(12) United States Patent (10) Patent No.: US 8,673,818 B2 Ruther Et Al

USOO8673818B2

(12) United States Patent (10) Patent No.: US 8,673,818 B2 Ruther et al. (45) Date of Patent: Mar. 18, 2014

(54) C2-PHENYL-SUBSTITUTED CYCLIC 4.338,122 A 7, 1982. Wheeler KETONOLS 4,351,666 A 9, 1982 Koerwer 4.409,153 A 10, 1983 Hodakowski 4,422,870 A 12/1983 Wheeler (75) Inventors: Michael Ruther, Leverkusen (DE); 4,436,666 A 3, 1984 Wheeler Hermann Hagemann, Leverkusen 4.484.942 A 11/1984 Kirino et al. (DE); Udo Schneider, Leverkusen (DE): 4,526,723 A 7, 1985 Wheeler et al. Markus Dollinger, Leverkusen (DE); 4,551,547 A 11/1985 Wheeler Peter Dahmen, Neuss (DE); Ulrike (Continued) Wachendorff-Neumann, Neuwied (DE); Reiner Fischer, Monheim (DE); FOREIGN PATENT DOCUMENTS Alan Graff, Leverkusen (DE); Thomas Bretschneider, Leverkusen (DE); CH 1999 OOO1642 9, 1999 Christoph Erdelen, Leichlingen (DE); DE 28 133 41 10, 1978 Mark Wilhelm Drewes, Langenfeld (Continued) (DE); Dieter Feucht, Eschborn (DE): OTHER PUBLICATIONS Folker Lieb, Leverkusen (DE) Chemical Reviews, (month unavailable) 1953, pp. 237-416, "The Reactions of Aliphatic Acid Chlorides” by N. O. V. Sonntag. (73) Assignee: Bayer Aktiengesellschaft, Leverkusen Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin, (DE) (month unavailable) 1977, p. 505 D.7.1.5. Reaktionen von Carbonsaeuren und Carbonsaeurenderivaten mit Basen. (*) Notice: Subject to any disclaimer, the term of this Chem. Pharm. Bull., 15 (8) pp. 1120-1122, (month unavailable) patent is extended or adjusted under 35 1967, “Studies on Antiviral Agents IV. Biological Activity of Tenu U.S.C. 154(b) by 0 days. azonic Acid Derivatives” by S. Suzuki, F. Sano and H. Yuki. The Journal of Antibiotics, vol. XXXVI, No. 11, Nov. 1983, pp. 1589-1591, “Synthesis and Biological Activities of Thiotetromycin (21) Appl. No.: 13/455,416 Analogs” by K. Tsuzuki and S. Omura. (22) Filed: Apr. 25, 2012 (Continued) Primary Examiner — Kahsay Habte (65) Prior Publication Data (74) Attorney, Agent, or Firm — Miles & Stockbridge, P.C. US 2012/O23845O A1 Sep. 20, 2012 (57) ABSTRACT Related U.S. Application Data The present invention relates to novel C-phenyl-substituted cyclic ketoenols of the formula (62) Division of application No. 13/029,497, filed on Feb. 17, 2011, now Pat. No. 8,193,120, which is a division of application No. 10/239,331, filed as application No. PCT/EPO1/03215 on Mar. 21, 2001, now Pat. No. 7,915,282. CKE Y (30) Foreign Application Priority Data Apr. 3, 2000 (DE) ...... 1OO 16544 W Z in which W is methyl, X is alkyl, alkenyl or alkinyl, Y is (51) Int. Cl. hydrogen, methyl, ethyl, i-propyl, alkenyl oralkinyl, and Z is C07C 49/597 (2006.01) hydrogen, alkyl, alkenyl or alkinyl, with the proviso that at CD7C 69/003 (2006.01) least one of X, Y, or Z represents a chain having at least two AOIN35/06 (2006.01) carbon atoms and with the further proviso that X is not ethyl AOIN37/10 (2006.01) when Z is hydrogen and Y is methyl, and CKE represents the (52) U.S. Cl. group USPC ...... 504/318: 568/329;568/376; 560/155 (58) Field of Classification Search USPC ...... 568/329,376; 504/318; 560/155 See application file for complete search history. (56) References Cited U.S. PATENT DOCUMENTS in which B is hydrogen, alkyl or alkoxyalkyl, A and Q' 3,542,809 A 11, 1970 Nakanishi 4,091,006 A 5/1978. Durden, Jr. et al. together are optionally Substituted alkanediyl or alkenediyl. 4,104,043 A 8, 1978. Durden, Jr. et al. Q is represents hydrogen or C-C-alkyl, and G represents 4,175,135 A 11, 1979 Haines hydrogen or an acyl or acyl-like group, to a plurality of 4,209,532 A 6, 1980 Wheeler processes for their preparation and to their use as pesticides 4,256,659 A 3, 1981 Wheeler and herbicides. 4,283,348 A 8, 1981 Wheeler 4,303,669 A 12, 1981 D’Silva 8 Claims, No Drawings US 8,673,818 B2 Page 2

(56) References Cited 2003/OO73851 A1 4/2003 Lieb et al. 2003/0171219 A1 9, 2003 Lieb et al. U.S. PATENT DOCUMENTS 2003/0216260 A1 11/2003 Ruther et al. 2005, OO38021 A1 2/2005 Lieb et al. 4,613,617 9, 1986 Sousa 4,632,698 12, 1986 Wheeler FOREIGN PATENT DOCUMENTS 4,659,372 4, 1987 Wheeler 4,925,868 5, 1990 Terao et al. DE 100 16544 10, 2001 5,045,560 9, 1991 Fischer et al. DE 10016554 10, 2001 5,091,537 2, 1992 Fischer et al. EP O3 555 99 2, 1990 5,094,681 3, 1992 Kraemer et al. EP O456053 11, 1991 5,116,836 5, 1992 Fischer et al. EP O456063 11, 1991 5, 186,737 2, 1993 Fischer et al. EP O528156 7, 1992 5,207,817 5, 1993 Kraemer et al. EP O596.298 10, 1993 5,225,434 7, 1993 Bertram et al. EP O647637 8, 1994 5,258,527 11, 1993 Krauskopfet al. EP O7O6527 1, 1995 5,262,383 11, 1993 Fischer et al. EP 95O1798 1, 1995 5,321,122 6, 1994 Kuramoto et al. EP O837847 4f1998 5,393,729 2, 1995 Fischer et al. EP O915846 5, 1999 5,420,155 5, 1995 Kulagowski et al. 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Organic Preparations and Procedures Int., 7(4), pp. 155-158, (month 6,200,932 3, 2001 Fischer et al. unavailable) 1975, "Synthesis of Chlorocarbonyl Ketenes” by S. 6,251,830 6, 2001 Fischer et al. Naskanishi and K. Butler. 6,251,833 6, 2001 Erdelen et al. J. Chem. Soc., Chem. Commun., (month unavailable) 1987, pp. 6.255,342 T/2001 Lieb et al. 1228-1230, "An Asymmetric Synthesis of Thiotetronic Acids using 6,271,180 8, 2001 Lieb et al. Chriality Transfer via an Allyl Xanthate-toDithiocarbonate Rear 6,288,102 9, 2001 Hagemann et al. rangement. X-Ray Crystal Structure of (5R)-2,5-Dihydro-4- 6,316,486 11, 2001 Lieb et al. hydroxy-5-methyl-3-phenyl-5-prop-1'-enyl-2-oxothiophene” by 6,359,151 3, 2002 Lieb et al. 6,380,246 4, 2002 Lieb et al. M.S. Chambers, E. J. Thomas and D. J. Williams. 6,388,123 5, 2002 Lieb et al. J. Chem. Soc. C. (month unavailable) 1967, pp. 405-409, "Constitu 6,391.912 5, 2002 Hagemann et al. ents of the Higher Fungi. Part IV. Involutin, a Diphenyl 6,410,480 6, 2002 Muehlebach et al. Cyclopenteneone from Paxillus involutus (Oeder ex Fries)” by R. L. 6,417,370 T/2002 Lieb et al. Edwards, G. C. Elsworthy and N. Kale. 6,451,843 9, 2002 Lieb et al. Arch. Pharm., 309, (month available) 1976, pp. 558-564, “Zur 6,458,965 10, 2002 Lieb et al. Synthese von Kawalactonderivaten” by A. M. Chirazi, T. Kappe and 6,469,196 10, 2002 Fischer et al. E. Ziegler. 6,472.419 10, 2002 Fischer et al. J. Heterocycl. Chem. Apr. 10, 1973, pp. 223-228, “Synthesis of 6,486,343 11, 2002 Lieb et al. Heterocycles. 174 (1.2) Substituted Thiazines and Bisthiazinyls from 6,504,036 1, 2003 Lieb et al. Dithiooxamide and Trichlorophenyl Malonates' by R. Ketcham (3), 6,511.942 1, 2003 Lieb et al. 6,515, 184 2, 2003 Fischer et al. Th. Kappe and E. Ziegler. 6,794, 183 9, 2004 Wildli et al. J. Chem. Soc., Perkin Trans. I. (month unavailable) 1985, pp. 1567 6,933,261 8, 2005 Lieb et al. 1576, “Synthesis of (E)- and (Z)-Pulvin' by A. C. Campbell, M. S. 7,256,158 8, 2007 Lieb et al. Maidment, J. H. Pick and D. F. M. Stevenson. 7,915,282 3, 2011 Ruther et al. Liebigs Ann. Chem. (month unavailable) 1985, pp. 1095-1098, 8, 168,832 5, 2012 Fischer et al. “Cyclisierung von N-Acylalanin-und N-Acylglycinestern” by R. 8, 193,120 6, 2012 Ruther et al...... 504,318 Schmierera and H. Mildenberger. 2002/0010204 1, 2002 Lieb et al. Indian J. Chem. 6, (month unavailable) 1968, pp. 341-345, 2002/0022575 2, 2002 Fischer et al. “Isoquinoline Derivatives: Part XVIII—Formation of I-Alkyl-(or 2002fOO726.17 6, 2002 Hagemann et al. alkryl)-3-methyl-7-chloro-(or 5-chloro)-isoquinolines” by B. Bhat 2002fO161034 A1 10, 2002 Hagemann et al. tacharya. US 8,673,818 B2 Page 3

(56) References Cited CAS Registry Database No. 81598-12-1; 2-Ethenylbenzeneacetic Acid; Nov. 16, 1984. OTHER PUBLICATIONS CAS Registry Database No. 19418-96-3; 2-(1- Methylethyl)Benzeneacetic Acid; Nov. 16, 1984. Chemistry & Industry (London), Nov. 9, 1968, p. 1568. “Use of CAS Registry Database No. 6331-04-0; 2,4-Dimethylbenzeneacetic molecular sieves in the methyl esterification of carboxylic acids” by Acid; Nov. 16, 1984. CAS Registry Database No. 166519-12-6; 2,6-Bis(1- H. R. Harrison, W. M. Haynes, P. Arthur and E. J. Eisenbraum. Methylethyl)Benzeneacetyl; Aug. 18, 1995. Chem. Ber, 91. (month unavailable) 1958, p. 2849, “Ringschluesse CAS Registry Database No. 90705-86-5; 2,4- mit Malonsaeure-dicloriden” by K. H. Boltze and K. Heidenbluth. Dimethylbenzeneacetyl Chloride; Nov. 16, 1984. J. Org. Chem... vol. 44, No. 26, (month unavailable) 1979, pp. 4906 CAS Registry Database No. 79998-80-4; 2-(1- 4912, “Novel Photochemical Synthesis of 2-Aryl-1,3- Methylethyl)Benzeneacetyl Chloride; Nov. 16, 1984. cyclohexanediones” by T. N. Wheeler. CAS Registry Database No. 79929-33-2; 2.4.6- Tetrahedron Letters, vol.27, No. 24, pp. 2763-2766, (month unavail Trimethylbenzeneacetyl Iodide; Nov. 16, 1984. able) 1986, "Dimethyl Arylmalonates From Cerium(IV) Ammonium CAS Registry Database No. 52629-47-7; 2-4-6-Tris(1- Nitrate Promoted Reactions of Dimethyl Malonate With Aromatic Methylethyl)Benzeneacetyl; Nov. 16, 1984. Compounds in Methanol” by E. Baciocchi. D. Dell'Aira, and R. CAS Registry Database No. 181129-75-9: 5-Methyl-2-(1- RuZZiconi. Methylethyl)Benzeneacetic Acid, Ethyl Ester; Sep. 24, 1996. Tetrahedron Letters, vol. 48, No. 36, pp. 7519-7526, (month unavail CAS Registry Database No. 170635-30-0; 4-Ethenyl-2- able) 1992, "Alkylation and Acylation of 5-Phenylsulphonyl- and Methylbenzeneacetic Acid, 1,1-Dimethylethyl Ester; Nov. 28, 1995. 5-Cyanobutyrolactones” by J. Micklefield, M. H. Block and A. R. CAS Registry Database No. 169602-49-7; 2.4.6- Battersby. Trimethylbenzeneacetic Acid, Butyl Ester; Nov. 3, 1995. Monatsch, 95, (month unavailable) 1964, pp. 147-155, "Synthesen CAS Registry Database No. 105337-78-8; 2-Ethylbenzeneacetic von Heterocyclen, 52. Mitt. Ueber Derivate des 2-Phenyl-4- Acid, Ethyl Ester; Nov. 22, 1986. hydroxyl-1,3-thiazinons-(6) 1” by E. Ziegler and E. Steiner. CAS Registry Database No. 105337-16-4; 2,4- Ann. Chim. (month unavailable) 1970, t. 5, pp. 11-22, "Addition Des Dimethylbenzeneacetic Acid, Ethyl Ester Nov. 22, 1986. Reactifs Nucleophiles Sur L’Hydrogene Selenie” by P. L. Canadian Office Action Based on Patent Application No. 2,404.868 Compagnon and M. Miocque. Dated Dec. 18, 2009. Journal of Economic Entomology, (month unavailable) 1973, pp. Opposition to EP 1 280 770 B1, documents dated May 20, 2013 and 584-586, vol. 66, No. 2, "Esters of 3-Hydroxy-2-Arylindones, a New Apr. 19, 2013, 66 pages. Class of Acaricide1” by A. A. Sousa, J. A. Durden, Jr., and J. F. Allais, A., et al., “Derives de la Serie des acides Stephen. benzoylphenylacetiques anti-inflammatoires et analgesiclues.” Eur, J. Houben-Weyl: Methoden der Organischen Chemie, vol. 8, (month Med. Chem.–Chimica Therapeutica, pp. 381-389, vol. 9, No. 4 unavailable) 1952, pp. 467-469, H. Henecka. (Jul.-Aug. 1974). Organikum, 15th edition, Berlin (month unavailable) 1977, p. 499, D. Wenner, W. “Hydolysis of Acrylacetonitriles.” Contrubution No. 7.3. 5. Reaktionen mit metallorganischen Verbindungen. 153 from the Research Laboratories of Hoffman-La Roche Inc., Organikum, 15th edition, Berlin (month unavailable) 1977, pp. 519 Journal of Organic Chemistry, pp. 548-551, vol. 15 (1950). 521, D.7.4.2. Reaktionen vinyloger Biektronendonorverbindungen. Casanova, J., et al., “The Neighboring Sulfonium Group in Ester Jasna Peter-Katalinic et al., “Umwandlung von 6-Methylen-tricyclo Hydrolysis,” Journal of the American Chemical Society, vol. 3.2.1. 02.7 oct-3-en-8-onen mit Ameisensaure in kermethylierts 89(10):2411-2416 (May 10, 1967). Phenylassigsauren'. Helvetica Chimica Acta, vol. 57, Fasc. 1 (1974), Fischer, R. and H.C. Weiss, “Spirotetramat (Movento(R)—discovery, pp. 223-266. Synthesis and physico-chemical properties.” Bayer CropScience B. Van Zanten et al., “Synthesis of Alkyl-Substituted 3-Phenyl-4 Journal 61: 127-140 (2008). Hydroxycoumarins”. Recueil de Travaux Chimiques, vol. 79, 1960, Nauen, R., et al., “Biological profile of spirotetramat (Movento(R)—a pp. 1211-1222. new two-way systemic (ambimobile) insecticide against Sucking pest European Patent Office, Notice of Opposition to European PatentNo. species.” Bayer CropScience Journal 61:245-278 (2008). EP 1 280770B1 (Bayer Aktiengesellschaft), Mar. 15, 2011. Bruck, E., et al., “Movento(R), an innovative ambimobile insecticide Canadian Office Action based on Canadian Application No. for Sucking insect pest control in agriculture: Biological profile and 2,404,868 dated Dec. 18, 2009. field performance.” Crop Protection 28:838-844 (2009). CAS Registry Database No. 100863-17-0; 2,4,6- English Translation of European Decision Revoking EP 1 280 770 Triethylbenzeneacetic Acid; Dated Mar. 15, 1986. which was filed as EP 01917 102.4 dated Jul. 15, 2013. CAS Registry Database No. 100256-33-5; 2,6-Diethylbenzeneacetic Acid; Feb. 15, 1986. * cited by examiner US 8,673,818 B2 1. 2 C2-PHENYL-SUBSTITUTED CYCLIC WO 97/16 436, WO 97/19 941, WO 97/36 868, WO KETONOLS 98/05638, WO 99/43649, WO 99/48869 and WO99/55673. Certain 5-phenyl-1,3-thiazine derivatives which are unsub This application is a Divisional Application of U.S. appli stituted in the phenyl ring have already become known (cf. E. cation Ser No. 13/029,497, filed Feb. 17, 2011, which is a Ziegler and E. Steiner, Monatsh.95, 147 (1964), R. Ketcham, Divisional of U.S. Ser. No. 10/239,331, filed Dec. 16, 2002, T. Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 now U.S. Pat. No. 7,915,282, which is a National Stage Appli (1973)), a possible use of these compounds as pesticides not cation of PCT/EP01/03215, filed Mar. 21, 2001, which claim being mentioned. 5-Phenyl-1,3-thiazine derivatives which priority to German Application 100 16 544.3, filed Apr. 3, 10 are substituted in the phenyl ring and have herbicidal, acari 2000, each hereby incorporated by reference in their entire cidal and insecticidal activity are described in WO94/14785, ties. WO 96/02 539, WO 96/35 664, WO 97/01 535, WO 97/02 The present invention relates to novel C-phenyl-substi 243, WO 97/02 243, WO 97/36 868, WO 99/05638, WO tuted cyclic ketoenols, to a plurality of processes for their 99/43649, WO 99/48869 and WO99/55673. preparation and to their use as pesticides and herbicides. Pharmacological properties of 3-acyl-pyrrolidine-2,4-di 15 It is known that certain Substituted 2-arylcyclopentanedi ones have already been described (S. Suzuki et al. Chem. ones have herbicidal and acaricidal properties (cf., for Pharm. Bull. 15 1120 (1967)). Furthermore, N-phenylpyrro example, U.S. Pat. Nos. 4,283,348; 4.338,122; 4,436,666: lidine-2,4-diones have been synthesized by R. Schmierer and 4,526,723; 4,551,547; 4,632,698; WO 96/01798: WO 96/03 H. Mildenberger (Liebigs Ann. Chem. 1985, 1095). A bio 366, WO 97/14 667 and also WO 98/3928.1, WO 99/43649, logical activity of these compounds has not been described. EP-A-0262399 and GB-A-2266888 disclose compounds WO99/48869, WO 99/55673). Moreover, compounds of a of a similar structure (3-aryl-pyrrolidine-2,4-diones) of similar structure are known: 3-hydroxy-5,5-dimethyl-2-phe which, however, no herbicidal, insecticidal or acaricidal nylcyclo-pent-2-en-1-one from the publication Micklefield et activity has become known. Unsubstituted bicyclic 3-aryl 25 al., Tetrahedron, (1992), 7519-26 and the natural product pyrrolidine-2,4-dione derivatives (EP-A-355.599 and EP-A- 415 211) and substituted monocyclic 3-aryl-pyrrolidine-2,4- involutine (-)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy dione derivatives (EP-A-377.893 and EP-A-442 077) having 2-(4-hydroxyphenyl)-cyclopent-2-en-one from the publica herbicidal, insecticidal or acaricidal activity are known. tion Edwards et al., J. Chem. Soc. S. (1967), 405-9. An insec Also known are polycyclic 3-arylpyrrolidine-2,4-dione 30 ticidal or acaricidal activity is not described. Moreover, 2-(2, derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione 4,6-trimethylphenyl)-1,3-indanedione is known from the derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298. EP-A-613 884, EP-A-613 885, WO 94/01 997, WO95/26 publication.J. Economic Entomology, 66, (1973), 584 and the 954, WO95/20572, EP-A-0 668 267, WO 96/25 395, WO Offenlegungsschrift DE-A 2 361 084, with herbicidal and 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868. 35 acaricidal activities being mentioned. WO 97/43275, WO 98/05638, WO 98/06721, WO 98/25928, WO 99/16748, WO 99/24437. WO99/43649. WO99/48869 It is known that certain substituted 2-arylcyclohexanedi and WO 99/55673). ones have herbicidal and acaricidal properties (U.S. Pat. Nos. It is known that certain substituted A-dihydrofuran-2-one 4,175,135, 4,209,432, 4,256,657, 4,256,658, 4,256,659, derivatives have herbicidal properties (cf. DE-A-4 014.420). 40 4,257,858, 4,283,348, 4,303,669, 4,351,666, 4,409,153, The synthesis of the tetronic acid derivatives used as starting 4,436,666, 4,526,723, 4,613,617, 4,659,372, DE-A 2 813 materials (such as, for example, 3-(2-methyl-phenyl)-4-hy 341, and also Wheeler, T. N.J. Org. Chem. 44, 4906 (1979)), droxy-5-(4-fluorophenyl)-A-dihydrofuran-2-one) is like WO99/43649, WO 99/48869, WO 99/55673). wise described in DE-A-4 014.420. However, the activity and the activity spectrum of these Compounds of a similar structure are known from the 45 publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, compounds are, in particular at low application rates and 1985, (8) 1567-76, without any insecticidal and/or acaricidal concentrations, not always entirely satisfactory. Furthermore, activity being mentioned. Furthermore, 3-aryl-A-dihydro the compatibility of these compounds with plants is not furanone derivatives having herbicidal, acaricidal and insec always Sufficient. ticidal properties are known from EP-A-528156, EP-A-0647 50 This invention, accordingly, provides novel compounds of 637, WO95/26 345, WO 96/20 196, WO 96/25 395, WO the formula (I) 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO99/48869 and WO99/55673.3-Aryl-A-dihydrothiphe none derivatives are likewise known (WO95/26 345, 96/25 55 395, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO (I) 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673). Certain phenyl-pyrone derivatives which are unsubstituted CKE Y in the phenyl ring have already become known (cf. A. M. 60 Chirazi, T. Kappe and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem. Ber. 91, 2849), a possible use of these compounds as pesticides not being mentioned. Phenyl-pyrone derivatives which are sub in which stituted in the phenyl ring and have herbicidal, acaricidal and 65 insecticidal properties are described in EP-A-588 137, WO W represents hydrogen, alkyl, alkenyl or alkinyl, 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, X represents alkyl, alkenyl or alkinyl, US 8,673,818 B2 3 4 Y represents hydrogen, methyl, ethyl, i-propyl, alkenyl or represents in each case optionally halogen-, alkyl-, alkinyl, halogenoalkyl-, alkoxy-, halogenoalkoxy-, cyano- or Z represents hydrogen, alkyl, alkenyl or alkinyl, nitro-substituted aryl, arylalkyl or hetaryl, with the proviso that at least one of the radicals W, X, Y or Z B represents hydrogen, alkyl or alkoxyalkyl, or represents a chain having at least two carbon atoms, A and B together with the carbon atom to which they are CKE represents one of the groups attached represent a saturated or unsaturated unsub stituted or substituted cycle which optionally contains at least one heteroatom, (1) D represents hydrogen or represents an optionally Sub O-G, 10 stituted radical from the group consisting of alkyl, A alkenyl, alkinyl, alkoxyalkyl, Saturated or unsaturated >1 \ cycloalkyl in which optionally one or more ring mem N bers are replaced by heteroatoms, arylalkyl, aryl, D1 15 hetarylalkyl and hetaryl or O A and D together with the atoms to which they are

(2) attached represent a saturated or unsaturated cycle which is unsubstituted or substituted in the A.D moi ety and which optionally contains at least one heteroa tom, or A and Q' together represent alkanediyl or alkenediyl. each of which is optionally substituted by hydroxyl or by in each case optionally Substituted alkyl, alkoxy, (3) alkylthio, cycloalkyl, benzyloxy or aryl or 25 Q" represents hydrogen or alkyl, Q, Q, Q and Q independently of one another each represent hydrogen or alkyl, Q represents hydrogen, alkyl, alkoxyalkyl, alkylthio alkyl, optionally substituted cycloalkyl (in which 30 optionally one methylene group is replaced by oxy gen or Sulphur) or optionally Substituted phenyl, or (4) Q and Q together with the carbon atom to which they are attached represent a saturated or unsaturated unsubstituted or substituted cycle which optionally 35 contains a heteroatom, G represents hydrogen (a) or represents one of the groups (5)

40 (b)

(d)

50 (e)

(7)

55 (f) (g)

in which A represents hydrogen, represents in each case option in which ally halogen-substituted alkyl, alkenyl, alkoxyalkyl, E represents a metal ion equivalent or an ammonium alkylthioalkyl, represents saturated or unsaturated, 65 ion, optionally substituted cycloalkyl in which optionally L represents oxygen or Sulphur, at least one ring atom is replaced by a heteroatom, or M represents oxygen or Sulphur, US 8,673,818 B2 5 6 R" represents in each case optionally halogen-substi -continued tuted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, (I-4) polyalkoxyalkyl or optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl which may be inter rupted by at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, R represents in each case optionally halogen-substi tuted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl 10 (I-5) or represents in each case optionally Substituted cycloalkyl, phenyl or benzyl, R. R. and R independently of one another each represent in each case optionally halogen-substi tuted alkyl, alkoxy, alkylamino, dialkylamino, 15 alkylthio, alkenylthio, cycloalkylthio and represent in each case optionally Substituted phenyl, benzyl, (I-6) phenoxy or phenylthio. R and R' independently of one another each repre sent hydrogen, in each case optionally halogen Substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted phe nyl, represent optionally Substituted benzyl, or

together with the Natom to which they are attached (I-7) represent a cycle which is optionally interrupted by 25 oxygen or Sulphur. Depending, interalia, on the nature of the Substituents, the compounds of the formula (I) can be present as geometrical and/or optical isomers or mixtures of isomers in varying so compositions, which can be separated, if desired, in a cus tomary manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use and also compositions comprising them. In the following, for simplicity, however, the compounds of the formula (I) are is always referred to, although both pure compounds and, if in which appropriate, mixtures having different proportions of iso A, B, D, G, Q, Q, Q, Q, Q, Q, W, X, Y and Zare each meric compounds are intended. as defined above. Including the meanings (1) to (7) of the group CKE, the Including the various meanings of (a), (b), (c), (d), (e), (f) following principal structures (I-1) to (I-7) result: 40 and (g) of the group G, the following principal structures (I-1-a) to (I-1-g) result if CKE represents the group (1): (I-1) e G O X (I-1-a) 45 A B N Y, N D O W Z 50 (I-2) e G O X A

