Myzus Test (Spray Treatment) 15 g/ha, an efficacy of 80%. Solvents: 78 parts by weight of acetone I-1-a-2, I-1-a-4, I-1-a-5, I-1-a-7. I-1-a-11, I-1-a-12, I-1-a- 1.5 parts by weight of dimethylformamide 18, I-1-a-19, I-1-a-21, I-1-a-21, I-1-a-22, I-1-b-2, I-1-b-18, Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether I-1-c-1, I-1-c-4, I-1-c-5, I-1-c-20, I-2-a-6, I-2-b-2, I-2-b-5, To produce a suitable preparation of active compound, 1 I-2-b-6, I-2b-8, I-2-b-10, I-2-b-11, I-2-c-2, I-2-c-3, I-2-c-4, part by weight of active compound is mixed with the stated I-2-c-5, I-8-b-1, I-8-b-2. amounts of solvents and emulsifier, and the concentrate is In this test, for example, the following compound of the diluted with emulsifier-containing water to the desired con Preparation Example showed, at an application rate of 500 centration. g/ha, an efficacy of 80%: Discs of Chinese cabbage (Brassica pekinensis) which are I-1-a-14. infested by all stages of the green peach aphid (Myzus persi 25 cae) are sprayed with an active compound preparation of the Example E desired concentration. After the desired period of time, the effect in % is deter mined. 100% means that all aphids have been killed: 0% Herbicidal Pre-Emergence Action means that none of the aphids have been killed. Seeds of monocotyledonous and dicotyledonous weed and In this test, for example, the following compounds of the 30 crop plants are placed in Sandy loam in wood fiber pots and Preparation Examples show, at an application rate of 500 covered with soil. The test compounds, formulated in the g/ha, an efficacy of 80%. form of wettable powders (WP) or as emulsion concentrates I-1-a-1, I-1-a-2, I-1-a-3, I-1-a-4, I-1-a-5, I-1-a-7, I-1-a-8 (EC), are then, as an aqueous Suspension with a water appli I-1-a-9, I-1-a-11, I-1-a-18, I-1-a-19, I-1-a-20, I-1-a-22, I-1 cation rate of 800 l/ha (converted), with 0.2% of wetting agent a-24, I-1-b-1, I-1-b-2, I-1-b-9, I-1-b-11, I-1-c-1, I-1-c-2, I-1 35 added, applied to the Surface of the covering soil. c-3, I-1-c-4, I-1-c-6, I-1-c-7, I-1-c-8, I-1-c-9, I-1-c-12, I-1-c- After the treatment, the pots are placed in agreenhouse and 20. I-2-a-2, I-2-a-4, I-2-a-5, I-2-a-6, I-2-a-9, I-2-b-2, I-2-b-3, kept under growth conditions for the test plants. The visual I-2-b-4, I-2-b-6, I-2-b-7, I-2-b-9, I-2-b-10, I-2-b-11, I-2-b-12, assessment of the emergence damage on the test plants is I-2-b-13, I-2-c-2, I-2-c-4, I-2-c-5, I-8-b-2. carried out after a trial period of 3 weeks by comparison with 40 untreated controls (herbicidal effect in percent (%): 100% Example C effect the plants have died, 0% effect—like control plants). Here, the following compounds, for example, controlled Nilaparvata Lugens Test (Hydroponic Treatment) Avena sativa, Lolium multiflorum and Setaria viridis at an Solvents: 78 parts by weight of acetone application rate of 320 g/ha with 70% efficacy: 1.5 parts by weight of dimethylformamide 45 I-1-a-8, I-1-a-14, I-1-a-21, I-1-a-7. Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 Example F part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is Herbicidal Post-Emergence Action diluted with emulsifier-containing water to the desired con 50 Seeds of monocotyledonous and dicotyledonous weed and centration. The active compound preparation is pipetted into water. crop plants are placed in Sandy loam in wood fiber pots, The stated concentration refers to the amount of active com covered with soil and cultivated in a greenhouse under good pound per volume unit of water (mg/l=ppm). After the desired growth conditions. Two to three weeks after sowing, the test period of time, the water is infected with the brown plant plants are treated at the one-leaf stage. The test compounds, hopper (Nilaparvata lugens). 