US 20100311593A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0311593 A1 Fischer et al. (43) Pub. Date: Dec. 9, 2010

(54) HALOALKYLMETHYLENEOXYPHENYL- AOIPI3/00 (2006.01) SUBSTITUTED KETOENOLS C07D 207/00 (2006.01) C07D 305/12 (2006.01) (75) Inventors: Reiner Fischer, Monheim (DE): CD7C 49/00 (2006.01) Thomas Bretschneider, Lohmar C07D 23/00 (2006.01) (DE); Stefan Lehr, Liederbach C07C 229/00 (2006.01) (DE); Eva-Maria Franken, Lyon C07C 69/76 (2006.01) (FR): Olga Malsam, Rosrath (DE); CD7C 24I/00 (2006.01) Arnd Voerste, Koln (DE); Ulrich CD7C 63/04 (2006.01) Görgens, Ratingen (DE); Jan (52) U.S. Cl...... 504/219;564/170; 514/622:504/336; Dittgen, Frankfurt (DE); Dieter Feucht, Eschborn (DE); Isolde 504/236; 514/248; 544/235; 540/545; 514/211.08; Hauser-Hahn, Leverkusen (DE); 548/544; 549/319; 568/379: 548/366.4; 560/37; Christopher Hugh Rosinger, 560/76; 560/105:564/149; 562/493 Hofheim (DE); Alfred Angermann, Kriftel (DE) (57) ABSTRACT The invention relates to novel compounds of the formula (I), Correspondence Address: STERNE, KESSLER, GOLDSTEIN & FOX P.L. L.C. (I) 1100 NEW YORKAVENUE, N.W. WASHINGTON, DC 20005 (US) (73) Assignee: Bayer Cropscience AG, Monheim (DE) (21) Appl. No.: 12/639,536 (22) Filed: Mar. 11, 2010 in which W, X, Y, Z and CKE are each as defined above, to several methods and intermediates for preparation thereof (30) Foreign Application Priority Data and to the use thereofas pesticides and/or herbicides. The invention also relates to selective herbicidal composi Mar. 11, 2009 (EP) ...... O91548883 tions which comprise firstly haloalkylmethyleneoxyphenyl Substituted ketoenols and secondly a compound which Publication Classification improves crop plant compatibility. (51) Int. Cl. The present invention further relates to the enhancement of AOIN 43/46 (2006.01) the action of crop protection compositions comprising espe CD7C 233/00 (2006.01) cially haloalkylmethyleneoxyphenyl-substituted ketoenols, AOIN 37/18 (2006.01) by the addition of ammonium or phosphonium salts and AOIN 43/58 (2006.01) optionally penetration enhancers, to the corresponding com AOIP 5/00 (2006.01) positions, to methods for production thereof and to the use CO7D 487/04 (2006.01) thereof in crop protection as insecticides and/or acaricides CO7D 49.8/04 (2006.01) and/or for preventing undesired plant growth. US 2010/03 11593 A1 Dec. 9, 2010

HALOALKYLMETHYLENEOXYPHENYL used as starting compounds (for example 3-(2-methylphe SUBSTITUTED KETOENOLS nyl)-4-hydroxy-5-(4-fluorophenyl)-A-dihydrofuranone (2)) is likewise described in DE-A-4014.420. Compounds of similar structure with no report of insecticidal and/or acari 0001. The present invention relates to novel haloalkylm cidal efficacy are known from the publication Campbellet al., ethyleneoxyphenyl-substituted ketoenols, to several methods J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. 3-Aryl for preparation thereof and to the use thereof as pesticides A-dihydrofuranone derivatives with herbicidal, acaricidal and/or herbicides. The invention also provides selective her and insecticidal properties are additionally known from: EP bicidal compositions which comprise firstly haloalkylmeth A-528 156, EP-A-647 637, WO95/26954, WO 96/20 196, yleneoxyphenyl-substituted ketoenols and secondly a com WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 pound which improves crop plant compatibility. 243, WO 97/36 868, WO 98/05 638, WO 98/06 721, WO 0002 The present invention further relates to the enhance 99/16 748, WO 98/25928, WO 99/43649, WO 99/48869, ment of the action of crop protection compositions compris WO 99/55 673, WO 01/23354, WO 01/74. 770, WO 01/17 ing especially haloalkylmethyleneoxyphenyl-substituted 972, WO 04/024688, WO 04/080962, WO 04/111042, WO ketoenols by the addition of ammonium orphosphonium salts 05/092 897, WO 06/000 355, WO 06/029 799, WO 07/048, and optionally penetration enhancers, to the corresponding 545, WO 07/073,856, WO 07/096,058, WO 07/121,868, WO compositions, to methods for production thereof and to the 07/140,881, WO 08/067,911, WO 08/083,950, WO 09/015, use thereof in crop protection as insecticides and/or acari 801, WO 09/039,975. cides and/or for preventing undesired plant growth. I0007 3-Aryl-A-dihydrothiphenone derivatives are 0003 Pharmaceutical properties of 3-acylpyrrolidine-2,4- known from WO95/26 345, 96/25395, WO 97/01 535, WO diones have been described before (S. Suzuki et al. Chem. 97/02243, WO 97/36868, WO 98/05638, WO 98/25928, WO Pharm. Bull. 15 1120 (1967)). In addition, N-phenylpyrroli 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO dine-2,4-diones have been synthesized by R. Schmierer and 01/17972, WO 01/23354, WO 01/74770, WO 03/013249, H. Mildenberger (Liebigs Ann. Chem. 1985, 1095). Biologi WO 04/080 962, WO 04/111 042, WO 05/092897, WO cal efficacy of these compounds has not been described. 06/029799 and WO 07/096,058. 0004 EP-A-0262399 and GB-A-2266 888 disclose com 0008 Particular phenylpyrone derivatives unsubstituted pounds of similar structure (3-arylpyrrolidine-2,4-diones), in the phenyl ring have already become known (cf. A. M. which are not, however, known to have any herbicidal, insec Chirazi, T. Kappe uand E. Ziegler, Arch. Pharm. 309, 558 ticidal or acaricidal action. Known compounds with herbi (1976) and K.-H. Boltze and K. Heidenbluth, Chem. Ber. 91, cidal, insecticidal oracaricidal action are unsubstituted, bicy 2849), though no possible usability as a pesticide is reported clic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599, for these compounds. Phenylpyrone derivatives substituted in EP-A-415 211 and JP-A-12-053 670) and also substituted the phenyl ring and having herbicidal, acaricidal and insecti monocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A- cidal properties are described in EP-A-588 137, WO 96/25 377 893 and EP-A-442 077). 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 0005 Additionally known are polycyclic 3-arylpyrroli 97/16 436, WO 97/19941, WO 97/36 868, WO 98/05638, dine-2,4-dione derivatives (EP-A-442 073) and 1H-arylpyr WO99/43649, WO 99/48869, WO 99/55673, WO 01/17972, rolidinedionederivatives (EP-A-456063, EP-A-521334, EP WO 01/74770, WO 03/013249, WO 04/080962, WO 04/111 A-596 298, EP-A-613 884, EP-A-613 885, WO95/01 971, 042, WO 05/092897, WO 06/029799 and WO 07/096,058. WO95/26954, WO95/20572, EP-A-0 668 267, WO 96/25 Additionally described are isomeric pyran-3,5-diones in WO 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 08/071.405 and WO 09/074,314. 97/36868, WO 97/43275, WO 98/05638, WO 98/06721, WO 0009 Particular 5-phenyl-1,3-thiazine derivatives unsub 98/25928, WO 99/24437, WO 99/43649, WO 99/48869, WO stituted in the phenyl ring have already become known (cf. E. 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO Ziegler and E. Steiner, Monatsh.95, 147 (1964), R. Ketcham, 03/013249, WO 03/062244, WO 2004/007448, WO 2004/ T. Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 024 688, WO 04/065366, WO 04/080962, WO 04/111042, (1973)), though no possible application as a pesticide is WO 05/044791, WO 05/044796, WO 05/048710, WO reported for these compounds. 5-Phenyl-1,3-thiazine deriva 05/049569, WO 05/066125, WO 05/092897, WO 06/000355, tives Substituted in the phenyl ring and having herbicidal, WO 06/029799, WO 06/056281, WO 06/056282, WO acaricidal and insecticidal action are described in WO94/14 06/089633, WO 07/048.545, DEA 102 00505 9892, WO 785, WO 96/2 5395, WO 96/35 664, WO 97/01 535, WO 07/073,856, WO 07/096,058, WO 07/121,868, WO 07/140, 97/02 243, WO 97/02 243, WO 97/36 868, WO 99/43649, 881, WO 08/067,873, WO 08/067,910, WO 08/067,911, WO WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, 08/138,551, WO 09/015,801, WO 09/039,975, WO 09/049, WO 03/013249, WO 04/080 962, WO 04/111 042, WO 851, WO 09/115,262, EP application 08170489). Also known 05/092897, WO 06/029799 and WO 07/096,058. are ketal-substituted 1H-arylpyrrolidine-2,4-diones from 0010. It is known that particular substituted 2-arylcyclo WO 99/16748, and (spiro)-ketal-substituted N-alkoxy pentanediones possess herbicidal, insecticidal and acaricidal alkoxy-substituted arylpyrrolidinediones from JP-A-14 205 properties (cf., for example, U.S. Pat. Nos. 4,283,348; 4.338, 984 and Ito M. et al. Bioscience, Biotechnology and Bio 122; 4,436,666; 4,526,723; 4,551,547; 4,632,698; WO96/01 chemistry 67, 1230-1238, (2003). The addition of safeners to 798: WO 96/03 366, WO 97/14 667 and WO 98/39281, WO ketoenols is likewise known in principle from WO 99/43649, WO99/48869, WO 99/55673, WO 01/17972, WO 03/013249. Also known from WO 06/024411 are herbicidal 01/74770, WO 03/062244, WO 04/080962, WOO4/111042, compositions comprising ketoenols. WO05/092897, WO06/029799, WO07/080,066, WO07/096, I0006. It is known that particular substituted A-dihydro 058, WO 09/019,005, WO 09/019,015 and EP application furan-2-one derivatives possess herbicidal properties (cf. DE 08166352). Also known are similarly substituted com A-4014 420). The synthesis of the tetronic acid derivatives pounds; 3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1- US 2010/03 11593 A1 Dec. 9, 2010

one from the publication Micklefield et al., Tetrahedron, in which (1992), 7519-26 and the natural substance Involutin, (-)-cis 5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphe 0018 W is hydrogen, alkyl, halogen, haloalkyl, alkoxy or nyl)cyclopent-2-enone from the publication Edwards et al., J. haloalkoxy, Chem. Soc. S. (1967), 405-9. No insecticidal or acaricidal 0019 X is alkyl, alkenyl, alkynyl, halogen, alkoxy, action is described. Also known is 2-(2,4,6-trimethylphenyl)- haloalkyl, haloalkoxy or cyano, 1.3-indanedione from the publication J. Economic Entomol ogy, 66, (1973), 584 and the published specification DE-A2 0020 Y is hydrogen, alkyl, alkoxy or halogen, 361084, with a report of herbicidal and acaricidal effects. Z is a group 0011. It is known that particular substituted 2-arylcyclo 0021 hexanediones possess herbicidal, insecticidal and acaricidal properties (U.S. Pat. Nos. 4,175,135, 4.256,657, 4.256,658, 4,256,659, 4,257,858, 4,283,348, 4,303,669, 4,351,666, 4,409,153, 4,436,666, 4,526,723, 4,613,617, 4,659372, DE-A2,813,341, and Wheeler, T. N., J. Org. Chem. 44, 4906 (1979)), WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO 03/013249, WO 04/080962, WO 04/111 042, WO 05/092897, WO 06/029799, WO 07/096,058, WO 08/071,405, WO 08/110,307, WO 08/110, 308 and WO 08/145,336. 0012. It is known that particular substituted 4-arylpyrazo lidine-3,5-diones possess acaricidal, insecticidal and herbi in which J and Jare each independently hydrogen or halo cidal properties (cf., for example, WO 92/16510, EP-A- gen and J is halogen or a haloalkyl group, 508126, WO 96/11574, WO 96/21652, WO 99/47525, WO 0022. CKE is one of the groups 01/17 351, WO 01/17 352, WO 01/17 353, WO 01/17972, WO 01/17973, WO 03/028466, WO 03/062244, WO 04/080 962, WO 04/111042, WO 05/005428, WO 05/016873, WO 05/092897, WO 06/029799 and WO 07/096,058). (1) 0013. It is known that particular tetrahydropyridones pos sess herbicidal properties (JP 0832530). Also known are spe cific 4-hydroxytetrahydropyridones with acaricidal, insecti cidal and herbicidal properties (JP 11 152273). Additionally disclosed have been 4-hydroxytetrahydropyridones as pesti cides and herbicides in WO 01/79204 and WO 07/096,058. 0014. It is known that particular 5,6-dihydropyrone derivatives, as protease inhibitors, have antiviral properties (2) (WO95/14012). Additionally known is 4-phenyl-6-(2-phen ethyl)-5,6-dihydropyrone from the synthesis of kavalactone derivatives (Kappe et al., Arch. Pharm. 309,558-564 (1976)). Also known are 5,6-dihydropyrone derivatives as intermedi ates (White, J. D., Brenner, J. B., Deinsdale, M. J. J. Amer. Chem. Soc. 93, 281-282 (1971)). 3-Phenyl-5,6-dihydropy rone derivatives with applications in crop protection are described in WOO1/98288 and WO 07/09658. (3) 0015) 4-Phenyl-substituted 1.2-oxazine-3,5-diones were described as herbicides for the first time in WO 01/17972. Additionally described were 4-acyl-substituted 1,2-oxazine-3,5-diones as pesticides, but in particular as herbicides and growth regulators, for example in EP-A-3948 89; WO92/07837, U.S. Pat. No. 5,728,831, and as herbicides and pesticides in WO 03/048.138. 0016. The herbicidal and/or acaricidal and/or insecticidal (4) efficacy and/or breadth of action and/or the plant compatibil ity of the known compounds, especially with respect to crop plants, is, however, not always satisfactory. 0017 Novel compounds of the formula (I) have now been found (5) (I) US 2010/03 11593 A1 Dec. 9, 2010

an S=N , S(O)—N- or -continued

(6)

group I0025 or is optionally Q- and Q-substituted C-C- alkylene which may optionally be interrupted by oxy (7) gen, 0026 A is hydrogen, in each case optionally halogen substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, or is saturated or unsaturated, optionally substituted cycloalkyl in which at least one ring atom is optionally replaced by a heteroatom, or in each case optionally halogen-, alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl, (8) 0027 B is hydrogen, alkyl or alkoxyalkyl, or O 0028 A and B together with the carbon atom to which A * G they are bonded are a saturated or unsaturated, unsub stituted or Substituted cycle optionally containing at N A. least one heteroatom, D1 : 0029 D is hydrogen oran optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxyalkyl, Saturated or unsaturated cycloalkyl in which one or more (9) ring members are optionally replaced by heteroatoms, or in each case optionally substituted arylalkyl, aryl, hetarylalkyl or hetaryl, or 0030 A and D together with the atoms to which they are bonded are a saturated or unsaturated cycle which is unsubstituted or substituted in the A, D moiety and optionally contains at least one (in the case of CKE=8 and 11 one further) heteroatom, or (10) A B I0031) A and Q' together are in each case optionally Substituted alkanediyl or alkenediyl, which may option Q! Q or ally be interrupted by at least one heteroatom, Q? -E-G 0032) a O e d (11) A B 9 : O 2 p-na| --G d