B N Y, 55 (I-1-b) O

O W Z (I-3) G O e X 60

A B N Y, S 65 US 8,673,818 B2 7 8 -continued Including the various meanings (a), (b), (c), (d), (e), (f) and (I-1-c) (g) of the group G, the following principal structures (I-2-a) to (I-2-g) result if CKE represents the group (2):

5 (I-2-a) A OH X

10 I Y O O W Z (I-1-d) 15 (I-2-b) 1s,O A 2O X B \ Y O 25 O W Z (I-1-e)

(I-2-c)

(I-1-f) 40 (I-2-d)

(I-2-e) (I-1-g) 50 p-r\ ?' A X R5

55 I Y O O W Z

(I-2-f) 60

in which 65 A, B, D, E, L, M, W, X,Y,Z, R1, R,R,R,R, R and R7 are each as defined above. US 8,673,818 B2 9 10 -continued -continued (I-2-g) L. R. (I-3-e) V / O-P 5 A X Ys

10 S

(I-3-f) in which A, B, E, L, M, W, X,Y,Z, R',R,R,R,R,R and R7 are each as defined above. Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-3-a) to

(I-3-g) result if CKE represents the group (3): (I-3-a): (I-3-b): 20 (I-3-g)

(I-3-a) A OH X 25 B \ Y S O W Z 30 in which A, B, E, L, M, W, X, Y, Z, R', R,R,R,R,RandR are (I-3-b) each as defined above. O 35 Depending on the position of the Substituent G, the com pounds of the formula (I-4) can be present in two isomeric R1 forms of the formulae (I-5-A) and (I-5-B) A O X

B \ 40 G (I-4-A) Y S A O X O W Z ... p. / \ Y O O W Z

(I-3-c) (I-4-B) A 50 D / / Y O 55 O W Z

"" which is meant to be indicated by the dashed line in the 60 formula (I-4). 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. Mixtures of the compounds of the formulae (I-4-A) and (I-4- B) can be separated, if desired, in a known manner by physical 65 methods, for example by chromatographic methods. For reasons of clarity, hereinbelow in each case only one of the possible isomers is given. This does not exclude that the US 8,673,818 B2 11 12 compounds may, if appropriate, be present in the form of the -continued isomer mixtures or in the respective other isomeric form. (I-4-f) Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-4-a) to 5 (I-4-g) result if CKE represents the group (4): (I-4-a): (I-4-b):

(I-4-a) 10

(I-4-g)

2O R7-N (I-4-b)

25 in which A, D, E, L, M, W, X, Y, Z, R, R,R,R,R, R and R7 are each as defined above. Including the various meanings (a), (b), (c), (d), (e), (f) and so (g) of the group G, the following principal structures (I-5-a) to (I-5-g) result if CKE represents the group (5): (I-5-a): (I-5-b):

(I-4-c) (I-5-a)

D (I-4-d) (I-5-b)

(I-4-e) (I-5-c) US 8,673,818 B2 13 14 -continued -continued (I-5-d) (I-6-B) A O X B

Q Q? f W Z 10 G

which is meant to be indicated by the dashed line in the (I-5-e) formula (I). 15 The compounds of the formulae (I-6-A) and (I-6-B) can be present both as mixtures and in the form of their pure isomers. Mixtures of the compounds of the formulae (I-6-A) and (I-6- B) can be separated, if desired, by physical methods, for example by chromatographic methods. For reasons of clarity, hereinbelow in each case only one of the possible isomers is given. This does not exclude that the compounds may, if appropriate, be present in the form of the isomer mixtures or in the respective other isomeric form. Including the various meanings (a), (b), (c), (d), (e), (f) and (I-5-f) 25 (g) of the group G, the following principal structures (I-6-a) to (I-6-g) result:

(I-6-a) 30 A OH X B

35 Q Q? O W Z (I-5-g)

(I-6-b) O

40 1s, A X B

45 Q Q? O W Z (I-6-c) L in which | A, E, L, M, W, X, Y, Z, R', R. R. R. R. Rand R7 are 50 O-C-M-R2 each as defined above. A X Depending on the position of the Substituent G, the com B pounds of the formula (I-6) can be present in the two isomeric forms of the formula (I-6-A) and (I-6-B) 55 Q Q? O W Z (I-6-A) (I-6-d) G O-SO-R A O X 60 A X B B

65 Q Q2 O w Z Q Q? O W Z US 8,673,818 B2 15 16 -continued For reasons of clarity, hereinbelow in each case only one of (I-6-e) the possible isomers is given. This does not exclude that the L compound may, if appropriate, be present in the form of the -R' isomer mixture or in the respective other isomeric form. p-PS 5 A X R Including the various meanings (a), (b), (c), (d), (e), (f) and B (g) of the group G, the following principal structures (I-7-a) to (I-7-g) result:

10 Q Q? O W Z (I-7-a) O E (I-6-f) A X 15 B

Q Q? O W Z L (I-6-g)

O ls N1 R6 A X Y. 25 (I-7-b) B

30 Q Q? O W Z in which A, B, Q, Q, E, L, M, W, X,Y,Z, R', R,R,R,R,R and 35 R7 are each as defined above. Depending on the position of the Substituent G, the com pounds of the formula (I-7) can be present in 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): 40 (I-7-c)

(I-7-A) 45 B A O X

Y Q >()–( ) 50 Q5 Q6 O w Z (I-7-B) B A O X

Q3 55 (I-7-d) Q () ()-y Q: Q6 W Z G 60

The compounds of the formulae (I-7-A) and (I-7-B) can be present both as mixtures and in the form of their pure isomers. Mixtures of the compounds of the formulae (I-7-A) and (I-7- 65 B) can be separated, if desired, by physical methods, for example by chromatographic methods. US 8,673,818 B2 17 18 -continued in which (I-7-e) A, B, D, W, X, Y and Z are each as defined above are obtained when

N-acylamino acid esters of the formula (II)

10 (II) COR A B X

N 15 D1

O W Y

(I-7-f) Z

in which A, B, D, W, X, Y and Z are each as defined above

25 and R represents alkyl (preferably C-C-alkyl). are condensed intramolecularly in the presence of a diluent and in the presence of a base. 30 (B) Moreover, it has been found that substituted 3-phenyl-4- hydroxy-A-di-hydrofuranone derivatives of the formula (I-2-a)

(I-7-g)

35 (I-2-a) A HO X B \ Y 40 O O W Z

in which 45 in which A, B, W, X,Y and Zare each as defined above are obtained A, B, E, L, M, Q, Q, Q, Q, W, X, Y, Z, R, R2, R, R, when R. Rand Rare each as defined above. carboxylic esters of the formula (III) Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes 50 described below: (A) Substituted 3-phenylpyrrolidine-2,4-diones or their enols (III) of the formula (I-1-a)

(I-1-a)

in which 65 A, B, W, X, Y, Z and R are each as defined above are condensed intramolecularly in the presence of a diluent and in the presence of a base. US 8,673,818 B2 19 20 (C) Furthermore, it has been found that substituted 3-phenyl in which 4-hydroxy-A-di-hydrothiophenone derivatives of the for A and Dare each as defined above or their silyl enol ethers mula (I-3-a) of the formula (Va)

(Va) (I-3-a) CHA A HO X B D-C-OSi(R) \ Y 10 in which S A, D and Rare each as defined above O W Z are reacted with ketene acid halides of the formula (VI)

15 in which (VI) A, B, W, X, Y and Z are each as defined above COHal are obtained when B-ketocarboxylic esters of the formula (IV) Y CCEO

(IV) in which 25 W, X, Y and Z are each as defined above and Hal represents halogen (preferably chlorine or bromine), if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor. Furthermore, it has been found 30 (E) that the novel substituted phenyl-1,3-thiazine derivatives of the formula (I-5-a)

(I-5-a) in which 35 A, B, W, X, Y, Z and Rare each as defined above and V represents hydrogen, halogen, alkyl (preferably C-C- alkyl) or alkoxy (preferably C-C-alkoxy) are cyclized intramolecularly, if appropriate in the pres 40 ence of a diluent and in the presence of an acid. (D) Furthermore, it has been found that the novel substituted in which 3-phenylpyrone derivatives of the formula (I-4-a) A, W, X, Y and Z are each as defined above are obtained 45 when (I-4-a) thioamides of the formula (VII) O X O (VII) S D Y 50 \ / HN-C-A A OH W Z in which 55 A is as defined above are reacted with ketene acid halides in which of the formula (VI) A, D, W, X, Y and Z are each as defined above are obtained when (VI) carbonyl compounds of the formula (V) 60 COHal

(V) Y CCEO

D-C-CH-A 65 US 8,673,818 B2 21 22 in which in which Hal, W, X, Y and Z are each as defined above, A, B, Q, Q, Q, Q, W, X, Y and Z are each as defined if appropriate in the presence of a diluent and if appropriate above in the presence of an acid acceptor. are obtained when 6-aryl-5-keto-hexanoic esters of the formula (IX) Furthermore, it has been found (F) that compounds of the formula (I-6-a) (IX) A B Qs Q6 X (I-6-a) 10 A OH X ROC B Q Q W Y )-( )-y 15 Z Q Q2 O W Z in which A, B, Q, Q, Q, Q, W, X, Y and Z are each as defined in which above and R represents alkyl (preferably C-C-alkyl) are condensed intramolecularly in the presence of a diluent A, B, Q', Q, W, X, Y and Z are each as defined above and in the presence of a base; are obtained when (H) that compounds of the formulae (I-1 (a-g)) to (I-7(a-g)) shown above in which A, B, D, G, Q, Q, Q, Q, Q, Q, ketocarboxylic esters of the formula (VIII) 25 W, X, Y and Z are each as defined above, where one, at most two, radicals W, X, Y or Z represent (VIII) R’ C—C or Q Q2 30 R22 HC=CH, R’ represents hydrogen or C-C-alkyl, preferably hydrogen 35 or C-C-alkyl and particularly preferably hydrogen, are obtained when compounds of the formulae (I-1'(a-g)) to

(I-1) in which

A, B, Q, Q, W, X,Y and Z are each as defined above and 45 R represents alkyl (in particular C-C-alkyl) are cyclized intramolecularly, if appropriate in the pres ence of a diluent and in the presence of a base. Moreover, it has been found 50 (G) that compounds of the formula (I-7-a) (I-2) A OG X

(I-7-a) B 55 \ Yi O O. W. Z. (I-3) 60 A OG X B \ Yi S 65 US 8,673,818 B2 23 24 -continued -continued

(I-4) (X-b) R22 Alk M HCECH-S-Ak Alk

in which alk preferably represents C-C-alkyl and R" preferably represents C-C-alkyl or phenyl, 10 R’ preferably represents hydrogen or C-C-alkyl, par ticularly preferably hydrogen or C-C2-alkyl and very particularly preferably hydrogen, (I-5) in the presence of a solvent, if appropriate in the presence 15 of a base and a catalyst, particularly Suitable catalysts being palladium complexes. Moreover, it has been found (I) that the compounds of the formulae (I-1-b) to (I-7-b) shown above in which A, B, D, Q, Q, Q, Q, Q, Q, R', W, X,Y and Zare each as defined above are obtained when compounds of the formulae (I-1-a) to (I-7-a) shown above in which A, B, D, Q, Q, Q, Q, Q, Q, W, X,Y and Zare each as defined above are in each case (I-6) 25 (C.) reacted with acid halides of the formula (XI)

(XI) Hal RI

30 O

O W Z. in which

35 R" is as defined above and Hal represents halogen (in particular chlorine or bromine) O (I-7) (B) reacted with carboxylic anhydrides of the formula (XII) 40 R" CO-O CO R' (XII) in which R" is as defined above, if appropriate in the presence of a diluent and if appropriate 45 in the presence of an acid binder, (J) that the compounds of the formulae (I-1-c) to (I-7-c) shown above in which A, B, D, Q, Q, Q, Q, Q, Q, R, M, W, X, Y and Z are each as defined above and L repre sents oxygen are obtained when compounds of the formu 50 in which lae (I-1-a) to (I-7-a) shown above in which A, B, D, Q', Q, Q, Q, Q, Q, W, X,Y and Zare each as defined above are A, B, D, G, Q, Q, Q, Q, Q, Q, W, X,Y and Zare each in each case as defined above and where the apostrophe means that reacted with chloroformic esters or chloroformic thioesters one, at most two, radicals W, X, Y and Z in this process represent chlorine, bromine, iodine, preferably bromine, 55 of the formula (XIII) with the proviso that the other radicals W, X, Y or Z do not represent alkenyl or alkinyl R2-M-CO Cl (XIII) are reacted with silylacetylenes of the formula (X-a) or in which vinylstannanes of the formula (X-b) 60 R° and Mare each as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, Alk (K) that compounds of the formulae (I-1-c) to (I-7-c) shown R22-CEC-Si-Alk above in which A, B, D, Q, Q, Q, Q, Q, Q, R. M. W. V 65 X, Y and Z are in each case as defined above and L repre R21 sents Sulphur are obtained when compounds of the formu lae (I-1-a) to (I-7-a) shown above in which A, B, D, Q', Q, US 8,673,818 B2 25 26 Q, Q, Q, Q, W, X, Y and Z are in each case as defined in which above are in each case reacted with chloromonothioformic Me represents a mono- or divalent metal (preferably an esters or chlorodithioformic esters of the formula (XIV) alkali metal or alkaline earth metal. Such as lithium, Sodium, potassium, magnesium or calcium), trepresents the number 1 or 2, (XIV) R", R', R' independently of one another each represents M-R2 hydrogen or alkyl (preferably C-C-alkyl). if appropriate in the presence of a diluent, S (O) that compounds of the formulae (I-1-g) to (I-7-g) shown 10 above in which A, B, D, L, Q, Q, Q, Q, Q, Q, R. R. in which W, X,Y and Zare each as defined above are obtained when Mand Rare each as defined above, compounds of the formulae (I-1-a) to (I-7-a) shown above if appropriate in the presence of a diluent and if appropriate in which A, B, D, Q, Q, Q, Q, Q, Q, W, X,Y and Zare in the presence of an acid binder 15 each as defined above are in each case and (C) reacted with isocyanates or isothiocyanates of the formula (L) that compounds of the formulae (I-1-d) to (I-7-d) shown (XIX) above in which A, B, D, Q, Q, Q, Q, Q, Q, R, W, X, Y and Z are each as defined above are obtained when compounds of the formulae (I-Ia) to (I-7-a) shown above in which A, B, D, Q, Q, Q, Q, Q, Q, W, X, Y and Z are in which each as defined above are in each case Rand L are each as defined above, reacted with sulphonyl chlorides of the formula (XV) if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or R SO, Cl (XV) (B) reacted with carbamoyl chlorides or thiocarbamoyl chlo 25 in which rides of the formula (XX) R is as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, (XX) (M) that compounds of the formulae (I-1-e) to (I-7-e) shown 30 above in which A, B, D, L. Q', Q, Q, Q, Q, Q, R. R. W, X,Y and Zare each as defined above are obtained when compounds of the formulae (I-1-a) to (I-7-a) shown above in which A, B, D, Q, Q, Q, Q, Q, Q, W, X,Y and Zare each as defined above are in each case reacted with phos 35 in which phorus compounds of the formula (XVI) L. Rand Rare each as defined above, if appropriate in the presence of a diluent and if appropriate (XVI) in the presence of an acid binder. R4 Furthermore, it has been found that the novel compounds / 40 of the formula (I) have very good activity as pesticides, pref Hall-P erably as insecticides, acaricides and herbicides. LNs The formula (I) provides a general definition of the com pounds according to the invention. Preferred substituents or ranges of the radicals listed in the formulae mentioned here in which 45 inabove and hereinbelow are illustrated below. L. Rand Rare each as defined above and W preferably represents hydrogen, C t-C-alkyl, C-C-alk Hal represents halogen (in particular chlorine or bromine), enyl or ethinyl. if appropriate in the presence of a diluent and if appropriate X preferably represents C-C-alkyl, C-C-alkenyl or ethi in the presence of an acid binder, nyl. (N) that compounds of the formulae (I-1-f) to (I-7-f) shown 50 Y preferably represents hydrogen, methyl, ethyl, i-propyl. above in which A, B, D, E, Q, Q, Q, Q, Q, Q, W, X,Y C-C-alkenyl or ethinyl. and Z are each as defined above are obtained when com Z preferably represents hydrogen, C-C-alkyl, C-C-alk pounds of the formulae (I-1-a) to (I-7-a) shown above in enyl or ethinyl which A, B, D, Q, Q, Q, Q, Q, Q, W, X, Y and Z are with the proviso that at least one of the radicals W, X, Y and each as defined above are in each case 55 Z represents a chain having at least two carbon atoms. reacted with metal compounds or amines of the formulae CKE preferably represents one of the groups (XVII) or (XVIII) Me(OR), (XVII) (1) 60 o1 G A O (XVIII) R R n N Y - \, , N R12 65 D1 US 8,673,818 B2 27 28 -continued mono- or disubstituted by C-Cs-alkyl, C-Co-cycloalkyl, G (2) C-C-halogenoalkyl, C-C-alkoxy, C-C-alkylthio. o1 halogen or phenyl, or A A, B and the carbon atom to which they are attached prefer 5 ably represent C-C-cycloalkyl which is substituted by an - \, , alkylenediyl group which optionally contains one or two O not directly adjacent oxygen and/or Sulphur atoms and which is optionally C-C-alkyl-substituted, or by an alky O lenedioxyl group or by alkenedithioyl group which, G (3) 10 together with the carbonatom to which it is attached, forms O1 a further five- to eight-membered ring, or A A, B and the carbon atom to which they are attached prefer - \ . ably represent C-C-cycloalkyl or Cs-Cs-cycloalkenyl in S 15 which two substituents together with the carbon atoms to which they are attached represent in each case optionally O C-C-alkyl-, C-C-alkoxy- or halogen-substituted

(4) C-C-alkanediyl, C-C-alkenediyl or C-C-alkanedi enediyl in which optionally one methylene group is replaced by oxygen or Sulphur. D preferably represents hydrogen, in each case optionally halogen-substituted C-C2-alkyl, C-Cs-alkenyl, C-Cs alkinyl, C-Co-alkoxy-C-C-alkyl optionally halogen (5) C-C-alkyl-C-C-alkoxy- or C-Ca-halogenoalkyl-sub 25 stituted C-Cs-cycloalkyl in which optionally one ring member is replaced by oxygen or Sulphur or in each case optionally halogen-, C-C-alkyl-, C-C-halogenoalkyl-, C-C-alkoxy-, C-C-halogenoalkoxy-, cyano- or nitro Substituted phenyl, hetaryl having 5 or 6 ring atoms (for 30 example furanyl, imidazolyl pyridyl, thiazolyl pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazoyl), phenyl-C-C- (6) alkyl or hetaryl-C-C-alkyl having 5 or 6 ring atoms (for example furanyl, imidazolyl pyridyl, thiazolyl pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazoyl), or 35 A and D together represent in each case optionally substituted C-C-alkanediyl or C-C-alkenediyl in which optionally one methylene group is replaced by a carbonyl group, oxygen or Sulphur, possible Substituents being in each (7) case: halogen, hydroxyl, mercapto or in each case option 40 ally halogen-substituted C-Co-alkyl, C-C-alkoxy, C-C-alkylthio, C-C-7-cycloalkyl, phenyl or benzyloxy, or a further C-C-alkanediyl grouping, C-C-alkenediyl grouping or abutadienyl grouping which is optionally Sub stituted by C-C-alkyl or in which optionally two adjacent 45 substituents together with the carbon atoms to which they are attached form a further saturated or unsaturated cycle having 5 or 6 ring atoms (in the case of the compound of the A preferably represents hydrogen or in each case optionally formula (I-1), A and D, together with the atoms to which halogen-substituted C-C2-alkyl, C-Cs-alkenyl, C-Co they are attached, then represent, for example, the groups alkoxy-C-C-alkyl, C-Co-alkylthio-C-C-alkyl, 50 AD-1 to AD-10 mentioned further below) which cycle may optionally halogen-, C-C-alkyl- or C-C-alkoxy-Substi contain oxygen or Sulphur, or which may optionally con tuted C-Cs-cycloalkyl in which optionally one or two not tain one of the groups below directly adjacent ring members are replaced by oxygen and/or Sulphur or represents in each case optionally halo gen-, C-C-alkyl-C-C-halogenoalkyl-, C-C-alkoxy-, 55 C-C-halogenoalkoxy-, cyano- or nitro-substituted phe nyl or naphthyl, hetaryl having 5 to 6 ring atoms (for example furanyl, pyridyl, imidazolyl, triazolyl pyrazolyl, pyrimidyl, thiazolyl or thienyl), phenyl-C-C-alkyl or 60 naphthyl-C-C-alkyl. B preferably represents hydrogen, C-C2-alkyl or C-Cs alkoxy-C-C-alkyl, or A, B and the carbon atom to which they are attached prefer ably represent saturated C-Co-cycloalkyl or unsaturated 65 Cs-Co-cycloalkyl in which optionally one ring member is replaced by oxygen or Sulphur and which are optionally US 8,673,818 B2 29 30 -continued G preferably represents hydrogen (a) or represents one of the groups

(b)

O A and Q' preferably together represent C-C-alkanediyl or (d) C-C-alkenediyl, each of which is optionally mono- or disubstituted by identical or different substituents selected 15 from the group consisting of halogen, hydroxyl, C-Co (e) alkyl, C-C-alkoxy, C-C-alkylthio, C-C-7-cycloalkyl, each of which is optionally mono- to trisubstituted by identical or different halogens, and benzyloxy and phenyl, each of which is optionally mono- to trisubstituted by (f) identical or different substituents selected from the group consisting of halogen, C-C-alkyl and C-C-alkoxy, and (g) which furthermore optionally contains one of the groups below 25

in particular (a), (b), (c) or (g) 30 in which E represents a metal ion equivalent or an ammonium ion, L represents oxygen or sulphur and M represents oxygen or Sulphur. R" particularly preferably represents in each case optionally 35 halogen-substituted C-Co-alkyl, C-Co-alkenyl, C-C- alkoxy-C-C-alkyl, C-Cs-alkylthio-C-C-alkyl, poly C-Cs-alkoxy-C-C-alkyl or optionally halogen-, C-C- alkyl or C-C-alkoxy-Substituted C-Cs-cycloalkyl in which optionally one or more (preferably not more than 40 two) not directly adjacent ring members are replaced by oxygen and/or Sulphur, represents optionally halogen-, cyano-, nitro-, C-C- alkyl-, C-C-alkoxy-, C-C-halogenoalkyl-, C-C- halogenoalkoxy-, C-C-alkylthio- or C-C-alkylsul 45 phonyl-substituted phenyl, represents optionally halogen-, nitro-, cyano-, C-C- alkyl-C-C-alkoxy-, C-C-halogenoalkyl- or C-C- halogenoalkoxy-Substituted phenyl-C-C-alkyl, represents optionally halogen- or C-C-alkyl-substituted or is bridged by a C-C-alkanediyl group or by an oxygen 50 5- or 6-membered hetaryl (for example pyrazolyl, thia atom, or Zolyl, pyridyl, pyrimidyl, furanyl or thienyl), Q' preferably represents hydrogen or C-Ca-alkyl. represents optionally halogen- or C-C-alkyl-substituted Q’, Q, Q and Q independently of one another each prefer phenoxy-C-C-alkyl or ably represent hydrogen or C-C-alkyl. represents optionally halogen-, amino- or C-C-alkyl Q preferably represents hydrogen, C1-Co-alkyl, C, -Co 55 substituted 5- or 6-membered hetaryloxy-C-C-alkyl alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, option (for example pyridyloxy-C-C-alkyl, pyrimidyloxy ally C-C-alkyl- or C-C-alkoxy-Substituted C-C-cy C-C-alkylorthiazolyloxy-C-C-alkyl). Rpreferably cloalkyl in which optionally one methylene group is represents in each case optionally halogen-substituted replaced by oxygen or Sulphur or optionally halogen C1-Co-alkyl, C-Co-alkenyl, C-Cs-alkoxy-C-Cs C-C-alkyl-, C-C-alkoxy-, C-C-halogenoalkyl-, 60 alkyl, poly-C-C-alkoxy-C-C-alkyl, C-C-halogenoalkoxy-, cyano- or nitro-substituted phe represents optionally halogen-, C-C-alkyl- or C-C- nyl, or alkoxy-Substituted C-Cs-cycloalkyl or Q and Q together with the carbon atom to which they are represents in each case optionally halogen-, cyano-, nitro attached preferably represent an optionally C-C-alkyl-, C-C-alkyl-, C-C-alkoxy-, C-C-halogenoalkyl- or C-C-alkoxy- or C-C-halogenoalkyl-substituted C-C-7- 65 C-C-halogenoalkoxy-Substituted phenyl or benzyl. ring in which optionally one ring member is replaced by R preferably represents optionally halogen-substituted oxygen or Sulphur. C-Cs-alkyl or represents in each case optionally halogen US 8,673,818 B2 31 32 C-C-alkyl-, C-C-alkoxy-, C-Ca-halogenoalkyl-, with the proviso that at least one of the radicals W, X, Y or Z C-Ca-halogenoalkoxy-, cyano- or nitro-substituted phe represents a chain having at least two carbon atoms, where at nyl or benzyl. most only one of the radicals W, X, Y or Z may represent RandR independently of one another each preferably rep C-C-alkenyl or ethinyl. resent in each case optionally halogen-substituted C-C- CKE particularly preferably represents one of the groups alkyl, C-Cs-alkoxy, C-C-alkyl-amino, di-(C-Cs-alkyl) amino, C-Cs-alkylthio, C-Cs-alkenylthio, C-C-7- cycloalkylthio or represent in each case optionally (1) halogen-, nitro-, cyano-, C-C-alkoxy-, C-C-halo G 10 o1 genoalkoxy-, C-C-alkylthio-, C-Ca-halogenoalky A lthio-, C-C-alkyl- or C-C-halogenoalkyl-substituted phenyl, phenoxy or phenylthio. - \, , RandR independently of one another each preferably rep D1 N resent hydrogen, represent in each case optionally halo O gen-substituted C-Cs-alkyl, C-C-cycloalkyl, C-Cs 15 alkoxy, C-Cs-alkenyl, C-Cs-alkoxy-C-C-alkyl, G (2) represent optionally halogen-, C-C-halogenoalkyl-, O1 C-Cs-alkyl- or C-Cs-alkoxy-Substituted phenyl, option A ally halogen-, C-C-alkyl-, C-Cs-halogenoalkyl- or - \ . C-C-alkoxy-substituted benzyl or together represent an O optionally C-C-alkyl-substituted C-C-alkylene radical in which optionally one carbonatom is replaced by oxygen O or Sulphur. G (3) R" preferably represents hydrogen, represents in each case 25 o1 optionally halogen-substituted C-C-alkyl or C-Cs A alkoxy, represents optionally halogen-, C-C-alkyl- or C-C-alkoxy-Substituted C-Cs-cycloalkyl in which - \, , optionally one methylene group is replaced by oxygen or S 30 Sulphur, or represents in each case optionally halogen O