55 formulated as wettable powders (WP) or as emulsion concen After the desired period of time, the effect in % is deter trates (EC), are then, as an aqueous Suspension with a water mined. 100% means that all plant hoppers have been killed; application rate of 800 l/ha (converted), with 0.2% of wetting 0% means that none of the plant hoppers have been killed. agent added, sprayed onto the green parts of the plants. After In this test, the compound of Preparation Example I-2-a-2 the test plants have been kept in the greenhouse under opti showed, at a concentration of 20 ppm, an efficacy of 80%. 60 mum growth conditions for about 3 weeks, the effect of the preparations is rated visually in comparison to treated con Example D trols (herbicidal effect in percent (%): 100% effect=the plants have died, 0% effect—like control plants). Tetranychus Test: OP-Resistant/Spray Treatment Here, the following compounds, for example, controlled (TETRUR) 65 Avena sativa, Echinochloa crus-galli, Lolium multiflorum Solvents: 78 parts by weight of acetone and Setaria viridis at an application rate of 320 g/ha with 1.5 parts by weight of dimethylformamide >70% efficacy: US 8,629,084 B2 143 144 I-1-a-8, I-1-a-11, I-1-a-12, I-1-a-13, I-1-a-14, I-1-a-21, I-1-c-1, I-1-c-6, I-1-c-11, I-1-c-12, I-2-b-10, I-2-c-3, I-8-b-2. 10 days after application Example G Application rate Summer wheat Summer wheat g of a.i./ha observed (%) observed (%) Herbicidal Post-Emergence Action Example I-2-b-10 2OO 70 Seeds of monocotyledonous and dicotyledonous weed and 100 50 crop plants are placed into Sandy loam in wood fiberpots or in 50 30 65 plastic pots, covered with soil and cultivated in a greenhouse, 25 15 60 10 Example I-2-b-10 + 200 - 100 2O during the vegetation period also outdoors outside of the mefenpyr 100 + 100 10 greenhouse, under good growth conditions. Two to three 50 - 1 OO 5 40 weeks after sowing, the test plants are treated at the one- to 25 - 1 OO 5 15 three-leaf stage. The test compounds, formulated as wettable powders (WP) or liquid (EC), are, in various dosages at a water application rate of 300 l/ha (converted), with wetting 15 agent (0.2 to 0.3%) added, sprayed onto the plants and the surface of the soil. Three to four weeks after the treatment of 28 days after application the test plants, the effect of the preparations is rated visually in comparison to treated controls (herbicidal effect in 96) (%): Application rate Summer wheat 100% effect—the plants have died, 0% effect—like control g of a.i./ha observed (%) plants). Example I-2-b-10 2OO 75 Use of Safeners 1OO 50 50 40 If it is additionally to be tested as to whether safeners can 25 25 improve the plant compatibility of test Substances in the case Example I-2-b-10 + 200 - 100 2O of crop plants, the following options are used for applying the 25 mefenpyr 100 + 100 5 safener: SO-1OO O seeds of the crop plants are, before Sowing, dressed with 25 + 1 OO O the Safener Substance (the amount of Safener Stated in percent, based on the weight of the seed) before the application of the test Substances, the crop plants 30 Example H are sprayed with the Safenerata certain application rate per hectare (usually 1 day before the application of the Critical