0023 in which group 0024. U is —S——S(O)— —S(O)— —O 0033 or, 0034 B and Q together with the atoms to which they are bonded area Saturated or unsaturated cycle which is unsubstituted or substituted in the B. Q. moiety and optionally contains at least one heteroatom, or D., I0035) D and Q' together with the atoms to which they are bonded area Saturated or unsaturated cycle which is unsubstituted or substituted in the D. Q. moiety and optionally contains at least one heteroatom, US 2010/03 11593 A1 Dec. 9, 2010

10036) Q' is hydrogen, alkyl, alkoxyalkyl, optionally I0049 R is in each case optionally halogen-substi Substituted cycloalkyl in which one methylene group is tuted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, or optionally replaced by oxygen or Sulphur, or is option in each case optionally Substituted cycloalkyl, phenyl ally substituted phenyl, or benzyl, 0037 Q, Q, Q and Q are each independently hydro gen or alkyl, 0050 R, R and Rare each independently in each I0038. Q is hydrogen, in each case optionally substi case optionally halogen-substituted alkyl, alkoxy, tuted alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthio alkylamino, dialkylamino, alkylthio, alkenylthio. alkyl, or is optionally substituted cycloalkyl in which cycloalkylthio, or in each case optionally Substituted one or two methylene groups are optionally replaced by phenyl, benzyl, phenoxy or phenylthio. oxygen or Sulphur, or is optionally Substituted phenyl, or 10051) RandR are each independently hydrogen, in 0039 Q' and Q together with the carbonatom to which each case optionally halogen-substituted alkyl, they are bonded are an unsubstituted or substituted cycle cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally optionally containing one heteroatom, or 10040 Qand Q together with the carbonatom to which substituted phenyl, optionally substituted benzyl, or, they are bonded are a saturated or unsaturated, unsub together with the nitrogen atom to which they are stituted or Substituted cycle optionally containing at bonded, a cycle optionally interrupted by oxygen or least one heteroatom, or Sulphur. I0041) A and Q together with the carbon atom to which 0.052 The compounds of the formula (I) may be present in they are bonded are a saturated or unsaturated, unsub different composition, also depending on the type of substitu stituted or Substituted cycle optionally containing at ents, as geometric and/or optical isomers or isomer mixtures, least one heteroatom, or which can optionally be separated in a customary manner. I0042 A and Q together with the carbon atom to which Both the pure isomers and the isomer mixtures are usable in they are bonded are a saturated or unsaturated, unsub inventive compositions and their action can be enhanced by stituted or Substituted cycle optionally containing at inventive ammonium or phosphonium salts. For the sake of least one heteroatom, simplicity, reference is always made hereinafter to com 0043. G is hydrogen (a) or one of the groups pounds of the formula (I), although this means both the pure compounds and possibly also mixtures with different propor (b) tions of isomeric compounds. 0053 Taking account of the meanings (1) to (11) of the CKE group, the following principal structures (I-1) to (I-11) arise:

(I-1) G (d) Y X A (e) >1 N FV S Z. - \ ?y. O W (f) (I-2) (g) G Y X A FV Z. "YN V 2,X1 0044 in which O W 0045 E is one metal ion equivalent or one ammo (I-3) nium ion, G 004.6 L is oxygen or sulphur, Y X 0047 M is oxygen or sulphur, A I0048) R' is in each case optionally halogen-substi N FVX1 Z. tuted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, poly alkoxyalkyl, or is optionally halogen-alkyl- or P1-Y V 2, alkoxy-substituted cycloalkyl which may be inter rupted by at least one heteroatom, or is in each case O W optionally Substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, US 2010/03 11593 A1 Dec. 9, 2010

-continued -continued (I-4) (I-11)

(I-5)

in which 0054 A, B, D, G, Q, Q, Q, Q, U, W, X,Y and Zare each as defined above. 0055 Taking account of the different meanings (a), (b), (I-6) (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-1-a) to (I-1-g), arise when CKE is the group (1),

(I-7)

(I-8)

(I-9)

(I-1-c):

(I-10)

US 2010/03 11593 A1 Dec. 9, 2010

0057 Taking account of the different meanings (a), (b), -continued (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-2-a) to (I-2-g), arise when CKE is the group (2), (I-1-d): (I-2-a): A OH X B Y / s. Z O —7 Y O W

O-SO-R Y A X

B Z (I-1-g): \ A Xy O o Y

O W

in which 0056 A, B, D, E, L, M, W, X, Y, Z, R. R. R. R. R. R. and Rare each as defined above. US 2010/03 11593 A1 Dec. 9, 2010

-continued -continued

L R6 | / O-C-N A X Y.

"|O W /- ,Y O W in which 0058 A, B, E, L, M, W, X,Y,Z, R', R,R,R,R, R and E R" are each as defined above. A Yo x 0059 Taking account of the different meanings (a), (b), B Z (c), (d), (e), (f) and (g) of the G group, the following principal y / s. structures (I-3-a) to (I-3-g), arise when CKE is the group (3), S - fy

O W (I-3-a): A OH X

B Z S Y ( - Vys.

O W (I-3-b): O

A-v O X in which 0060 A, B, E, L, M, W, X,Y,Z, R', R,R,R,R, R and B VZ Rare each as defined above. y / S. 0061. Depending on the position of the substituent G, the S - Y compounds of the formula (I-4) may be present in the two O W isomeric forms of the formulae (I-4-A) and (I-4-B), (I-3-c): \Y.M.R. G (I-4-A) A c/ X A x B V-Z V-Z Y ( SSs. p. ( y ( , S o Y O —7 Y O W US 2010/03 11593 A1 Dec. 9, 2010

-continued -continued (I-4-c):

A O X (I-4-B) p-( ) ( S. Z O / - Vy

O W

which is expressed by the broken line in the formula (I-4). 0062. The compounds of the formulae (I-4-A) and (I-4-B) may be present either as mixtures or in the form of pure isomers thereof. Mixtures of the compounds of the formulae (I-4-A) and (I-4-B) can optionally be separated in a manner known perse by physical methods, for example by chromato graphic methods. 0063 For reasons of better clarity, only one of the possible isomers in each case is shown hereinafter. This does not rule out the possibility that the compounds may be present in the form of the isomer mixtures or in the other isomeric form in each case. 0064. Taking account of the different meanings (a), (b), (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-4-a) to (I-4-g), arise when CKE is the group (4),

in which 0065 A, D, E, L, M, W, X,Y,Z, R', R,R,R,R, R and Rare each as defined above. US 2010/03 11593 A1 Dec. 9, 2010

0066 Taking account of the different meanings (a), (b),

(c), (d), (e), (f) and (g) of the G group, the following principal -continued structures (I-5-a) to (I-5-g), arise when CKE is the group (5),

(I-5-a):

in which 0067 A, E, L, M, W, X,Y,Z, R', R,R,R,R, R and R7 are each as defined above. 0068. Depending on the position of the substituent G, the compounds of the formula (I-6) may be present in the two isomeric forms of the formulae (I-6-A) and (I-6-B),

(I-6-A)

A fO X B / X7 (I-5-d): Q Q? O W (I-6-B) A O X B / x/

Q Q? W

G

which is expressed by the broken line in the formula (I-6). 0069. The compounds of the formulae (I-6-A) and (I-6-B) may be present either as mixtures or in the form of pure isomers thereof. Mixtures of the compounds of the formulae (I-6-A) and (I-6-B) can optionally be separated by physical methods, for example by chromatographic methods. 0070 For reasons of better clarity, only one of the possible isomers in each case is shown hereinafter. 0071. This does not rule out the possibility that the com pounds may be present in the form of the isomer mixtures or in the other isomeric form in each case. US 2010/03 11593 A1 Dec. 9, 2010

0072 Taking account of the different meanings (a), (b), (c), (d), (e), (f) and (g) of the G group, the following principal -continued structures (I-6-a) to (I-6-g), arise when CKE is the group (6),

(I-6-a):

1s,O A X B / s"

in which Q Q? O W A, B, Q, Q, E, L, M, W, X, Y, Z, R. R. R. R. R. Rand (I-6-c): R7 are each as defined above. 0073. Depending on the position of the substituent G, the compounds of the formula (I-7) may be present in the two V isomeric forms of the formulae (I-7-A) and (I-7-B), which is )-y-R expressed by the broken line in the formula (I-7): A O X

B / s' (I-7-A)

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

A O-SO-R B X (I-7-B) V-Z Q /- VyS.

0074 The compounds of the formulae (I-7-A) and (I-7-B) may be present either as mixtures or in the form of pure isomers thereof. Mixtures of the compounds of the formulae (I-7-A) and (I-7-B) can optionally be separated by physical methods, for example by chromatographic methods. 0075 For reasons of better clarity, only one of the possible isomers in each case is shown hereinafter. This does not rule out the possibility that the compound may be present in the form of the isomer mixtures or in the other isomeric form in each case. US 2010/03 11593 A1 Dec. 9, 2010 11

0076 Taking account of the different meanings (a), (b), -continued (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-7-a) to (I-7-g), arise when CKE is the group (7).

in which A, B, E, LM, Q, Q, U, W, X,Y,Z, R',R,R,R,R,R and R7 are each as defined above. 0077 Depending on the position of the substituent G, the compounds of the formula (I-8) may be present in the two isomeric forms (I-8-A) and (I-8-B),

(I-8-A) O X Da Z N X-( SC: A1 v Y / W (I-8-B) G Y. X PN / y-Z N N SCy A1 v Y O W

which is expressed by the broken line in the formula (I-8). 0078. The compounds of the formulae (I-8-A) and (I-8-B) may be present either as mixtures or in the form of pure isomers thereof. Mixtures of the compounds of the formulae (I-8-A) and (I-8-B) can optionally be separated in a manner known perse by physical methods, for example by chromato graphic methods. 007.9 For reasons of better clarity, only one of the possible isomers in each case is shown hereinafter. This does not rule out the possibility that the compounds may be present in the form of the isomer mixtures or in the other isomeric form in each case. US 2010/03 11593 A1 Dec. 9, 2010 12

0080 Taking account of the different meanings (a), (b), (c), (d), (e), (f) and (g) of the G group, the following principal (I-8-f) -continued structures (I-8-a) to (I-8-g), arise when CKE is the group (8), O X D

N / / SCs" O X A1 Y D O W n W Z V E N X-( SS: (I-8-g) A1 v Y OH W O X D n V-Z (I-8-b) N X-( SS A1 / Y O X O W D n V-Z R6 1-(N1 N SS A1 X-( Y Y. O W in which A, D, E, L, M, W, X, Y, Z, R. R. R. R. R. R. and R7 are o R1 each as defined above. I0081. Depending on the position of the substituent G, the compounds of the formula (I-9) may be present in the two isomeric forms of the formulae (I-9-A) and (I-9-B), which is (I-8-c) expressed by the broken line in the formula (I-9): O X D a. W Z G (I-9-A)

N SS A1 X-( SA Y A B X O W V-Z 1={ Q Y\ \, ( - fy, M-R2 / (I-8-d) D

(I-9-B) O X D n W Z

N ) ( SSs. A1 v Y sc?O W Y: I0082. The compounds of the formulae (I-9-A) and (I-9-B) (I-8-e) may be present either as mixtures or in the form of pure O X isomers thereof. Mixtures of the compounds of the formulae D (I-9-A) and (I-9-B) can optionally be separated in a manner n W Z known perse by physical methods, for example by chromato graphic methods. N X-( SS: I0083. For reasons of better clarity, only one of the possible A1 Ev Y isomers in each case is shown hereinafter. This does not rule O W out the possibility that the compounds may be present in the form of the isomer mixtures or in the other isomeric form in l=4-R each case. Ys I0084. Taking account of the different meanings (a), (b), (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-9-a) to (I-9-g), arise when CKE is the group (9), US 2010/03 11593 A1 Dec. 9, 2010 13

-continued

in which A, B, D, E, LM, Q, Q, W, X,Y,Z,R,R,R,R,R,R and R" are each as defined above. I0085 Depending on the position of the substituent G, the compounds of the formula (I-10) may be present in the two isomeric forms of the formulae (I-10-A) and (I-10-B),

(I-10-A)

Q S-(\, \ /–7 s.y O (I-10-B) A B O X Q! / s' Q \, / - Vy O W

which is expressed by the broken line in the formula (I-10). I0086. The compounds of the formulae (I-10-A) and (I-10 B) may be present either as mixtures or in the form of pure isomers thereof. Mixtures of the compounds of the formulae (I-10-A) and (I-10-B) can optionally be separated in a manner known perse by physical methods, for example by chromato graphic methods. I0087. For reasons of better clarity, only one of the possible isomers in each case is shown hereinafter. This does not rule US 2010/03 11593 A1 Dec. 9, 2010 out the possibility that the compounds may be present in the

form of the isomer mixtures or in the other isomeric form in -continued each case. 0088. Taking account of the different meanings (a), (b), (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-10-a) to (I-10-g), arise when CKE is the group (10),

(I-10-g):

(I-10-c): in which A, B, E, L, M, Q, Q, W, X, Y, Z, R. R. R. R. R. Rand R" are each as defined above. I0089. Depending on the position of the substituent G, the compounds of the formula (I-11) may be present in the two isomeric forms of the formulae (I-11-A) and (I-11-B), which is expressed by the broken line in the formula (I-11).

(I-11-A)

(I-10-d): OY - Vy M D O (I-11-B) A B O X V-Z {Y \, ( - Vys. M D O W US 2010/03 11593 A1 Dec. 9, 2010

0090 The compounds of the formulae (I-11-A) and (I-11 B) may be present either as mixtures or in the form of pure -continued isomers thereof. Mixtures of the compounds of the formulae (I-11-e): (I-11-A) and (I-11-B) can optionally be separated in a manner known perse by physical methods, for example by chromato graphic methods. 0091 For reasons of better clarity, only one of the possible isomers in each case is shown hereinafter. This does not rule out the possibility that the compounds may be present in the form of the isomer mixtures or in the other isomeric form in each case. 0092. Taking account of the different meanings (a), (b), (c), (d), (e), (f) and (g) of the G group, the following principal structures (I-11-a) to (I-11-g), arise when CKE is the group (11), (I-11-f):

(I-11-g):

(I-11-b):

(I-11-c): in which A, B, D, E, L, M, W, X,Y,Z, R', R,R,R,R, R and R7 are each as defined above. 0093. It has additionally been found that the novel com pounds of the formula (I) are obtained by one of the processes described hereinafter: 0094 (A) Substituted 3-phenylpyrrolidine-2,4-diones or enols thereof, of the formula (I-1-a)

(I-11-d): (I-1-a) US 2010/03 11593 A1 Dec. 9, 2010

0.095 in which 0112 (C) It has additionally been found that substituted 0.096 A, B, D, W, X,Y and Zare each as defined above, 3-phenyl-4-hydroxy-A-dihydrothiophenone derivatives O097 are obtained when of the formula (I-3-a) 0.098 N-acylamino acid esters of the formula (II) (I-3-a) A HO X B FV Z. (II) S y (\ }^yS

O W D1 4N -HZ 0113 in which 0114 A, B, W, X, Y and Z are each as defined above, W -'six 0115 are obtained when Y 0116 -ketocarboxylic esters of the formula (IV) 0099 in which 01.00 A, B, D, W, X,Y and Zare each as defined above, (IV) 01.01 and I0102 R is alkyl (preferably C-C-alkyl). 0103) are intramolecularly condensed in the presence of a diluent and in the presence of a base. 0104 (B) It has also been found that substituted 3-phenyl 4-hydroxy-A-dihydrofuranone derivatives of the formula (I-2-a)

0117 in which (I-2-a) 0118 A, B, W, X,Y,Z and Rare each as defined above and 0119 V is hydrogen, halogen, alkyl (preferably C-C- alkyl) or alkoxy (preferably C-C-alkoxy), 0120 are intramolecularly cyclized, optionally in the presence of a diluent and in the presence of an acid. I0121 (D) It has additionally been found that the novel substituted 3-phenylpyrone derivatives of the formula (I-4- a) 01.05 in which 01.06 A, B, W, X, Y and Z are each as defined above, (I-4-a) 01.07 are obtained when O X