C-C-alkyl C-C-alkoxy-, C-Ca-halogenoalkyl-, (4) C-Ca-halogenoalkoxy-, nitro- or cyano-Substituted phe nyl, phenyl-C-C-alkyl or phenyl-C-C-alkoxy. R'' preferably represents hydrogen or C-Cs-alkyl, or R" and R'' together preferably represent C-C-alkanediyl. 35 R" and R'' are identical or different and each preferably represents C-C-alkyl, or RandR' together preferably represent a C-C-alkanediyl (5) radical which is optionally substituted by C-C-alkyl, 40 C-C-halogenoalkyl or by optionally halogen-, C-C- alkyl-C-C-halogenoalkyl-, C-C-alkoxy-, C-C-halo genoalkoxy-, nitro- or cyano-Substituted phenyl. R'' and R' independently of one another each preferably represent hydrogen, represent optionally halogen-Substi 45 (6) tuted C-C-alkyl or represent optionally halogen-C-C- alkyl-C-C-alkoxy-, C-Ca-halogenoalkyl-C-C-halo genoalkoxy-, nitro- or cyano-Substituted phenyl, or R'' and R' together with the carbonatom to which they are attached preferably representa carbonyl group or represent 50 optionally halogen-, C-C-alkyl- or C-C-alkoxy-Substi tuted Cs-C7-cycloalkyl in which optionally one methylene (7) group is replaced by oxygen or Sulphur. R" and R' independently of one another each particularly preferably represent C-Co-alkyl, C-Co-alkenyl, 55 C-Co-alkoxy, C-Co-alkylamino, C-Co-alkeny lamino, di-(C1-Co-alkyl)amino or di-(C-Co-alkenyl) amino. W particularly preferably represents hydrogen, C-C-alkyl, 60 C-C-alkenyl or ethinyl. X particularly preferably represents C-C-alkyl, C-C-alk A particularly preferably represents in each case optionally enyl or ethinyl. fluorine- or chlonne-substituted C-C-alkyl, C-C- Y particularly preferably represents hydrogen, methyl, ethyl, alkoxy-C-C-alkyl, optionally C-C2-alkyl- or C-C- i-propyl, C-C-alkenyl or ethinyl. 65 alkoxy-Substituted C-C-cycloalkyl or (but not in the case Z particularly preferably represents hydrogen, C-C-alkyl, of the compounds of the formulae (I-4), (I-6) and (I-7)) in C-C-alkenyl or ethinyl each case optionally fluorine-, chlorine-, bromine-, C-C- US 8,673,818 B2 33 34 alkyl-C-C-halogenoalkyl-C-C-alkoxy-C-C-halo -continued genoalkoxy-, cyano- or nitro-Substituted phenyl or benzyl. B particularly preferably represents hydrogen or C-C-alkyl, AD-4 O A, B and the carbon atom to which they are attached particu N larly preferably represent saturated or unsaturated Cs-C7 N cycloalkyl in which optionally one ring member is replaced AD-5 by oxygen or Sulphur and which is optionally monosubsti tuted by C-C-alkyl, trifluoromethyl or C-C-alkoxy, or 10 A, B and the carbon atom to which they are attached particu N larly preferably represent C-C-cycloalkyl which is sub stituted by an alkylenediyl group which optionally con tains one or two not directly adjacent oxygen and/or AD-6 Sulphur atoms and which is optionally methyl- or ethyl Substituted, or by an alkylenedioxyl group or by an alky 15 lenedithiol group which, together with the carbon atom to N which it is attached, forms a further 5- or 6-membered ring, O A, B and the carbon atom to which they are attached particu AD-7 larly preferably represent C-C-cycloalkyl or Cs-C-cy cloalkenyl in which two substituents together with the car N bonatoms to which they are attached represent in each case N optionally C-C-alkyl- or C-C-alkoxy-substituted C-C-alkanediyl, C-C-alkenediyl or butadienediyl. 25 D particularly preferably represents hydrogen, represents in AD-8 each case optionally fluorine-substituted C-C-alkyl, C-C-alkenyl, C-C-alkoxy-C-C-alkyl, represents N optionally C-C-alkyl-, C-C-alkoxy- or C-C-halo C N genoalkyl-substituted C-C-cycloalkyl in which option 30 ally one methylene group is replaced by oxygen or (but not in the case of the compounds of the formula (I-1)) repre AD-9 sents phenyl or pyridyl, each of which is optionally mono or disubstituted by substituents selected from the group consisting of fluorine, chlorine, bromine, C-C-alkyl, 35 C-Ca-halogenoalkyl, C-C-alkoxy and C-C-halo genoalkoxy, or A and D together particularly preferably represent optionally AD-10 substituted C-C-alkanediyl in which one methylene group may be replaced by a carbonyl group (but not in the 40 case of the compounds of the formula (I-1)), by oxygen or by Sulphur, possible Substituents being C-C2-alkyl, or A and D (in the case of the compounds of the formula (I-1)) together with the atoms to which they are attached repre sent one of the groups AD-1 to AD-10: 45 O A and Q' together particularly preferably represent Ca-Ca AD-1 alkanediyl which is optionally mono- or disubstituted by identical or different substituents selected from the group 50 consisting of C-C2-alkyl and C-C2-alkoxy, or N Q' particularly preferably represents hydrogen. Q’ particularly preferably represents hydrogen. AD-2 Q, Q and Q independently of one another each particularly 55 preferably represent hydrogen or C-C-alkyl. Q particularly preferably represents hydrogen, C-C-alkyl or represents C-C-cycloalkyl which is optionally mono N or disubstituted by methyl or methoxy, or 60 Q and Q together with the carbon to which they are attached AD-3 particularly preferably represent an optionally C-C- alkyl- or C-C-alkoxy-Substituted Saturated Cs-C-mem bered ring in which optionally one ring member is replaced N 65 by oxygen or Sulphur. G particularly preferably represents hydrogen (a) or repre sents one of the groups US 8,673,818 B2 35 36 alkoxy-C-C-alkyl, represents phenyl which is optionally (b) monosubstituted by fluorine, chlorine, bromine, trifluo romethyl, C-C-alkyl or C-C-alkoxy, represents benzyl which is optionally monosubstituted by fluorine, chlorine, bromine, C-C-alkyl, trifluoromethyl or C-C-alkoxy. (c) R" particularly preferably represents C1-Co-alkyl, Cs-Co-alk enyl or C-C-alkoxy-C-C-alkyl. R and R7 together particularly preferably represent an (d) 10 optionally methyl- or ethyl-substituted C-alkylene radical in which optionally one methylene group is replaced by oxygen or Sulphur. (e) In the radical definitions mentioned as being particularly preferred, halogen represents fluorine, chlorine, bromine and 15 iodine, and in particular fluorine, chlorine and bromine. W very particularly preferably represents hydrogen, methyl, (f) ethyl, i-propyl, vinyl or ethinyl. X very particularly preferably represents methyl, ethyl, (g) n-propyl, iso-propyl, vinyl or ethinyl, Y very particularly preferably represents hydrogen, methyl, ethyl, i-propyl. vinyl or ethinyl. Z very particularly preferably represents hydrogen, methyl, 25 ethyl, n-propyl, i-butyl, vinyl or ethinyl, in particular (a), (b) or (c), with the proviso that at least one of the radicals W, X, Y or Z in which represents a chain having at least two carbon atoms where at E represents a metal ion equivalent or an ammonium ion, most only one of the radicals W, X, Y or Z may represent vinyl L represents oxygen or Sulphur and or ethinyl, M represents oxygen or Sulphur. 30 R" particularly preferably represents in each case optionally CKE very particularly preferably represents one of the fluorine- or chlorine-substituted C-C-alkyl, C-C-alk groups enyl, C-C-alkoxy-C-C-alkyl, C-C-alkylthio-C-C- alkyl or optionally fluorine-, chlorine-, C-C2-alkyl- or C-C-alkoxy-substituted C-C-cycloalkyl in which 35 (1) optionally one or two not directly adjacent ring members G are replaced by oxygen, o1 represents phenyl which is optionally mono- or disubsti A tuted by fluorine, chlorine, bromine, cyano, nitro, - \, , C-C-alkyl, C-C-alkoxy, C-C-halogenoalkyl or 40 N C-C-halogenoalkoxy, D1 R° particularly preferably represents in each case optionally O fluorine-substituted C-Cs-alkyl, C-Cs-alkenyl or C-C- alkoxy-C-C-alkyl, G (2) represents optionally C-C-alkyl- or C-C2-alkoxy-Sub 45 o1 stituted C-C-cycloalkyl or A represents phenyl or benzyl, each of which is optionally monosubstituted by fluorine, chlorine, bromine, cyano, - \, , nitro, C-C-alkyl, C-C-alkoxy, trifluoromethyl or tri O fluoromethoxy. 50 R particularly preferably represents optionally fluorine-sub O stituted C-C-alkyl or represents phenyl which is option G (3) ally monosubstituted by fluorine, chlorine, bromine, o1 C-C-alkyl, C-C-alkoxy, trifluoromethyl, trifluoro A methoxy, cyano or nitro, 55 R" particularly preferably represents C-C-alkyl, C-C- - N alkoxy, C-C-alkyl-amino, di-(C-C-alkyl)amino, S C-C-alkylthio, C-C-alkenylthio, C-C-cycloalkylthio or represents phenyl, phenoxy or phenylthio, each of which O is optionally monosubstituted by fluorine, chlorine, bro 60 (4) mine, nitro, cyano, C-C-alkoxy, C-C-halogenoalkoxy, C-C-alkylthio, C-C-halogenoalkylthio, C-C-alkyl or trifluoromethyl. Rparticularly preferably represents C1-Co-alkoxy or C-C- alkylthio. 65 Rparticularly preferably represents hydrogen, C1-Co-alkyl, C-C-cycloalkyl, C-C-alkoxy, C-C-alkenyl, C-C- US 8,673,818 B2 37 38 -continued Q' very particularly preferably represents hydrogen. (5) Q’ very particularly preferably represents hydrogen. Q, Q and Q independently of one another each very par ticularly preferably represent hydrogen or methyl. Q very particularly preferably represents hydrogen, methyl, ethyl or propyl, or Q and Q together with the carbon to which they are attached (6) very particularly preferably represent a saturated C-C- 10 ring which is optionally monosubstituted by methyl or methoxy. G very particularly preferably represents hydrogen (a) or represents one of the groups 15

(7) (b) usO (c) L --- R2, 25 A very particularly preferably represents in each case option ally fluorine-substituted C-C-alkyl or C-C2-alkoxy-C- in which C-alkyl, cyclopropyl, cyclopentyl or cyclohexyland, only L represents oxygen or Sulphur and in the case of the compounds of the formula (I-5), repre M represents oxygen or Sulphur. sents optionally fluorine-, chlorine-, bromine-, methyl-, R" very particularly preferably represents C-C-alkyl, ethyl-, n-propyl-, iso-propyl-, methoxy-, ethoxy-, trifluo C-C-alkenyl, C-C-alkoxy-C-alkyl, C-C-alkylthio romethyl-, trifluoromethoxy-, cyano- or nitro-substituted C-alkyl or cyclohexyl or cyclopropyl which is optionally phenyl. monosubstituted by fluorine, chlorine, methyl or methoxy, B very particularly preferably represents hydrogen, methyl or 35 represents phenyl which is optionally monosubstituted by ethyl, or fluorine, chlorine, bromine, cyano, nitro, methyl, meth A, B and the carbon atom to which they are attached very oxy, trifluoromethyl or trifluoromethoxy, particularly preferably represent Saturated Cs-C-cy cloalkyl in which optionally one ring member is replaced R very particularly preferably represents in each case option ally fluorine-substituted C-C-alkyl, C-C-alkenyl or by oxygen or Sulphur and which is optionally monosubsti 40 tuted by methyl, ethyl, propyl, isopropyl, trifluoromethyl, C-C-alkoxy-C-C-alkyl, phenyl or benzyl. methoxy, ethoxy, propoxy or butoxy or W most particularly preferably represents hydrogen, methyl, A, B and the carbon atom to which they are attached very ethyl or i-propyl. particularly preferably represent C-cycloalkyl which is X most particularly preferably represents methyl, ethyl, Substituted by an alkylenedioxyl group which contains two 45 i-propyl or vinyl, oxygen atoms which are not directly adjacent, or Y most particularly preferably represents hydrogen, methyl, A, B and the carbonatom to which they are attached represent ethyl, i-propyl, vinyl or ethinyl, Cs-C-cycloalkyl or Cs-C-cycloalkenyl in which two Sub Z most particularly preferably represents hydrogen, methyl, stituents together with the carbon atoms to which they are ethyl, n-propyl or i-butyl, attached very particularly preferably represent C-C-al 50 kanediyl or C-C-alkenediyl or butadienediyl. with the proviso that at least one of the radicals W, X, Y or Z D very particularly preferably represents hydrogen, repre represents a chain having at least two carbon atoms, where at sents in each case optionally fluorine-substituted C-C- most only one of the radicals W, X, Y or Z may represent vinyl alkyl, C-C-alkenyl, C-C-alkoxy-C-C-alkyl, cyclo or ethinyl, propyl, cyclopentyl or cyclohexyl or (but not in the case of 55 CKE most particularly preferably represents one of the the compounds of the formula (I-1)) represents pyridyl or groups phenyl which is optionally monosubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, (1) ethoxy or trifluoromethyl, 60 G O o1 A and D together very particularly preferably represent A optionally substituted C-C-alkanediyl in which option - \, , ally one carbon atom is replaced by oxygen or Sulphur N A and Q' together very particularly preferably represent 65 D1 C-C-alkanediyl which is optionally mono- or disubsti O tuted by methyl or methoxy, or US 8,673,818 B2 39 40 -continued desired, i.e. including combinations between the respective G (2) ranges and preferred ranges. They apply both to the end o1 products and, correspondingly, to the precursors and interme diates. A Preference according to the invention is given to the com - \, , pounds of the formula (I) which contain a combination of the O meanings listed above as being preferred (preferable). Particular preference according to the invention is given to O the compounds of the formula (I) which contain a combina (4) 10 tion of the meanings listed above as being particularly pre ferred. Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being very par 15 ticularly preferred. (6) Most preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being most preferred. Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl may in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy. Unless stated otherwise, optionally substituted radicals may be mono- or poly Substituted and, in the case of poly Sub A most particularly preferably represents methyl, 25 stitutions, the substituents may be identical or different. B most particularly preferably represents methyl, Besides the compounds mentioned in the Preparation A, B and the carbon atoms to which they are attached most Examples, the following compounds of the formula (I-1-a) particularly preferably represent Saturated Cs-C-cy may be specifically mentioned: cloalkyl in which optionally one ring member is replaced 30 by oxygen and which is optionally monosubstituted by TABLE 1 methyl, ethyl, methoxy, ethoxy. A and B together represent OH X A B N Y -HC CH 35 D1 N O W Z

40 A. B D D most particularly preferably represents hydrogen or (but CH H not in the case of the compound of the formula (I-1)) C2H5 H CH7 H represents fluorine-substituted phenyl, i-CH7 H G most particularly preferably represents hydrogen (a) or 45 CHg H represents one of the groups i-CAHg H S-CHg H t-C4H9 H CH CH (b) C2H5 CH CH7 CH 50 i-CH7 CH CHg CH i-CAHg CH S-CHg CH t-C4H9 CH C2H5 C2H5 55 CH7 CH7 a CH R' most particularly preferably represents C-C-alkyl, C-C2-alkoxymethyl, R’ most particularly preferably represents C-C-alkyl. 60 For CKE=(6) Uls C 13 A and Q' together most particularly preferably represent C-C-alkanediyl and B and Q’ each most particularly preferably represent hydro gen. 65 The abovementioned general or preferred radical defini tions or illustrations can be combined with each other as

US 8,673,818 B2 43 44 TABLE 16 TABLE 16-continued OH X OH X A A B N Y B N Y O O

O W Z O W Z

10 A. B A. B

Table 17: A and B are each as given in Table 16 W=CH: X-CHY-CH=CH: Z—H. Table 18: A and B are each as given in Table 16 25 W=CH: X=CHY CH: Z—H. s Table 19: A and B are each as given in Table 16 W=CH: X=CH; Y—CH: Z—H. A C 13 Table 20: A and B are each as given in Table 16 30 W=CH; X=CH; Y—CH: Z—H. Table 21: A and B are each as given in Table 16 W=CHs: X=CHs:Y—CHs: Z—H. Table 22: A and B are each as given in Table 16 35 W=CH: X-C=CH; Y—CH: Z—H. Table 23: A and B are each as given in Table 16 ( )— W=CH: X=CH-CHY CH: Z—H. Table 24: A and B are each as given in Table 16 40 W=CH: X=CH:Y—CH: Z—H. Table 25: A and B are each as given in Table 16 W—H: X-CHY-C=CH; Z—H. Table 26: A and B are each as given in Table 16 45 W—H: X-CHY-CH=CH: Z—H. Table 27: A and B are each as given in Table 16 W—H; X—CHs; Y—CH: Z H. Table 28: A and B are each as given in Table 16

50 W—H; X=CH: Y=CH: Z H. Table 29: A and B are each as given in Table 16 W—H; X—CH: Y—H; Z=CHs. Table 30: A and B are each as given in Table 16 W—H; X=CH:Y=CH: Z=CHs. 55 Using, in accordance with process (A), ethyl N-(2-methyl -CH2-CH-(CH)-CH 4-ethinyl-phenylacetyl)-1-aminocyclohexane-carboxylate as starting material, the course of the process according to the -cis invention can be represented by the following equation: -CH-CH-CH-CH 60 L- cis CH3 2CH -CH-CH CH-(CH)- O 1. base 2. H+ |- city 65 COCHs US 8,673,818 B2 45 -continued OH CH3 HC CH O -- ls Hebase N CECH 5 CO H3C CH3 HN CH5 COC O H3C C2H5 OH 10 Using, in accordance with process (B), ethyl O-(2,4,6- triethyl-phenylacetyl)-2-hydroxyisobutyrate, the course of 21 the process according to the invention can be represented by CH3 the following equation: O O CH 15 HC CO.C.H.C2 Using, for example in accordance with process (E), (chlo rocarbonyl) 2-(2,6-dimethyl-4-ethyl)-phenyl ketene and D1 1. base thiobenzamide as starting materials, the course of the process O CH5 --> 2. H+ according to the invention can be represented by the follow ing equation: O C2H5

H5C2 CH3 25 -- C=O

21 CH3 COC 30 S ( ) { Hipbase NH2 H5C2 CH3 35 OH Using, in accordance with process (C), ethyl 2-(2,6-dim ethyl-4-ethyl-phenyl)-4-(4-methoxy)-benzylmercapto-4- / S methyl-3-oxo-Valerate, the course of the process according to the invention can be represented by the following equation: CH3 N 40 O

HCO Using, in accordance with process (F), ethyl 5-(2,4-di ethyl-6-methyl-phenyl)-2,3-tetramethylene-4-oxo-valerate, 45 the course of the process according to the invention can be H3C CH3 represented by the following equation: acid S CH -e- O CH 50 H.C.1. O C2H5 O CH CH 3 CH5 COC2H5 CH5 HO 55

HC N H3C S CH O 60

Using, for example in accordance with process (D), (chlo rocarbonyl) 2-(2-ethyl-4,6-dimethyl)-phenylketene and Using, in accordance with process (G), ethyl 5-(2,4,6- acetone as starting materials, the course of the process 65 triethyl-phenyl)-phenyl-2,2-dimethyl-5-oxo-hexanoate, the according to the invention can be represented by the follow course of the process according to the invention can be rep ing equation: resented by the following equation: US 8,673,818 B2

one and acetic anhydride as starting materials, the course of C2H5 the process according to the invention can be represented by COCHs the following equation: H3C base CH5 -> 5 HC HC-CO H3C CH3 O C2H5 OH y C2H5 HC-CO N - 8Se. - HO 10 CH5 O HC H3C C2H5 O 15

Using, in accordance with process (H), 3-(2,6-dimethyl 4-bromo)-phenyl-4-4-(pentamethylene)-pyrrolidine-2,4-di one as starting material, the course of the reaction can be 20 represented by the following scheme: Using, in accordance with process (J), 8-(2,6-diethyl-4- OH CH3 methyl)-phenyl)-1-aza-bicyclo-4.3.0'-nonane-7,9-dione as and ethoxyethyl chloroformate as starting materials, the N HCEC-Si(CH) course of the process according to the invention can be rep Br — - resented by the following equation: 8Se. HN catalyst

O CH3 O OH CH3 O | C N C2CH HN O-CHs He O CH3 base

Using, in accordance with process (IC), 3-(2,6-dimethyl 4-ethinyl-phenyl)-5,5-dimethylpyrrolidine-2,4-dione and pivaloyl chloride as starting materials, the course of the pro- CH cess according to the invention can be represented by the following equation: O H5C2

CH 45 CH5-O-(CH)-O215 22 | O CH5 HC "HC 22CH HC3 COC CH3 O H3C N --base 50 HN

O Using, in accordance with process (K), 3-(2-ethyl-4,6- 55 dimethyl-phenyl)-4-hydroxy-5-methyl-6-(3-pyridyl)-pyrone and methyl chloromonothioformate as starting materials, the course of the reaction can be represented as follows:

60 OH CH S CH3 / \ / \ C us OCH base O RN 65 O Using, in accordance with process (IB), 3-(2-ethyl-4,6- HC CH5 dimethyl-phenyl)-4-hydroxy-5-phenyl-A-dihydrofuran-2- US 8,673,818 B2 49 -continued

OH C2H5 HC-1 \ C.H., NaOHT - HN

O CHs 10

Using, in accordance with process (L), 3-(2,6-dimethyl-4- Na(+) ethyl-phenyl)-5,5-penta-methylene-pyrrolidine-2,4-dione 15 and methanesulfonyl chloride as starting materials, the course Q (-)C2H5 of the reaction can be represented by the following equation: HC N CH5 HN

OH CH3 O C2H5 \ C2H5 + CI-SO2-CH -e- base 25 Using, in accordance with process (O), variant C. 3-(2,4- HN diethyl-6-methyl-phenyl)-4-hydroxy-5-tetramethylene-A- dihydro-furan-2-one and ethyl isocyanate as starting materi O CH

als, the course of the reaction can be represented by the O-SOCH following equation: 30

OH CH

Using, in accordance with process (M), 3-(2,4-diethyl-6- methyl-phenyl)-4-hydroxy-5,5-dimethyl-A-dihydrofuran 2-one and 2.2.2-trifluoroethyl methanethio-phosphonyl chlo 40 ride as starting materials, the course of the reaction can be represented by the following equation:

45 CH3 OH C2H5 i OCH2CF HC CI-k \ C2H5 -- -e-CH base O 50 O CH Using, in accordance with process (O), variant B, 3-(4-

ethinyl-2,6-dimethyl-phenyl)-5-methyl-pyrrolidine-2,4-di one and dimethylcarbamoyl chloride as starting materials, the course of the reaction can be represented by the following 55 scheme:

60 OH CH3 C us N 1 CH H3C

N CECHE -e-CH Using, in accordance with process (N), 3-(2,4,6-triethyl HN -HCI phenyl)-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dione and 65 NaOH as components, the course of the process according to the invention can be represented by the following equation: US 8,673,818 B2 51 52 -continued (Chem. Reviews 52,237-416 (1953); Bhattacharya, Indian J. Chem. 6,341-5, 1968) CH3 or when acylamino acids of the formula (XXIII) ON NYCH, (XXIII) O CH A CO2H X B N CECH N 10 D1 O W Y

Z The compounds of the formula (II) 15 in which A, B, D, W, X, Y and Z are each as defined above are (II) esterified (Chem. Ind. (London) 1568 (1968)). A COR X The compounds of the formula (XXIII) B N D1 (XXIII) A CO2H O X W Y B 25 N Z D1 O W Y

Z in which 30 A, B, D, W, X, Y, Z and Rare each as defined above in which which are required as starting materials in the process (a) A, B, D, W, X, Y and Z are each as defined above according to the invention are novel. are novel. The acylamino acid esters of the formula (II) are obtained, 35 Compounds of the formula (XXIII) are obtained when for example, when amino acid derivatives of the formula amino acids of the formula (XXIV) (XXI) (XXIV) 40 A CO2H (XXI) A COR Dr Dr D1 NH NH D1 45 in which A, B and Dare each as defined above in which are acylated with substituted phenyl acetyl halides of the A, B, Rand D are each as defined above formula (XXII) are acylated with substituted phenylacetyl halides of the for 50 mula (XXII) (XXII)