Concentration Test/Soil Insects—Treatment of test Substances) Transgenic Plants the safener is applied together with the test Substance as a Test insect: Diabrotica balteata—larvae in the soil tank mix (the amount of safener is stated in g/ha or as a 35 Solvent: 7 parts by weight of acetone ratio, based on the herbicide). Emulsifier: 1 part by weight of alkylaryl polyglycol ether By comparing the effect of test Substances on crop plants To produce a suitable preparation of active compound, 1 without or with safener treatment, it is possible to assess the part by weight of active compound is mixed with the stated effect of the safener substance. 40 amount of solvent, the stated amount of emulsifier is added Container Trials with Cereal in a Greenhouse and the concentrate is diluted with water to the desired con Mefenpyr 1 day prior to herbicide application centration. The preparation of active compound is poured onto the soil. Here, the concentration of active compound in the prepara 10 days after application 45 tion is virtually immaterial; only the amount by weight of active compound per unit volume of soil, which is stated in Application rate Summer wheat ppm (mg/l), matters. The soil is filled into 0.251 pots, and g of a.i./ha observed (%) these are allowed to stand at 20° C. Example I-1-a-3 100 40 Immediately after the preparation, 5 pregerminated corn 50 30 50 25 2O grains of the cultivar YIELD GUARD (trademark of Mon 12.5 10 Santo Comp., USA) are placed into each pot. After 2 days, the Example I-1-a-3 + 1OO - 100 2O appropriate test insects are placed into the treated soil. After a mefenpyr SO-1OO 10 further 7 days, the efficacy of the active compound is deter 25 - 1 OO 5 12.5 + 100 O mined by counting the corn plants that have emerged (1 55 plant=20% activity). Example I Heliothis virescens Test Treatment of Transgenic Plants 10 days after application 60 Solvent: 7 parts by weight of acetone Application rate Summer wheat Emulsifier: 1 part by weight of alkylaryl polyglycol ether g of a.i./ha observed (%) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated Example I-1-c-1 12.5 50 Example I-1-c-1 + 12.5 + 100 15 amount of solvent and the stated amount of emulsifier, and the mefenpyr 65 concentrate is diluted with water to the desired concentration. Soybean shoots (Glycine max) of the cultivar Roundup Ready (trademark of Monsanto Comp. USA) are treated by

US 8,629,084 B2 149 150 diethyl 1-(2,4-dichorophenyl)-4,5-dihydro-5-methyl-1H the general formula (IIb) pyrazole-3,5-dicarboxylate (mefenpyr-diethyl) 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), 2-propenyl-1-Oxa-4-azaspiro4.5 decane-4-carbodithio (IIb) ate (MG-838), X3 X2 1,8-naphthalic anhydride, C-(1,3-dioxolan-2-ylmethoximino)phenylacetonitrile ? SAS (oxabetrinil), 4. 21 O 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-prope nyl)acetamide (PPG-1292), 10 3-dichloroacetyl-2,2-dimethyloxazolidine (R-28725), OnA2 ls R15, 3-dichloroacetyl-2.2.5-trimethyloxazolidine (R-29148), 4-(4-chloro-o-tolyl)butyric acid, and/or of the general formula (Ic) 4-(4-chlorophenoxy)butyric acid, diphenylmethoxyacetic acid, 15 methyl diphenylmethoxyacetate, (IIc) ethyl diphenylmethoxyacetate, O methyl 1-(2-chlorophenyl)-5-phenyl-1H-pyrazole-3-car boxylate, R17, ethyl 1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3- --- carboxylate, k ethyl 1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole-3- carboxylate, wherein ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)-1H