01.08 carboxylic esters of the formula (III) O o D y \ A N ×M (III) A OH W

0.122 in which 21 0123 A, D, W, X, Y and Z are each as defined above, --z 0.124 are obtained when 0.125 carbonyl compounds of the formula (V) W -'six

(V) 01.09 in which 0110 A, B, W, X,Y,Z and Rare each as defined above, D-C-CH-A 0111 are intramolecularly condensed in the presence of a diluent and in the presence of a base. US 2010/03 11593 A1 Dec. 9, 2010

0.126 in which 0.144 in which 0127. A and D are each as defined above, (0145 Hal, W, X, Y and Z are each as defined above, I0128 or the silyl enol ethers thereof, of the formula (Va) 0146 optionally in the presence of a diluent and option (Va) ally in the presence of an acid acceptor. CHA 0.147. It has additionally been found, D-C-OSi(R)so 0148 (F) that compounds of the formula (I-6-a)

0129 in which (I-6-a) O130 A, D and Rare each as defined above, A OH X 0131) are reacted with ketenoyl halides of the formula (VI) B o yM (VI) \ Žy Q COHall O2 O W & / CECEO 0.149 in which 0150 A, B, Q, Q, W, X, Y and Z are each as defined above, (0132) in which 0151 are obtained when 0.133 W, X, Y and Z are each as defined above and 0152 ketocarboxylic esters of the formula (VIII) 0.134 Hal is halogen (preferably chlorine or bromine), 0.135 optionally in the presence of a diluent and option ally in the presence of an acid acceptor. (VIII) 0136. It has additionally been found, Q Q2 0137 (E) that the novel substituted phenyl-1,3-thiazine ROC derivatives of the formula (I-5-a) (I-5-a) X -HZ 1. O / WS Z W 2. us11) W is 0.153 in which A S OH 0154 A, B, Q, Q, W, X, Y and Z are each as defined above, and 0.138 in which 0155 R is alkyl (especially C-Cs-alkyl), are intramo 0.139 A, W, X, Y and Z are each as defined above, lecularly cyclized, optionally in the presence of a diluent 0140 are obtained when thioamides of the formula and in the presence of a base. (VII) 0156 It has also been found (VII) O157 (G) that compounds of the formula (I-7-a) S HN-C-A

(I-7-a) 0141 in which 0.142 A is as defined above, 0.143 are reacted with ketenoyl halides of the formula (VI) (VI) X

o COHall v Z Y y’(V /)--- in which W 0158 0159) A, B, Q, Q, U, W, X, Y and Zare each as defined above, US 2010/03 11593 A1 Dec. 9, 2010

(0160 are obtained when 0.177 f) are reacted with compounds of the formula 0.161 6-aryl-5-ketohexanoic esters of the formula (IX) (XI)

(IX) A B Q Q X (XI) X. N X O -N-x-HZ Zn/ \ Ul W Y Y( - Ul W O (0162 in which (0163 A, B, Q, Q, U, W, X,Y and Zare each as defined above and 0.178 in which (0164 R is alkyl (preferably C1-Co-alkyl). 0.179 W, X, Y and Z are each as defined above, 0.165 are intramolecularly condensed in the presence of 0180 and U' is NH or O-R where R is as defined a diluent and in the presence of a base. above, 0166 (H) It has additionally been found that the com 0181 optionally in the presence of a diluent and option pounds of the formula (I-8-a) ally in the presence of a base, or 0182 Y) are reacted with compounds of the formula (I-8-a) (XII) OH X A a. N y Z ) ( . (XII) D1 Ev Y A X O W N- COR 8 Zn/* Y-n-Sp 2 (0167 in which X1 (0168 A, D, W, X, Y and Z are each as defined above, Y VE O (0169 are obtained when W 0170 compounds of the formula (X) 0183 in which (X) 0184 A, D, W, X,Y,Z and Rare each as defined above, A n N Y H 0185 optionally in the presence of a diluent and option ally in the presence of a base. D1 N NH 0186. It has also been found that the novel compounds of the formula (I-9-a) are obtained by one of the methods described hereinafter: (0171 in which 0187 (I) Substituted tetrahydropyridine-2,4-diones or the 0172 A and D are each as defined above, enols thereof, of the formula (I-9-a) 0173 C.) are reacted with compounds of the formula (VI)

(VI) (I-9-a) X

o COHall y X(M /)--- W

0.174 in which (0175 Hal, W, X, Y and Z are each as defined above, 0176 optionally in the presence of a diluent and option ally in the presence of an acid acceptor, or US 2010/03 11593 A1 Dec. 9, 2010

0188 in which 0203 in which (0189 A, B, D, Q, Q, W, X,Y and Zare each as defined 0204 A, B, Q', Q, W, X, Y and Z are each as defined above, above, 0205 and 0.190 are obtained when (0206 R is alkyl (preferably C1-Co-alkyl). 0191 N-acylamino acid esters of the formula (XIII) 0207 are converted, optionally in the presence of a dilu ent and optionally in the presence of a base. 0208. It has additionally been found that the novel com (XIII) A pounds of the formula (I-11-a) are obtained by one of the B COR processes described hereinafter: Q! 0209 (K) Substituted oxazine-3,5-diones or the enols X thereof, of the formula (I-11-a) Q? N D1 o

(I-11-a) Ow1N Žs,M Y

(0192 in which (0193 A, B, D, Q, W, X, Y and Z are each as defined above, 0194 and (0195 R is alkyl (preferably C-C-alkyl), Y 0196) are intramolecularly condensed in the presence of a diluent and in the presence of a base. 0210 in which (0197) It has additionally been found that 0211 A, B, D, W, X, Y and Z are each as defined above, 0198 (J) substituted 5,6-dihydropyrones of the formula 0212 are obtained when (I-10-a) 0213 N-acylamino acid esters of the formula (XV)

(I-10-a) (XV) s-orA O DN X D o Ow1N ŽSzM Y Y 0214 in which (0199 in which 0215 A, B, D, W, X,Y and Z are each as defined above, (0200 A, B, Q, Q, W, X, Y and Z are each as defined and above, 0216) R is alkyl (preferably C1-Co-alkyl). 0217 are intramolecularly condensed in the presence of 0201 are obtained when a diluent and in the presence of a base. 0202 O-acylhydroxycarboxylic esters of the formula 0218. It has also been found (XIV) 0219 (L) that the compounds of the formulae (I-1-b) to (I-11-b) shown above, in which A, B, D, Q, Q, Q, Q, R', (XIV) U, W, X, Y and Z are each as defined above are obtained A when compounds of the formulae (I-1-a) to (I-11-a) shown B COR above, in which A, B, D, Q, Q, Q, Q, U, W, X, Y and Z Q! are each as defined above, are reacted in each case X 0220 (C) with acid halides of the formula (XVI) Q? O

O M (XVI) w1N Žsz Hal r RI O US 2010/03 11593 A1 Dec. 9, 2010 20

0221 in which obtained when compounds of the formulae (I-1-a) to (I-11 0222 R is as defined above and a) shown above, in which A, B, D, Q, Q, Q, Q, U, W, X, 0223 Hal is halogen (especially chlorine or bromine) Y and Zare each as defined above, are reacted in each case 0224 or 0246 with phosphorus compounds of the formula 0225 (B) with carboxylic anhydrides of the formula (XXI) (XVII) R" CO-O CO-R' (XVII) 4 (XXI) R 0226 in which 1. 0227) R' is as defined above, Hall-PNRs 0228 optionally in the presence of a diluent and option L ally in the presence of an acid binder; 0229 (M) that the compounds of the formulae (I-1-c) to 0247 in which (I-11-c) shown above, in which A, B, D, Q', Q, Q, Q, R, 0248 L. Rand Rare each as defined above and M, U, W, X, Y and Z are each as defined above and L is 0249 Hal is halogen (especially chlorine or bromine), oxygen, are obtained when compounds of the formulae 0250 optionally in the presence of a diluent and option (I-1-a) to (I-11-a) shown above, in which A, B, D, Q, Q, ally in the presence of an acid binder, Q, Q, U, W, X, Y and Z are each as defined above, are 0251 (Q) that compounds of the formulae (I-1-f) to (I-11 reacted in each case f) shown above, in which A, B, D, E, Q, Q, Q, Q, U, W. 0230 with chloroformic esters or chloroformic thio X, Y and Z are each as defined above, are obtained when esters of the formula (XVIII) compounds of the formulae (I-1-a) to (I-11-a), in which A, R2-M-CO Cl (XVIII) B, D, Q, Q, Q, Q, U, W, X,Y and Z are each as defined 0231 in which above, are reacted in each case 0232 R and Mare each as defined above, 0252 with metal compounds oramines of the formulae 0233 optionally in the presence of a diluent and option (XXII) and (XXIII)) ally in the presence of an acid binder; Me(OR), (XXII) 0234 (N) that compounds of the formulae (I-1-c) to (I-11 c) shown above, in which A, B, D, Q, Q, Q, Q, R. M., U. W, X,Y and Zare each as defined above and L is sulphur (XXIII) are obtained when compounds of the formulae (I-1-a) to (I-11-a) shown above, in which A, B, D, Q, Q, Q, Q, U. U, W, X, Y and Z are each as defined above are reacted in each case 0235 with chloromonothioformic esters or chlo rodithioformic esters of the formula (XIX) 0253 in which 0254 Me is a mono- or divalent metal (preferably an alkali metal or alkaline earth metal Such as lithium, (XIX) Sodium, potassium, magnesium or calcium), or an st ammonium ion S

0236 in which N 0237 M and Rare each as defined above, R11 Y: 0238 optionally in the presence of a diluent and option ally in the presence of an acid binder, 0255 t is the number 1 or 2 and 0239 and 0256 R', R'', R'' are each independently hydrogen or 0240 (O) that compounds of the formulae (I-1-d) to (I-11 alkyl (preferably C-C-alkyl). d) shown above, in which A, B, D, Q, Q, Q, Q, R. U, 0257 optionally in the presence of a diluent, W, X,Y and Zare each as defined above, are obtained when 0258 (R) that compounds of the formulae (I-1-g) to (I-11 compounds of the formulae (I-1-a) to (I-11-a) shown g) shown above, in which A, B, D, L. Q', Q, Q, Q, R. above, in which A, B, D, Q, Q, Q, Q, U, W, X,Y and Z R7, U. W, X, Y and Z are each as defined above, are are each as defined above, are reacted in each case obtained when compounds of the formulae (I-1-a) to (I-11 0241 with sulphonyl chlorides of the formula (XX) a) shown above, in which A, B, D, Q, Q, Q, Q, U, W, X, Y and Z are each as defined above, in each case R SO, Cl (XX) 0259 (O) are reacted with isocyanates or isothiocyanates 0242 in which of the formula (XXIV) 0243 R is as defined above, 0244 optionally in the presence of a diluent and option R N=C=L (XXIV) ally in the presence of an acid binder, 0260 in which 0245 (P) that compounds of the formulae (I-1-e) to (I-11 0261) R' and L are each as defined above, e) shown above, in which A, B, D, L. Q', Q, Q, Q, R. 0262 optionally in the presence of a diluent and option R. U, W, X, Y and Z are each as defined above, are ally in the presence of a catalyst, or US 2010/03 11593 A1 Dec. 9, 2010 21

0263 (B) are reacted with carbamyl chlorides or thiocar bamyl chlorides of the formula (XXV) -continued

(I-6)

(XXV) L R6 ls SN C R7 (I-7) 0264 in which 0265 L, Rand R7 are each as defined above, 0266 optionally in the presence of a diluent and option ally in the presence of an acid binder, 0267 (S) that compounds of the formulae (I-1-a) to (I-11 g) shown above, in which A, B, D, G, Q', Q, Q, Q, U.W. (I-8) X, Y and Z are each as defined above, are obtained when the bromine or iodine atom in compounds of the formulae (I-1') to (I-11'), in which A, B, D, G, Q, Q, Q, Q, U, W. X and Y are each as defined above and Z is preferably bromine or iodine

(I-9) (I-1) no X

A o Z. N x( B y 2, O W G (I-2) (I-10') No X

A o Z. N ( B O \ , O W G (I-3) (I-11) No X A Z. B N \ x1, O W G (I-4) A No X

o Z x is exchanged with halogenated alcohols, for example trifluo roethanol of the formula (XXVI) /O \ \ 2(WYy Z OH (XXVI) O W in the presence of a solvent, in the presence of a copper salt G (I-5) (e.g. Cu(I)I) and in the presence of a base (for example potas No X sium tert-butoxide, sodium hydride). N FV Z. 0268. It has additionally been found that the novel com e1 pounds of the formula (I) have very good efficacy as pesti A-(S )—K /Yy cides, preferably as insecticides, acaricides and/or herbicides. 0269. It has now also been found that, surprisingly, par O W ticular haloalkylmethyleneoxyphenyl-substituted ketoenols, when applied together with the compounds which improve US 2010/0311593 A1 Dec. 9, 2010 22 crop plant compatibility described hereinafter (safeners/anti 0279 m is 0 or 1: dotes), prevent damage to the crop plants extremely effi (0280 R is OR, SR or NR'R' or a saturated or ciently and can be used particularly advantageously as unsaturated 3- to 7-membered heterocycle having at broadly active combination preparations for selective control least one nitrogen atom and up to 3 heteroatoms, pref of undesired plants in useful plant crops, for example in erably from the group of O and S, which is attached via cereals, but also maize, rape, Soya and rice. the nitrogen atom to the carbonyl group in (S1) and 0270. The invention also provides selective herbicidal which is unsubstituted or substituted by radicals from compositions comprising an effective content of an active the group of (C-C)-alkyl, (C-C)-alkoxy and option ingredient combination, comprising, as components, ally substituted phenyl, preferably a radical of the for (0271 a') at least one compound of the formula (I) in which mula OR, NHR, or N(CH3)2, in particular of the CKE, W, X, Y and Z are each as defined above formula OR; and (0281 R is hydrogen oran unsubstituted or substituted (0272 (b") at least one compound which improves crop aliphatic hydrocarbon radical, preferably having a total of 1 to 18 carbon atoms; plant compatibility (safener). (0282 R is hydrogen, (C-C)-alkyl, (C-C)-alkoxy 0273. The safeners are preferably selected from the group or substituted or unsubstituted phenyl: consisting of: (0283 R is H. (C-Cs)-alkyl, (C-Cs)-haloalkyl, (C- (0274 S1) compounds of the formula (S1) Cl)-alkoxy-(C-Cs)-alkyl, cyano or COOR, where R. is hydrogen, (C-C)-alkyl, (C-Cs-haloalkyl, (C-C)- alkoxy-(C-C)-alkyl, (C-C)-hydroxyalkyl, (C-C2)- (S1) cycloalkyl or tri-(C-C)-alkylsilyl; (0284) R. R. R. are identical or different and are hydrogen, (C-Cs-alkyl, (C-Cs-haloalkyl, (C-C2)-cy cloalkyl or substituted or unsubstituted phenyl; 0285 preferably: (0286 a) compounds of the dichlorophenylpyrazoline (0275 where the symbols and indices are each defined as 3-carboxylic acid type (S1"), preferably compounds follows: such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5- (0276 n is a natural number from 0 to 5, preferably methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4- from 0 to 3: dichlorophenyl)-5-(ethoxy-carbonyl)-5-methyl-2-pyra (0277) R' is halogen, (C-C)-alkyl, (C-C)-alkoxy, Zoline-3-carboxylate (S1-1) (“mefenpyr(-diethyl)"), nitro or (C-C)-haloalkyl: and related compounds, as described in WO-A-91/ (0278 W is an unsubstituted or substituted divalenthet 07874; erocyclic radical from the group of partially unsaturated (0287 b) derivatives of dichlorophenylpyrazolecar or aromatic five-membered heterocycles having 1 to 3 boxylic acid (S1), preferably compounds such as ethyl hetero ring atoms from the group of N and O, where at 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxy least one nitrogen atom and at most one oxygen atom is late (51-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropy present in the ring, preferably a radical from the group of lpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlo (W) to (W), rophenyl)-5-(1,1-dimethylethyl)pyrazole-3- carboxylate (S1-4) and related compounds, as described in EP-A-333 131 and EP-A-269 806; (WI) 0288 c) derivatives of 1,5-diphenylpyrazole-3-car boxylic acid (S1'), preferably compounds such as ethyl NY N 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxy late (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyra zole-3-carboxylate (S1-6) and related compounds, as described, for example, in EP-A-268554; (W) 0289 d) compounds of the triazolecarboxylic acid type (S1), preferably compounds such as fenchlorazole(- ethyl), i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloro-me thyl-(1H)-1,2,4-triazole-3-carboxylate (S1-7), and related compounds, as described in EP-A-174562 and (W) EP-A-346 620; 0290 e) compounds of the 5-benzyl- or 5-phenyl-2- isoxazoline-3-carboxylic acid or the 5,5-diphenyl-2- isoxazoline-3-carboxylic acid type (S1), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2- isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2- (W) isoxazoline-3-carboxylate (S1-9) and related com pounds, as described in WO-A-91/08202, or 5.5- diphenyl-2-isoxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (S1-11) (“isoxadifen-ethyl”) or n-propyl 5,5-diphenyl-2-isox azolinecarboxylate (S1-12) or ethyl 5-(4-fluorophenyl)- US 2010/03 11593 A1 Dec. 9, 2010 23