(XXII) 55 COHall

COHall 60 in which W, X, Y and Z are each as defined above and Hal represents chlorine or bromine, for example according to Schotten-Baumann (Organikum, in which VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 65 505). W, X, Y and Z are each as defined above and The compounds of the formula (XXII) are novel. They can Hal represents chlorine or bromine be prepared by processes which are known in principle (see, US 8,673,818 B2 53 54 for example, H. Henecka, Houben-Weyl, Methoden der in which Organischen Chemie, Vol. 8, pp. 467-469 (1952)). A, B, D, W, X, Y, Z and Rare each as defined above The compounds of the formula (XXII) are obtained, for used in the above process (A) can be prepared when amino example, by reacting Substituted phenylacetic acids of the nitriles of the formula (XXVI) formula (XXV) 5

(XXVI) (XXV)

CO2H in which 15 A, B and Dare each as defined above in which are reacted with substituted phenylacetyl halides of the for W, X, Y and Z are each as defined above mula (XXII) with halogenating agents (for example thionyl chloride, thio nyl bromide, oxalyl chloride, phosgene, phosphorus trichlo (XXII) ride, phosphorus tribromide orphosphorus pentachloride), if X appropriate in the presence of a diluent (for example option ally chlorinated aliphatic or aromatic hydrocarbons such as toluene or methylene chloride), attemperatures from -20°C. Y to 150° C., preferably from -10° C. to 100° C. 25 COHal Some of the compounds of the formulae (XXI) and (XXIV) are known, and/or they can be prepared by known Z W processes (see, for example, Compagnon, Miocque Ann. Chim. (Paris) 145, S. 11-22, 23-27 (1970)). in which The substituted cyclic aminocarboxylic acids of the for 30 W, X, Y, Z and Hal are each as defined above mula (XXIV) in which A and B form a ring are generally obtainable by the Bucherer-Bergs synthesis or by the Strecker to give compounds of the formula (XXVII) synthesis and are in each case obtained in different isomer forms. Thus, under the conditions of the Bucherer-Bergs syn (XXVII) thesis, the isomers (for simplicity called B below), in which 35 X the radicals R and the carboxyl group are equatorial are pre dominantly obtained, while under the conditions of the Strecker synthesis the isomers (for simplicity called (obelow) Y in which the amino group and the radicals Rare equatorial are N predominantly obtained. 40 CEN Z W O X B A R H NH R H CO2H COH NH in which 45 sys)- 2 sys)- 2 A, B, D, W, X, Y and Z are each as defined above H H and these are Subsequently subjected to acidic alcoholysis. Bucherer-Bergs synthesis Strecker synthesis The compounds of the formula (XXVII) are likewise novel. (3 isomer) (C. isomer) 50 The compounds of the formula (III) (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. III Jitrangeri, Can. J. Chem. 53,3339 (1975). A COR (III) Furthermore, the starting materials of the formula (II) 55 Dr O (II) A COR X B 60 D1 N

O W Y in which

Z 65 A, B, W, X, Y, Z and Rare each as defined above required as starting materials in the process (B) according to the invention are novel. US 8,673,818 B2 55 56 They can be prepared by methods known in principle. The compounds of the formula (XXIX) are commercially Thus, the compounds of the formula (III), for example, are available. obtained when The compounds of the formula (XXV) 2-hydroxycarboxylic esters of the formula (XXVIII) (XXV)

(XXVIII) COH A COR D1 Y OH Z WX in which in which A, B and Rare each as defined above 15 W, X, Y and Z are each as defined above are acylated with substituted phenylacetyl halides of the for and mula (XXII) Y may furthermore represent —C=C Si(CH) are obtained, for example, when phenylacetic esters of the formula (XXX) (XXII) (XXX)

25 COHall Y COR Z WX 30 in which in which W, X, Y, Z and Rare each as defined above W, X, Y, Z and Hal are each as defined above are hydrolysed in the presence of acids or bases, in the pres (Chem. Reviews 52,237-416 (1953)). ence of a solvent, under generally known standard conditions. 35 The compounds of the formula (XXX) are novel. Furthermore, compounds of the formula (I) are obtained The compounds of the formula (XXX) when substituted phenylacetic acids of the formula (XXV)

(XXX) (XXV) 40

CO2H Y COR 45 Z WX in which W, X, Y, Z and Rare each as defined above, and in which 50 Y may furthermore represent —C=C Si(CH) W, X, Y and Z are each as defined above are obtained, for example, are alkylated with C.-halogenocarboxylic esters of the for when phenylacetic esters of the formula (XXX-a) mula (XXIX) 55 (XXX-a) (XXIX) Y COR AX" 60 B Hal Z WX in which A, B and Rare each as defined above and in which 65 R, W, X, Y and Z are each as defined above, Hal represents chlorine or bromine. and one or two of the radicals, in particular one radical, W, X, The compounds of the formula (XXV) are novel. Y or Z represents chlorine, bromine or iodine, in particular US 8,673,818 B2 57 58 bromine, with the proviso that the other radicals W, X, Y or Z in which do not represent alkenyl or alkinyl, W, X, Y, R and Z are each as defined above are acylated are reacted with silylacetylenes of the formula (X-a) or vinyl with 2-benzylthio-carbonyl halides of the formula (XXX) stannanes of the formula (X-b) (XXXI) A B (X-a) Alk M H-CEC-S-Ak V 10 W.( V. ) X.Hal R21 (X-b) R22 Alk in which M HCECH-S-Ak A, B and V are each as defined above and 15 Hal represents halogen (in particular chlorine or bromine) Alk in the presence of strong bases (see, for example, M. S. Chambers, E.J. Thomas, D.J. Williams, J. Chem. Soc. Chem. in which Alk preferably represents C-C-alkyl, Commun., (1987), 1228). R" preferably represents C-C-alkyl or phenyl and Some of the benzylthio-carbonyl halides of the formula (XXXI) are known, and/or they can be prepared by known R’ is as defined above processes (J. Antibiotics (1983), 26, 1589). The halogenocar in the presence of a solvent, if appropriate in the presence of bonylketenes of the formula (VI) required as starting mate a base and a catalyst (preferably one of the palladium com rials in the above process (D) and (E) are novel. They can be plexes mentioned above). prepared in a simple manner by methods which are known in 25 Some of the phenylacetic esters of the formula (XXX-a) principle (cf. for example, Org. Prep. Proced. Int., 7, (4), are known from the applications WO 96/35 664, WO 97/02 155-158, 1975 and DE 1945 703). Thus, for example, the 243, WO 97/01535, WO 97/36868 or WO 98/05638, or they compounds of the formula (VI) can be prepared by processes described therein. Furthermore, phenylacetic esters of the formula (XXX) are 30 (VI) obtained by the processes (P) and (Q) described further below. The compounds of the formula (IV)

35 (IV)

in which 40 W, X, Y and Z are each as defined above and Hal represents chlorine or bromine are obtained when substituted phenylmalonic acids of the formula (XXXII) 45 (XXXII) Z W in which COOH M A, B, V, W, X, Y, Z and R are each as defined above 50 Y CH required as starting materials in the above process (C) are V novel. COOH They can be prepared by methods known in principle. X The compounds of the formula (IV) are obtained, for example when substituted phenylacetic esters of the formula 55 in which (XXX) W, X, Y and Z are each as defined above are reacted with acid halides, such as, for example, thionyl chloride, phosphorus(V) chloride, phosphorus(III) chloride, (XXX) oxalyl chloride, phosgene or thionyl bromide, if appropriate in the presence of catalysts, such as, for example, diethylfor COR mamide, methyl-sterylformamide or triphenylphosphine and, if appropriate, in the presence of bases, such as, for example, pyridine or triethylamine. The substituted phenylmalonic acids of the formula 65 (XXXII) are novel. They can be prepared in a simple manner by known processes (cf., for example, Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 517 ff. US 8,673,818 B2 59 60 EP-A-528 156, WO 96/35 664, WO 97/02 243, WO in which 97/01535, WO 97/36868 and WO 98/05638). A and D are each as defined above required as starting Thus, phenylmalonic acids of the formula (XXXII) materials for the process (D) according to the invention or their silyl enol ethers of the formula (Va)

(XXXII) (Va) CHA COH D-C-OSi(R) 10

CO2H in which A, D and Rare each as defined above are commercially available, generally known compounds or 15 compounds which are obtainable by known processes. in which The preparation of the ketene acid chlorides of the formula W, X,Y and Zare each as defined above are obtained when (VI) required as starting materials for carrying out the process phenylmalonic esters of the formula (XXXIII) (E) according to the invention has already been described above. The thioamides of the formula (VII)

(XXXIII) (VII) HN COR Y-A 25 M S COR in which A is as defined above in which 30 required for carrying out the process (E) according to the invention are compounds which are generally known in W, X, Y, Z and Rare each as defined above are initially organic chemistry. hydrolysed in the presence of a base and a solvent and Sub sequently carefully acidified (EP-528 156, WO 96/35 664, The compounds of the formula (VI) WO 97/02 243). 35 Some of the malonic esters of the formula (XXXIII) (VIII) Q Q? ROC (XXXIII) CO X 40 COR A B

COR W Y 45 Z in which in which

W, X, Y, Z and Rare each as defined above 50 A, B, Q, Q, W, X, Y, Z and Rare each as defined above are known. required as starting materials in the above process (F) are They can be prepared by generally known methods of novel. organic chemistry (cf., for example, Tetrahedron Lett. 27. They can be prepared by methods known in principle. 2763 (1986), Organikum, VEB Deutscher Verlag der Wissen The 5-aryl-4-ketocarboxylic esters of the formula (VIII) schaften, Berlin 1977, p. 587 ff., WO 96/35664, WO 55 are obtained, for example, when 5-aryl-4-ketocarboxylic 97/02243, WO 97/01535, WO 97/36868, WO 98/05638 and acids of the formula (XXXIV) WO 99/47525). The carbonyl compounds of the formula (V) (XXXIV) 60 Q Q2 (V) O Y CO2H

D ls CH-A 65 US 8,673,818 B2 61 62 in which The compounds of the formula (XXXV) are obtained, for W, X, Y, Z. A, B, Q' and Q are each as defined above are example, esterified (cf., for example, Organikum, 15" edition, Berlin, when dicarboxylic monoester chlorides of the formula 1977, page 499) or alkylated (see Preparation Example). (XXXVI), The 5-aryl-4-ketocarboxylic acids of the formula (XXXIV) (XXXVI)

(XXXIV) 10 Q Q2

Y CO2H in which 15 A, B, Q, Q and Rare each as defined above and Hal represents chlorine or bromine or carboxylic anhydrides of the formula (XXXVII) in which (XXXVII) A, B, Q, Q, W, X, Y and Z are each as defined above A O are novel but can be prepared by methods known in principle (see Preparation Example). The 5-aryl-4-ketocarboxylic acids of the (XXXIV) are B O obtained, for example, when 2-phenyl-3-oxo-adipicesters of 25 Q? the formula (XXXV) Q O

in which (XXXV) A, B, Q' and Q are each as defined above are acylated with 30 a phenylacetic ester of the formula (XXX)

(XXX) 35 ORS in which A, B, D', D, W, X, Y and Zare each as defined above and 40 RandR each represent alkyl (in particular C-Cs-alkyl) in which and in which, if the compound of the formula (XXXVII) is W, X,Y,Z and Rare each as defined above in the presence used, R represents hydrogen of a diluent and in the presence of a base (cf., for example, M. are decarboxylated, if appropriate in the presence of a diluent 45 S. Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. and if appropriate in the presence of a base oran acid (cf., for Chem. Commun., (1987), 1228, cf. also the Preparation example, Organikum, 15" edition, Berlin, 1977, pages 519 to Examples). 521). Some of the compounds of the formulae (XXXVI) and (XXXVII) are known compounds of organic chemistry, and/ The compounds of the formula (XXXV) 50 or they can be prepared in a simple manner by methods known in principle. The compounds of the formula (IX)

(XXXV)

55 (IX) Q Q Q Q6 ROC CO X 60 A. B in which A, B, Q, Q, W, X, Y, Z. R. Rare each as defined above W Y and in which, if the compound of the formula (XXXVII) is used, R represents hydrogen 65 are novel. US 8,673,818 B2 63 64 in which The compounds of the formula (XXXIX) A, B, Q, Q, Q, Q, W, X,Y,Z and Rare each as defined above

required as starting materials in the above process (G) are (XXXIX) novel. They can be prepared by methods known in principle. The 6-aryl-5-ketocarboxylic esters of the formula (IX) are obtained, for example, when 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII) 10

(XXXVIII) x Q Q Q Q 15 in which Y CO2H A, B, Q, Q, Q, Q, W, X, Y, Z, R and Rare each as defined above are novel and can be obtained when dicarboxy lic anhydrides of the formula (XLI) in which (XLI) Q: A A, B, Q, Q, Q, Q, W, X, Y and Z are each as defined Q B above Q3 are esterified (cf., for example, Organikum, 15" edition, Ber 25 COR 6 lin, 1977, page 499). Q COR The 6-aryl-5-ketocarboxylic acids of the formula (XXX VIII) 30 in which (XXXVIII) A, B, Q, Q, Q, Q and Rare each as defined above are x Q, Q Q Q condensed with a substituted phenylacetic ester of the for mula (XXX)

Y CO2H 35 (XXX)

ORS in which 40 A, B, Q, Q, Q, Q, W, X, Y and Z are each as defined above are novel. They can be prepared by methods known in prin ciple, for example by hydrolysing and decarboxylating 45 in which substituted 2-phenyl-3-oxo-heptanedioic esters of the for W, X, Y, Z and Rare each as defined above mula (XXXIX) in the presence of a diluent and in the presence of a base. Some of the compounds of the formula (XLI) are known, (XXXIX) 50 and/or they can be prepared by known processes. The compounds of the formula (XXX) have already been described under the precursors for the process (B) or are described explicitly as examples in processes (P) and (Q) 55 below. (P) Thus, furthermore, compounds of the formula (XXX),

(XXX) in which 60 A, B, Q, Q, Q, Q, W, X, Y and Z are each as defined OR8 above and Rand Rare each alkyl (preferably C1-Co-alkyl). if appropriate in the presence of a diluent and if appropriate in 65 the presence of a base or acid (cf., for example, Organikum, 15" edition, Berlin, 1977, pages 519 to 521). US 8,673,818 B2 65 66 in which in which W, X, Y, Z and Rare each as defined above are obtained X represents alkyl, when acylphenylacetic esters of the formula (XLII) W. Y and Z each represent hydrogen or alkyl and 5 R represents alkyl are furthermore obtained when pheny (XLII) lacetic esters of the formula (XXX-c),