m is 0, 1, 2, 3, 4 or 5, pyrazole-3-carboxy late, 25 ethyl 1-(2,4-dichlorophenyl)-5-phenyl-1H-pyrazole-3- A represents one of the divalent heterocyclic groupings carboxylate, shown below: ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxy late, N N N ethyl 5-phenyl-2-isoxazoline-3-carboxylate, 30 ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-car NYS y NY Y boxylate, o )=N 1,3-dimethylbut-1-yl 5-chloroquinoline-8-oxyacetate, RI 9 R19 R19 4-allyloxybutyl 5-chloroquinoline-8-oxyacetate, OR20 1-allyloxyprop-2-ylS-chloroquinoline-8-oxyacetate, 35 O methyl 5-chloroquinoxaline-8-oxyacetate, ethyl 5-chloroquinoline-8-oxyacetate, allyl 5-chloroquinoxaline-8-oxyacetate, 2-oxoprop-1-yl5-chloroquinoline-8-oxyacetate, diethyl 5-chloroquinoline-8-oxymalonate, 40 diallyl 5-chloroquinoxaline-8-oxymalonate, n is 0, 1, 2, 3, 4 or 5, diethyl 5-chloroquinoline-8-oxymalonate, A represents optionally C1-C4-alkyl- and/or C-Ca 4-carboxychroman-4-ylacetic acid (AC-304415), alkoxy-carbonyl- and/or C-C-alkenyloxy-carbonyl 4-chlorophenoxyacetic acid, Substituted alkanediyl having 1 or 2 carbon atoms, 3,3'-dimethyl-4-methoxybenzophenone, 45 R" represents hydroxyl, mercapto, amino, C1-Co-alkoxy, 1-bromo-4-chloromethylsulfonylbenzene, C-C-alkylthio, C-C-alkylamino or di(C-C-alkyl)- 1-4-(N-2-methoxybenzoylsulfamoyl)phenyl-3-methy amino, lurea (also known as N-(2-methoxybenzoyl)-4-(methy R" represents hydroxyl, mercapto, amino, C-C-alkoxy, laminocarbonyl)aminobenzenesulfonamide), C-C-alkenyloxy, C-C-alkenyloxy-C-C-alkoxy, 1-4-(N-2-methoxybenzoylsulfamoyl)phenyl-3,3-dim 50 C-C-alkylthio, C-C-alkylamino or di(C-C-alkyl)- ethylurea, amino, 1-4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl-3-me R" represents in each case an optionally fluoro, chloro or bromo-Substituted C-C-alkyl, thylurea, R7 represents hydrogen, in each case an optionally fluoro, 1-4-(N-naphthylsulfamoyl)phenyl-3,3-dimethylurea, chloro or bromo-Substituted C-C-alkyl, C-C-alkenyl N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylami or C-C-alkynyl, C-C-alkoxy-C-C-alkyl, dioxola nocarbonyl)benzenesulfonamide, nyl-C-C-alkyl, furyl, furyl-C-C-alkyl, thienyl, thia and/or one of the following compounds Zolyl, piperidinyl, or an optionally fluoro, chloro or of the general formula (IIa) bromo- or C-C-alkyl-substituted phenyl, 60 R" represents hydrogen, in each case an fluoro, chloro or bromo-substituted C-C-alkyl, C-C-alkenyl or (IIa) C-C-alkynyl, C-C-alkoxy-C-C-alkyl, dioxolanyl C-C-alkyl, furyl, furyl-C-C-alkyl, thienyl, thiazolyl, (X), it piperidinyl, or an optionally fluoro, chloro or bromo- or Clu21 l R14, 65 C-C-alkyl-substituted phenyl, R7 and R' also together represent C-C-alkanediyl or C-Cs-Oxaalkanediyl, each of which may be optionally US 8,629,084 B2 151 152 substituted by C-C-alkyl, phenyl, furyl, a fused ben each case optionally cyano- or halogen-substituted Zenering or by two substituents which, together with the C-C-alkenyl or C-C-alkynyl, optionally cyano-, C atom to which they are attached, form a 5- or 6-mem halogen- or C-C-alkyl-substituted C-C-cycloalkyl, bered carbocycle, or optionally nitro-, cyano-, halogen-, C-C-alkyl-, R" represents hydrogen, cyano, halogen, or represents in 5 C-Ca-haloalkyl-, C-C-alkoxy- or C-C-haloalkoxy each case an optionally fluoro, chloro or bromo-Substi substituted phenyl, or together with R represents in tuted C-C-alkyl, C-C-cycloalkyl or phenyl, each case optionally C-C-alkyl-substituted C-C-al R" represents hydrogen, in