5-phenyl-2-isoxazoline-3-carboxylate (S1-13), as 0303 S3) Compounds of the formula (S3) described in patent application WO-A-95/07897. 0291 S2) Quinoline derivatives of the formula (S2) (S3) (S2) O 21 Na RC l R N H-(R'), N N O R O NT,ls Re? 0304 where the symbols and indices are each defined as 0292 where the symbols and indices are each defined as follows: follows: 10293 R' is halogen, (C-C)-alkyl, (C-C)-alkoxy, (0305) R' is (C-C)-alkyl, (C-C)-haloalkyl, (C-C)- nitro or (C-C)-haloalkyl; alkenyl, (C-C)-haloalkenyl, (C-C2)-cycloalkyl, pref 0294 n is a natural number from 0 to 5, preferably erably dichloromethyl; from 0 to 3: (0306 R. Rare identical or different and are hydro 0295 R is OR, SR or NR'R' or a saturated gen, (C-C)-alkyl, (C-C)-alkenyl, (C-C)-alkynyl, 0296 or unsaturated 3- to 7-membered heterocycle (C-C)-haloalkyl, (C-C)-haloalkenyl, (C-C)-alkyl having at least one nitrogenatom and up to 3 heteroa carbamoyl-(C-C)-alkyl, (C-C)-alkenylcarbamoyl toms, preferably from the group of O and S, which is (C-C)-alkyl, (C-C)-alkoxy-(C-C)-alkyl, dioxola attached via the nitrogen atom to the carbonyl group nyl-(C-C)-alkyl, thiazolyl, furyl, furylalkyl, thienyl, in (S2) and which is unsubstituted or substituted by piperidyl, substituted or unsubstituted phenyl, or R radicals from the group of (C-C)-alkyl, (C-C)- alkoxy and optionally substituted phenyl, preferably a and R together form a substituted or unsubstituted radical of the formula OR, NHR' or N(CH), in heterocyclic ring, preferably an oxazolidine, thiazoli particular of the formula OR; dine, piperidine, morpholine, hexahydropyrimidine or (0297 R is hydrogen oran unsubstituted or substituted benzoxazine ring; aliphatic hydrocarbon radical, preferably having a total 0307 preferably: of 1 to 18 carbon atoms; 0308 active ingredients of the dichloroacetamide (0298) R' is hydrogen, (C-C)-alkyl, (C-C)-alkoxy type which are frequently used as pre-emergence or substituted or unsubstituted phenyl: safeners (Soil-acting safeners). Such as, for example, 0299 T is a (C- or C)-alkanediyl chain which is unsubstituted or substituted by one or two (C-C)-alkyl (0309 “dichlormid' (N,N-diallyl-2,2-dichloroaceta radicals or by (C-C)-alkoxycarbonyl: mide) (S3-1), (0300 preferably: 0310 “R-29148” (3-dichloroacetyl-2,2,5-trimethyl 0301 a) compounds of the 8-quinolinoxyacetic acid 1.3-oxazolidine) from Stauffer (S3-2), type (S2a), preferably 1-methylhexyl (5-chloro-8- 0311 “R-28725” (3-dichloroacetyl-2,2-dimethyl-1, quinolinoxy)acetate ("cloquintocet-mexyl (S2-1), 1.3- 3-oxazolidine) from Stauffer (S3-3), dimethyl-but-1-yl (5-chloro-8-quinolinoxy)acetate (S2 2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate 0312 “benoxacor (4-dichloroacetyl-3,4-dihydro-3- (S2-3), 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy) methyl-2H-1,4-benzoxazine) (S3-4), acetate (S2-4), ethyl (5-chloro-8-quinolinoxy)acetate 0313 “PPG-1292 (N-allyl-N-(1,3-dioxolan-2-yl) (S2-5), methyl (5-chloro-8-quinolinoxy)acetate (S2-6), methyldichloroacetamide) from PPG Industries (S3 allyl (5-chloro-8-quinolinoxy)acetate (S2-7), 2-(2-pro 5), pylideneiminoxy)-1-ethyl (5-chloro-8-quinolinoxy)ac etate (S2-8), 2-oxo-prop-1-yl (5-chloro-8-quinolinoxy) 0314 “DKA-24” (N-allyl-N-(allylaminocarbonyl) acetate (S2-9) and related compounds, as described in methyldichloroacetamide) from Sagro-Chem (S3 EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP 6), A-0 492 366, and also (5-chloro-8-quinolinoxy)acetic 0315 “AD-67” or “MON4660” (3-dichloroacetyl-1- acid (S2-10), its hydrates and salts, for example its oxa-3-azaspiro4.5 decane) from Nitrokemia or lithium, Sodium, potassium, calcium, magnesium, alu Monsanto (S3-7), minium, iron, ammonium, quaternary ammonium, Sul 0316 “TI-35” (1-dichloroacetylazepane) from TRI phonium or phosphonium salts, as described in WO-A- 2002/34048; Chemical RT (S3-8) 0302) b) compounds of the (5-chloro-8-quinolinoxy) 0317 “diclonon' (dicyclonon) or “BAS145138” or malonic acid type (S2), preferably compounds such as “LAB145138” (S3-9) (3-dichloroacetyl-2.5.5-trim diethyl (5-chloro-8-quinolinoxy)malonate, diallyl ethyl-1,3-diazabicyclo4.3.Ononane) from BASF, (5-chloro-8-quinolinoxy)malonate, methyl ethyl 0318 “furilazole' or “MON. 13900” ORS)-3-dichlo (5-chloro-8-quinolinoxy)malonate and related com roacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3 pounds, as described in EP-A-0 582 198. 10) and also its (R)-isomer (S3-11). US 2010/03 11593 A1 Dec. 9, 2010 24

0319 S4) N-Acylsulphonamides of the formula (S4) 0333 among these, preference is given to compounds and salts thereof of the N-acylsulphonamide type, for example of the formula (S4) below, which are known, for example, from WO-A-97745O16

(S4) 4 R o O Rp O sas (RD").np (S4a)

\ / N2 N S-N O XD O ( ) \( /)."

0334 in which 0335) R' is (C-C)-alkyl, (C-C)-cycloalkyl, where 0320 where the symbols and indices are each defined as the 2 last-mentioned radicals are substituted by V, Sub follows: stituents from the group of halogen, (C-C)-alkoxy, 0321 X, is CH or N: halo-(C-C)-alkoxy and (C-C)-alkylthio and, in the case of cyclic radicals, also (C-C)-alkyl and (C-C)- 0322 R is CO NR,R or NHCO-R7: haloalkyl: 0323 R is halogen, (C-C)-haloalkyl, (C-C)-ha 0336) R' is halogen, (C-C)-alkyl, (C-C)-alkoxy, loalkoxy, nitro, (C-C)-alkyl, (C-C)-alkoxy, (C-C)- CF, alkylsulphonyl, (C-C)-alkoxycarbonyl or (C-C)- 0337 m, is 1 or 2; alkylcarbonyl: 0338 V, is 0, 1, 2 or 3: I0324 R, is hydrogen, (C-C)-alkyl, (C-C)-alkenyl 0339 and also or (C-C)-alkynyl: 0340 acylsulphamoylbenzamides, for example of the 0325 R, is halogen, nitro, (C-C)-alkyl, (C-C)-ha formula (S4) below, which are known, for example, loalkyl, (C-C)-haloalkoxy, (C-C)-cycloalkyl, phe from WO-A-99/16744, nyl, (C-C)-alkoxy, cyano, (C-C)-alkylthio, (C-C)- alkyl-Sulphinyl, (C-C)-alkylsulphonyl, (C-C)- alkoxycarbonyl or (C-C)-alkylcarbonyl: (S4b) R 10326) R, is hydrogen, (C-C)-alkyl, (C-C)-cy O O R cloalkyl, (C-C)-alkenyl, (C-C)-alkynyl, (C-C)-cy N | y- D")mp cloalkenyl, phenyl or 3- to 6-membered heterocyclyl | o which contains V, heteroatoms from the group of nitro O O H gen, oxygen and Sulphur, where the last seven radicals are substituted by V, Substituents from the group of 0341 for example those in which halogen, (C-C)-alkoxy, (C-C)-haloalkoxy, (C-C)- 0342 R5-cyclopropyl and (R)-2-OMe ("cyprosul famide, S4-1), alkylsulphinyl, (C-C)-alkylsulphonyl, (C-C)-cy 0343 R-cyclopropyl and (R)-5-C-OMe (S4 cloalkyl, (C-C)-alkoxycarbonyl, (C-C)-alkylcarbo 2). nyl and phenyl and, in the case of cyclic radicals, also 0344) Rethyl and (R)-2-OMe (S4-3), (C-C)-alkyl and (C-C)-haloalkyl: (0345) R-isopropyl and (R)=5-C1-2-OMe (S4-4) 0327 R, is hydrogen, (C-C)-alkyl, (C-C)-alkenyl and or (C-C)-alkynyl, where the last three radicals are (0346) R-isopropyl and (R)-2-OMe (S4-5) Substituted by V, radicals from the group of halogen, and also hydroxy, (C-C)-alkyl, (C-C)-alkoxy and (C-C)- 0347 compounds of the N-acylsulphamoylphenylurea alkylthio, or type of the formula (S4c), which are known, for 0328 R, and R, together with the nitrogen atom example, from EP-A-365484, bearing them form a pyrrolidinyl or piperidinyl radical; 0329) R, is hydrogen, (C-C)-alkylamino, di-(C- (S4c) Cl)-alkylamino, (C-C)-alkyl, (C-C)-cycloalkyl, where the last 2 radicals are substituted by v, substitu R / y-(R'). ents from the group of halogen, (C-C)-alkoxy, halo N N S-N (C-C)-alkoxy and (C-C)-alkylthio and, in the case of RD/, H O H V / cyclic radicals, also (C-C)-alkyl and (C-C)-ha loalkyl; 0348 in which 0330 n is 0, 1 or 2: (0349 Rand Rare each independently hydrogen, 0331 m, is 1 or 2; (C-Cs)-alkyl, (C-Cs)-cycloalkyl, (C-C)-alkenyl, 0332 V, is 0, 1, 2 or 3: (C-C)-alkynyl, US 2010/03 11593 A1 Dec. 9, 2010 25

0350 R" is halogen, (C-C)-alkyl, (C-C)-alkoxy, 0371 S8) Compounds of the formula (S8), as described CF, in WO-A-98/27049, 0351 m, is 1 or 2; 0352 for example 0353 1-4-(N-2-methoxybenzoylsulphamoyl)phenyl-3- (S8) methylurea, R? O 0354 1-4-(N-2-methoxybenzoylsulphamoyl)phenyl-3, 3-dimethyl urea, 1-g N 0355 1-4-(N-4,5-dimethylbenzoylsulphamoyl)phenyl (R')FF - l - O F R. 3-methylurea. X. 0356 S5) Active ingredients from the class of the hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), for example 0372 in which 0357 ethyl 3,4,5-triacetoxybenzoate, 3,5- 0373 X is CH or N, dimethoxy-4-hydroxybenzoic acid, 3.5-dihydroxy 0374 n is, if X=N, an integer from 0 to 4 and benzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicy clic acid, 2-hydroxycinnamic acid, 1,2-dihydro-2- 0375 is, if X—CH, an integer from 0 to 5, oxo-6-trifluoromethylpyridine-3-carboxamide, 2,4- 0376) R' is halogen, (C-C)-alkyl, (C-C)-haloalkyl, dichlorocinnamic acid, as described in WO-A-2004/ (C-C)-alkoxy, (C-C)-haloalkoxy, nitro, (C-C)- 084631, WO-A-2005/015994, WO-A-2005/016001. alkylthio, (C-C)-alkylsulphonyl, (C-C)-alkoxycar 0358 S6) Active ingredients from the class of the 1,2- bonyl, optionally Substituted phenyl, optionally substi dihydroquinoxalin-2-ones (S6), for example tuted phenoxy, 0359 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxa 0377 R. is hydrogen or (C-C)-alkyl, lin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroqui 0378 R is hydrogen, (C-Cs)-alkyl, (C-C)-alkenyl, noxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1, (C-C)-alkynyl or aryl, where each of the carbon-con 2-dihydro-quinoxalin-2-one hydrochloride, 1-2- taining radicals mentioned above is unsubstituted or (diethylamino)ethyl-6,7-dimethyl-3-thiophen-2- substituted by one or more, preferably by up to three, ylquinoxalin-2(1H)-one, 1-(2- identical or different radicals from the group consisting methylsulphonylaminoethyl)-3-(2-thienyl)-1,2- of halogen and alkoxy; or salts thereof, dihydroquinoxalin-2-one, as described in WO-A- 2005/11263.O. preferably compounds in which 0360 S7) Compounds of the formula (S7), as described 0379 X is CH, in WO-A-1998/38856, 0380 n is an integer from 0 to 2, (0381) R' is halogen, (C-C)-alkyl, (C-C)-haloalkyl, (C-C)-alkoxy, (C-C)-haloalkoxy, (S7) A 0382 R is hydrogen or (C-C)-alkyl, Ho1 0383 R is hydrogen, (C-C)-alkyl, (C-C)-alkenyl, (C-C)-alkynyl or aryl, where each of the carbon-con spin taining radicals mentioned above is unsubstituted or C N H N substituted by one or more, preferably by up to three, (RE'), - (R) identical or different radicals from the group consisting 2 2 of halogen and alkoxy; or salts thereof, 0384 S9) Active ingredients from the class of the 3-(5- tetrazolylcarbonyl)-2-quinolones (S9), for example 0361 where the symbols and indices are each defined as 0385) 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetra follows: Zolylcarbonyl)-2-quinolone (CAS Reg. No.: 219479 0362) R, R are each independently halogen, (C- 18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetra Cl)-alkyl, (C-C)-alkoxy, (C-C)-haloalkyl, (C-C)- Zolylcarbonyl)-2-quinolone (CAS Reg. No.: 95855 alkylamino, di-(C-C)-alkylamino, nitro: 00-8), as described in WO-A-1999/000020. 0363 A is COOR or COSR. 0386 S10) Compounds of the formula (S10) or (S10") 0364) R. R. are each independently hydrogen, (C- (0387 as described in WO-A-2007/023719 and Cl)-alkyl, (C-C)-alkenyl, (C-C)-alkynyl, WO-A-2007/023764 cyanoalkyl, (C-C)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl or alkylammonium, 0365 n is 0 or 1 (S10a) 0366 ne, n are each independently 0, 1 or 2, 0367 preferably: 0368 diphenylmethoxyacetic acid, 0369 ethyl diphenylmethoxyacetate, 0370 methyl diphenylmethoxyacetate (CAS Reg. No.: 41858-19-9) (S7-1). US 2010/03 11593 A1 Dec. 9, 2010 26