O C (XXX-c) ( 10 X

ORS Y Z. - O 15 W, X, Y and Rare each as defined above and Z W Z represents alkyl are reduced with suitable reducing agents (such as, for example, Zn/HCl, hydrogen/catalyst, hydrazine/base), if appropriate in the presence of a solvent. The compounds of the formula (XLII) are novel. in which Compounds of the formula (XLII) X represents alkyl, R represents alkyl and (XLII) W. Y and Z may represent, in addition to hydrogen and 25 alkyl, chlorine and bromine O are dehalogenated in the presence of a solvent and in the C ( presence of a reducing agent (for example hydrogen in the presence of a noble-metal catalyst Such as, for example, pal OY ladium or platinum). 30 Z. - The compounds of the formula (XXX-c) are known from the patent applications cited at the outset or can be prepared in which by the processes described therein. W, X, Y, Z and Rare each as defined above are obtained Some of the compounds of the formulae (I-1'a) to (I-8-a) in when phenylacetic esters of the formula (XXX-b) 35 which A, B, D, Q, Q, Q, Q, Q, Q, W, X, Y and Z are each as defined above, required as starting materials in the above process (H), are known (WO 96/35 664, WO 97/02 (XXX-b) 243, WO 97/01535, WO 97/36868, WO 98/05638) or they 40 can be prepared by the processes described therein. OR8 Some of the coupling agents of the formulae (X-a) and Y (X-b) O Z 45 WX 22 (X-a) R Alk in which M CEC-S-Ak W, X, Y and Rare each as defined above and V Z represents hydrogen are Friedel-Crafts acylated, if R21 appropriate in the presence of a solvent, using a carbonyl 50 (X-b) chloride or carboxylic anhydride in the presence of an acid or R22 Alk a Lewis acid (for example aluminium chloride, iron(III) bro M mide). HCECH-S-Ak The compounds (XXX-b) are known or can be prepared by Alk the processes described in the literature cited at the outset. 55 (Q) Phenylacetic esters of the formula (XXX). in which (XXX) Alk, R and Rare each as defined above 60 are commercially available, or they can be prepared in a OR8 simple manner by generally known processes. Y The acid halides of the formula (XI), carboxylic anhy O drides of the formula (XII), chloroformic esters or chlorofor Z 65 mic thioesters of the formula (XIII), chloromonothioformic WX esters or chlorodithioformic esters of the formula (XIV), sul phonyl chlorides of the formula (XV), phosphorus com US 8,673,818 B2 67 68 pounds of the formula (XVI) and metal hydroxides, metal Suitable bases (deprotonating agents) for carrying out the alkoxides or amines of the formulae (XVII) and (XVII) and process (B) according to the invention are all customary pro isocyanates of the formula (XIX) and carbamoyl chlorides of ton acceptors. Preference is given to using alkali metal and the formula (XX) furthermore required as starting materials alkaline earth metal oxides, hydroxides and carbonates, such for carrying out the processes (I), (J), (K), (L), (M), (N) and as sodium hydroxide, potassium hydroxide, magnesium (O) according to the invention are generally known com oxide, calcium oxide, Sodium carbonate, potassium carbon pounds of organic or inorganic chemistry. ate and calcium carbonate, which can also be employed in the Moreover, the compounds of the formulae (V), (VII), (XI) presence of phase-transfer catalysts, such as, for example, to (XX), (XXI), (XXIV), (XXVI), (XXVIII), (XXIX), triethylbenzylammonium chloride, tetrabutylammonium (XXXI), (XXXVI), (XXXVII) and (XLI) are known from the 10 bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium patent applications cited at the outset, and/or they can be chloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). prepared by the methods given therein. Alkali metals such as Sodium and potassium can also be used. The process (A) is characterized in that compounds of the Furthermore, alkali metal and alkaline earth metal amides and formula (II) in which A, B, D, W, X, Y, Z and Rare each as hydrides, such as sodium amide, Sodium hydride and calcium defined above are Subjected to an intramolecular condensa 15 hydride, and additionally also alkali metal alkoxides, such as tion in the presence of a base. Sodium methoxide, Sodium ethoxide and potassium tert-bu Suitable diluents for the process (A) according to the toxide can be employed. invention are all inert organic Solvents. Preference is given to When carrying out the process (B) according to the inven using hydrocarbons, such as toluene and Xylene, furthermore tion, the reaction temperatures can be varied within a rela ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol tively wide range. In general, the reaction is carried out at dimethyl ether and diglycol dimethyl ether, moreover polar temperatures between 0° C. and 250° C., preferably between Solvents, such as dimethyl Sulphoxide, Sulpholane, dimethyl 50° C. and 150° C. formamide and N-methyl-pyrrolidone, and also alcohols, The process (B) according to the invention is generally Such as methanol, ethanol, propanol, iso-propanol, butanol, carried out under atmospheric pressure. iso-butanol and tert-butanol. 25 When carrying out the process (B) according to the inven Suitable bases (deprotonating agents) for carrying out the tion, the reaction components of the formula (III) and the process (A) according to the invention are all customary deprotonating bases are generally employed in approxi proton acceptors. Preference is given to using alkali metaland mately equimolaramounts. However, it is also possible to use alkaline earth metal oxides, hydroxides and carbonates, such a relatively large excess (up to 3 mol) of one component or the as sodium hydroxide, potassium hydroxide, magnesium 30 other. oxide, calcium oxide, Sodium carbonate, potassium carbon The process (C) is characterized in that compounds of the ate and calcium carbonate, which can also be employed in the formula (IV) in which A, B, V, W, X,Y,Z and Rare each as presence of phase-transfer catalysts, such as, for example, defined above are cyclized intramolecularly in the presence of triethylbenzylammonium chloride, tetrabutylammonium an acid and, if appropriate, in the presence of a diluent. bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium 35 Suitable diluents for the process (C) according to the inven chloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). tion are all inert organic solvents. Preference is given to using Alkali metals such as Sodium and potassium can also be used. hydrocarbons, such as toluene and Xylene, furthermore halo Furthermore, alkali metal and alkaline earth metal amides and genated hydrocarbons such as dichloromethane, chloroform, hydrides, such as Sodium amide, Sodium hydride and calcium ethylene chloride, chlorobenzene, dichlorobenzene, more hydride, and additionally also alkali metal alkoxides, such as 40 overpolar solvents, such as dimethyl Sulphoxide, Sulpholane, Sodium methoxide, sodium ethoxide and potassium tert-bu dimethyl formamide and N-methyl-pyrrolidone. Further toxide can be employed. more, it is possible to employ alcohols such as methanol, When carrying out the process (A) according to the inven ethanol, propanol, iso-propanol, butanol, isobutanol and tert tion, the reaction temperatures can be varied within a rela butanol. tively wide range. In general, the reaction is carried out at 45 If appropriate, the acid used can also serve as diluent. temperatures between 0° C. and 250° C., preferably between Suitable acids for the process (C) according to the inven 50° C. and 150° C. tion are all customary inorganic and organic acids, such as, for The process (A) according to the invention is generally example, hydrohalic acids, Sulphuric acid, alkyl-, aryl- and carried out under atmospheric pressure. haloalkylsulphonic acids, in particular halogenated alkylcar When carrying out process (A) according to the invention, 50 boxylic acids, such as, for example, trifluoroacetic acid. the reaction components of the formula (II) and the deproto When carrying out the process (C) according to the inven nating bases are generally employed in approximately tion, the reaction temperatures can be varied within a rela double-equimolaramounts. However, it is also possible to use tively wide range. In general, the reaction is carried out at a larger excess (up to 3 mol) of one component or the other. temperatures between 0° C. and 250° C., preferably between The process (B) is characterized in that compounds of the 55 50° C. and 150° C. formula (III) in which A, B, W, X, Y, Z and Rare each as The process (C) according to the invention is generally defined above are Subjected to an intramolecular condensa carried out under atmospheric pressure. tion in the presence of a diluent and in the presence of a base. When carrying out the process (C) according to the inven Suitable diluents for the process (B) according to the inven tion, the reaction components of the formulae (IV) and the tion are all inert organic solvents. Preference is given to using 60 acid are employed, for example, in equimolar amounts. How hydrocarbons, such as toluene and Xylene, furthermore ever, it is also possible, if appropriate, to use the acid as ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol Solvent or as catalyst. dimethyl ether and diglycol dimethyl ether, moreover polar The process (D) according to the invention is characterized Solvents, such as dimethyl Sulphoxide, Sulpholane, dimethyl in that carbonyl compounds of the formula (V) or enol ethers formamide and N-methyl-pyrrolidone, and also alcohols, 65 thereof of the formula (V-a) are reacted with ketene acid Such as methanol, ethanol, propanol, iso-propanol, butanol, halides of the formula (VI) in the presence of a diluent and, if iso-butanol and tert-butanol. appropriate, in the presence of an acid acceptor. US 8,673,818 B2 69 70 Suitable diluents for the process (D) according to the tyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and invention are all inert organic Solvents. Preference is given to diglycol dimethyl ether, moreover polar solvents, such as using hydrocarbons, such as toluene and Xylene, furthermore dimethyl Sulphoxide, Sulpholane, dimethylformamide and ethers, such as dibutyl ether, glycol dimethyl ether and dig N-methyl-pyrrolidone. It is furthermore possible to use alco lycol dimethyl ether, moreover polar solvents, such as dim hols, such as methanol, ethanol, propanol, iso-propanol, ethyl sulphoxide, sulpholane, dimethylformamide or N-me butanol, isobutanol, tert-butanol. thyl-pyrrolidone. Suitable bases (deprotonating agents) for carrying out the Suitable acid acceptors for carrying out the process variant process (F) according to the invention are all customary pro D) according to the invention are all customary acid accep ton acceptors. Preference is given to using alkali metal and tOrS. 10 alkaline earth metal oxides, hydroxides and carbonates, such Preference is given to using tertiary amines, such as tri as sodium hydroxide, potassium hydroxide, magnesium ethylamine, pyridine, diazabicyclooctane (DABCO), diaz oxide, calcium oxide, Sodium carbonate, potassium carbon abicycloundecane (DBU), diazabicyclononene (DBN), ate and calcium carbonate, which can also be employed in the Hünig base and N,N-dimethyl-aniline. presence of phase-transfer catalysts, such as, for example, When carrying out the process variant D) according to the 15 triethylbenzylammonium chloride, tetrabutylammonium invention, the reaction temperatures can be varied within a bromide, Adogen 464 (methyltrialkyl (Cs-Co)ammonium relatively wide range. Advantageously, the reaction is carried chloride) or TDA 1 (tris-(methoxyethoxyethyl)-amine). out at temperatures between 0° C. and 250° C., preferably Alkali metals such as sodium or potassium can also be used. between 50° C. and 220° C. Furthermore, alkali metal and alkaline earth metal amides and The process (D) according to the invention is advanta hydrides, such as sodium amide, Sodium hydride and calcium geously carried out under atmospheric pressure. hydride, and additionally also alkali metal alkoxides, such as When carrying out the process (D) according to the inven Sodium methoxide, Sodium ethoxide and potassium tert-bu tion, the reaction components of the formulae (V) and (VI) in toxide can be employed. which A, D, W, X, Y and Zare each as defined above and Hal When carrying the process (F) according to the invention, represents halogen, and, if appropriate, the acid acceptors, are 25 the reaction temperatures can be varied within a relatively generally employed in approximately equimolar amounts. wide range. In general, the reaction is carned out attempera However, it is also possible to use a relatively large excess (up tures between -75° C. and 250° C., preferably between -50° to 5 mol) of one component or the other. C. and 150°C. The process (F) according to the invention is The process (E) according to the invention is characterized generally carned out under atmospheric pressure. in that thioamides of the formula (VII) are reacted with ketene 30 When carrying out the process (F) according to the inven acid halides of the formula (VI) in the presence of a diluent tion, the reaction components of the formula (VIII) and the and, if appropriate, in the presence of an acid acceptor. deprotonating bases are generally employed in approxi Suitable diluents for the process variant E) according to the mately equimolaramounts. However, it is also possible to use invention are all inert organic Solvents. Preference is given to a relatively large excess (up to 3 mol) of one component or the using hydrocarbons, such as toluene and Xylene, furthermore 35 other. ethers, such as dibutyl ether, glycol dimethyl ether and dig The process (G) is characterized in that compounds of the lycol dimethyl ether, moreover polar solvents, such as dim formula (IX) in which A, B, Q, Q, Q, Q, W, X,Y,Z and R' ethylsulphoxide, sulpholane, dimethylformamide and N-me are each as defined above are Subjected to an intramolecular thyl-pyrrolidone. condensation in the presence of bases. Suitable acid acceptors for carrying out the process (E) 40 Suitable diluents for the process (G) according to the according to the invention are all customary acid acceptors. invention are all organic solvents which are inert towards the Preference is given to using tertiary amines, such as tri reaction participants. Preference is given to using hydrocar ethylamine, pyridine, diazabicyclooctane (DABCO), diaz bons, such as toluene and Xylene, furthermore ethers, such as abicycloundecane (DBU), diazabicyclononene (DBN), dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether Hünig base and N,N-dimethyl-aniline. 45 and diglycol dimethyl ether, moreoverpolar solvents, such as When carrying out the process (E) according to the inven dimethyl Sulphoxide, Sulpholane, dimethylformamide and tion, the reaction temperatures can be varied within a rela N-methyl-pyrrolidone. Alcohols, such as methanol, ethanol, tively wide range. Advantageously, the reaction is carried out propanol, iso-propanol, butanol, isobutanol and tert-butanol at temperatures between 0° C. and 250° C., preferably can also be used. between 20° C. and 220° C. 50 Suitable bases (deprotonating agents) for carrying out the The process (E) according to the invention is advanta process (H) according to the invention are all customary geously carried out under atmospheric pressure. proton acceptors. When carrying out the process (E) according to the inven Preference is given to using alkali metal and alkaline earth tion, the reaction components of the formulae (VII) and (VI) metal oxides, hydroxides and carbonates, such as Sodium in which A, W, X, Y and Z are each as defined above and Hal 55 hydroxide, potassium hydroxide, magnesium oxide, calcium represents halogen, and, if appropriate, the acid acceptors, are oxide, Sodium carbonate, potassium carbonate and calcium generally employed in approximately equimolar amounts. carbonate, which can also be employed in the presence of However, it is also possible to use a relatively large excess (up phase-transfer catalysts, such as, for example, triethylbenzy to 5 mol) of one component or the other. lammonium chloride, tetrabutylammonium bromide, The process (F) is characterized in that compounds of the 60 Adogen 464 (methyltrialkyl (Co-Co)ammonium chloride) or formula (VIII) in which A, B, Q, Q, W, X, Y, Z and Rare TDA 1 (tris-(methoxyethoxyethyl)-amine). Alkali metals each as defined above are subjected to an intramolecular Such as sodium and potassium can also be used. Furthermore, condensation in the presence of a base. alkali metal and alkaline earth metal amides and hydrides, Suitable diluents for the process (F) according to the inven Such as Sodium amide, sodium hydride and calcium hydride, tion are all organic solvents which are inert towards the reac 65 and additionally also alkali metal alkoxides, such as Sodium tion participants. Preference is given to using hydrocarbons, methoxide, sodium ethoxide and potassium tert-butoxide can Such as toluene and Xylene, furthermore ethers. Such as dibu be employed. US 8,673,818 B2 71 72 When carrying the process (G) according to the invention, Suitable diluents for the process (I-C) according to the the reaction temperatures can be varied within a relatively invention are all solvents which are inert towards the acid wide range. In general, the reaction is carried out attempera halides. Preference is given to using hydrocarbons, such as tures between 0° C. and 250° C., preferably between 50° C. benzine, benzene, toluene, Xylene and tetralin, furthermore and 150° C. halogenated hydrocarbons, such as methylene chloride, chlo The process (G) according to the invention is generally roform, carbon tetrachloride, chlorobenzene and o-dichlo carried out under atmospheric pressure. robenzene, moreover ketones, such as acetone and methyl When carrying out the process (G) according to the inven isopropyl ketone, furthermore ethers, such as diethyl ether, tion, the reaction components of the formula (IX) and the tetrahydrofuran and dioxane, additionally carboxylic esters, 10 Such as ethyl acetate, and also strongly polar solvents, such as deprotonating bases are generally employed in approxi dimethylsulphoxide and sulpholane. The hydrolytic stability mately equimolar amounts. However, it is also possible to use of the acid halide permitting, the reaction can also be carried a relatively large excess (up to 3 mol) of one component or the out in the presence of water. other. Suitable acid binders for the reaction according to the For carrying out the process (H) according to the invention, 15 process (I-C) according to the invention are all customary palladium(0) complexes are suitable as catalysts. Preference acid acceptors. Preference is given to using tertiary amines, is given to, for example, tetrakis-(triphenylphosphine)palla Such as triethylamine, pyridine, diazabicyclooctane dium or bis-(triphenylphosphine)-palladium dichloride/ (DABCO), diazabicyclo-undecene (DBU), diazabicyclonon triphenyl phosphine. ene (DBN), Hünig base and N,N-dimethyl-aniline, further Suitable acid acceptors for carrying out the process (H) more alkaline earth metal oxides, such as magnesium oxide according to the invention are inorganic or organic bases. and calcium oxide, moreover alkali metal and alkaline earth These preferably include alkaline earth metal or alkali metal metal carbonates, such as sodium carbonate, potassium car hydroxides, acetates, carbonates orbicarbonates. Such as, for bonate and calcium carbonate, and also alkali metal hydrox example, sodium hydroxide, potassium hydroxide, barium ides Such as sodium hydroxide and potassium hydroxide. hydroxide or ammonium hydroxide, Sodium acetate, potas 25 The reaction temperatures in the process (I-C) according to sium acetate, calcium acetate or ammonium acetate, sodium the invention can be varied within a relatively wide range. In carbonate, potassium carbonate or ammonium carbonate, general, the reaction is carried out at temperatures between Sodium bicarbonate or potassium bicarbonate, alkali metal –20° C. and +150° C., preferably between 0° C. and 100° C. fluorides, such as, for example, caesium fluoride, and also When carrying out the process (I-C) according to the inven tertiary amines, such as trimethylamine, triethylamine, tribu 30 tion, the starting materials of the formulae (I-1-a) to (I-7-a) tylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, and the carbonyl halide of the formula (XI) are generally in pyridine, N-methylpiperidine, N-methylmorpholine, N.N- each case employed in approximately equivalent amounts. dimethylaminopyridine, diazabicyclooctane (DABCO), However, it is also possible to employ a relatively large excess diazabicyclononene (DBN) or diazabicycloundecene (DBU). (up to 5 mol) of the carbonylhalide. Work-up is carried out by Suitable diluents for carrying out the process (H) according 35 customary methods. to the invention are water, organic solvents and any mixtures The process (I-8) is characterized in that compounds of the thereof. Examples include: aliphatic, alicyclic or aromatic formulae (I-1-a) to (I-7-a) are reacted with carboxylic anhy hydrocarbons. Such as, for example, petroleum ether, hexane, drides of the formula (XII), if appropriate in the presence of a heptane, cyclohexane, methylcyclohexane, benzene, toluene, diluent and if appropriate in the presence of an acid binder. Xylene or decalin; halogenated hydrocarbons, such as, for 40 Preferred diluents for the process (I-B) according to the example, chlorobenzene, dichlorobenzene, methylene chlo invention are those diluents which are also preferred when ride, chloroform, carbon tetrachloride, dichloroethane, acid halides are used. Otherwise, it is also possible for a trichloroethane or tetrachloroethylene; ethers, such as diethyl carboxylic anhydride employed in excess to act simulta ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl neously as a diluent. ether, dioxane, tetrahydrofuran, 1.2-dimethoxyethane, 1.2- 45 In the process (I-B), acid binders which are added, if appro diethoxyethane, diethylene glycol dimethyl ether or anisole; priate, are preferably those acid binders which are also pre alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, ferred when acid halides are used. sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxy In the process (I-B) according to the invention, the reaction ethanol, methoxyethanol, diethylene glycol monomethyl temperatures can be varied within a relatively wide range. In ether, diethylene glycol monomethyl ether; water. 50 general, the reaction is carried out at temperatures between The reaction temperature in the process (H) according to –20° C. and +150° C., preferably between 0° C. and 100° C. the invention can be varied within a relatively wide range. In When carrying out the process (I-B) according to the inven general, the reaction is carried out attemperatures between 0° tion, the starting materials of the formulae (I-1-a) to (I-7-a) C. and +140°C., preferably between 50° C. and +100° C. and the carboxylic anhydride of the formula (XII) are gener When carrying out the process (H) according to the inven 55 ally each employed in approximately equivalent amounts. tion, the coupling agents of the formula (X-al) or (X-b) and However, it is also possible to use a relatively large excess (up compounds of the formulae (I-1'-a) to (I-8-a) are employed in to 5 mol) of the carboxylic anhydride. Work-up is carried out a molar ratio of from 1:1 to 5:1. preferably from 1:1 to 2:1. In by customary methods. general, 0.005 to 0.5 mol, preferably 0.01 mol to 0.1 mol of In general, the adopted procedure is to remove diluent and catalyst is employed per mole of the compounds of the for 60 excess carboxylic anhydride and also the carboxylic acid mulae (I-1'-a) to (I-8-a). The base is usually employed in formed by distillation or by washing with an organic solvent CXCSS. 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-7-a) are in each case reacted with car formulae (I-1-a) to (I-7-a) are in each case reacted with chlo bonylhalides of the formula (XI), if appropriate in the pres 65 roformic esters or chloroformic thiol esters of the formula ence of a diluent and if appropriate in the presence of an acid (XV), if appropriate in the presence of a diluent and if appro binder. priate in the presence of an acid binder. US 8,673,818 B2 73 74 Suitable diluents for the reaction according to the process The reaction can be carried out at atmospheric pressure or (J) according to the invention are all customary acid accep under elevated pressure and is preferably carried out at atmo tors. Preference is given to using tertiary amines. Such as spheric pressure. Work-up is carried out by customary meth triethylamine, pyridine, DABCO, DBU, DBA, Hünig base ods. and N,N-dimethyl-aniline, furthermore alkaline earth metal 5 The process (L) according to the invention is characterized oxides, such as magnesium oxide and calcium oxide, more in that compounds of the formulae (I-1-a) to (I-7-a) are in over alkali metal carbonates and alkaline earth metal carbon each case reacted with sulphonyl chlorides of the formula ates, such as Sodium carbonate, potassium carbonate and (XV), if appropriate in the presence of a diluent and if appro calcium carbonate, and also alkali metal hydroxides Such as priate in the presence of an acid binder. Sodium hydroxide and potassium hydroxide. 10 In the preparation process (L), approximately 1 mol of Suitable diluents for the process (J) according to the inven sulphonyl chloride of the formula (XV) is reacted per mole of tion are all solvents which are inert towards the chloroformic starting material of the formula (I-1-a to I-7-a), at from -20 to esters or chloroformic thiol esters. Preference is given to 150° C., preferably at from 20 to 70° C. using hydrocarbons, such as benzine, benzene, toluene, 15 Suitable diluents which are added if appropriate are all Xylene and tetralin, furthermore halogenated hydrocarbons, inert polar organic solvents, such as ethers, amides, nitriles, such as methylene chloride, chloroform, carbon tetrachlo Sulphones, Sulphoxides or halogenated hydrocarbons, such as ride, chlorobenzene and o-dichlorobenzene, moreover methylene chloride. ketones, such as acetone and methyl isopropyl ketone, fur Preference is given to using dimethyl Sulphoxide, tetrahy thermore ethers, such as diethyl ether, tetrahydrofuran and drofuran, dimethyl-formamide and methylene chloride. dioxane, additionally carboxylic esters, such as ethyl acetate, If, in a preferred embodiment, the enolate salt of the com and also strongly polar solvents, such as dimethyl Sulphoxide pounds (I-1-a) to (I-7-a) is prepared by addition of strong and Sulpholane. deprotonating agents (such as, for example, Sodium hydride When carrying out the process (J) according to the inven or potassium tert-butoxide), it is not necessary to add further tion the reaction temperatures can be varied within a rela 25 acid binders. tively wide range. If the reaction is carried out in the presence If acid binders are employed, these are customary inor of a diluent and an acid binder, the reaction temperatures are ganic or organic bases, for example sodium hydroxide, generally between -20°C. and +100°C., preferably between Sodium carbonate, potassium carbonate, pyridine, triethy O° C. and 50° C. lamine. The process (J) according to the invention is generally 30 The reaction can be carried out at atmospheric pressure or carried out under atmospheric pressure. under elevated pressure and is preferably carried out at atmo When carrying out the process (J) according to the inven spheric pressure. Work-up is carried out by customary meth tion, the starting materials of the formulae (I-1-a) to (I-7-a) ods. and the appropriate chloroformic ester or chloroformic thiol The process (M) according to the invention is characterized ester of the formula (XIII) are generally in each case in that compounds of the formulae (I-1-a) to (I-7-a) are in employed in approximately equivalent amounts. However, it each case reacted with phosphorus compounds of the formula is also possible to employ a relatively large excess (up to 2 (XVI), if appropriate in the presence of a diluent and if appro mol) of one component or the other. Work-up is carried out by priate in the presence of an acid binder. customary methods. In general, precipitated salts are 40 In the preparation process (M), 1 to 2, preferably 1 to 1.3, removed and the reaction mixture that remains is concen mol of the phosphorus compound of the formula (XVI) are trated by Stripping the diluent. reacted per mole of the compounds (I-1-a) to (I-7-a) at tem The process (K) according to the invention is characterized peratures between -40°C. and 150° C., preferably between in that compounds of the formulae (I-1-a) to (I-7-a) are in -10 and 110°C., to give compounds of the formulae (I-1-e) to each case reacted with compounds of the formula (XIV) in the 45 (I-7-e). presence of a diluent and, if appropriate, in the presence of an Suitable solvents which are added if appropriate are all acid binder. inert polar organic solvents, such as ethers, amides, nitriles, In the preparation process (K), approximately 1 mol of alcohols, Sulphides, Sulphones, Sulphoxides, etc. chloromonothioformic ester or chlorodithioformic ester of Preference is given to using acetonitrile, dimethyl SulphoX 50 ide, tetrahydrofuran, dimethylformamide, methylene chlo the formula (XIV) is reacted per mole of starting material of ride. the formulae (I-1-a) to (I-7-a), at from 0 to 120°C., preferably Suitable acid binders which are added if appropriate are from 20 to 60° C. customary inorganic or organic bases such as hydroxides, Suitable diluents which are added if appropriate are all carbonates or amines. Examples include Sodium hydroxide, inert polar organic solvents, such as ethers, amides, Sul 55 Sodium carbonate, potassium carbonate, pyridine, triethy phones, Sulphoxides, but also halogenoalkanes. lamine. Preference is given to using dimethyl Sulphoxide, tetrahy The reaction can be carried out at atmospheric pressure or drofuran, dimethyl-formamide or methylene chloride. under elevated pressure and is preferably carried out under If, in a preferred embodiment, the enolate salt of the com atmospheric pressure. Work-up is carried out by customary pounds (I-1-a) to (I-7-a) is prepared by addition of strong 60 methods of organic chemistry. The resulting end products are deprotonating agents, such as, for example, Sodium hydride preferably purified by crystallization, chromatographic puri or potassium tert-butoxide, it is not necessary to add further fication or by so-called “incipient distillation’, i.e. removal of acid binders. the Volatile components under reduced pressure. If acid binders are employed, these are customary inor The process (N) is characterized in that compounds of the ganic or organic bases, for example sodium hydroxide, 65 formulae (I-1-a) to (I-7-a) are reacted with metal hydroxides Sodium carbonate, potassium carbonate, pyridine, triethy or metal alkoxides of the formula (XVII) or amines of the lamine. formula (XVIII), if appropriate in the presence of a diluent. US 8,673,818 B2 75 76 Preferred diluents for the process (N) according to the From the order of the Thysanura, for example, Lepisma invention are ethers, such as tetrahydrofuran, dioxane, diethyl saccharina. ether, or else alcohols, such as methanol, ethanol, isopro From the order of the Collembola, for example, Onychi panol, but also water. lirtiS drinatti.S. The process (N) according to the invention is generally 5 From the order of the Orthoptera, for example, Acheta carried out under atmospheric pressure. domesticus, Gryllotalpa spp., Locusta migratoria migrato The reaction temperatures are generally between -20°C. rioides, Melanoplus spp. and Schistocerca gregaria. From the order of the Blattaria, for example, Blatta Orien and 100° C., preferably between 0° C. and 50° C. talis, Periplaneta americana, Leucophaea maderae and Blat The process (O) according to the invention is characterized 10 tella germanica. in that compounds of the formulae (I-1-a) to (I-7-a) are in From the order of the Dermaptera, for example, Forficula each case reacted with (O-O.) compounds of the formula auricularia. (XIX), if appropriate in the presence of a diluent and if appro From the order of the Isoptera, for example, Reticulitermes priate in the presence of a catalyst, or (O-3) with compounds spp. of the formula (XX), if appropriate in the presence of a diluent 15 From the order of the Phthiraptera, for example, Pediculus and if appropriate in the presence of an acid binder. humanus corporis, Haematopinus spp., Linognathus spp., In the preparation process (O-O.), approximately 1 mol of Trichodectes spp. and Damalinia spp. isocyanate of the formula (XIX) is reacted per mole of start From the order of the Thysanoptera, for example, Herci ing material of the formulae (I-1-a) to (I-7-a), at from 0 to nothrips femoralis, Thrips tabaci, Thrips palmi and Franklin 100° C., preferably at from 20 to 50° C. 20 iella Occidentalis. Suitable diluents which are added if appropriate are all From the order of the Heteroptera, for example, Eurygaster inert organic solvents, such as ethers, amides, nitriles, Sul spp., Dysdercus intermedius, Piesma quadrata, Cimex lectu phones and Sulphoxides. larius, Rhodnius prolixus and Triatoma spp. If appropriate, catalysts may be added to accelerate the From the order of the Homoptera, for example, Aleurodes reaction. Very advantageously, the catalysts which are 25 brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis employed are organotin compounds, such as, for example, gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis dibutyltin dilaurate. The reaction is preferably carried out at fabae, Aphis pomi, Eriosoma lanigerum, Hvalopterus arun atmospheric pressure. dinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphun In the preparation process (O-3), approximately 1 mol of avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, carbamoyl chloride of the formula (XX) is reacted per mole of 30 Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, starting material of the formulae (I-1-a) to (I-7-a), at from -20 Lecanium corni, Saissetia oleae, Laodelphax striatellus, to 150° C., preferably at from 0 to 70° C. Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Suitable diluents which are added if appropriate are all Pseudococcus spp. and Psylla spp. inert polar organic solvents, such as ethers, amides, Sul From the order of the Lepidoptera, for example, Pectino phones, Sulphoxides or halogenated hydrocarbons. 35 phora gossypiella, Bupalus piniarius, Chematobia brumata, Preference is given to using dimethyl Sulphoxide, tetrahy Lithocolletis blancardella, Hyponomeuta padella, Plutella drofuran, dimethyl-formamide or methylene chloride. xylostella, Malacosoma neustria, Euproctis chrysorrhoea, If, in a preferred embodiment, the enolate salt of the com Lymantria spp., Bucculatrix thurberiella, Phyllocnistis cit pounds (I-1-a) to (I-7-a) is prepared by addition of strong rella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, deprotonating agents (such as, for example, sodium hydride 40 Heliothis spp., Mamestra brassicae, Panolis flammea, or potassium tert-butoxide), it is not necessary to add further Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, acid binders. Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kueh If acid binders are employed, these are customary inor niella, Galleria mellonella, Tineola bisselliella, Tinea pel ganic or organic bases, for example sodium hydroxide, lionella, Hofmannophila pseudospretella, Cacoecia podana, Sodium carbonate, potassium carbonate, triethylamine or 45 Capua reticulana, Choristoneura filmiferana, Clysia ambig pyridine. uella, Homona magnanima, Tortrix viridana, Cnaphalocerus The reaction can be carried out at atmospheric pressure or spp. and Oulema oryzae. under elevated pressure and is preferably carried out at atmo From the order of the Coleoptera, for example, Anobium spheric pressure. Work-up is carried out by customary meth punctatum, Rhizopertha dominica, Bruchidius Obtectus, ods. 50 Acanthoscelides Obtectus, Hylotrupes bajulus, Agelastica The active compounds having good plant tolerance and alni, Leptinotarsa decemlineata, Phaedon cochleariae, favourable warm-blood toxicity are suitable for controlling Diabrotica spp., Psylliodes chrysocephala, Epillachna animal pests, in particular insects, arachnids and nematodes, varivestis, Atomaria spp., Oryzaephilus surinamensis, which are encountered in agriculture, in forestry, in the pro Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, tection of stored products and of materials, and in the hygiene 55 Cosmopolites Sordidus, Ceuthorrhynchus assimilis, Hypera sector. They are preferably used as crop protection agents. postica, Dermestes spp., Trogoderma spp., Anthrenus spp., They are active against normally sensitive and resistant spe Attagenus spp., Lyctus spp., Melligethes aeneus, Ptinus spp., cies and against all or some stages of development. The Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tene abovementioned pests include: brio molitor; Agriotes spp., Conoderus spp., Melolontha From the order of the Isopoda, for example, Oniscus asel 60 melolontha, Amphimallon solstitialis, Costelytra zealandica lus, Armadillidium vulgare and Porcellio scaber: and Lissorhoptrus Oryzophilus. From the order of the Diplopoda, for example, Blaniulus From the order of the Hymenoptera, for example, Diprion guttulatus. spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis From the order of the Chilopoda, for example, Geophilus and Vespa spp. Carpophagus and Scutigera spp. 65 From the order of the Diptera, for example, Aedes spp., From the order of the Symphyla, for example, Scutigerella Anopheles spp., Culex spp., Drosophila melanogaster, Musca immaculata. spp., Fannia spp., Caliphora erythrocephala, Lucilia spp., US 8,673,818 B2 77 78 Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppo Tackifiers such as carboxymethylcellulose and natural and bosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., synthetic polymers in the form of powders, granules or lati Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, ces, such as gum arabic, polyvinyl alcohol and polyvinyl Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus acetate, as well as natural phospholipids such as cephalins Oleae, Tipula paludosa, Hvlemyia spp. and Liriomyza spp. and lecithins, and synthetic phospholipids, can be used in the From the order of the Siphonaptera, for example, Xenop formulations. Other additives can be mineral and vegetable sylla cheopis and Ceratophyllus spp. oils. From the class of the Arachnida, for example, Scorpio It is possible to use colorants such as inorganic pigments, maurus, Latrodectus mactans, Acarus siro, Argas spp., Orni for example iron oxide, titanium oxide and Prussian Blue, and thodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyl 10 locoptruta oleivora, Boophilus spp., Rhipicephalus spp., organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes and metal phthalocyanine dyestuffs, and trace nutrients such spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., as salts of iron, manganese, boron, copper, cobalt, molybde Bryobia praetiosa, Panonychus spp., Tetranychus spp., num and zinc. Hemitarisonemus spp. and Brevipalpus spp. 15 The formulations generally comprise between 0.1 and 95% The plant-parasitic nematoden include, for example, by weight of active compound, preferably between 0.5 and Pratylenchus spp., Radopholus similis, Dity lenchus dipsaci, 90%. Tvlenchulus semipenetrans, Heterodera spp., Globodera The active compound according to the invention can be spp., Meloidogyne spp., Aphelen.choides spp., Longidorus present in its commercially available formulations and in the spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchus use forms, prepared from these formulations, as a mixture spp. with other active compounds, such as insecticides, attracta At certain concentrations or application rates, the com nts, sterilizing agents, bactericides, acaricides, nematicides, pounds according to the invention may, if appropriate, also be fungicides, growth-regulating Substances or herbicides. The used as herbicides and microbicides, for example as fungi insecticides include, for example, phosphoric acid esters, car cides, antimycotics and bactericides. If appropriate, they may 25 bamates, carboxylates, chlorinated hydrocarbons, pheny also be used as intermediates or precursors for the synthesis of lureas and Substances produced by microorganisms, inter further active compounds. alia. The active compounds can be converted into the customary Particularly favourable examples of co-components in formulations, such as solutions, emulsions, wettable pow mixtures are the following compounds: ders, Suspensions, powders, dusts, pastes, soluble powders, 30 Fungicides: granules, Suspension-emulsion concentrates, natural and Syn aldimorph, ampropylfos, ampropylfoS potassium, andoprim, thetic materials impregnated with active compound, and anilazine, azaconazole, azoxystrobin, microencapsulations in polymeric Substances. benalaxyl, benodanil, benomyl, benzamacril, benzamacril These formulations are produced in a known manner, for isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blas example by mixing the active compounds with extenders, that 35 ticidin-S, bromuconazole, bupirimate, buthiobate, is, liquid solvents, and/or solid carriers, optionally with the calcium polysulphide, capsimycin, captafol, captan, car use of surfactants, that is emulsifiers and/or dispersants, and/ bendazim, carboxin, carvon, quinomethionate, chlo or foam-formers. benthiazone, chlorfenazole, chloroneb, chloropicrin, chlo If the extender used is water, it is also possible to employ rothalonil, chloZolinate, cloZylacon, cufraneb, cymoxaniil, for example organic solvents as auxiliary solvents. Essen 40 cyproconazole, cyprodinil, cyprofuram, tially, Suitable liquid solvents are: aromatics such as Xylene, debacarb, dichlorophen, diclobutrazole, diclofluanid, toluene or alkylnaphthalenes, chlorinated aromatics or chlo diclomeZine, dicloran, diethofencarb, difenoconazole, rinated aliphatic hydrocarbons such as chlorobenzenes, chlo dimethirimol, dimethomorph, diniconazole, diniconazole roethylenes or methylene chloride, aliphatic hydrocarbons M. dinocap, diphenylamine, dipyrithione, ditalimfos, Such as cyclohexane or paraffins, for example petroleum frac 45 dithianon, dodemorph, dodine, draZOXolon, tions, mineral and vegetable oils, alcohols such as butanol or edifenphos, epoxiconazole, etaconazole, ethirimol, etridiaz glycol and also their ethers and esters, ketones such as ole, acetone, methyl ethyl ketone, methyl isobutyl ketone or famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, cyclohexanone, strongly polar solvents such as dimethylfor fenitropan, fenpiclonil, fempropidin, fenpropimorph, fen mamide and dimethyl Sulphoxide, and also water. 50 tin acetate, fentin hydroxide, ferbam, ferimZone, fluazi As solid carriers there are suitable: nam, flumetover, fluoromide, fluguinconazole, flurprimi for example ammonium salts and ground natural minerals dol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, Such as kaolins, clays, talc, chalk, quartz, attapulgite, mont fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, morillonite ordiatomaceous earth, and ground synthetic min furalaxyl, furametpyr, furcarbonil, furconazole, furcona erals, such as highly disperse silica, alumina and silicates; as 55 Zole-cis, furmecyclox, solid carriers for granules there are suitable: for example guaZatine, crushed and fractionated natural rocks such as calcite, hexachlorobenzene, hexaconazole, hymexazole, marble, pumice, Sepiolite and dolomite, and also synthetic imazalil, imibenconazole, iminoctadine, iminoctadine albe granules of inorganic and organic meals, and granules of silate, iminoctadine triacetate, iodocarb, ipconazole, organic material Such as sawdust, coconut shells, maize cobs 60 iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, and tobacco stalks; as emulsifiers and/or foam-formers there isovaledione, are suitable: for example nonionic and anionic emulsifiers, kasugamycin, kresoxim-methyl, copper preparations, such Such as polyoxyethylene fatty acid esters, polyoxyethylene as: copper hydroxide, copper naphthenate, copper oxy fatty alcohol ethers, for example alkylaryl polyglycol ethers, chloride, copper Sulphate, copper oxide, oxine-copper and alkylsulphonates, alkyl Sulphates, arylsulphonates and also 65 Bordeaux mixture, protein hydrolysates; as dispersants there are suitable: for mancopper, mancoZeb, maneb, meferimZone, mepanipyrim, example lignin-Sulphite waste liquors and methylcellulose. mepronil, metalaxyl, metconazole, methasulfocarb, meth