each case an optionally kanediyl or C-Cs-Oxaalkanediyl. hydroxyl-, cyano-, halogen- or C-C-alkoxy-Substi X' represents nitro, cyano, carboxyl, carbamoyl, formyl, tuted C-C-cycloalkyl or tri-(C-C-alkyl)-silyl, 10 Sulfamoyl, hydroxyl, amino, halogen, C-C-alkyl, R" represents hydrogen, cyano, halogen, or represents in C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, each case an optionally fluoro, chloro or bromo-Substi and tuted C-C-alkyl, C-C-cycloalkyl or phenyl, X represents nitro, cyano, carboxyl, carbamoyl, formyl, X' represents nitro, cyano, halogen, C1-C4-alkyl, C-C- Sulfamoyl, hydroxyl, amino, halogen, C-C-alkyl, haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, 15 C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy. X represents hydrogen, cyano, nitro, halogen, C-C- 8. The composition as claimed in claim 7, wherein the crop alkyl, C-C-haloalkyl, C-C-alkoxy or C-C-ha plant compatibility-improving compound comprises at least loalkoxy, one of X represents hydrogen, cyano, nitro, halogen, C-C- cloquintocet-mexyl, alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-ha fenchlorazole-ethyl, loalkoxy, isoxadifen-ethyl, and/or the following compounds mefenpyr-diethyl, of the general formula (IId) furilazole, fenclorim, 25 cumyluron, (IId) dymron, compound IIe-5, or R23 compound IIe-11; O N (X) wherein the compounds IIe-5 or IIe-11 have the following N SA f 21 --(x) 30 formulae:

(IIe-5) O 35 HN s SO1 (IIe)

40 O OCH

(IIe-11) 45 O CH3

HN wherein t is 0, 1, 2, 3, 4 or 5, 50 SO1 V is 0, 1, 2, 3, 4 or 5, R’ represents hydrogen or C-C-alkyl, O OCH R represents hydrogen or C-C-alkyl, R" represents hydrogen, in each case optionally cyano-, 9. The composition of claim 7, wherein the crop plant halogen- or C-C-alkoxy-Substituted C-C-alkyl, 55 compatibility-improving compound is mefenpyr-diethyl. C-C-alkoxy, C-C-alkylthio. C-C-alkylamino or 10. A method for controlling unwanted vegetation, com di (C-C-alkyl)-amino, or in each case optionally prising contacting the composition of claim 7 with the Veg cyano-, halogen- or C-C-alkyl-substituted C-C-cy etation or its habitat. cloalkyl, C-C-cycloalkyloxy, C-C-cycloalkylthio or 11. A method for controlling unwanted vegetation, com C-C-cycloalkylamino, 60 prising contacting a compound of claim 1 and a crop plant R represents hydrogen, optionally cyano-, hydroxyl-, compatibility-improving compound, separately in close tem halogen- or C-C-alkoxy-Substituted C-C-alkyl, in poral Succession, or as a mixture, with the unwanted vegeta each case optionally cyano- or halogen-substituted tion or its habitat; C-C-alkenyl or C-C-alkynyl, or optionally cyano-, wherein the crop plant-compatibility-improving com halogen- or C-C-alkyl-substituted C-C-cycloalkyl, 65 pound is at least one of R represents hydrogen, optionally cyano-, hydroxyl-, 4-dichloroacetyl-1-Oxa-4-azaspiro4.5 decane (AD-67, halogen- or C-C-alkoxy-Substituted C-C-alkyl, in MON-4660),

US 8,629,084 B2 155 156 A represents one of the divalent heterocyclic groupings of the general formula (IId) shown below:

(IId) N N N R23 NY N y NY Y (X) o )=N s N SA R22 21 -- (Y R1 9 R19 R19 OR20 R24 2 - S. (X ), O 10 SO O

or of the general formula (IIe) 15 n is 0, 1, 2, 3, 4 or 5, A represents optionally C1-C4-alkyl- and/or C-C- (IIe)