(0408 “disulfoton” (O,O-diethyl S-2-ethylthioethyl -continued phosphorodithioate) (S13-7), (S10) 04.09 “dietholate” (O,O-diethyl O-phenyl phospho O Z-Ro. rothioate) (S13-8), “mephenate” (4-chlorophenyl methylcarbamate) (S13-9). 0410 S14) Active ingredients which, in addition to a (Ro') g : 1N O O herbicidal effect against harmful plants, also have a 21 -N-I-y-. Safener effect on crop plants such as rice. Such as, for M H example, O 0411) “dimepiperate” or “MY-93.” (S-1-methyl-1- phenylethyl piperidine-1-carbothioate), which is known as a safener for rice against molinate herbicide 0388 in which damage, (0389) R' is halogen, (C-C)-alkyl, methoxy, nitro, 0412 “daimuron” or “SK 23” (1-(1-methyl-1-phe cyano, CF. OCF nylethyl)-3-p-tolylurea), which is known as a safener 0390 Y, Z are each independently O or S, for rice against imaZoSulphuron herbicide damage, 0391 n is an integer from 0 to 4, 0413 “cumyluron'—“JC-940” (3-(2-chlorophenyl 0392 R is (C-C)-alkyl, (C-C)-alkenyl, (C-C)- methyl)-1-(1-methyl-1-phenylethyl)-urea, see JP-A- cycloalkyl, aryl; benzyl, halobenzyl, 60087254), which is known as a safener for rice 0393 R is hydrogen or (C-C)-alkyl. against Some herbicide damage, 0394 S11) Active ingredients of the oxyimino com 0414 “methoxyphenone' or “NK 049 (3,3'-dim pound type (S11), which are known as seed dressings, ethyl-4-methoxybenzophenone), which is known as a Such as, for example, safener for rice against Some herbicide damage, 0395 “oxabetrinil (Z)-1,3-dioxolan-2-ylmethoxy 0415 “CSB (1-bromo-4-(chloromethylsulphonyl) imino(phenyl)acetonitrile) (S11-1), which is known benzene) from Kumiai, (CAS Reg. No. 54091-06-4), as seed dressing Safener for millet against metolachlor which is known as a safener against Some herbicide damage, damage in rice. 0396 “fluxofenim (1-(4-chlorophenyl)-2.2.2-trif 0416. S15) Active ingredients which are primarily used luoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl) as herbicides, but also have safener effect on crop plants, Oxime) (S11-2), which is known as seed dressing for example safener for millet against metolachlor damage, and 0417 (2,4-dichlorophenoxy)acetic acid (2,4-D), 0397) “cyometrinil' or “CGA-43089” (Z)-cya nomethoxyimino(phenyl)acetonitrile) (S11-3), 0418 (4-chlorophenoxy)acetic acid, which is known as seed dressing safener for millet 0419 (R.S)-2-(4-chloro-o-tolyloxy)propionic acid against metolachlor damage. (mecoprop), 0398 S12) Active ingredients from the class of the 0420 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), isothiochromanones (S12). Such as, for example, methyl 0421 (4-chloro-o-tolyloxy)acetic acid (MCPA), (3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)meth 0422 4-(4-chloro-o-tolyloxy)butyric acid, oxyacetate (CAS Reg. No.: 205121-04-6) (S12-1) and 0423 4-(4-chlorophenoxy)butyric acid, related compounds from WO-A-1998/13361. 0424 3,6-dichloro-2-methoxybenzoic acid (dicamba), 0399) S13) One or more compounds from group (S13): 0425 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxy 04.00 “naphthalic anhydride' (1.8-naphthalenedi benzoate (lactidichlor-ethyl). carboxylic anhydride) (S13-1), which is known as 0426. The most preferred compounds components (b") seed dressing safener for corn against thiocarbamate which improve crop plant compatibility are cloquintocet herbicide damage, mexyl, fenchlorazol ethyl ester, isoxadifen-ethyl, mefenpyr 04.01 “fenclorim' (4,6-dichloro-2-phenylpyrimi diethyl, fenclorim, cumyluron, S4-1 and S4-5, particular dine) (S13-2), which is known as a safener for preti emphasis being given to mefenpyr-diethyl. Cyprosulfamide lachlor in Sown rice, (S4-1) is likewise emphasized. 0402 "flurazole' (benzyl 2-chloro-4-trifluorom 0427. It has now been found that, surprisingly, the above ethyl-1,3-thiazole-5-carboxylate) (S13-3), which is defined active ingredient combinations of compounds of the known as seed dressing safener for millet against general formula (I) and Safeners (antidotes) from group (b') alachlor and metolachlor damage, listed above, coupled with very good useful plant compatibil 0403 “CL-304415” (CAS Reg. No.: 31541-57-8) ity, have a particularly high herbicidal efficacy and can be 0404 (4-carboxy-3,4-dihydro-2H-1-benzopyran-4- used in different crops, especially in cereals (in particular acetic acid) (S13-4) from American Cyanamid, which wheat), but also in soya, potatoes, maize and rice, for selective is known as a safener for corn against imidazolinone weed control. damage, 0428. In this context, it is considered to be surprising that, 04.05 “MG-191” (CAS Reg. No.: 96420-72-3) from a multitude of known safeners or antidotes which are (2-dichloromethyl-2-methyl-1,3-dioxolane) (513-5) capable of antagonizing the damaging effect of a herbicide on from Nitrokemia, which is known as a safener for the crop plants, specifically the compounds of group (b") COrn, listed above are suitable for virtually completely eliminating 0406 “MG-838” (CAS Reg. No.: 133993-74-5) the damaging effect of compounds of the formula (I) on the 0407 (2-propenyl 1-oxa-4-azaspiro4.5 decane-4- crop plants, without significantly impairing the herbicidal carbodithioate) (S13-6) from Nitrokemia, efficacy toward the weeds. US 2010/03 11593 A1 Dec. 9, 2010 27

0429 Emphasis is given here to the particularly advanta geous effect of the particularly preferred and most preferred -continued combination partners from group (b"), especially with regard (5) to protection of cereal plants, for example wheat, barley and rye, but also maize and rice, as crop plants. 0430. The inventive compounds are defined in general terms by the formula (I). Preferred substituents and ranges of the radicals shown in the formulae mentioned above and hereinafter are detailed as follows: 0431) W is preferably hydrogen, C-C-alkyl, halogen, C-C-alkoxy, C-C-haloalkyl or C-C-haloalkoxy, (6) 0432 X is preferably halogen, C-C-alkyl, C-C-alk enyl, C-C-alkynyl, C-C-alkoxy, alkyl, C-C-ha loalkoxy or cyano, 0433 Y is preferably hydrogen, halogen, C-C-alkyl or C-C-alkoxy, 0434 Z is preferably a group

(7)

0435 in which J and J’ are preferably each indepen dently hydrogen, fluorine or chlorine, and J is prefer ably halogen or C-Ca-haloalkyl, 0436 CKE is preferably one of the groups (8)

(1) o-G A - Y - -N (9)

(2)

(10)

(3)

(11)

(4) US 2010/03 11593 A1 Dec. 9, 2010 28

0437 U is preferably —S —S(O)— —S(O) , loalkyl-substituted C-Cs-cycloalkyl, in which one ring —O—, member is optionally replaced by oxygen or Sulphur, or in each case optionally halogen-, C-C-alkyl-, C-C- haloalkyl-, C-C-haloalkoxy-, cyano- or nitro-substi O R13 tuted phenyl, hetaryl having 5 or 6 ring atoms (for N-C, \/ -=N-R1, MT-D 13 RNT-N-N A S=N-R1,- MT-D 13 example furanyl, imidazolyl pyridyl, thiazolyl pyra R14a Zolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl), phenyl Q C-C-alkyl or hetaryl-C-C-alkyl having 5 or 6 ring atoms (for example furanyl, imidazolyl pyridyl, thiaz S(O)=N-R13 or cis-- olyl pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl), O Q 0445 A and D together are preferably in each case optionally Substituted C-C-alkanediyl or C-C-alk -(CH)-O-C- enediyl, in which one methylene group is optionally replaced by a carbonyl group, oxygen or Sulphur, and 0446 where possible Substituents in each case are: 0438 in which n is preferably the number 0, 1 or 2, 0447 halogen, hydroxyl, mercapto or in each case 0439 A is preferably hydrogen or in each case option optionally halogen-substituted C-Co-alkyl, C-C- ally halogen-substituted C-C2-alkyl, C-Cs-alkenyl, alkoxy, C-C-alkylthio, C-C7-cycloalkyl, phenyl or C-Co-alkoxy-C-C-alkyl, C-Co-alkylthio-C-C- benzyloxy, or a further C-C-alkanediyl moiety, alkyl, optionally halogen-, C-C-alkyl- or C-C- C-C-alkenediyl moiety or a butadienyl moiety, alkoxy-Substituted C-Cs-cycloalkyl in which one or which is optionally substituted by C-C-alkyl or in two ring members not directly adjacent are optionally which two adjacent substituents with the carbon replaced by oxygen and/or Sulphur, or is in each case optionally halogen-C-C-alkyl-, C-C-haloalkyl-, atoms to which they are bonded optionally form a C-C-alkoxy, C-C-haloalkoxy, cyano- or nitro-Sub further saturated or unsaturated cycle having 5 or 6 stituted phenyl, naphthyl, hetaryl having 5 to 6 ring ring atoms (in the case of the compound (I-1), A and atoms (for example furanyl, pyridyl, imidazolyl, triaz D together with the atoms to which they are bonded olyl pyrazolyl pyrimidyl, thiazolyl or thienyl), phenyl are then, for example, the AD-1 to AD-10 groups C-C-alkyl or naphthyl-C-C-alkyl, further down), which may contain oxygen or Sulphur, 0440 B is preferably hydrogen, C-C2-alkyl or C-C- or in which one of the following groups alkoxy-C-C-alkyl or 0441 A, B and the carbon atom to which they are 13 bonded are preferably saturated C-Co-cycloalkyl or \ ,R N OR unsaturated Cs-Co-cycloalkyl, in which one ring mem C; =N-R13; FN-N \ ber is optionally replaced by nitrogen, oxygen or Sulphur / Y4. / OR 16a and which is optionally mono- or disubstituted by C-C-alkyl, C-C-alkoxy, C-C-alkenyloxy, C-C- Sa alkoxy-C-C-alkyl, C-C-cycloalkyl-C-C-alkoxy, SR O la S Fa C-Co-cycloalkyl, C-C-haloalkoxy, C-C-alkoxy ^ R R C-C-alkoxy, where the aforementioned radicals are / YsRica. X. X. also possible nitrogen Substituents, or s O s S s 0442 A, B and the carbon atom to which they are bonded are preferably C-C-cycloalkyl which is sub stituted by an optionally C-C-alkyl-substituted alky O lenediyl group optionally containing one or two oxygen and/or Sulphur atoms which are not directly adjacent, or O us by an alkylenedioxyl or by an alkylenedithioyl group, ls O R19a which group forms a further five- to eight-membered O R19 or ring with the carbon atom to which it is bonded, or 0443 A, B and the carbon atom to which they are s" bonded are preferably C-Cs-cycloalkyl or Cs-Cs-cy O cloalkenyl, in which two substituents together with the carbon atoms to which they are bonded are in each case optionally C-C-alkyl-C-C-alkoxy- or halogen-sub 0448) is optionally present, or stituted C-C-alkanediyl, C-C-alkenediyl or C-C- 0449) A and Q' together with the carbonatoms to which alkadienediyl in which one methylene group is option they are bonded are in each case preferably C-C-al ally replaced by oxygen or Sulphur, kanediyl or C-C-alkenediyl each optionally mono- or 0444 D is preferably hydrogen, in each case optionally disubstituted identically or differently by halogen, halogen-substituted C-C2-alkyl, C-Cs-alkenyl, hydroxyl, by C-Co-alkyl, C-C-alkenyl, C-C- C-Cs-alkynyl, C-Co-alkoxy-C-C-alkyl, optionally alkoxy, C-C-alkylthio, C-C7-cycloalkyl each option halogen-, C-C-alkyl-, C-C-alkoxy- or C-Ca-ha ally mono- to trisubstituted identically or differently by US 2010/03 11593 A1 Dec. 9, 2010 29

halogen, or by benzyloxy or phenyl each optionally haloalkyl-substituted C-C, ring in which one or two mono- to trisubstituted identically or differently by halo ring members are optionally replaced by oxygen or Sul gen, C-C-alkyl or C-C-alkoxy, and which also phur, optionally contains one of the following groups: 0459 A and Q together with the carbonatoms to which they are bonded are preferably a saturated or unsatur ated, optionally C-C-alkyl-, C-C-alkoxy- or C-C- O R13 15 haloalkyl-substituted C-C, ring in which one ring N \ 13 M N /ORIsa member is optionally replaced by oxygen or Sulphur, -C: =N-R1'; )-N-N : \ s / Y4. / OR 16a 0460 G is preferably hydrogen (a) or one of the groups Sa N/ S R17a O R17a (b)

/ YsRica. S R18a; O R18a; O O ul (c) us O R19a O R19 or s" (d) (e) 0450 or is bridged by a C-C-alkanediyl group or by One OXygen atom, or 0451 B and Q together are preferably optionally (f) C-C2-alkyl-substituted C-C-alkanediyl which may optionally be interrupted by oxygen, or (g) 10452 D and Q' together are preferably C-C-al kanediyl optionally mono- or disubstituted identically or differently by C-C-alkyl, C-C-alkoxy, or 10453 Q' is preferably hydrogen, C-C-alkyl, C-C- alkoxy-C-C-alkyl, optionally fluorine-, chlorine-, especially (a), (b), (c) or (g) C-C-alkyl-C-C-haloalkyl- or C-C-alkoxy-Substi 0461 in which tuted C-Cs-cycloalkyl in which one methylene group is 0462 E is one metal ion equivalent or one ammo optionally replaced by oxygen or Sulphur, or optionally nium ion, halogen-, C-C-alkyl-, C-C-haloalkyl-, C-C-ha 0463 L is oxygen or sulphur and loalkoxy-, cyano- or nitro-substituted phenyl, 0464 M is oxygen or sulphur, 0454) Q, Q, Q and Q are preferably each indepen 0465) R' is preferably in each case optionally halogen dently hydrogen or C-C-alkyl, Substituted C-Co-alkyl, C-Co-alkenyl, C-C- 10455 Q is preferably hydrogen, C-C-alkyl, C-C- alkoxy-C-C-alkyl, poly-C-C-alkoxy-C-C-alkyl or alkoxy, C-C-alkoxy-C-C-Q-alkyl, C-C-alkylthio optionally halogen-C-C-alkyl- or C-C-alkoxy-Sub C-C2-alkyl, optionally C-C-alkyl- or C-C-alkoxy stituted C-Cs-cycloalkyl in which one or more (prefer Substituted C-C-cycloalkyl in which one or two ably not more than two) ring members not directly adja methylene groups are optionally replaced by oxygen or cent are optionally replaced by oxygen and/or Sulphur, Sulphur, or optionally halogen-, C-C-alkyl-, C-C- 0466 is optionally halogen-, cyano-, nitro-, C-C- alkoxy-, C-C-haloalkyl-, C-C-haloalkoxy-, cyano alkyl-, C-C-alkoxy-, C-C-haloalkoxy-, C-C- or nitro-substituted phenyl, or alkylthio- or C-C-alkylsulphonyl-substituted phe 10456) Q' and Q with the carbonatom to which they are nyl, bonded are preferably optionally a C-C-alkyl-C-C- 0467 is optionally halogen-, nitro-, cyano-, C-C- alkoxy- or C-C-haloalkyl-substituted C-C, ring in alkoxy-, C-C-haloalkyl- or C-C-haloalkoxy-Sub which one ring member is optionally replaced by oxy stituted phenyl-C-C-alkyl, gen or Sulphur, 0468) is optionally halogen- or C-C-alkyl-substi 10457 Qand Q together with the carbonatom to which tuted 5- or 6-membered hetaryl (for example pyra they are bonded are preferably an optionally C-C- Zolyl, thiazolyl pyridyl, pyrimidyl, furanyl or thie alkyl-, C-C-alkoxy- or C-C-haloalkyl-substituted, nyl), Saturated or unsaturated C-C, ring in which one or two 0469 is optionally halogen- or C-C-alkyl-substi ring members are optionally replaced by oxygen or Sul tuted phenoxy-C-C-alkyl, or phur, 0470 is optionally halogen-, amino- or C-C-alkyl 10458) A and Q together with the carbonatoms to which substituted 5- or 6-membered hetaryloxy-C-C- they are bonded are preferably a saturated or unsatur alkyl (for example pyridyloxy-C-C-alkyl, pyrim ated, optionally C-C-alkyl-, C-C-alkoxy- or C-C- idyloxy-C-C-alkyl or thiazolyloxy-C-C-alkyl). US 2010/03 11593 A1 Dec. 9, 2010 30