US 8,673,818 B2 81 82 popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus 2-(2-chloro-6-fluorophenyl)-4-4-(1,1-dimethylethyl)phe thuringiensis, Baculoviridae, Beauveria bassiana, Beau nyl-4,5-dihydro-oxazole, veria tenella, bendiocarb, benfuracarb, bensultap, ben 2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione, Zoximate, betacyfluthrin, bifenazate, bifenthrin, bioetha 2-chloro-N-4-(1-phenylethoxy)-phenyl-amino-carbo nomethrin, bio-permethrin, BPMC, bromophos A, nyl-benzamide, bufencarb, buprofezin, butathiofos, butocarboxim, 2-chloro-N-4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl butylpyridaben, amino-carbonyl-benzamide, cadusafos, carbaryl, carbofuran, carbophenothion, carbo 3-methylphenyl propylcarbamnate. Suifan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, 4-4-(4-ethoxyphenyl)-4-methylpentyl-1-fluoro-2-phe 10 noxy-benzene, chlorfenvinphos, chlorfluaZuron, chlormephos, chlorpyri 4-chloro-2-(1,1-dimethylethyl)-5-[2-(2,6-dimethyl-4-phe fos, chlorpyrifos M. chlovaporthrin, cis-resmethrin, noxyphenoxy)ethylthio-3(2H)-pyridazinone, cispermethrin, clocythrin, cloethocarb, clofenteZine, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridi cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalo nyl)methoxy-3 (2H)-pyridazinone, thrin, cyhexatin, cypermethrin, cyromazine, 15 4-chloro-5-(6-chloro-3-pyridinyl)methoxy-2-(3,4-dichlo deltamethrin, demeton M, demeton S, demeton-S-methyl, rophenyl)-3(2H)-pyridazinone, diafenthiuron, diazinon, dichlorvos, diflubenzuron, Bacillus thuringiensis strain EG-2348, dimethoate, dimethylvinphos, diofenolan, disulfoton, 2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid, docusat-sodium, dofenapyn, 2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro4.5 eflusilanate, emamectin, empenthrin, endosulfan, Ento dec-3-en-4-ylbutanoate, mopfihora spp., esfenvalerate, ethiofencarb, ethion, etho 3-(6-chloro-3-pyridinyl)methyl-2-thiazolidinylidene-cy prophos, etofenproX, etoxazole, etrimfos, fenamiphos, anamide, dihydro-2-(nitromethylene)-2H-1,3-thiazine-3 fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, (4H)-carboxaldehyde, fenoxacrim, fenoxycarb, fempropathrin, fenpyrad, fenpy ethyl 2-1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazi rithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, 25 nyloxyethyl-carbamate, fluaZuron, flubrocythrinate, flucycloxuron, flucythrinate, N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine, flufenoXuron, flutenzine, fluvalinate, fonophos, foSme N-(4-chlorophenyl)-3-4-(difluoromethoxy)phenyl-4,5-di thilan, fosthiazate, fubfenprox, furathiocarb, hydro-4-phenyl-1H-pyrazole-1-carboxamide, granulosis viruses, N-(2-chloro-5-thiazolyl)methyl-N'-methyl-N'-nitro halofenozide, HCH, heptenophos, hexaflumuron, hexythia 30 guanidine, Zox, hydroprene, N-methyl-N'-(1-methyl-2-propenyl)-1,2-hydrazinedicar imidacloprid, isazofos, isofenphos, isoxathion, ivermectin, bothioamide, nuclear polyhedrosis viruses, N-methyl-N'-2-propenyl-1,2-hydrazinedicarbothioamide, lambda-cyhalothrin, lufenuron, O.O-diethyl 2-(dipropylamino)-2-oxoethyl-ethylphos malathion, mecarbam, metaldehyde, methamidophos, meth 35 phoramidothioate. arhizium aniisopliae, metharhizium flavoviride, methi A mixture with other known active compounds, such as dathion, methiocarb, methomyl, methoxyfenozide, metol herbicides, or with fertilizers and growth regulators is also carb, metoxadiaZone, mevinphos, milbemectin, possible. monocrotophos, The active compounds according to the invention can fur naled, nitenpyram, nithiazine, novaluron, 40 thermore be present when used as insecticides in their com omethoate, oxamyl, Oxydemethon M, mercially available formulations and in the use forms, pre Paecilomyces fumosoroseus, parathion A, parathion M, per pared from these formulations, as a mixture with Synergistic methrin, phenthoate, phorate, phosalone, phosmet, phos agents. Synergistic agents are compounds which increase the phamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos action of the active compounds, without it being necessary for M, profenofos, promecarb, propoXur, prothiofos, pro 45 the synergistic agent added to be active itself. thoate, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, The active compound content of the use forms prepared pyridaben, pyridathion, pyrimidifen, pyriproxyfen, from the commercially available formulations can vary quinalphos, within widelimits. The active compound concentration of the ribavirin, use forms can be from 0.0000001 to 95% by weight of active salithion, Sebufos, Silafluofen, spinosad, Sulfotep, Sulprofos, 50 compound, preferably between 0.0001 and 1% by weight. tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, The compounds are employed in a customary manner teflubenzuron. tefluthrin, temephos, temivinphos, terbu appropriate for the use forms. fos, tetrachlorvinphos, thetacy permethinn, thiamethoxam, When used against hygiene pests and pests of stored prod thiapronil, thiatriphos, thiocyclam hydrogen oxalate, ucts, the active compound is distinguished by an excellent thiodicarb, thiofanox, thuringiensin, tralocythrin, tralom 55 residual action on wood and clay as well as a good stability to ethrin, triarathene, triazamate, triaZophos, triaZurone, alkali on limed substrates. trichlophenidine, trichiorfon, triflumuron, trimethacarb, The active compounds according to the invention act not vamidothion, vaniliprole, Verticillium lecanii, only against plant, hygiene and stored product pests, but also YI 5302, in the veterinary medicine sector against animal parasites Zeta-cypermethrin, Zolaprofos, 60 (ectoparasites). Such as hard ticks, soft ticks, mange mites, (1R-cis)-5-(phenylmethyl)-3-furanyl-methyl-3-(dihydro leaf mites, flies (biting and licking), parasitic fly larvae, lice, 2-oxo-3(2H)-furanylidene)-methyl-2,2-dimethylcyclo hair lice, feather lice and fleas. These parasites include: propalecarboxylate, From the order of the Anoplurida, for example, Hae (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropan matopinus spp., Linognathus spp., Pediculus spp., Phtirus ecarboxylate, 65 spp. and Solenopotes spp. 1-(2-chloro-5-thiazolyl)methyltetrahydro-3,5-dimethyl-N- From the order of the Mallophagida and the suborders nitro-1,3,5-triazine-2(1H)-imine, Amblycerina and Ischnocerina, for example, Trimenopon US 8,673,818 B2 83 84 spp., Menopon spp., Trinoton spp., Bovicola spp., Weineck the active compounds in an amount of 1 to 80% by weight, iella spp., Lepikentron spp., Damalina spp., Trichodectes directly or after 100 to 10 000-fold dilution, or they can be spp. and Felicola spp. used as a chemical bath. From the order Diptera and the suborders Nematocerina It has furthermore been found that the compounds accord and Brachycerina, for example, Aedes spp., Anopheles spp., ing to the invention also have a strong insecticidal action Culex spp., Simulium spp., Eusimulium spp., Phlebotomus against insects which destroy industrial materials. spp., Lutzomyia spp., Culicoides spp., Chrysops spp., The following insects may be mentioned as examples and Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota as being preferred—but without any limitation: spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea Beetles, such as 10 Hylotrupes bajulus, Chlorophorus pilosis, Anobium punc spp., Stomoxys spp., Haematobia spp., Morelia spp., Fannia tatum, Xestobium rufo villosum, Ptilinuspecticornis, Dendro spp., Glossina spp., Caliphora spp., Lucilia spp., Chry bium pertinex, Ernobius mollis, Priobium carpini, Lyctus somyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus lin spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., earis, Lyctus pubescens, Trogoxylon aequale, Minthes rugi Lipoptena spp. and Mellophagus spp. 15 collis, Xvleborus spec. Tryptodendron spec. Apate monachus, From the order of the Siphonapterida, for example Pulex Bostrychus capucins, Heterobostrychus brunneus and spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyl Sinoxylon spec. Dinoderus minutus. lus spp. Hymenopterons, such as From the order of the Heteropterida, for example, Cimex Sirex juvencus, Urocerus gigas, Urocerus gigas taignus spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp. and Urocerus augur From the order of the Blattarida, for example Blatta orien Termites, such as talis, Periplaneta americana, Blattela germanica and Supella Kalotermes flavicollis, Cryptotermes brevis, Heterotcrimes spp. indicola, Reticulitermes flavipes, Reticulitermes Santonensis, From the subclass of the Acaria (Acarida) and the orders of Reticulitermes lucifigus, Mastotermes darwiniensis, Zooter the Meta- and Mesostigmata, for example, Argas spp., Orni 25 mopsis nevadensis and Coptotermes formosanus. thodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Bristletails, such as Lepisma saccarina. Boophilus spp., Dermacentor spp., Haemophysalis spp., Industrial materials in the present connection are to be Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., understood as meaning non-living materials, such as, prefer Raillietia spp., Pneumonyssus spp., Sternostoma spp. and ably, plastics, adhesives, sizes, papers and cards, leather, 30 wood and processed wood products and coating composi Varroa spp. tions. From the order of the Actinedida (Prostigmata) and Acari Wood and processed wood products are materials to be dida (Astigmata), for example, Acarapis spp., Cheyletiella protected, especially preferably, from insect infestation. spp., OrnithOcheyletia spp., Myobia spp., Psorergates spp., Wood and wood processed wood products which can be Demodex spp., Trombicula spp., Listrophorus spp., Acarus 35 protected by the agents according to the invention or mixtures spp., Trophagus spp., Caloglyphus spp., Hypodectes spp., comprising these are to be understood as meaning, for Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes example: building timber, wooden beams, railway sleepers, spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., bridge components, boat jetties, wooden vehicles, boxes, pal Cytodites spp. and Laminosioptes spp. lets, containers, telegraph poles, wood panelling, wooden The active compounds according to the invention are also 40 windows and doors, plywood, chipboard, joinery or wooden suitable for controlling arthropods which infest agricultural products which are used quite generally in house-building or productive livestock, Such as, for example, cattle, sheep, in building joinery. goats, horses, pigs, donkeys, camels, buffalo, rabbits, chick The active compounds can be used as Such, in the form of ens, turkeys, ducks, geese and bees, other pets, such as, for concentrates or in generally customary formulations, such as example, dogs, cats, caged birds and aquarium fish, and also 45 powders, granules, Solutions, Suspensions, emulsions or so-called test animals, such as, for example, hamsters, guinea pastes. pigs, rats and mice. By controlling these arthropods, cases of The formulations mentioned can be prepared in a manner death and reduction in productivity (for meat, milk, wool, known per se, for example by mixing the active compounds hides, eggs, honey etc.) should be diminished, so that more with at least one solvent or diluent, emulsifier, dispersing economic and easier animal husbandry is possible by use of 50 agent and/or binder or fixing agent, a water repellent, if appro the active compounds according to the invention. priate siccatives and UV stabilizers and if appropriate dye The active compounds according to the invention are used stuffs and pigments, and also other processing auxiliaries. in the Veterinary sector in a known manner by enteral admin The insecticidal compositions or concentrates used for the istration in the form of for example, tablets, capsules, preservation of wood and wood-derived timber products potions, drenches, granules, pastes, boluses, the feed-through 55 comprise the active compound according to the invention in a process and Suppositories, by parenteral administration, Such concentration of 0.0001 to 95% by weight, in particular 0.001 as, for example, by injection (intramuscular, Subcutaneous, to 60% by weight. intravenous, intraperitoneal and the like), implants by nasal The amount of the compositions or concentrates employed administration, by dermal use in the form, for example, of depends on the nature and occurrence of the insects and on the dipping or bathing, spraying, pouring on and spotting on, 60 medium. The optimum amount employed can be determined washing and powdering, and also with the aid of moulded for the use in each case by a series of tests. In general, articles containing the active compound. Such as collars, ear however, it is sufficient to employ 0.0001 to 20% by weight, marks, tail marks, limb bands, halters, marking devices and preferably 0.001 to 10% by weight, of the active compound, the like. based on the material to be preserved. When used for cattle, poultry, pets and the like, the active 65 Solvents and/or diluents which are used are an organic compounds can be used as formulations (for example pow chemical solvent or solvent mixture and/or an oily or oil-like ders, emulsions, free-flowing compositions), which comprise organic chemical solvent or solvent mixture of low volatility US 8,673,818 B2 85 86 and/or a polar organic chemical solvent or solvent mixture The plasticizers originate from the chemical classes of and/or water, and if appropriate an emulsifier and/or wetting phthalic acid esters, such as dibutyl, dioctyl or benzylbutyl agent. phthalate, phosphoric acid esters, such as tributyl phosphate, Organic chemical solvents which are preferably used are adipic acid esters, such as di-(2-ethylhexyl)adipate, Stearates, oily or oil-like solvents having an evaporation number above Such as butyl Stearate or amyl Stearate, oleates, such as butyl 35 and a flashpoint above 30° C., preferably above 45° C. oleate, glycerol ethers or higher molecular weight glycol Substances which are used as such oily or oil-like water ethers, glycerol esters and p-toluenesulphonic acid esters. insoluble solvents of low volatility are appropriate mineral Fixing agents are based chemically on polyvinyl alkyl oils or aromatic fractions thereof, or solvent mixtures con ethers, such as, for example, polyvinyl methyl ether or taining mineral oils, preferably white spirit, petroleum and/or 10 ketones, such as benzophenone or ethylenebenzophenone. alkylbenzene. Possible solvents or diluents are, in particular, also water, if Mineral oils having a boiling range from 170 to 220°C., appropriate as a mixture with one or more of the abovemen white spirit having a boiling range from 170 to 220° C. tioned organic chemical solvents or diluents, emulsifiers and spindle oil having a boiling range from 250 to 350° C., petro dispersing agents. leum and aromatics having a boiling range from 160 to 280° 15 Particularly effective preservation of wood is achieved by C., terpentine oil and the like, are advantageously employed. impregnation processes on a large industrial scale, for In a preferred embodiment, liquid aliphatic hydrocarbons example vacuum, double vacuum or pressure processes. having a boiling range from 180 to 210°C. or high-boiling The ready-to-use compositions can also comprise other mixtures of aromatic and aliphatic hydrocarbons having a insecticides, if appropriate, and also one or more fungicides, boiling range from 180 to 220° C. and/or spindle oil and/or if appropriate. monochloronaphthalene, preferably C-monochloronaphtha Possible additional mixing partners are, preferably, the lene, are used. insecticides and fungicides mentioned in WO94/29268. The The organic oily or oil-like solvents of low volatility which compounds mentioned in this document are an explicit con have an evaporation number above 35 and a flashpoint above stituent of the present application. 30°C., preferably above 45° C. can be replaced in part by 25 Especially preferred mixing partners which may be men organic chemical solvents of high or medium Volatility, pro tioned are insecticides, such as chlorpyriphos, phoxim, viding that the solvent mixture likewise has an evaporation Silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltam number above 35 and a flashpoint above 30° C., preferably cthrin, permcethrin, imidacloprid, NI-25, flufenoxuron, above 45° C., and that the insecticide/fungicide mixture is hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxide soluble or emulsifiable in this solvent mixture. 30 and triflumuron, and also fungicides, such as epoxyconazole, According to a preferred embodiment, some of the organic hexaconazole, azaconazole, propiconazole, tebuconazole, chemical solvent or solvent mixture is replaced by an ali cyproconazole, metconazole, imazalil, dichlorfluanid, phatic polar organic chemical solvent or solvent mixture. tolylfluanid, 3-iodo-2-propinyl-butyl carbamate, N-octyl Aliphatic organic chemical solvents containing hydroxyl isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3- and/or ester and/or ether groups, such as, for example, glycol 35 OC. ethers, esters or the like, are preferably used. The compounds according to the invention can at the same Organic chemical binders which are used in the context of time be employed for protecting objects which come into the present invention are the synthetic resins and/or binding contact with saltwater or brackish water, Such as hulls, drying oils which are known perse, are water-dilutable and/or screens, nets, buildings, moorings and signalling systems, are soluble or dispersible or emulsifiable in the organic 40 against fouling. chemical Solvents employed, in particular binders consisting Fouling by sessile Oligochaeta, such as Serpulidae, and by of or comprising an acrylate resin, a vinyl resin, for example shells and species from the Ledamorpha group (goose bar polyvinyl acetate, polyester resin, polycondensation or poly nacles). Such as various Lepas and Scalpellum species, or by addition resin, polyurethane resin, alkyd resin or modified species from the Balanomorpha group (acorn barnacles), alkyd resin, phenolic resin, hydrocarbon resin, Such as 45 Such as Balanus or Pollicipes species, increases the frictional indene-cumarone resin, silicone resin, drying vegetable oils drag of ships and, as a consequence, leads to a marked and/or drying oils and/or physically drying binders based on increase in operation costs owing to higher energy consump a natural and/or synthetic resin. tion and additionally frequent residence in the dry dock. The synthetic resin used as the binder can be employed in Apart from fouling by algae, for example Ectocarpus sp. the form of an emulsion, dispersion or Solution. Bitumen or 50 and Ceramium sp., fouling by sessile Entomostraka groups, bituminous Substances can also be used as binders in an which come under the generic term Cirripedia (cirriped crus amount of up to 10% by weight. Dyestuffs, pigments, water taceans), is of particular importance. repelling agents, odour correctants and inhibitors or anticor Surprisingly, it has now been found that the compounds rosive agents and the like which are known per se can addi according to the invention, alone or in combination with other tionally be employed. 55 active compounds, have an outstanding antifouling action. It is preferred according to the invention for the composi Using the compounds according to the invention, alone or tion or concentrate to comprise, as the organic chemical in combination with other active compounds, allows the use binder, at least one alkyd resin or modified alkyd resin and/or of heavy metals such as, for example, in bis-(trialkyltin) Sul one drying vegetable oil. Alkyd resins having an oil content of phides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper more than 45% by weight, preferably 50 to 68% by weight, 60 (I) oxide, triethyltin chloride, tri-n-butyl (2-phenyl-4-chlo are preferably used according to the invention. rophenoxy)tin, tributyltin oxide, molybdenum disulphide, All or some of the binder mentioned can be replaced by a antimony oxide, polymeric butyl titanate, phenyl-(bispyri fixing agent (mixture) or a plasticizer (mixture). These addi dine)-bismuth chloride, tri-n-butyltin fluoride, manganese tives are intended to prevent evaporation of the active com ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, pounds and crystallization or precipitation. They preferably 65 Zinc ethylenebisthiocarbamate, Zinc salts and copper salts of replace 0.01 to 30% of the binder (based on 100% of the 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc binder employed). ethylene-bisthiocarbamate, Zinc oxide, copper(I) ethylene US 8,673,818 B2 87 88 bisdithiocarbamate, copper thiocyanate, copper naphthenate employed in domestic insecticide products for controlling and tributyltinhalides to be dispensed with, or the concentra these pests alone or in combination with other active com tion of these compounds 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 developmental 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. OCCitanus. Preferably suitable components in combinations 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 algicides such as 10 phagus domesticus, Ornithodorus moubat, Rhipicephalus 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1.3, sanguineus, Trombicula alfreddugesi, Neutrombicula autum 5-triazine, dichlorophen, diuron, endothal, fentine acetate, nalis, Dermatophagoides pteronissimus, Dermatophagoides isoproturon, methabenzthiaZuron, oxyfluorfen, quinoc forinae. lamine and terbutryn; From the order of the Araneae, for example, Aviculariidae, fungicides such as 15 Araneidae. benzobthiophenecarboxylic acid cyclohexylamide S.S.- From the order of the Opiliones, for example, Pseudoscor dioxide, dichlofluanid, fluor-folpet, 3-iodo-2-propinylbutyl piones chelifer, Pseudoscorpiones cheiridium, Opiliones carbamate, tolylfluanid and azoles Such as phalangium. aZaconazole, cyproconazole, epoxyconazole, hexacona From the order of the Isopoda, for example. Onliscus asel Zole, metconazole, propiconazole and tebuconazole; lus, Porcellio Scaber: molluscicides such as From the order of the Diplopoda, for example, Blaniulus fentin acetate, metaldehyde, methiocarb, niclosamid, guttulatus, Polydesmus spp. thiodicarb and trimethacarb: From the order of the Chilopoda, for example, Geophilus or conventional antifouling active compounds Such as spp. 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodometh 25 From the order of the Zygentoma, for example, Ctenolepi ylparatrylsulphone, 2-(N,N-di-methylthiocarbamoylthio)-5- Sma spp., Lepisma Saccharina, Lepismodes inquilinus. nitrothiaZyl, potassium, copper, Sodium and Zinc salts of From the order of the Blattaria, for example, Blatta Orien 2-pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabu tallies, Blattella germanica, Blattella asahinai, Leucophaea tyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulphonyl)- maderae, Panchlora spp., Parcoblatta spp., Periplaneta aus pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetra-meth 30 tralasiae, Periplaneta americana, Periplaneta brunnea, ylthiuram disulphide and 2,4,6-trichlorophenylmaleiimide. Periplaneta fuliginosa, Supella longipalpa. The antifouling compositions used comprise the active From the order of the Saltatoria, for example, Acheta compound according to the invention of the compounds domesticus. according to the invention in a concentration of 0.001 to 50% From the order of the Dermaptera, for example, Forficula by weight, in particular 0.01 to 20% by weight. 35 auricularia. Moreover, the antifouling compositions according to the From the order of the Isoptera, for example, Kalotermes invention comprise the customary components such as, for spp., Reticulitermes spp. example, those described in Ungerer, Chem. Ind. 1985, 37, From the order of the Psocoptera, for example, Lepinatus 730–732 and Williams, Antifouling Marine Coatings, Noyes, spp., LipOscelis spp. Park Ridge, 1973. 40 From the order of the Coleptera, for example, Anthrenus Besides the algicidal, fungicidal, molluscicidal active spp., Attagenus spp., Dermestes spp., Latheticus Oryzae, compounds and insecticidal active compounds according to Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus the invention, antifouling paints comprise, in particular, bind granarius, Sitophilus Oryzae, Sitophilus zeanais, Stegobium CS. paniceum. Examples of recognized binders are polyvinyl chloride in a 45 From the order of the Diptera, for example, Aedes aegypti, Solvent system, chlorinated rubber in a solvent system, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., acrylic resins in a solvent system, in particular in an aqueous Caliphora erythrocephala, Chrysozona pluvialis, Culex system, vinyl chloride/vinyl acetate copolymer systems in the quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila form of aqueous dispersions or in the form of organic solvent spp., Fannia canicularis, Musca domcstica, Phlebotomus systems, butadiene/styrenefacrylonitrile rubbers, drying oils 50 spp., Sarcophaga carnaria, Simulium spp., Stomoxys calci Such as linseed oil, resin esters or modified hardened resins in trans, Tipula paludosa. combination with tar or bitumens, asphalt and epoxy com From the order of the Lepidoptera, for example, Achroia pounds, Small amounts of chlorine rubber, chlorinated grisella, Galleria mellonella, Plodia interpunctella, Tinea polypropylene and vinyl resins. cloacella, Tinea pellionella, Tineola bisselliella. If appropriate, paints also comprise inorganic pigments, 55 From the order of the Siphonaptera, for example, Cteno organic pigments or colorants which are preferably insoluble cephalides canis, Ctenocephalides felis, Pulex irritans, in saltwater. Paints may furthermore comprise materials such Tunga penetrans, Xenopsylla cheopis. as colophonium to allow controlled release of the active com From the order of the Hymenoptera, for example, Cam pounds. Furthermore, the paints may comprise plasticizers, ponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius modifiers which affect the rheological properties and other 60 umbratus, Monomorium pharaonis, Paravespula spp., Tet conventional constituents. The compounds according to the ramorium caespitum. invention or the abovementioned mixtures may also be incor From the order of the Anoplura, for example, Pediculus porated into self-polishing antifouling systems. humanus capitis, Pediculus humanus corporis, Phthirus The active compounds are also suitable for controlling pubis. animal pests, in particularinsects, arachnids and mites, which 65 From the order of the Heteroptera, for example, Cimex are found in enclosed spaces such as, for example, dwellings, hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma factory halls, offices, vehicle cabins and the like. They can be infestans. US 8,673,818 B2 89 90 They are used in the household insecticides sector alone or The compounds according to the invention have strong in combination with other Suitable active compounds such as herbicidal activity and a broad activity spectrum when used phosphoric esters, carbamates, pyrethroids, growth regula on the soil or on above-ground parts of plants. To a certain tors or active compounds from other known classes of insec extent, they are also suitable for the selective control of mono ticides. cotyledonous and dicotyledonous weeds in monocotyledon They are used in aerosols, pressure-free spray products, for ous and dicotyledonous crops, both by the pre-emergence and example pump and atomizer sprays, automatic fogging sys by the post-emergence method. tems, foggers, foams, gels, evaporator products with evapo At certain concentrations or application rates, the active rator tablets made of cellulose or polymer, liquid evaporators, compounds according to the invention can also be employed gel and membrane evaporators, propeller-driven evaporators, 10 for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermedi energy-free, or passive, evaporation systems, moth papers, ates or precursors for the synthesis of other active com moth bags and moth gels, as granules or dusts, in baits for pounds. spreading or in bait stations. All plants and plant parts can be treated in accordance with The active compounds according to the invention can be 15 the invention. Plants are to be understood as meaning in the used as defoliants, desiccants, haulm killers and, especially, present context all plants and plant populations such as as weedkillers. Weeds in the broadest sense are understood to desired and undesired wild plants or crop plants (inclusive of mean all plants which grow in locations where they are undes naturally occurring crop plants). Crop plants can be plants ired. which can be obtained by conventional plant breeding and Whether the substances according to the invention act as optimization methods or by biotechnological and recombi total or selective herbicides depends essentially on the nant methods or by combinations of these methods, inclusive amount used. of the transgenic plants and inclusive of the plant varieties The active compounds according to the invention can be protectable or not protectable by plant breeders’ rights. Plant used, for example, in connection with the following plants: parts are to be understood to mean all above-ground and Dicotyledonous Weeds of the Genera: 25 underground parts and organs of plants, such as shoot, leaf. Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aph flower and root, examples which may be mentioned being anes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, seeds, roots, tubers and rhizomes. The plant parts also include Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galin harvested material, and vegetative and generative propaga soga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepi 30 tion material, for example cuttings, tubers, rhizomes, offsets dium, Lindernia, Matricaria, Mentha, Mercurialis, Mulugo, and seeds. Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portu Treatment according to the invention of the plants and plant laca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Sal parts with the active compounds is carried out directly or by sola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, allowing the compounds to act on their Surroundings, envi Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, 35 ronment or storage space by the customary treatment meth Urtica, Veronica, Viola, Xanthium. ods, for example by immersion, spraying, evaporation, fog Dicotyledonous Crops of the Genera: ging, scattering, painting on and, in the case of propagation Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, material, in particular in the case of seed, also by applying one Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Or more COatS. Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia. 40 As already mentioned above, it is possible to treat all plants Monocotyledonous Weeds of the Genera: and their parts according to the invention. In a preferred Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, embodiment, wild plant species and plant varieties, or those Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cype obtained by conventional biological breeding, such as cross rus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, ing or protoplast fusion, and parts thereof, are treated. In a Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Het 45 further preferred embodiment, transgenic plants and plant eranthera, Imperata, Ischaemum, Leptochloa, Lolium, varieties obtained by genetical engineering, if appropriate in Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, combination with conventional methods (Genetic Modified Rottboelia, Sagittaria, Scirpus, Setaria, Sorghum. Organisms), and parts thereofare treated. The term “parts” or Monocotyledonous Crops of the Genera: “parts of plants’ or “plant parts” has been explained above. Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, 50 Particularly preferably, plants of the plant varieties which Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, are in each case commercially available or in use are treated Zea. according to the invention. However, the use of the active compounds according to the Depending on the plant species or plant varieties, their invention is in no way restricted to these genera, but also location and growth conditions (soils, climate, vegetation extends in the same manner to other plants. 55 period, diet), the treatment according to the invention may The active compounds according to the invention are Suit also result in superadditive (“synergistic) effects. Thus, for able, depending on the concentration, for the total control of example, reduced application rates and/or a widening of the weeds, for example on industrial terrain and rail tracks, and activity spectrum and/or an increase in the activity of the on paths and areas with and without tree plantings. Similarly, Substances and compositions to be used according to the the active compounds according to the invention can be 60 invention, better plant growth, increased tolerance to high or employed for controlling weeds in perennial crops, for low temperatures, increased tolerance to drought or to water example forests, decorative tree plantings, orchards, vine or soil salt content, increased flowering performance, easier yards, citrus groves, nut orchards, banana plantations, coffee harvesting, accelerated maturation, higher harvestyields, bet plantations, tea plantations, rubber plantations, oil palm plan ter quality and/or a higher nutritional value of the harvested tations, cocoa plantations, soft fruit plantings and hop fields, 65 products, better storage stability and/or processability of the on lawns, turf and pastureland, and for the selective control of harvested products are possible which exceed the effects weeds in annual crops. which were actually to be expected. US 8,673,818 B2 91 92 The transgenic plants or plant varieties (i.e. those obtained These formulations are produced in a known manner, for by genetical engineering) which are preferred according to example by mixing the active compounds with extenders, that the invention include all plants which, in the genetic modifi is to say liquid solvents and/or solid carriers, optionally with cation, received genetic material which imparted particularly the use of Surfactants, that is to say emulsifiers and/or dis advantageous useful properties (“traits') to these plants. persants and/or foam formers. Examples of Such properties are better plant growth, If the extender used is water, it is also possible to use, for increased tolerance to high or low temperatures, increased example, organic solvents as auxiliary solvents. Liquid sol tolerance to drought or to water or soil salt content, increased vents which are mainly suitable are: aromatics, such as flowering performance, easier harvesting, accelerated matu Xylene, toluene or alkylnaphthalenes, chlorinated aromatics ration, higher harvest yields, better quality and/or a higher 10 and chlorinated aliphatic hydrocarbons, such as chloroben nutritional value of the harvested products, better storage Zenes, chloroethylenes or methylene chloride, aliphatic stability and/or processability of the harvested products. Fur hydrocarbons, such as cyclohexane or paraffins, for example ther and particularly emphasized examples of such properties petroleum fractions, mineral and vegetable oils, alcohols, area better defence of the plants againstanimal and microbial Such as butanol or glycol, and also their ethers, ketones, such pests, such as against insects, mites, phytopathogenic fungi, 15 as acetone, methyl ethyl ketone, methyl isobutyl ketone or bacteria and/or viruses, and also increased tolerance of the cyclohexanone, strongly polar solvents, such as dimethylfor plants to certain herbicidally active compounds. Examples of mamide and dimethyl Sulphoxide, and water. transgenic plants which may be mentioned are the important Suitable Solid carriers are: for example ammonium salts crop plants. Such as cereals (wheat, rice), maize, Soya beans, and ground natural minerals, such as kaolins, clays, talc, potatoes, cotton, oilseed rape and also fruit plants (with the chalk, quartz, attapulgite, montmorillonite or diatomaceous fruits apples, pears, citrus fruits and grapevines), and particu earth; and ground synthetic minerals, such as finely divided lar emphasis is given to maize, soya beans, potatoes, cotton silica, alumina and silicates; Suitable Solid carriers for gran and oilseed rape. Traits that are emphasized are in particular ules are: for example crushed and fractionated natural rocks, increased defence of the plants against insects by toxins Such as calcite, marble, pumice, Sepiolite, dolomite and Syn formed in the plants, in particular those formed by the genetic 25 thetic granules of inorganic and organic meals, and granules material from Bacillus thuringiensis (for example by the of organic material. Such as sawdust, coconut shells, maize genes CryIA(a), CryIA(b), CryIA(c), CryIIA, Cry IIIA, cobs and tobacco stalks; Suitable emulsifiers and/or foam CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and also com formers are: for example nonionic and anionic emulsifiers, binations thereof) (hereinbelow referred to as “Bt plants'). Such as polyoxyethylene fatty acid esters, polyoxyethylene Traits that are furthermore particularly emphasized are the 30 fatty alcohol ethers, for example alkylaryl polyglycol ethers, increased tolerance of the plants to certain herbicidally active alkylsulphonates, alkyl Sulphates, arylsulphonates and pro compounds, for example imidazolinones, sulphonylureas, tein hydrolysates; suitable dispersants are: for example ligno glyphosate orphosphinotricin (for example the "PAT gene). Sulphite waste liquors and methylcellulose. The genes which impart the desired traits in question can also Tackifiers, such as carboxymethylcellulose, natural and be present in combination with one another in the transgenic 35 synthetic polymers in the form of powders, granules or lati plants. Examples of “Bt plants' which may be mentioned are ces, such as gum arabic, polyvinyl alcohol and polyvinyl maize varieties, cotton varieties, soya bean varieties and acetate, and also natural phospholipids, such as cephalins and potato varieties which are sold under the trade names YIELD lecithins, and synthetic phospholipids can be used in the GARDR) (for example maize, cotton, soya beans), Knock formulations. Other possible additives are mineral and veg Out(R) (for example maize), StarLink R. (for example maize), 40 etable oils. Bollgard(R) (cotton), Nucotnir (cotton) and NewLeaf R (po It is possible to use colorants, such as inorganic pigments, tato). Examples of herbicide-tolerant plants which may be for example iron oxide, titanium oxide, Prussian blue, and mentioned are maize varieties, cotton varieties and Soya bean organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs varieties which are sold under the trade names Roundup and metal phthalocyanine dyestuffs, and trace nutrients. Such Ready R (tolerance to glyphosate, for example maize, cotton, 45 as salts of iron, manganese, boron, copper, cobalt, molybde soya bean), Liberty Link. R (tolerance to phosphinotricin, for num and zinc. example oilseed rape), IMIR (tolerance to imidazolinones) The formulations generally comprise between 0.1 and 95 and STS(R) (tolerance to sulphonylureas, for example maize). percent by weight of active compound, preferably between Herbicide-resistant plants (plants bred in a conventional man 0.5 and 90%. ner for herbicide tolerance) which may be mentioned include 50 For controlling weeds, the active compounds according to the varieties sold under the name Clearfield(R) (for example the invention, as Such or in their formulations, can also be maize). Of course, these statements also apply to plant vari used as mixtures with known herbicides and/or substances eties having these or still to be developed genetic traits, which which improve the compatibility with crop plants (“safen plants will be developed and/or marketed in the future. ers'), finished formulations or tank mixes being possible. The plants listed can be treated according to the invention 55 Also possible are mixtures with weed-killers comprising one in a particularly advantageous manner with the active com or more known herbicides and a safener. pound mixtures according to the invention. The preferred Possible components for the mixtures are known herbi ranges stated above for the active compounds also apply to the cides, for example treatment of these plants. Particular emphasis is given to the acetochlor, acifluorfen (-Sodium), aclonifen, alachlor, alloxy treatment of plants with the mixtures specifically mentioned 60 dim (-Sodium), ametryne, amicarbazone, amidochlor, ami in the present text. dosulfuron, anilofos, asulam, atrazine, aza-fenidin, azimsul The active compounds can be converted into the customary furon, BAS-662H, beflubutamid, benazolin (-ethyl), formulations, such as solutions, emulsions, wettable pow benfuresate, bensulfuron (-methyl), bentazon, benzfendi ders, Suspensions, powders, dusts, pastes, soluble powders, Zone, benzobicyclon, benzofenap, benzoylprop (-ethyl), granules, Suspo-emulsion concentrates, natural and synthetic 65 bialaphos, bifenox, bispyribac (-sodium), bromobutide, Substances impregnated with active compound, and microen bromo-fenoxim, bromoxynil, butachlor, butafenacil (-allyl), capsulations in polymeric Substances. butroxydim, butylate, cafen-Strole, caloxydim, carbetamide, US 8,673,818 B2 93 94 carfentraZone (-ethyl), chlomethoxyfen, chloramben, chlo A mixture with other known active compounds, such as ridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, fungicides, insecticides, acaricides, nematicides, bird repel chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, lents, plant nutrients and agents which improve soil structure, clefoxydim, clethodim, clodinafop (-propargyl), clomaZone, is also possible. clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransu lam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, The active compounds can be used as Such, in the form of cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, the formulations or in the use forms prepared therefrom by 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (—P), 10 further dilution, Such as ready-to-use solutions, Suspensions, diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzo emulsions, powders, pastes and granules. They are used in a quat, diflufenican, diflufenZopyr, dimefuron, dimepiperate, customary manner, for example by watering, spraying, atom dimethachlor, dimethametryn, dimethenamid, dimexyflam, izing, or broadcasting. dinitramine, diphenamid, diduat, dithiopyr, diuron, dymron, 15 epropodan, EPTC, esprocarb, ethal fluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxy-Sulfuron, eto The active compounds according to the invention can be applied both before and after emergence of the plants. They benzanid, fenoxaprop (-P-ethyl), fentraZamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasu can also be incorporated into the Soil before sowing. lam, fluazifop ( P-butyl), fluazolate, flu-carbazone (-so dium), flufenacet, flumetSulam, flumiclorac (-pentyl), flumi The amount of active compound used can vary within a oxazin, flumipropyn, flumetSulam, fluometuron, relatively wide range. It depends essentially on the nature of fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupro 25 the desired effect. In general, the amounts used are between 1 pacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), g and 10 kg of active compound per hectare of Soil Surface, fluridone, fluoroxypyr (-butoxypropyl, -meptyl), flurprimi preferably between 5g and 5 kg per ha. dol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, The preparation and use of the active compounds accord foramsulfuron, glufosinate (-ammonium), gly-phosate (-iso 30 ing to the invention is illustrated by the examples below. propylammonium), halosafen, haloxyflop (-ethoxyethyl, -P- methyl), hex-azinone, imazamethabenz (-methyl), PREPARATION EXAMPLES imaZamethapyr, imaZamox, imaZapic, imazapyr, imaZaquin, imazethapyr, imaZosulfuron, iodosulfuron (-methyl, -so 35 Example I-1-a-1 dium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyri-fop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesotrione, meta mitron, metaZachlor, methabenzthiazuron, metobenzuron, 40 metobromuron, (alpha-) metolachlor, metoSulam, metoXu ron, metribuzin, metSulfuron (-methyl), molinate, monolinu ron, naproanilide, napropamide, neburon, nicosulfuron, nor flurazon, orben-carb, oryzalin, oxadiargyl, oxadiazon, 45 oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelar gonsailure, pendimethalin, pendralin, pentoxaZone, phenme dipham, picolinafen, piperophos, pretilachlor, primisulfuron At 60° C., 7.4 g of the compound of Example II-1, dis (-methyl), profluaZol, prometryn, propachlor, propanil, pro 50 solved in 1 ml of anhydrous dimethylformamide (DMF), are paquizafop, propisochlor, propoxycarbazone (-Sodium), pro pyZamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), added dropwise to 6.5g of potassium tert-butoxide in 25 ml of pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, anhydrous DMF, and stirring is continued and the reaction is monitored by thin-layer chromatography. After the reaction pyribenZoxim, pyributicarb, pyridate, pyridatol, pyriftalid, 55 pyriminobac (-methyl), pyrithiobac (-Sodium), quinchlorac, has ended, 170 ml of ice-water are added, the mixture is, at quinmerac, quinoclamine, quizalofop (-p-ethyl, -p-tefuryl), from 0°C. to 10°C., acidified with conc. hydrochloric acid to rimsulfuron, Sethoxydim, simazine, simetryn, Sulcotnone, pH 2 and filtered off with suction, and the filter cake is washed SulfentraZone, Sulfometuron (-methyl), Sulfosate, Sulfosulfu 60 with ice-water. The residue is purified chromatographically ron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, ter on silica gel using the mobile phase methylene chloride/ butryn, thenylchlor, thiaflu-amide, thiazopyr, thidiazimin, methanol 9:1. thifensulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxy Yield: 3.90 g (A 58.00% of theory), m.p. 199° C. dim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, 65 The following compounds of the formula (I-a-1) were tridiphane, tri-fluralin, trifloxysulfuron, triflusulfuron (-me obtained similarly to Example (I-1-a-1) and in accordance thyl), tritosulfuron. with the general preparation instructions US 8,673,818 B2 95 96