alkoxy-carbonyl- and/or C-C-alkenyloxy-carbonyl Substituted alkanediyl having 1 or 2 carbon atoms, R'' represents hydroxyl, mercapto, amino, C1-Co-alkoxy, C-C-alkylthio. C-C-alkylamino or di(C-C-alkyl)- 21 amino, +-(X'), R" represents hydroxyl, mercapto, amino, C-C-alkoxy, N C-C-alkenyloxy, C-C-alkenyloxy-C-C-alkoxy, C-C-alkylthio, C-C-alkylamino or di(C-C-alkyl)- 25 amino, R' represents in each case an optionally fluoro, chloro or bromo-substituted C-C-alkyl, wherein R" represents hydrogen, in each case an optionally fluoro, t is 0, 1, 2, 3, 4 or 5, chloro or bromo-substituted C-C-alkyl, C-C-alkenyl 30 V is 0, 1, 2, 3, 4 or 5, or C-C-alkynyl, C-C-alkoxy-C-C-alkyl, dioxola nyl-C-C-alkyl, furyl, furyl-C-C-alkyl, thienyl, thia R represents hydrogen or C-C-alkyl, Zolyl, piperidinyl, or an optionally fluoro, chloro or R’ represents hydrogen or C-C-alkyl, bromo- or C-C-alkyl-substituted phenyl, R" represents hydrogen, in each case optionally cyano-, R" represents hydrogen, in each case an optionally fluoro, 35 halogen- or C-C-alkoxy-Substituted C-C-alkyl, chloro or bromo-Substituted C-C-alkyl, C-C-alkenyl C-C-alkoxy, C-C-alkylthio. C-C-alkylamino or or C-C-alkynyl, C-C-alkoxy-C-C-alkyl, dioxola di (C-C-alkyl)-amino, or in each case optionally nyl-C-C-alkyl, furyl, furyl-C-C-alkyl, thienyl, thia cyano-, halogen- or C-C-alkyl-substituted C-C-cy Zolyl, piperidinyl, or an optionally fluoro, chloro or cloalkyl, C-C-cycloalkyloxy, C-C-cycloalkylthio or bromo- or C-C-alkyl-substituted phenyl, 40 R'' and R'' also together represent C-C-alkanediyl or C-C-cycloalkylamino, C-C-Oxaalkanediyl, each of which may be optionally R represents hydrogen, optionally cyano-, hydroxyl-, substituted by C-C-alkyl, phenyl, furyl, a fused ben halogen- or C-C-alkoxy-substituted C-C-alkyl, in Zenering or by two substituents which, together with the each case optionally cyano- or halogen-substituted C atom to which they are attached, form a 5- or 6-mem 45 C-C-alkenyl or C-C-alkynyl, or optionally cyano-, bered carbocycle, halogen- or C-C-alkyl-substituted C-C-cycloalkyl, R" represents hydrogen, cyano, halogen, or represents in R represents hydrogen, optionally cyano-, hydroxyl-, each case an optionally fluoro, chloro or bromo-Substi halogen- or C-C-alkoxy-Substituted C-C-alkyl, in tuted C-C-alkyl, C-C-cycloalkyl or phenyl, each case optionally cyano- or halogen-substituted R" represents hydrogen, in each case an optionally 50 C-C-alkenyl or C-C-alkynyl, optionally cyano-, hydroxyl-, cyano-, halogen- or C-C-alkoxy-Substi halogen- or C-C-alkyl-substituted C-C-cycloalkyl, tuted C-C-alkyl, C-C-cycloalkyl or tri-(C-C- or optionally nitro-, cyano-, halogen-, C-C-alkyl-, alkyl)-silyl, C-Ca-haloalkyl-, C-C-alkoxy- or C-C-haloalkoxy R" represents hydrogen, cyano, halogen, or represents in substituted phenyl, or together with R represents in each case an optionally fluoro, chloro or bromo-Substi 55 each case optionally C-C-alkyl-substituted C-C-al tuted C-C-alkyl, C-C-cycloalkyl or phenyl, kanediyl or C-C-Oxaalkanediyl. X' represents nitro, cyano, halogen, C1-C4-alkyl, C-C- X' represents nitro, cyano, carboxyl, carbamoyl, formyl, haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, Sulfamoyl, hydroxyl, amino, halogen, C-C-alkyl, X represents hydrogen, cyano, nitro, halogen, C-Ca C-Ca-haloalkyl, C-C-alkoxy or C-Ca-haloalkoxy, alkyl, C-Ca-haloalkyl, C1-C4-alkoxy or C-Ca-ha 60 loalkoxy, and X represents hydrogen, cyano, nitro, halogen, C-C- X represents nitro, cyano, carboxyl, carbamoyl, formyl, alkyl, C-C-haloalkyl, C-C-alkoxy or C-C-ha Sulfamoyl, hydroxyl, amino, halogen, C-C-alkyl, loalkoxy, C-Ca-haloalkyl, C-C-alkoxy or C-C-haloalkoxy. and/or the following compounds, k k k k k