0471) R' is in each case optionally halogen-substituted 0484) R' and R'' are preferably each independently C1-Co-alkyl, C-Co-alkenyl, C-Cs-alkoxy-C-Cs C-Co-alkyl, C-Co-alkenyl, C-Co-alkoxy, C-Co alkyl, poly-C-C-alkoxy-C-C-alkyl, alkylamino, C-Co-alkenylamino, di-(C1-Co-alkyl) 0472) is optionally halogen-C-C-alkyl- or C-C- amino or di-(C-Co-alkenyl)amino. alkoxy-Substituted C-Cs-cycloalkyl or 0473 is in each case optionally halogen-, cyano-, 0485. In the radical definitions cited as preferred, halogen nitro-, C-C-alkyl-, C-C-alkoxy-, C-C-ha is fluorine, chlorine, bromine and iodine, especially fluorine, loalkyl- or C-C-haloalkoxy-Substituted phenyl or chlorine and bromine. benzyl, 0486 W is more preferably hydrogen, fluorine, chlorine, 0474 R is preferably optionally halogen-substituted bromine, C-C-alkyl, C-C-alkoxy, C-C-haloalkyl or C-Cs-alkyl or in each case optionally halogen-, C-C- C-C-haloalkoxy, alkyl-, C-Ca-haloalkyl-, C-C-haloalkoxy-, cyano- or 0487 X is more preferably chlorine, bromine, iodine, nitro-substituted phenyl or benzyl, 0475 R and Rare preferably each independently in C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C- each case optionally halogen-substituted C-C-alkyl, alkoxy, C-C-haloalkyl, C-C-haloalkoxy or cyano, C-Cs-alkoxy, C-Cs-alkylamino, di-(C-Cs-alkyl) 0488 Y is more preferably hydrogen, methyl, ethyl, fluo amino, C-C-alkenylthio. C-C7-cycloalkylthio or in rine, chlorine, bromine, iodine, methoxy or ethoxy, each case optionally halogen-, nitro-, cyano-, C-C- 0489 Z is more preferably the group alkoxy-, C-Ca-haloalkoxy-, C-C-alkylthio-, C-C- alkyl- or C-Ca-haloalkyl-substituted phenyl, phenoxy or phenylthio. 0476 R and R7 are preferably each independently hydrogen, in each case optionally halogen-substituted C-Cs-cycloalkyl, C-C-alkoxy, C-Cs-alkenyl, optionally halogen-, C-C-haloalkyl-, C-C-alkyl- or C-Cs-alkoxy-Substituted phenyl, optionally halogen C-C-alkyl-C-C-haloalkyl- or C-C-alkoxy-substi in which J and J are more preferably each independently tuted benzyl, or together are an optionally C-C-alkyl hydrogen, fluorine or chlorine, and J is fluorine, chlorine, Substituted C-C-alkylene radical in which one carbon trichloromethyl, difluoromethyl, difluorochloromethyl, atom is optionally replaced by oxygen or Sulphur, dichlorofluoromethyl or trifluoromethyl, 0477) R' is preferably hydrogen, in each case option ally halogen-substituted C-Cs-alkyl or C-Cs-alkoxy 0490 CKE is more preferably one of the groups (only in the case of the C=N R' group), optionally halogen-, C-C-alkyl- or C-C-alkoxy-Substituted (1) C-C-cycloalkyl in which one methylene group is G optionally replaced by oxygen or Sulphur, or is in each o1 case optionally halogen-, C-C-alkyl-, C-C-alkoxy-, A C-Ca-haloalkyl-, C-Ca-haloalkoxy-, nitro- or cyano Substituted phenyl, phenyl-C-C-alkyl, hetaryl-C-C- - \ . alkyl, or, only in the case of the C=N R' group, D1 N phenyl-C-C-alkoxy or hetaryl-C-C-alkoxy, O 0478 R'' is preferably hydrogen or C-C-alkyl or G (2) 0479) R' and R'' together are preferably optionally o1 C-C-alkyl-substituted C-C-alkanediyl which may A optionally be interrupted by oxygen or Sulphur, 0480 R'' and R'' are the same or different and are - \ . preferably each C-C-alkyl or O 0481) R'' and R' together are preferably a C-C- O alkanediyl radical or a C-alkanediyl radical which is optionally substituted by C-C-alkyl, C-C-haloalkyl G (3) or by optionally halogen-, C-C-alkyl-, C-C-ha o1 loalkyl-, C-C-alkoxy-, C-Ca-haloalkoxy-, nitro- or A cyano-Substituted phenyl, - \ . 0482 R'7" and R'' are preferably each independently S hydrogen, optionally halogen-substituted C-Cs-alkyl or optionally halogen-, C-C-alkyl-, C-C-alkoxy-, O C-Ca-haloalkyl-, C-Ca-haloalkoxy-, nitro- or cyano (4) substituted phenyl or 0483 R'7" and R'' together with the carbon atom to which they are bonded are preferably a carbonyl group or optionally halogen-, C-C-alkyl- or C-C-alkoxy substituted Cs-C7-cycloalkyl in which one methylene group is optionally replaced by oxygen or Sulphur, US 2010/03 11593 A1 Dec. 9, 2010

0492 A is more preferably hydrogen, in each case option -continued ally mono- to tri-fluorine- or -chlorine-substituted C-C- (5) alkyl, C-C-alkoxy-C-C-alkyl, optionally mono- to di-C-C-alkyl- or —C-C2-alkoxy-Substituted C-C-cy cloalkyl optionally interrupted by one oxygenatom or (but not in the case of the compounds of the formulae (I-3), (I-4), (I-6), (I-7), (I-9). (I-10) and (I-11)) in each case optionally mono- to di-fluorine-, -chlorine-, -bromine-, (6) —C-C-alkyl-, -C-C-haloalkyl-, -C-C-alkoxy-, —C-C-haloalkoxy-, -cyano- or -nitro-substituted phe nyl, pyridyl or benzyl, 0493 B is more preferably hydrogen, C-C-alkyl or C-C2-alkoxy-C-C-alkyl or 0494 A, B and the carbon atom to which they are bonded are more preferably saturated or unsaturated C-C7-cy (7) cloalkyl in which one ring member is optionally replaced by nitrogen, oxygen or Sulphur and which is optionally mono- to di-C-C-alkyl-, -C-C-alkoxy-C-C-alkyl-, -trifluoromethyl-, -C-C-alkoxy-, -C-C-alkeny loxy-, -trifluoroethoxy-, -C-C-alkoxy-C-C-alkoxy or —C-C-cycloalkylmethoxy-Substituted, where the aforementioned radicals are also possible nitrogen Sub (8) stituents, with the proviso that Q in that case is more preferably hydrogen or methyl, or 0495 A, B and the carbon atom to which they are bonded are more preferably Cs-C-cycloalkyl which is substituted by an optionally methyl- or ethyl-substituted alkylenediyl group optionally containing one or two oxygen or Sulphur (9) atoms not directly adjacent or by an alkylenedioxy group or by an alkylenedithiol group, which group forms, with the carbon atom to which it is bonded, a further five- or six membered ring, with the proviso that Q in that case is more preferably hydrogen or methyl, or 0496 A, B and the carbon atom to which they are bonded are more preferably C-C-cycloalkyl or Cs-C-cycloalk (10) enyl in which two substituents together with the carbon atoms to which they are bonded are in each case optionally C-C2-alkyl- or C-C2-alkoxy-Substituted C-C-al kanediyl, C-C-alkenediyl or butadienediyl, with the pro viso that Q in that case is more preferably hydrogen or methyl, 0497 D is more preferably hydrogen, in each case option (11) ally mono- to tri-fluorine-substituted C-C-alkyl, C-C- alkenyl, C-C-alkoxy-C-C-alkyl, in each case option ally mono- to di-C-C-alkyl-, -C-C-alkoxy- or —C- C-haloalkyl-substituted C-C-cycloalkyl in which one methylene group is optionally replaced by oxygen or (only in the case of the compounds of the formula (I-4)) is in each case optionally mono- to di-fluorine-, -chlorine-, -bro mine-, -C-C-alkyl-, -C-C-haloalkyl-, -C-C- 0491 U is more preferably —CH2—, —CH2—CH2—, alkoxy- or —C-Ca-haloalkoxy-Substituted phenyl or —O— or pyridyl, or 0498 A and D together are more preferably optionally mono- to disubstituted C-C-alkanediyl in which one methylene group may be replaced by a carbonyl group (but not in the case of the compounds of the formula (I-11)), oxygen or Sulphur, where possible Substituents are C-C- alkyl or C-C-alkoxy, or US 2010/03 11593 A1 Dec. 9, 2010 32

0499 A and D (in the case of the compounds of the for mono- to tetra-C-C-alkyl- or —C-C-alkoxy-C-C- mula (I-1)) together with the atoms to which they are alkyl-substituted alkylenedioxy group containing two oxy bonded are one of the groups AD-1 to AD-10: gen atoms not directly adjacent, to form a further 5- or AD-1 6-membered ring, or (0502. A and Q' together are more preferably C-C-al kanediyl which is optionally mono- or disubstituted iden tically or differently by C-C-alkyl or C-C-alkoxy, and N W which optionally contains the following group:

AD-2 D<.OR 15a

0503 in which AD-3 0504) R'' and R'' are more preferably the same or dif ferent and are each methyl or ethyl, or 0505 RandR'' together are more preferably a C-C- alkanediyl or C-alkenediyl radical which is optionally N substituted by methyl or ethyl, or AD-4 (0506) B and Q’ together are more preferably —CH2—, CH-CH , —CH2—CH2—CH2—, or —CH O—CH2—, or N N (0507 D and Q' together are more preferably C-C-al AD-5 kanediyl, or 0508 Q' is more preferably hydrogen, C-C-alkyl, C-C-alkoxy-C-C-alkyl, or optionally methyl- or meth oxy-Substituted C-C-cycloalkyl in which one methylene N group is optionally replaced by oxygen, 0509 Q is more preferably hydrogen, methyl or ethyl, AD-6 10510 Q, Q and Q are more preferably each indepen dently hydrogen or C-C-alkyl, 0511 Q is more preferably hydrogen, C-C-alkyl, N C-C-alkoxy, or optionally mono- to di-methyl- or meth oxy-Substituted C-C-cycloalkyl optionally interrupted AD-7 by one oxygen atom, or 0512 Q' and Q with the carbon to which they are bonded are more preferably optionally methyl- or methoxy-substi N N tuted C-C-cycloalkyl in which one methylene group is optionally replaced by oxygen, with the proviso that A and B in that case are more preferably each independently AD-8 hydrogen or methyl, or 0513 Q and Q together with the carbon to which they are bonded are more preferably an optionally C-C-alkyl- or C N N C-C2-alkoxy-Substituted Saturated C-C ring in which one or two ring members are optionally replaced by oxygen or Sulphur, with the proviso that A in that case is more AD-9 preferably hydrogen or methyl, or (0514) A and Q together with the carbon to which they are bonded are more preferably an optionally C-C2-alkyl- or C-C2-alkoxy-Substituted Saturated C-C ring in which one ring member is optionally replaced by oxygen or Sul AD-10 phur, with the proviso that B, Q, Q and Qin that case are more preferably each independently hydrogen or methyl, O (0515 A and Q together with the carbon atoms to which they are bonded are more preferably an optionally C-C- alkyl- or C-C2-alkoxy-Substituted Saturated or unsatur (0500 or ated Cs-Caring, with the proviso that B, Q, Q and Q in 0501) A and D together are more preferably C-C-al that case are more preferably each independently hydrogen kanediyl which is optionally substituted by an optionally or methyl, US 2010/03 11593 A1 Dec. 9, 2010

0516 G is more preferably hydrogen (a) or one of the —C-C-alkylthio-, -C-C-haloalkylthio-, -C-C- groups alkyl- or -trifluoromethyl-substituted phenyl, phenoxy or phenylthio. (b) 0528 R is more preferably C-C-alkoxy or C-C-alky lthio, (0529) R' is more preferably hydrogen, C-C-alkyl, C-C-cycloalkyl, C-C-alkoxy, C-C-alkenyl, C-C- (c) alkoxy-C-C-alkyl, optionally mono-fluorine-, -chlo rine-, -bromine-, -trifluoromethyl-, -C-C-alkyl- or —C-C-alkoxy-Substituted phenyl, optionally mono fluorine-, -chlorine-, -bromine-, -C-C-alkyl-, -trifluo (d) romethyl- or —C-C-alkoxy-substituted benzyl, 0530 R7 is more preferably C-C-alkyl, C-C-alkenyl or (e) C-C-alkoxy-C-C-alkyl, 0531) R' and R7 together are more preferably an option ally methyl- or ethyl-substituted Cas-alkylene radical in which one methylene group is optionally replaced by oxy (f) gen or Sulphur. (g) 0532. In the radical definitions cited as particularly pre ferred, halogen is fluorine, chlorine and bromine, especially fluorine and chlorine. 0533 W is even more preferably hydrogen, chlorine, methyl or ethyl, (g), especially (a), (b) or (c), 0534 X is even more preferably chlorine, methyl, ethyl, 0517 in which methoxy or ethoxy, 0518 E is one metal ion equivalent or one ammonium 0535 Y is even more preferably hydrogen, methyl orchlo ion, rine, 0519 L is oxygen or sulphur and 0536 Z is even more preferably the group 0520 M is oxygen or sulphur, 0521) R' is more preferably in each case optionally mono to tri-fluorine- or -chlorine-substituted C-C-alkyl, C-C-alkenyl, C-C-alkoxy-C-C-alkyl, C-C-alky J2 lthio-C-C-alkyl or optionally mono- to di-fluorine-, -chlorine-, -C-C-alkyl- or —C-C2-alkoxy-Substituted JI -- C-C-cycloalkyl in which one or two ring members not 3 directly adjacent are optionally replaced by oxygen, 0522 is optionally mono- to di-fluorine-, -chlorine in which J and J are even more preferably each indepen -bromine-, -cyano-, -nitro-, -C-C-alkyl-, -C-C- dently hydrogen or fluorine and J is fluorine, chlorine or alkoxy-, -C-C-haloalkyl- or —C-C-haloalkoxy trifluoromethyl, substituted phenyl, 0523 R is more preferably in each case optionally mono 0537 CKE is even more preferably one of the groups to tri-fluorine-substituted C-Cs-alkyl, C-Cs-alkenyl or C-C-alkoxy-C-C-alkyl, 0524 is optionally mono-C-C-alkyl- or —C-C- G (1) alkoxy-Substituted C-C-cycloalkyl or o1 0525) is in each case optionally mono- to di-fluorine A -chlorine-, -bromine-, -cyano-, -nitro-, -C-C-alkyl-, —C-C-alkoxy-, -trifluoromethyl- or -trifluo - \ . romethoxy-substituted phenyl or benzyl, D1 N 0526 R is more preferably optionally mono- to tri-fluo O rine-substituted C-C-alkyl or optionally mono-fluorine-, -chlorine-, -bromine-, -C-C-alkyl-, -C-C-alkoxy-, G (2) -trifluoromethyl-, -trifluoromethoxy-, -cyano- or -nitro o1 substituted phenyl, A 0527 R is more preferably C-C-alkyl, C-C-alkoxy, - \ . C-C-alkylamino, di-(C-C-alkyl)amino, C-C-alky O lthio, C-C-alkenylthio, C-C-cycloalkylthio, or in each case optionally mono-fluorine-, -chlorine-, -bromine-, -ni O tro-, -cyano-, -C-C-alkoxy-, -C-C-haloalkoxy-, US 2010/03 11593 A1 Dec. 9, 2010 34