(I-a-1)

Ex. No. m.p. C. Isomer

CH 154

CH 225

CH CH

115

222

CH CH CH

CH 114

CH CH 09

216

i-CAHg 60

CH7 97

233

211

210

CH CH CH 192

CH Hs (CH2)2— 181 -1-a-27 CH 222 -1-a-28 CH CH 278 CH CH 268 CH CH 248 US 8,673,818 B2 97 98 Example I-1-b-1

O H5C2

10 O HSC O CH HC 15

2.5g of the compound I-1-a-10 in 50 ml of anhydrous ethyl acetate are heated at reflux with 1.7 ml of triethylamine, 1.3 ml of isobutyryl chloride in 5 ml of anhydrous ethyl acetate are added dropwise, the mixture is stirred at reflux and the reaction is monitored by thin-layer chromatography. The Sol- 25 vent is distilled off and the residue is taken up in methylene chloride, washed with 50 ml of 0.5 N, NaOH, dried and concentrated using a rotary evaporator. The residue is then recrystallized from methyl tert-butyl ether (MTB ether)/n- hexane.

Yield: 2 g (A 65% of theory), m.p. 209° C.

The following compounds of the formula (I-1-b) are obtained similarly to Examples (I-1-b-1) and in accordance with the general preparation instructions

(I-1-b)

Ex. No. m.p. C. Isomer

CH 145 CH 135 CH 76 2O1 215 190 US 8,673,818 B2 99 100 Example I-1-c-1 2.51 g of the compound of the formula I-1-a-10 and 1.2 ml of triethylamine are initially charged. At from 0 to 10°C., 0.8 ml of ethyl chloroformate in 5 ml of anhydrous dichlo HSC romethane are added dropwise, the mixture is stirred at room temperature and the reaction is monitored by thin-layer chro HN matography. The mixture is then washed with 0.5 N NaOH and dried, and the solvent is distilled off. The residue is 10 HSC recrystallized from methyl tert-butyl ether/n-hexane. O Yield: 1.1 g (A30% of theory), m.p. 178° C. 15 CH The following compounds of the formula (I-1-c) are obtained similarly to Example (I-1-c-1) and in accordance with the general preparation instructions

(I-1-c) O R2-M ls, X B >1 N Y HN

O W Z

Ex. No. Z. A. B M R2 m.p. C. Isomer

H H —(CH2)2—O—(CH2)2— O CHs 194 B

CH H H CH CH O CHs 119

CH CH H —(CH2)2—CHOCH2—(CH2)2— O C2H5 171 B

CH H —(CH2)2—CHCH-(CH2)2— O i-CHg 155 B

CH H -(CH2)2 O-(CH2)2 - O CHs 215

CH CH C2H5 —(CH2)2—CHOCH -(CH2)2— O C2H5 137 B

CH CH C2H5 —(CH2)2—CHOCHs (CH2)2— O C2H5 168 B US 8,673,818 B2 101 102 Example II-1 Example II-11

CH3 O NH CH3 O O HSC HC H3C 10 OCH N OCH O H3C HSC 15 Example II-1 At an internal temperature of from 30 bis 40°C., 10.3 g of the compound of Example XXVII-1, as a suspension in 110 At 80°C., 7.5g of 2,4-diethyl-6-methyl-phenylacetic acid ml of methylene chloride, are added to 16.9 g of conc. sul and 9.2 ml of thionyl chloride are stirred until evolution of gas phuric acid, and the mixture is stirred for 2 h. 23 ml of dry has ceased. Excess thionyl chloride is distilled off and the methanol are added dropwise, and the mixture is stirred at residue is taken up in 30 ml of dry THF. At from 0 to 10°C., from 40 to 70° C. for 6 h. The solution is poured onto 0.18 kg this solution is added dropwise to 12.3 g of methyl 2-amino of ice, the product is extracted with methylene chloride and 2-methylpropanoate in 320 ml of dry THF admixed with 24.6 the organic phase is washed with an NaHCO solution. The ml of triethylamine, and the mixture is stirred at room tem 25 organic phase is dried and concentrated using a rotary evapo perature for 1 h. This solution is then concentrated using a rator, and the residue is recrystallized from MTB ether/n- rotary evaporator, the residue is taken up in methylene chlo hexane. ride and 1 NHCl, the product is extracted and the organic Yield: 8.7 g (76% of theory), m.p. 137° C. phase is dried and concentrated using a rotary evaporator. The The following compounds of the formula (II) are obtained residue is recrystallized from MTB ether/n-hexane. 30 similarly to Example (II-1) and in accordance with the gen Yield: 8.07 g. (A 66% of theory), m.p. 120-122°C. eral preparation instructions

(II) US 8,673,818 B2 103 104 -continued (II) R No X B. O

Y HN

O W Z

Ex. No. W X Y Z. A. B R m.p. C. Isomer II-28 CH, CH, CH=CH2 H —(CH2)2–CHOCH-(CH2)2— CH 234 B II-29 CH, CH C2H5 H -(CH2)2 CHOCH-(CH2)2 - CH 140 B

Example XXVII-1 Example I-2-a-1

2O O HSC OH H N O CN \ CH3 25 O H5C2 O CHCH

At 80° C., 7.68 g of 2,4-diethyl-6-methyl-phenylacetic acid and 9.1 ml of thionyl chloride are stirred until evolution 30 of gas has ceased. Excess thionyl chloride is distilled off, and At from 0 to 10°C., 16.6 g of the compound of Example the residue is taken up in 40 ml of dry toluene. At from 0 to 10° s C., this solution is added dropwise to 9 g of 4-amino-4-cyano- III-1, dissolved in 50 ml of anhydrous DMF, are added drop tetrahydropyran in 80 ml of dry THF admixed with 6.2 ml of wise to 8.4 g of potassium tert-butoxide in 50 ml of anhydrous triethylamine, and the mixture is stirred at room temperature 35 for 1 h. The Solution is then concentrated using a rotary DMF, and the mixture is stirred at room temperature for 8 h. evaporator, the residue is taken up in 1 NHCl in methylene After the reaction has ended, 1000 ml of 1 NHC1 are added chloride and the organic phase is dried and concentrated using d ith i li d the mixture is stirred for 30 a rotary evaporator. The residue is recrystallized from MTB- ropw1se W1un 1ce-cool1ng, and une m1XLure 1S Surred Ior ether/n-hexane. min. The precipitate is filtered off, washed with water and Yield: 10.3 g (A 85% of theory), m.p. 155° C. 40 dried under reduced pressure. Similarly to Example XXVII-1, Example XXVII-2 with m.p. 142°C. is obtained.

CH5 45 Yield: 11.5 g (A 80% of theory), m.p. 135° C.

NH CH3 O CN 50 The following compounds of the formula (I-2-a) are O obtained similarly to Example (I-2-a-1) and in accordance with the general preparation instructions

(I-2-a) OH X

A N Y B O O W Z

Ex. No. W X Y Z. A. B m.p. C.

I-2-a-2 C2H5, C2H5 H H —(CH2)2—CHOCH2—(CH2)2— Oil I-2-a-3 CH, CH, CH, H -(CH2)5 - 223-225 US 8,673,818 B2

-continued I-2-a-4 CH, CHs CH H -(CH2)2-CHOCH -(CH2)— 175-178 I-2-a-5 CH, CH5, C2H5 H —(CH2)2—CHOCH2—(CH2)2— Oil

Example I-2-b-1 Example I-2-b-2

10 O O CH=CH H3C O ls C(CH3)3 O CH3 H3C CH3 15 S CH CH O O O CHCH 1.2 g (2.76 mmol) of the compound of Example I-2-b-2 from WO97/02243 are initially charged in 20 ml of toluene, 3.5 g (11 mmol) of tributyl-vinyl tin, 133 mg (0.11 mmol) of 2.08 ml of triethylamine are added to 2.86 g of the com Pd(PPh) and 2 crystals of 2,6-di-t-butyl-4-methylcresol are pound of Example I-2-a-1 dissolved in 40 ml of dry methyl added the mixture is boiled at reflux overnight and then con 25 centrated using a rotary evaporator. ene chloride (CHCl). At 0-10°C., 1.5g of pivaloyl chloride For purification, the crude mixture is chromatographed on in 10 ml of CH2Cl are added, and the mixture is stirred at silica gel, where first excess tin compounds are eluted with room temperature for 20 h. cyclohexane and then, by changing the mobile phase to cyclo hexane/ethyl acetate (2:1), the product is eluted. Further puri fication was achieved by triturating the crude product with 30 petroleum ether. The reaction solution is washed first with 10% strength Yield: 0.46g (44% of theory) of colourless crystals of m.p. citric acid and then with 1 N NaOH, dried and concentrated 152-155o C. using a rotary evaporator, and the residue is stirred with The following compounds of the formula (I-2-b) are petroleum ether. obtained similarly to Examples (I-2-b-1) and (I-2-b-2) and in Yield: 2.2 g (a 60% of theory), m.p. 110-112°C. accordance with the general preparation instructions

(I-2-b) O

R1 ls, X A.

B N Y O

O W Z

Ex. No. W X Y Z. A. B RI m.p. C. I-2-b-3 H C2H5 CH H -(CH2)5 - t-CH-CH2 162-164 I-2-b-4 C-Hs C2H5 H H —(CH2)2—CHOCH2—(CH2)2— t-CHg Oil I-2-b-5 CH CH CH=CH, H —(CH2)2—CHOCH2—(CH2)2— t-CHg 158-160 I-2-b-6 CH CH CH=CH, H -(CH2)2 CHCH-(CH2)— t-CHg 143-145 I-2-b-7 CH CH CH=CH, H -HC CH- t-CHg 155-157

I-2-b-8 CH, CH=CH- CH H —(CH2)2—CHOCH2—(CH2)2— t-CHg 145 I-2-b-9 CH C2H5 CH H -(CH2)5 - t-CHg 96-98 I-2-b-10 CH C2H5 CH H —(CH2)2—CHOCH2—(CH2)2— t-CHg 90-93 I-2-b-11 C2Hs C2H5 C2H5 H (CH2)2—CHOCH2—(CH2)2— H5C2 CHCH Oil I-2-b-12 H CH CH=CH, CH -(CH2)2 CHOCH -(CH2)2 - S-CHg Oil I-2-b–13 H CH-CH, CH CH3 —(CH2)2—CHOCH -(CH2)2— i-CH7 Oil US 8,673,818 B2 107 108 Example III-1 The reaction solution is admixed with 100 ml of 1 NHCl and extracted with CHCl2, and the organic phase is dried and concentrated. The residue is purified by column chromatog raphy (cyclohexane:ethyl acetate, 5:1). Yield: 2.35 g (49% of theory, m.p. 148° C. COOCHs H3C CH3 O CH3 10 O CH O C2H5 CH3 O)--> At 80° C., 8.9 g of 2-ethyl-4-methyl-phenylacetic acid in 15 50 ml of dry toluene and 7.3 ml of thionyl chloride are stirred until evolution of gas has ceased. Excess thionyl chloride is distilled off and the residue is taken up in 30 ml of dry toluene. At 0-10°C., this solution is added dropwise to 8.6 g of ethyl 1 g of the compound of Example I-6-a-1 is initially charged 1-hydroxy-cyclohexanecarboxylate in 50 ml of dry toluene, in 20 ml of dry methylene chloride and admixed with 0.77ml and the mixture is stirred at reflux for 8h. The solution is then of triethylamine. 0.68 ml of pivaloyl chloride is dissolved in 1 ml of methylene chloride and added dropwise with ice-cool concentrated using a rotary evaporator. ing, and the mixture is stirred at room temperature for 2 h. Yield: 16.6 g (a 99% of theory) The reaction solution is extracted twice with 10% citric The residue is used without further purification for the acid solution and the organic phase is washed twice with 1 N condensation to give Example I-2-a-1. 25 NaOH, dried and concentrated. Yield: 1.2 g (92% of theory) oil. Example I-4-a-1 'H-NMR (500 MHz, CDC1): 8=1.1 (s, 9H, C(CH), 2.31 (s, 3H, Ar CH); 2.45 (q, 2H, Ar—CH2—CH) ppm 30 Example VIII-1

CH3 CH3 35

CH3

40 2.4 g of 2-ethyl-4,6-dimethyl-2-phenyl chlorocarbonyl O ketene are initially charged in ml of abs. Xylene, and 1.5g of 4-fluoropropiophenone in 20 ml of abs. xylene are added 22.8 g of crude product from Example XXXIV-1 are ini dropwise. The mixture is heated at reflux for 8 hours. The tially charged in 200 ml of dry acetone and admixed with 10.9 xylene solution is washed with water, dried over sodium 45 g of potassium carbonate, and 33.6 g (14.75 ml) of methyl Sulphate and concentrated under reduced pressure. Chro iodide are added dropwise. The mixture is stirred at reflux for matographic purification was carried out on silica gel using 16 h. the mobile phase toluene/ethanol 20:1. The solvent is distilled off and the residue is purified by Yield: 1 g (a 28% of theory), of m.p. 161-162° C. column chromatography (methylene chloride?petroleum 50 ether: 8:1). Example I-6-a-1 Yield: 3.5 g (30% of theory), oil The product is used directly for the cyclization to give Example I-6-a-1. Example XXXIV-1 55

CH CH ( ) 3 60 OH OH

5.3 g of the compound of Example VIII-1 are initially charged in 50 ml of dry DMF and mixed with 2.95 g of 65 CH3 potassium tert-butoxide, and the mixture is heated at 60° C. for 1 h. US 8,673,818 B2 109 110 11.2 g of monomethylcyclohexanedicarboxylate, 5.3 ml of 4-bromo-phenylacetate (according to Example XXVI-1 from thionyl chloride and a drop of DMF in 50 ml of dry toluene are WO 97/02243) in 70 ml of triethylamine, and 19.7 ml of heated at 100° C. until evolution of gas has ceased. The trimethylsilyl-acetylene are then added dropwise. Solvent is concentrated. The reaction is monitored by gas chromatography. Purification is carried out by silica gel column chromatog A solution of 50 ml LDA solution in 100 ml of dry THF is, 5 raphy using the mobile phase petroleum ether?ethyl acetate, at -15°C., admixed dropwise with a solution of 17.3 g of 20:1. methyl 2-ethyl-4-methyl-phenylacetate in 20 ml of dry THF, Yield: 6 g (73% of theory) and the mixture is stirred at this temperature for 30 min. At -15°C., a solution of the freshly prepared acid chloride Example XXII-1 described above in 15 ml of dry THF is then added dropwise. 10 The mixture is stirred at room temperature for 1 hour, and 150 ml of water and 40 g of ammonium chloride are then added. The intermediate is extracted with ether and the solu tion is concentrated. The residue is boiled at reflux with 100 15 g of KOH and 330 ml of water for two days. Yield: 23.70 g (91% of theory), oil CH Example XXV-1

39 g of the compound of Example XXV-2 in 300 ml of thionyl chloride are stirred at 50° C. until evolution of gas has ceased. OH 25 Excess thionyl chloride is distilled off and the residue is taken up in 30 ml of dry toluene and distilled. Yield: 37 g (87% of theory), b.p.:90-92° C. (0.05 mbar) Example XXV-2 th 30 Šs -ch CH3 O At room temperature, 4.7 g of lithium hydroxide, dissolved OH in 120 ml of water, are added dropwise to 26 g of the com CH pound of Example XXX-1 in 120 ml THF, and the mixture is stirred at room temperature for 8 h. The reaction Solution is concentrated using a rotary evapo rator, admixed with water and extracted with methyl tert 40 butyl ether. The aqueous phase is adjusted to pH 2 using concentrated 50 g of the compound of Example XXX-2 are admixed hydrochloric acid and the precipitate is filtered off with suc with 60 ml of ethanol, 30 ml of water and 25 g of potassium tion and dried. hydroxide, and the mixture is heated at reflux for hours. Yield: 14 g (59% of theory), m.p.: 156.3° C. 45 After the reaction has ended, the solvent is distilled off, the residue is dissolved in water and the mixture is acidified with Example XXX-1 conc. hydrochloric acid. The precipitate is filtered off with Suction, washed and dried. Yield: 41 g (93% of theory) 50 Example XXX-2 O Process (P) o1 CH Process (P HC CH 55 O th 1N Šs S-CH3 60 CH CH3

At room temperature and under an atmosphere of argon, 0.27g of copper(I) iodide, 0.745g of triphenylphosphine and 65 1 g of bis(triphenylphosphine)palladium dichloride are added with stirring to a solution of 7.32 g of methyl 2,6-dimethyl US 8,673,818 B2 111 112 60 g of the compound of Ex. XLfl-1 are dissolved in 600 ml The precipitate is filtered off with suction, washed and of ethanol and admixed with 50 ml of concentrated hydro dried. chloric acid, and 5 g of 10% Pd/C are added. Yield: 25 g (99% of theory), m.p. 55-56°C. At 120°C., a hydrogen pressure of 150 bar is applied to the reaction mixture. Example XXX-3 After the reaction has ended, the mixture is filtered, the solvent is distilled off and the residue is dissolved in 300 ml of methylene chloride, washed with 300 ml of water, dried and concentrated. 10 Process Q Yield: 51 g (91% of theory)

Example XLII-1 15

Process (P

O 2O H3C CH3

O-CH CH 20.8g of the compound methyl 2,6-diethyl-4-bromo-phe 25 nylacetate (according to Example XXVI-6 from WO O 97/02243) are dissolved in 100 ml of methanol. 7.2 g of Sodium acetate and 2 g of palladium hydroxide are added. The H3C compound is then hydrogenated under pressure using hydro 30 gen. 200 g of carbon disulphide and 86.7 g of aluminium chlo ride are initially charged. At 0°C., 50 g of methyl 2-meth ylphenylacetate and 28.2 g of propionyl chloride are added. After the reaction has ended, the solution is filtered and The solution is stirred at reflux for 4 hours. 35 concentrated. The residue is taken up in methylene chloride, washed with water, dried and concentrated. The Solution is then poured onto 1 kg of ice-water and extracted with 500 ml of methylene chloride. Yield: 12 g (77% of theory) The organic phase is washed with 10% strength hydrochlo ric acid and then with sodium carbonate solution, dried and 40 USE EXAMPLES concentrated. Yield: 60 g (91% of theory) Example A

Example XXV-3 45 Myzus Test Solvent: 7 parts by weight of dimethylformamide H3C Emulsifier: 1 part by weight of alkylaryl polyglycol ether 50 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of Solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired con O 55 centration. HO Cabbage leaves (Brassica oleracea) which are heavily infested by the peach aphids (Myzus persicae) are treated by HC being dipped into the preparation of active compound of the desired concentration. 30 g of the compound of Example XXX-3 in 32 ml of 60 After the desired period of time, the kill in 96 is determined. methanol and 16 ml of water are admixed with 12.2 g of 100% means that all aphids have been killed; 0% means that potassium hydroxide, and the mixture is stirred at reflux for 5 none of the aphids have been killed. h. In this test, the compounds of Preparation Examples I-2- The solution is concentrated and the residue is taken up in 65 a-4, I-2-b-5, I-2-b-6, I-1-a-6, I-1-c-4, I-4-a-1 exhibit, at an water, the mixture is washed with ethyl acetate and the aque exemplary active compound concentration of 1000 ppm, a ous phase is adjusted to pH 1 using cone. HC1. kill of 100% after 6 days. US 8,673,818 B2 113 114 Example B Example E Nephotettix Test Spodoptera Frugiperda Test

Solvent: 7 parts by weight of dimethylformamide 5 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is amounts of Solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired con 10 diluted with emulsifier-containing water to the desired con centration. centration. Rice seedlings (Oryza sativa) are treated by being dipped Cabbage leaves (Brassica oleracea) are treated by being into the preparation of active compound of the desired con dipped into the preparation of active compound of the desired centrated and are populated with the green rice leafhopper concentration and are populated with caterpillars of the army (Nephotettix cincticeps) while the leaves are still moist. 15 worm (Spodoptera frugiperda) while the leaves are still After the desired period of time, the kill in 96 is determined. moist. 100% means that all leafhoppers have been killed; 0% means After the desired period of time, the kill in 96 is determined. that none of the leafhoppers have been killed. 100% means that all caterpillars have been killed; 0% means In this test, the compounds of Preparation Examples I-2- that none of the caterpillars have been killed. b-9, I-2-a-4, I-1-a-9, I-1-a-8, I-1-a-2. I-1-a-1, I-1-a-3, I-4-a-1, In this test, the compound of Preparation Example I-2-a-3 exhibit, at an exemplary active compound concentration of exhibits, at an exemplary active compound concentration of 1000 ppm, a kill of 100% after 6 days. 1000 ppm, a kill of 100% after 7 days. Example C Example F 25 Phaedon Larvae Test Tetranychus Test (OP-Resistant/Dip Treatment) Solvent: 7 parts by weight of dimethylformamide Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 30 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired con diluted with emulsifier-containing water to the desired con centration. centration. Cabbage leaves (Brassica oleracea) are treated by being 35 Bean plants (Phaseolus vulgaris) which are heavily dipped into the preparation of active compound of the desired infested by all stages of the greenhouse red spider mite (Tet concentration and are populated with larvae of the mustard ranychus urticae) are dipped into a preparation of active beetle (Phaedon cochleariae) while the leaves are still moist. compound of the desired concentration. After the desired period of time, the kill in 96 is determined. After the desired period of time, the effect in % is deter 100% means that all beetle larvae have been killed; 0% means 40 mined. 100% means that all spidermites have been killed: 0% that none of the beetle larvae have been killed. means that none of the spider mites have been killed. In this test, the compounds of Preparation Examples I-2- In this test, the compounds of Preparation Examples I-2- a-3, I-2-b-8, I-2-b-6, I-1-a-2, I-1-a-3, I-1-a-21, I-4-a-1 a-4, I-2-b-10, I-2-b-11, I-2-b-8, I-2-b-2, I-1-a-3, I-1-a-21, exhibit, at an exemplary active compound concentration of I-1-c-4, I-4-a-1 exhibit, at an exemplary active compound 1000 ppm, a kill of 100% after 7 days. 45 concentration of 1000 ppm, a kill of 100% after 7 days. Example D Example G

Plutella Test Benisia Test 50 Solvent: 7 parts by weight of dimethylformamide Solvent: 7.5 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Emulsifier: 2.5 parts by weight of alkylaryl polyglycol To produce a suitable preparation of active compound, 1 ether part by weight of active compound is mixed with the stated To produce a suitable preparation of active compound, 1 amounts of solvent and emulsifier, and the concentrate is 55 part by weight of active compound is mixed with the stated diluted with emulsifier-containing water to the desired con amounts of Solvent and emulsifier, and the concentrate is centration. diluted with emulsifier-containing water to the desired con Cabbage leaves (Brassica oleracea) are treated by being centrations. dipped into the preparation of active compound of the desired Cotton plants (Gossypium hirsutum) which are infested by concentration and are populated with caterpillars of the owlet 60 eggs, larvae and pupae of the white fly Bemisia tabaci are moth (Plutella xylostella) while the leaves are still moist. dipped into a preparation of active compound of the desired After the desired period of time, the kill in 96 is determined. concentration. 100% means that all caterpillars have been killed: 0% means After the desired period of time, the kill in 96 is determined. that none of the caterpillars have been killed. 100% means that all animals have been killed; 0% means that In this test, the compounds of Preparation Examples I-1- 65 none of the animals have been killed. a-8, I-4-a-1 exhibit, at an exemplary active compound con In this test, the compounds of Preparation Examples I-2- centration of 1000 ppm, a kill of 100% after 7 days. b-9, I-2-a-4, I-2-b-10 exhibit, at an exemplary active com US 8,673,818 B2 115 116 pound concentration of 1000 ppm, a kill of 100% after 10 Example I days. Example H Pre-Emergence Test Post-Emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkyaryl polyglycol ether Solvent: 5 parts by weight of acetone Emulsifier: I part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated part by weight of active compound is mixed with the stated 10 amount of solvent, the stated amount emulsifier is added and amount of solvent, the stated amount of emulsifier is added the concentrate is diluted with water to the desired concen and the concentrate is diluted with water to the desired con tration. centration. Seeds of the test plants are sown in normal soil. After about Test plants of a height of 5-15 cm are sprayed with the 24 hours, the soil is sprayed with the preparation of active preparation of active compound Such that the particular 15 compound Such that the particular amounts of active com amounts of active compound desired are applied per unit area. pound desired are applied per unit area. The concentration of The concentration of the spray liquor is chosen such that the the spray liquor is chosen Such that the particular amounts of particular amount of active compound desired is applied in active compound desired are applied in 1000 l of water/ha. 1000 1 of water/ha. After three weeks, the degree of damage to the plants is After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the rated in % damage in comparison to the development of the untreated controls. untreated control. The figures denote: The figures denote: 0% no effect (like untreated control) 0% no effect (like untreated control) 100%=total destruction 100%=total destruction

Post-emergence gai?ha Wheat Cotton Alopecutrits Avenafatua Lolium Sorghum.

Ex. I-2-a-4 60 O O 95 8O 95 8O

Post emergence gai?ha Sugar beet Alopecurus Avena fatua Digitaria Lolium Setaria Ipomoea Polygonum

Ex. I-1-a-21 125 O 1OO 90 100 95 99 70 Ex. I-1-c-4 60 10 90 90 95 1OO 70 Post-emergence gai?ha Soya bean Digitaria Loium Setaria Sorghum. Gaium

Ex. I-1-a-5 125 10 90 100 95 8O Ex. I-1-a-3 125 8O 70 90 8O

Oilseed Post-emergence gai?ha Sugar beet rape Digitaria Loium Setaria Sorghum. Gaium

Ex. I-I-a-2 125 O O 8O 70 95 8O 8O Post-emergence gai?ha Sugar beet Cotton Alopectiris Avena fattia Digitaria Setaria

Ex. I-1-a-9 15 10 O 1OO 95 95 1OO Post-emergence gai?ha Sugar beet Cotton Digitaria Echinochloa Setaria Sorghum.

Ex. I-1-a-8 60 10 O 95 1OO 100 95 Post-emergence gai?ha Digitaria Loium Setaria Sorghum.

Ex. I-1-a-6 125 95 8O 95 100 Post-emergence gai?ha Wheat Soya bean Cotton Digitaria Loium Setaria

Ex. I-2-b-12 125 O O 95 90 95 Ex. I-2-b–13 125 10 O O 8O 70 95 Post-emergence gai?ha Wheat Sugar beet Cotton Digitaria Echinochloa Setaria Sorghum.

Ex. I-4-a-1 125 2O O O 100 90 95 90 Post-emergence gai?ha Wheat Lolium Cassia Soianum Viola

Ex. I-2-b-10 125 10 8O 95 8O 90 Soya Pre-emergence gai?ha. Wheat Maize Sugar beet bean Alopecurus Avena fatua Bromus Lolium Setaria US 8,673,818 B2

-continued Ex. I-2-a-4 125 5 O O 100 8O 70 1OO 100 Ex. I-1-a-8 60 O 10 O O 100 90 100 1OO 100 Pre-emergence gai?ha Alopectirus Avena fattia Digitaria Echinochloa Lolium Setaria

Ex. I-1-a-3 125 100 95 1OO 100 1OO 100 Pre-emergence gai?ha Alopectiris Avenafatua Echinochloa

Ex. I-1-a-6 60 90 8O 90 Pre-emergence gai?ha Sugar beet Soya bean Alopect truts Digitaria Lolium Setaria Veronica

Ex. I-4-a-1 125 O O 100 100 1OO 100 95 Ex. I-1-a-21 125 O O 100 100 1OO 100 1OO Ex. I-1-a-9 125 O O 100 100 1OO 100 90 Pre-emergence gai?ha Wheat Soya bean Alopecurus Echinochloa Lolium Setaria Chenopodium

Ex. I-1-a-5 60 O O 1OO 100 1OO 100 70 Soya Pre-emergence gai?ha bean Alopectiris Bromus Cypertis Digitaria Lolitim Setaria Abutio

Ex. I-1-c-4 125 2O 95 100 1OO 100 1OO 100 70

Example J 25 After the desired period of time, the kill of the insects is determined. Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants What is claimed is:

Test insects: Diabrotica balteata—larvae in Soil 30 1. A compound of the formula (I-6-A) and/or (I-6-B) Solvent: 7 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether (I-6-A) To produce a suitable preparation of active compound, I G part by weight of active compound is mixed with the stated 35 O1 x amount of solvent, the stated amount of emulsifier is added A and the concentrate is diluted with water to the desired con Y andfor centration. QB C) ( ) The preparation of active compound is poured onto the soil. Q? Here, the concentration of the active compound in the prepa 40 O W Z ration is almost irrelevant, only the amount by weight of (I-6-B) active compound per Volume unit of soil, which is stated in O X ppm (mg/l), matters. The soil is filled into 0.251 pots and these A are allowed to stand at 20° C. Immediately after preparation, 5 pre-germinated maize 45 Y corns of the varietyYIELD GUARD (trade mark of Monsanto QB O) ( ) Comp., USA) are placed into each pot. After 2 days, the test Q? insects are placed into the treated soil. After a further 7 days, O W Z the efficacy of the active compound is determined by counting Y the maize plants that have emerged (1 plant=20% efficacy). 50

Example K in which Heliothis Virescens Test Treatment of Transgenic W represents methyl, Plants 55 X represents C-C-alkyl, C-C-alkenyl or ethinyl, Y represents hydrogen, methyl, ethyl, i-propyl, C-C- Solvent: 7 parts by weight of acetone alkenyl or ethinyl, Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 Z represents hydrogen, C-C-alkyl, C-C-alkenyl or ethi part by weight of active compound is mixed with the stated 60 nyl, amount of solvent and the stated amount of emulsifier, and the with the proviso that at least one of the radicals X, Y or Z concentrate is diluted with water to the desired concentration. represents a chain having at least two carbon atoms and Soya bean shoots (glycine max) of the variety Roundup with the further proviso that X is not ethyl when Z is Ready (trade mark of Monsanto Comp. USA) are treated by hydrogen and Y is methyl, being dipped into the preparation of active compound of the 65 desired concentration and are populated with the tobacco B represents hydrogen, budworm Heliothis virescens while the leaves are still moist. A and Q' together represent Ca-alkanediyl. US 8,673,818 B2 119 120 Q represents hydrogen, and -continued G represents hydrogen (a) or (I-6-b)

(b) A O X us R1 s B ) ( ) Y, 10 in which Q R" represents C1-Co-alkyl, Ca-Ca-alkenyl, C-C2 Q? O W Z alkoxy-C-alkyl, C-C-alkylthio-C-alkyl or cyclo hexyl or cyclopropyl which is optionally monosubsti in which A, B, D, G, Q', Q, W, X, Y and Z are each as tuted by fluorine, chlorine, methyl or methoxy, or 15 represents phenyl which is optionally monosubsti defined in claim 1, tuted by fluorine, chlorine, bromine, cyano, nitro, where one or at most two radicals X, Y or Z represent methyl, methoxy, trifluoromethyl or trifluo R’ C=C romethoxy. O 2. A process for preparing a compound of the formula (I), wherein R22 (A) a compound of the formula (I-6-a) HCECH

OH X (I-6-a) 25 and R' represents hydrogen, A is obtained by reacting a compound of the formula (I-6 B Y

30 O W Z (I-6)

A VO X in which A, B, Q, Q, W, X,Y and Zare each as defined in claim 1, 35 B \ is obtained by intramolecular cyclization of a ketocar Y', boxylic ester of the formula (VIII) (VIII) Q Q? O wi Z.

Q Q2 40 in which A, B, D, G, Q, W, X, Y and Zare each as defined in claim 1, and Q is as defined above, and where the apostrophe means that one or at most two radicals X, Y and Z in this process represent 45 chlorine, bromine or iodine, with the proviso that the other radicals X, Y and Z do not represent alkenyl or alkinyl with a silylacetylene of the for mula (X-a) or a vinylstannane of the formula (X-b) in which 50 (X-a) A, B, Q', Q, W, X, Y and Z are each as defined in Alk claim 1, and A R represents alkyl, R22-CEC-Si-Alk V if appropriate in the presence of a diluent and if appro R21 55 priate in the presence of a base; or R22 Alk (B) a compound of the formula (I-6-a) or (I-6-b) M HCECH-S-Ak V Alk (I-6-a) A OH X 60 in which B Alk represents C-C-alkyl, ) ( ) Y, or R" represents C-C-alkyl or phenyl, and 65 R’ represents hydrogen, Q , O W Z in the presence of a solvent, if appropriate in the pres ence of a base and a catalyst; or US 8,673,818 B2 121 122 (C) a compound of the formula (I-6-b) shown above in in which which A, B, D, Q, Q, R', W, X, Y and Z are each as R" represents C-C-alkyl, C-C-alkenyl, C-C- defined in claim 1 is obtained by reacting a compound of alkoxy-C-alkyl, C-C-alkylthio-C-alkyl or cyclo the formula (I-6-a) shown above in which A, B, D, Q', hexyl or cyclopropyl which is optionally monosubsti 5 tuted by fluorine, chlorine, methyl or methoxy, or Q, W, X, Y and Z are each as defined in claim 1, represents phenyl which is optionally monosubsti (C.) with an acid halide of the formula (XI) tuted by fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluo romethoxy. (XI) Hal RI 4. A compound of the formula (I) according to claim 1, 10 wherein W represents methyl, O X represents methyl, ethyl, n-propyl, iso-propyl, vinyl or ethinyl, Y represents hydrogen, methyl, ethyl, i-propyl, vinyl or in which 15 ethinyl, R" is as defined in claim 1 and Z represents hydrogen, methyl, ethyl, n-propyl, i-butyl, Hal represents halogen vinyl or ethinyl, O with the proviso that at least one of the radicals X, Y or Z (B) with a carboxylic anhydride of the formula (XII) represents a chain having at least two carbon atoms, where at most only one of the radicals X, Y or Z may R" CO-O CO-R' (XII) represent vinyl or ethinyl, and with the further proviso that X is not ethyl when Z is hydrogen and Y is methyl, in which R" is as defined in claim 1, B represents hydrogen, methyl or ethyl, if appropriate in the presence of a diluent and if appro A and Q' together represent Ca-alkanediyl. priate in the presence of an acid binder. 25 Q’ represents hydrogen, and 3. A compound of the formula (I) according to claim 1, G represents hydrogen (a) or wherein W represents methyl, (b) X represents C-C-alkyl, C-C-alkenyl or ethinyl, O Y represents hydrogen, methyl, ethyl, i-propyl, C-C- 30 alkenyl or ethinyl, Zrepresents hydrogen, C-C-alkyl, C-C-alkenyl or ethi us nyl, with the proviso that at least one of the radicals X, Y or Z in which represents a chain having at least two carbon atoms, 35 R" represents C1-Co-alkyl, Ca-Ca-alkenyl, C-C2 where at most only one of the radicals X, Y or Z may alkoxy-C-alkyl, C-C-alkylthio-C-alkyl or cyclo represent C-C-alkenyl or ethinyl, and with the further hexyl or cyclopropyl which is optionally monosubsti proviso that X is not ethyl when Z is hydrogen and Y is tuted by fluorine, chlorine, methyl or methoxy, methyl, represents phenyl which is optionally monosubstituted 40 by fluorine, chlorine, bromine, cyano, nitro, methyl, B represents hydrogen or C-C-alkyl, methoxy, trifluoromethyl or trifluoromethoxy. A and Q' together represent Ca-alkanediyl. 5. A pesticide or herbicide that comprises at least one Q represents hydrogen, and compound of the formula (I) according to claim 1. G represents hydrogen (a) 6. A method for controlling animal pests comprising allow ing a compound of the formula (I) according to claim 1 to act 45 on pests and/or their habitat. 7. A method of controlling undesirable vegetation compris (b) ing using a compound of formula (I) according to claim 1. 8. A process for preparing a pesticides or herbicide com prising mixing a compound of the formula (I) according to us 50 claim 1 with extenders and/or surfactants.

k k k k k