-continued -continued

(3) (11) 1. A - \ . S

O (4) 0538 U is even more preferably —CH2—, —CH2— CH , —O— or

(5)

0539 A is even more preferably hydrogen, in each case optionally mono- to tri-fluorine-substituted C-C-alkyl or C-C2-alkoxy-C-C-alkyl, or is cyclopropyl, cyclopentyl or cyclohexyl, and in the case of the compounds of the (6) formula (I-5) is optionally mono- to di-fluorine-, -chlo rine-, -bromine-, -methyl-, -ethyl-, -n-propyl-, -isopropyl-, -methoxy-, -ethoxy-, -trifluoromethyl-, -trifluo romethoxy-, -cyano- or -nitro-substituted phenyl, 0540 B is even more preferably hydrogen, methyl or ethyl, or 0541 A, B and the carbon atom to which they are bonded (7) are even more preferably saturated C-C-cycloalkyl in which one ring member is optionally replaced by nitrogen, oxygen or Sulphur and which is optionally mono- or di methyl-, -ethyl-, -methoxymethyl-, -ethoxymethyl-, -methoxyethyl-, -ethoxyethyl-, -trifluoromethyl-, -meth oxy-, -ethoxy-, -propoxy-, -butoxy-, -methoxyethoxy-, -ethoxyethoxy-, -allyloxy-, -trifluoroethoxy- or-cyclopro pylmethoxy-substituted, where the aforementioned radi (8) cals are also possible nitrogen Substitutents, with the pro viso that Q in that case is even more preferably hydrogen, O 0542 A, B and the carbon atom to which they are bonded are even more preferably C-cycloalkyl which is optionally Substituted by an alkylidenediyl group optionally inter rupted by one oxygen atom or by an alkylenedioxy group (9) optionally containing two oxygen atoms not directly adja cent, to form a further 5- or 6-membered ring (which may be mono- or di-methyl-substituted), with the proviso that Q in that case is even more preferably hydrogen, or 0543 A, B and the carbon atom to which they are bonded are even more preferably Cs-C-cycloalkyl or Cs-C-cy cloalkenyl, in which two substituents together with the carbon atoms to which they are bonded are C-C-al (10) kanediyl or C-C-alkenediyl or butadienediyl, with the proviso that Q in that case is even more preferably hydro gen, 0544 D is even more preferably hydrogen, in each case optionally mono- to tri-fluorine-substituted C-C-alkyl, C-C-alkenyl, C-C-alkoxy-C-C-alkyl, or is cyclopro pyl, cyclopentyl or cyclohexyl, or (in the case of the com pounds of the formula (I-4)) is in each case optionally US 2010/03 11593 A1 Dec. 9, 2010

mono-fluorine-, -chlorine-, -methyl-, -ethyl-, -n-propyl-, -isopropyl-, -methoxy-, -ethoxy- or -trifluoromethyl-Sub -continued stituted phenyl or pyridyl, (c) O 0545 A and D together are even more preferably option R2, ally mono-methyl- or -methoxy-substituted C-C-al --- kanediyl in which one carbon atom is optionally replaced by a carbonyl group (but not in the case of the compound of —SO, R (d) or E (f), the formula (I-11)), oxygen or sulphur, or is the AD-1 group, or 0558 in which 0546 A and D together are even more preferably C-Cs 0559 L is oxygen or sulphur, alkanediyl which is optionally substituted by an optionally 056.0 M is oxygen or sulphur and mono- to di-C-C-alkyl-substituted alkylenedioxy group 0561 E is one metal ion equivalent or one ammonium containing two oxygenatoms not directly adjacent, to form 1On, a further 5-membered ring, or 0562) R' is even more preferably in each case optionally mono-chlorine-substituted C-C-alkyl, C-C-alkenyl, (0547 A and Q' together are even more preferably option C-C-alkoxy-C-alkyl, C-C-alkylthio-C-alkyl, or in ally mono- or di-methyl- or -methoxy-Substituted C-C- each case optionally mono-fluorine-, -chlorine-, -methyl alkanediyl which optionally contains the following group: or -methoxy-Substituted cyclopropyl or cyclohexyl, optionally mono-fluorine-, -chlorine-, -bromine-, -cyano-, -nitro-, -methyl-, -methoxy-, -trifluoromethyl- or -trifluo OR 15a romethoxy-Substituted phenyl, ><. 10563 R’ is even more preferably in each case optionally mono-fluorine-substituted C-Cs-alkyl, C-C-alkenyl or (0548 in which R'' and R' together are even more C-C-alkoxy-C-C-alkyl, phenyl or benzyl, preferably a C-C-alkanediyl or C-alkenediyl radical, 10564) R is even more preferably C-Cs-alkyl, O 0565 W is especially preferably hydrogen, methyl or (0549 B and Q together are even more preferably ethyl, CH2—CH2—CH2—, or —CH2—O—CH2—, or 0566 X is especially preferably chlorine, methyl or ethyl, 0550 D and Q' together are even more preferably C-C- 0567 Y is especially preferably hydrogen, alkanediyl, or 0568 Z is especially preferably OCH CF in the 3 posi 0551 Q' is even more preferably hydrogen, methyl, ethyl, tion, propyl, isopropyl, cyclopropyl, cyclopentyl or cyclohexyl, 0569 Z is especially preferably also OCH CF in the 4 0552. Q is even more preferably hydrogen, methyl or position, ethyl, (0570 Z is especially preferably likewise OCH CF in 0553 Q, Q and Q are even more preferably each inde the 5 position, pendently hydrogen or methyl, 0571 CKE is especially preferably one of the groups 0554. Q is even more preferably hydrogen, methyl, ethyl, propyl, methoxy or ethoxy, or optionally mono-methyl- or -methoxy-Substituted C-C-cycloalkyl optionally inter (1) rupted by one oxygen atom, or o-G 0555 Q' and Q with the carbon atom to which they are A bonded are even more preferably optionally methyl- or - \ . methoxy-substituted C-C-cycloalkyl in which one meth N ylene group is optionally replaced by oxygen, with the D1 proviso that A and B are each hydrogen, or O 0556 Qand Q together with the carbon to which they are (2) bonded are even more preferably an optionally mono-me O-G thyl- or-methoxy-substituted, saturated C-C ring option A ally interrupted by one oxygen atom, with the proviso that - \ . A, B, Q and Q in that case are even more preferably O hydrogen, 0557 G is even more preferably hydrogen (a) or one of the O groups (6)

(b) 1s, US 2010/03 11593 A1 Dec. 9, 2010 36

0588 Preference is given in accordance with the invention -continued to the compounds of the formula (I) in which there is a (8) combination of the definitions listed above as preferred (pref erably). 0589 Particular preference is given in accordance with the invention to the compounds of the formula (I) in which there is a combination of the definitions listed above as particularly preferred. 0590 Very particular preference is given in accordance 0572 A is especially preferably methyl or ethyl, with the invention to the compounds of the formula (I) in 0573 B is especially preferably hydrogen or methyl, which there is a combination of the definitions listed above as 0574 A, B and the carbon atom to which they are bonded even more preferred. are especially preferably Saturated C-C-cycloalkyl in 0591 Special preference is given in accordance with the which one ring member is optionally replaced by oxygen invention to the compounds of the formula (I) in which there and which is optionally mono- or di-methyl-, -ethyl-, -methoxymethyl-, -methoxy-, -ethoxy-, -propoxy-, -bu is a combination of the definitions listed above as especially toxy-, -trifluoroethoxy-substituted, or preferred. 0575 A, B and the carbon atom to which they are bonded 0592 Emphasis is given to compounds of the formula (I) are especially preferably C-cycloalkyl which is optionally in which G is hydrogen. Substituted by an alkylenedioxy group containing two oxy 0593 Saturated or unsaturated hydrocarbon radicals such gen atoms not directly adjacent, to form a further 5- or as alkyl, alkanediyl or alkenyl may, also in conjunction with 6-membered ring which may be mono- or di-methyl-sub heteroatoms, for example in alkoxy, as far as possible, each be stituted, 0576 D is especially preferably hydrogen, or straight-chain or branched. 0577 A and D together are especially preferably C-Cs 0594 Optionally substituted radicals may, unless stated alkanediyl in which one carbonatom is optionally replaced otherwise, be substituted once or more than once, and the by oxygen, or Substituents in the case of poly Substitutions may be the same 0578 A and D together are especially preferably C-Cs or different. alkanediyl which is optionally substituted by an optionally 0595 Apart from the compounds cited in the examples, mono- to di-methyl-substituted alkylenedioxy group optionally containing two oxygen atoms not directly adja specific mention should be made of the following compounds cent, to form a further 5-membered ring (with emphasis. A where Z—OCH CF: and D together are C-C-alkanediyl which is optionally Substituted by an alkylenedioxy group containing two oxy TABLE 1 gen atoms not directly adjacent, to form a further 5-mem bered ring), or 0579 A and Q' together are especially preferably C-C- alkanediyl. 0580 Q is especially preferably hydrogen, 0581 G is especially preferably hydrogen (a) or one of the groups

X W Y Z.

(b) CH H 4 CH H 5 C H 4 C H 5 (c) OCH H 4 OCH H 5 C2H5 H 4 M1 R2, C2H5 H 5 CH CH 4 CH CH 5 0582 in which C2H5 CH 4 0583 L is oxygen, C2H5 C2H5 4 0584) M is oxygen, CH C 4 0585) R' is especially preferably C-C-alkyl, C2H5 C 4 (0586) R is especially preferably C1-Co-alkyl. 0587. The radical definitions and illustrations generalized above or listed in preferred ranges can be combined as desired 0596 Useful inventive active ingredients are especially with one another, i.e. including between the particular ranges preferably compounds of the radical combinations for W, X, and preferred ranges. They apply correspondingly to the end Y and Z specified in Table 1 with the radical combinations for products, and to the precursors and intermediates. A, B and D cited in Tables 2a and 2b. US 2010/03 11593 A1 Dec. 9, 2010 37

-continued

CKE = (1)

Table 2a

A. B

---. HH suA

2 3

C 13

rty H CH

-CH-CH-CH-CH (CH2)4

-CH-CH-CH-(CH2)-

- (CH)-N-(CH2)- H -(CH2) (CH)- OCH - (CH)-N-(CH2)- OCH5

US 2010/03 11593 A1 Dec. 9, 2010 41

invention further provides, finally, for the use of these com TABLE 3-continued positions for controlling insect pests and/or spider mites and/ or unwanted plant growth. OH X 0603 The compounds of the formula (I) possess a broad A FV Z. insecticidal and/or acaricidal and/or herbicidal activity, but in specific cases the activity and/or plant tolerance leaves some CKE = (2) O N \ 5SS thing to be desired. 0604. The active ingredients can be used in the composi O W tions according to the invention in a broad concentration range. The concentration of the active ingredients in the for A. B mulation is typically 0.1%-50% by weight. H 0605 Formula (III) provides a definition of the ammo -CH-C-(CH2)- nium salts and phosphonium salts which, according to the invention, boost the activity of crop protection compositions (CH2)2OCH2CH3 comprising fatty acid biosynthase inhibitors 0599 Active ingredients emphasized are especially pref erably compounds with the radical combinations for W, X,Y (III) and Z specified in Table 1 and the radical combinations speci fied for A and B in Table 3. 0600. In the literature it has already been described how the action of various active ingredients can be boosted by R28 addition of ammonium salts. The salts in question, however, are detersive salts (for example WO95/017817) or salts which have relatively long alkyl substituents and/or aryl sub in which stituents and which have a permeabilizing action or which 0606 D is nitrogen orphosphorus, increase the active ingredient's solubility (for example EP-A 0607 D is preferably nitrogen, O 453 086, EP-A 0664 081, FR-A 2 600 494, U.S. Pat. No. 0608 R. R7, RandR independently of one another 4,844,734, U.S. Pat. No. 5,462,912, U.S. Pat. No. 5,538,937, represent hydrogen or in each case optionally substituted US-A 03/0224939, US-A 05/0009880, US-A 05/0096386). C-C-alkyl or mono- or polyunsaturated, optionally Sub Moreover, the prior art describes the action only for particular stituted C-Cs-alkylene, the Substituents being selectable active ingredients and/or particular applications of the corre from halogen, nitro and cyano, sponding compositions. In other cases, in turn, the salts in 0609 R. R7, RandR independently of one another question are those of Sulphonic acids, where the acids them preferably represent hydrogen or in each case optionally selves have a paralytic action on insects (U.S. Pat. No. 2,842, substituted C-C-alkyl, the substituents being selectable 476). A boost to action by ammonium Sulphate, for example, from halogen, nitro and cyano, is described by way of example for the herbicides glyphosate, 0610 R. R7, RandR independently of one another phosphinothricin and for phenyl-Substituted cyclic ketoenols particularly preferably represent hydrogen, methyl, ethyl, (U.S. Pat. No. 6,645,914, EP-A20036 106, WO 07/068,427). n-propyl, isopropyl. n-butyl, isobutyl, sec-butyl or tert A corresponding boost to action in the case of insecticides has butyl, already been described by WO 07/068,428. 0611. R. R. R. and R very particularly preferably 0601 The use of ammonium sulphate as a formulating represent hydrogen, assistant has also been described for certainactive ingredients 0612 n is 1, 2, 3 or 4, and applications (WO 92/16108), but its purpose therein is to 0613 n is preferably 1 or 2, stabilize the formulation, not to boost the action. I0614) R' is an organic or inorganic anion, 0602. It has now been found, likewise surprisingly, that the I0615I R' is preferably hydrogencarbonate, tetraborate, action of insecticides and/or acaricides and/or herbicides fluoride, bromide, iodide, chloride, monohydrogenphos from the class of the haloalkylmethyleneoxyphenyl-substi phate, dihydrogenphosphate, hydrogensulphate, tartrate, tuted ketoenols of the formula (I) can be boosted significantly Sulphate, nitrate, thiosulphate, thiocyanate, formate, lac through the addition of ammonium salts or phosphonium tate, acetate, propionate, butyrate, pentanoate or oxalate, salts to the application solution or through the incorporation I0616) R' is more preferably lactate, sulphate, nitrate, of these salts into a formulation comprising the haloalkylm thiosulphate, thiocyanate, oxalate or formate, ethyleneoxyphenyl-substituted ketoenols of the formula (I). 0617 R is most preferably sulphate. The present invention therefore provides for the use of ammo 0618 Combinations emphasized in accordance with the nium salts or phosphonium salts for boosting the action of invention of active ingredient, salt and penetration enhancer crop protection compositions which comprise as their active are listed in the table below. “Penetration enhancer as per test” ingredient herbicidal and/or insecticidal and/or acaricidal means here that any compound that acts as a penetration haloalkylmethyleneoxyphenyl-substituted ketoenols of the enhancer in the cuticle penetration test (Baur et al., 1997, formula (I). The invention likewise provides compositions Pesticide Science 51, 131-152) is suitable. which comprise herbicidal and/or acaricidal and/or insecti 0619. The ammonium salts and phosphonium salts of the cidal haloalkylmethyleneoxyphenyl-substituted ketoenols of formula (III) can be used in a broad concentration range to the formula (I) and action-boosting ammonium salts orphos boost the activity of crop protection compositions comprising phonium salts, including not only formulated active ingredi ketoenols. In general the ammonium salts or phosphonium ents but also ready-to-use compositions (spray liquors). The salts are used in the ready-to-use crop protection composition US 2010/03 11593 A1 Dec. 9, 2010 42 in a concentration of 0.5 to 80 mmol/l, preferably 0.75 to 37.5 0632 A further preferred group of penetration enhancers mmol/l, more preferably 1.5 to 25 mmol/l. In the case of a is that of alkanol alkoxylates of the formula formulated product the ammonium salt and/or phosphonium R-O-(-EO-)-(-PO-) R' (IV-b) salt concentration in the formulation is chosen such that it is within these stated general, preferred or particularly preferred in which ranges after the formulation has been diluted to the desired 0633 R is as defined above, active ingredient concentration. The concentration of the salt 0634) R' is as defined above, in the formulation is typically 1%-50% by weight. 0635 EO is CH-CH O , 0620. In one preferred embodiment of the invention the 0636 PO is activity is boosted by adding to the crop protection composi tions not only an ammonium salt and/orphosphonium salt but also, additionally, a penetration enhancer. It is considered -cis-i-o- entirely surprising that even in these cases an even greater CH boost to activity is observed. The present invention therefore likewise provides for the use of a combination of penetration enhancer and ammonium salts and/or phosphonium salts to 0637 p is a number from 1 to 10, and boost the activity of crop protection compositions which 0638 q is a number from 1 to 10. comprise insecticidal and/or acaricidal and/or herbicidal 0639 A further preferred group of penetration enhancers haloalkylmethyleneoxyphenyl-substituted ketoenols of the is that of alkanol alkoxylates of the formula formula (I) as active ingredient. The invention likewise pro R—O—(—PO—)-(EO—) R' (IV-c) vides compositions which comprise herbicidal and/or acari cidal and/or insecticidal haloalkylmethyleneoxyphenyl-Sub in which stituted ketoenols of the formula (I), penetration enhancers 0640 R is as defined above, and ammonium salts and/or phosphonium salts, including 0641) R' is as defined above, specifically not only formulated active ingredients but also 0642 EO is —CH2—CH2—O , ready-to-use compositions (spray liquors). The invention 0643 PO is additionally provides, finally, for the use of these composi tions for controlling harmful insects and/or spider mites and/ or undesired plant growth. -ci-i-o- 0621. In the present context, suitable penetration enhanc CH3 ers are all those Substances which are usually employed to improve penetration of agrochemically active ingredients into plants. In this context, penetration enhancers are defined 0644 r is a number from 1 to 10, and in that they penetrate from the aqueous spray liquor and/or the 0.645 s is a number from 1 to 10. spray coating into the cuticles of the plant, thus increasing the 0646 A further preferred group of penetration enhancers mobility of active ingredients in the cuticles. The method is that of alkanol alkoxylates of the formula described in the literature (Baur et al., 1997, Pesticide Science R-O-(-EO-)-(-BO-) R' (IV'-d) 51, 131-152) can be used for determining this property. 0622 Examples of useful penetration enhancers include in which alkanol alkoxylates. Penetration enhancers of the invention (0647 R and R' are as defined above, are alkanol alkoxylates of the formula (IV) (0648 EO is CH-CH O , 0649 BO is R-O-(-AO), R' (IV) in which 0623 R is straight-chain or branched alkyl having 4 to 20 -cis-cis-i-o- carbon atoms, CH 0624 R' is hydrogen, methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl, 0650 p is a number from 1 to 10 and 0625 AO is an ethylene oxide radical, a propylene oxide 0651 q is a number from 1 to 10. radical, a butylene oxide radical or is mixtures of ethylene 0652. A further preferred group of penetration enhancers oxide and propylene oxide radicals or butylene oxide radi is that of alkanol alkoxylates of the formula cals, and 0626 v is a number from 2 to 30. R—O—(—BO—)-(-EO—)—R' (IV'-e) 0627. One preferred group of penetration enhancers is that in which of alkanol alkoxylates of the formula 0653 RandR' are as defined above, 0654 BO is R-O-(-EO), R' (IV-a) in which 0628 R is as defined above, -CH-CH-CH-O-, 0629 R' is as defined above, CH 0630 EO is CH-CH-O-, and 0631 n is a number from 2 to 20. US 2010/03 11593 A1 Dec. 9, 2010

0655 EO is CH-CH O , 0676 A general definition of the alkanol alkoxylates is 0656 r is a number from 1 to 10 and given by the formulae above. These substances are mixtures 0657 s is a number from 1 to 10. of compounds of the stated type with different chain lengths. 0658. A further preferred group of penetration enhancers The indices therefore have average values which may also is that of alkanol alkoxylates of the formula deviate from whole numbers. R (IV-f) 0677. The alkanol alkoxylates of the formulae stated are in which known and in some cases are available commercially or can 0659 R' is as defined above, be prepared by known methods (cf. WO 98/35553, WO 00/35 0660 t is a number from 8 to 13, 278 and EP-A 0681 865). 0661 u is a number from 6 to 17. 0678 Suitable penetration enhancers also include, for 0662. In the formulae indicated above, example, substances which promote the availability of the 0663 R is preferably butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, 2-ethyl compounds of the formula (I) in the spray coating. These hexyl, nonyl, isononyl, decyl. n-dodecyl, isododecyl, lau include, for example, mineral or vegetable oils. Suitable oils ryl, myristyl, isotridecyl, trimethylnonyl, palmityl, Stearyl are all mineral or vegetable oils—modified or otherwise— or eicosyl. which can typically be used in agrochemical compositions. 0664 One example of an alkanol alkoxylate of the formula Mention may be made by way of example of sunflower oil, (IV-c) is 2-ethylhexyl alkoxylate of the formula rapeseed oil, olive oil, castor oil, colza oil, maize seed oil, cotton seed oil and Soya bean oil, or the esters of said oils. Preference is given to rapeseed oil, sunflower oil and their (IV-c-1) methyl or ethyl esters. CH-CH-CH-CH-CH-CH-O-(PO)-(EO)-H 0679 The concentration of penetration enhancer in the C2H5 compositions of the invention can be varied within a wide range. In the case of a formulated crop protection composi in which tion it is in general 1% to 95%, preferably 1% to 55%, more 0665 EO is CH-CH O , preferably 15%-40% by weight. In the ready-to-use compo 0666, PO is sitions (spray liquors) the concentrations are generally between 0.1 and 10 g/l, preferably between 0.5 and 5 g/l. 0680 Crop protection compositions of the invention may -CH-CH-O- also comprise further components, examples being Surfac CH3 tants and/or dispersing assistants or emulsifiers. 0681 Suitable nonionic surfactants and/or dispersing and assistants include all Substances of this type that can typically the numbers 8 and 6 represent average values. be used in agrochemical compositions. Preferably mention 0667 One example of an alkanol alkoxylate of the formula may be made of polyethylene oxide-polypropylene oxide (IV-d) is the formula block copolymers, polyethylene glycol ethers of linear alco hols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, and also polyvinyl alcohol, polyvi in which nylpyrrolidone, copolymers of polyvinyl alcohol and polyvi 0668 EO is CH-CH O , nylpyrrolidone, and copolymers of (meth)acrylic acid and 0669 BO is (meth)acrylic esters, and additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may be phosphated -CH-CH-CH-O-, and optionally may be neutralized with bases, mention being made, by way of example, of Sorbitol ethoxylates, and also CH polyoxyalkylenamine derivatives. and 0682 Suitable anionic surfactants include all substances the numbers 10, 6 and 2 represent average values. of this type that can typically be used in agrochemical com 0670 Particularly preferred alkanol alkoxylates of the for positions. Preference is given to alkali metal salts and alkaline mula (IV"-f) are compounds of this formula in which earth metal salts of alkylsulphonic acids or alkylarylsul 0671 t is a number from 9 to 12 and phonic acids. 0672 u is a number from 7 to 9. 0683. A further preferred group of anionic surfactants and/ 0673) A very particular preferred alkanol alkoxylate is that or dispersing assistants are the following salts that are of low of the formula (IV-f-1) solubility in plant oil: Salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesul phonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenol t is the average value 10.5 and Sulphonic acid and formaldehyde, and salts of lignoSulphonic u is the average value 8.4. acid. US 2010/03 11593 A1 Dec. 9, 2010 44

0684 Suitable additives which may be included in the method according to the invention can be illustrated by the formulations of the invention are emulsifiers, foam inhibitors, following reaction scheme: preservatives, antioxidants, dyes and inert filling materials. 0685 Preferred emulsifiers are ethoxylated nonylphenols, H3CO reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, and also ethoxylated and propoxylated arylalkylphenols, and also Sul H3C CH3 S CH phated or phosphated arylalkyl ethoxylates and/or arylalkyl O 3 ethoxypropoxylates, mention being made by way of example Acid -- of sorbitan derivatives, such as polyethylene oxide-sorbitan -O o1\or, fatty acid esters, and Sorbitan fatty acid esters. HSC 0686. Using, for example, according to method (A), ethyl O CH N-(2,6-dimethyl-4-trifluoroethoxyphenyl-acetyl)-1-ami CF nocyclohexanecarboxylate as the starting material, the course CH3 o of the method according to the invention can be illustrated by HO the following reaction scheme: HC N HC S CH CH O CF O n1''' O 1. Base 2. H+ H 0689. Using, for example, according to method (D), chlo N rocarbonyl 2,6-dimethyl-4-trifluoroethoxyphenylketene and HSCOC acetone as starting compounds, the course of the method CH according to the invention can be illustrated by the following OH CH3 reaction scheme:

N o1 Ner, FC O C H HN 3 N1 3

O CH CEO --

CH COC 0687 Using, for example, according to method (B), ethyl O O-(2,6-dimethyl-4-trifluoroethoxyphenyl-acetyl)-2-hy Base -- droxyisobutyrate, the course of the method according to the HC CH invention can be illustrated by the following reaction scheme: F. C O CH3 N1 OH

COCHs 21 H3C >/ HC CH3 O O CH HC O o1 Ner, 1. Base 2. H 0690. Using, for example, according to method (E), chlo rocarbonyl 2,6-dimethyl-4-trifluoroethoxyphenylketene and O CH thiobenzamide as starting compounds, the course of the method according to the invention can be illustrated by the following reaction scheme:

FCin 1 O C H3

CEO 21

CH3 COC S 0688 Using, for example, according to method (C), ethyl () { HeBase 2-(2,6-dimethyl-4-trifluoroethoxyphenyl)-4-(4-methoxy) NH2 benzylmercapto-4-methyl-3-oxovalerate, the course of the US 2010/03 11593 A1 Dec. 9, 2010

-continued -continued FC O " CH3 N1 CEO FC O -- 3 N1 / COC CH t N C CH3 O OH CH3 0691. Using, for example, according to method (F), ethyl N N o1 Ner, 5-(2,6-dimethyl-4-trifluoroethoxyphenyl)-2,3-trimethylene N 4-oxovalerate, the course of the method according to the invention can be illustrated by the following reaction scheme: O HC

0694. Using, for example, according to method (HE), CH3 hexahydropyridazine and dimethyl 2-(2,6-dimethyl-4-trif O luoroethoxy)phenylmalonate as starting materials, the course o1 Ner, of the method according to the invention can be illustrated by 1. Base the following reaction scheme: COC2H5 2. H H3C OH CH3 N1 H /-CF, -- N NH O)-( )–: CH3 O HC CO2CH FCin 1 O Her 0692. Using, for example, according to method (G), ethyl COCH 6-(2,6-dimethyl-4-trifluoroethoxy)phenyl-2-dimethyl-5- oxohexanoate, the course of the method according to the CH3 invention can be illustrated by the following reaction scheme: OH CH3 N N o1 Ner, H3C N H3C CO2C2H5 o1 Ner, Base O HC H3C 0695. Using, for example, according to method (Hy), O CH3 1-ethoxycarbonyl-2-(2,6-dimethyl-4-trifluoroethoxy)phe HC nylacetylhexahydropyridazine as the starting material, the course of reaction can be illustrated by the following scheme: H3C HO ( ) O 1N CF CH HC CH COCHs O W 1N N O CF He V Base 0693. Using, for example, according to method (HC), N hexahydropyridazine and chlorocarbonyl 2,6-dimethyl-4-tri O CH fluoroethoxyphenylketene as starting compounds, the course of reaction in the method according to the invention can be illustrated by the following reaction scheme: N N o1 Ner,

C. O CH3 0696. Using, for example, according to method (I), ethyl N-(2,6-dimethyl-4-trifluoroethoxyphenyl-acetyl)-1-ami US 2010/03 11593 A1 Dec. 9, 2010 46 nomethylcyclohexanecarboxylate as the starting material, the -continued course of the method according to the invention can be illus trated by the following reaction scheme:

/- CF CH3 O O 1. Base -- 2. H+ CH N H HSCOC CH 0699. Using, for example, according to method (LC), 3-(2-methyl-4-trifluoroethoxy-6-ethylphenyl)-5,5-dimeth OH CH3 ylpyrrolidine-2,4-dione and pivaloyl chloride as starting materials, the course of the method according to the invention S. O1Ne, can be illustrated by the following reaction scheme:

N H O CH HC CH3 OH 3 /Ner H3C O 3 ic--coa 0697. Using, for example, according to method (J), ethyl N HeCH O-(2,6-dimethyl-4-trifluoroethoxyphenylacetyl)-3-hydroxy H3C Base 2,2-dimethylpropionate, the course of the method according HN to the invention can be illustrated by the following reaction O C2H5 scheme: CH3 CH3 O CH CF HC O H3C H3C O

HC 1.... B38Se. O o1\er, E - H3C N HN

O CH O C2H5 /Nor, HC O 0700. Using, for example, according to method (L?), 3-(2, HO 6-dimethyl-4-trifluoroethoxyphenyl)-5,5-dimethylpyrroli HC dine-2,4-dione and acetic anhydride as starting compounds, N the course of the method according to the invention can be HC CH illustrated by the following reaction scheme: O O

0698. Using, according to method (K), ethyl N-methyl-N- CH3 />er, H.C-CO (2,6-dimethyl-4-trifluoroethoxy)phenylacetyl-1-ami OH O H3C HC-CO nooxycyclopentanecarboxylate as the starting material, the -- course of the method according to the invention can be illus H3C N Base trated by the following reaction scheme: HN CH5 O O CH3 CF ls CH3 />er, OS/ HC O CH3 O 1. Base H3C V He N 2. H+ HC N c/ HN C2H5 COC2H5 CH

0701. Using, for example, according to method(M), 8-(2, 6-dimethyl-4-trifluoroethoxy)phenyl)-1-azabicyclo[4,3,0' US 2010/03 11593 A1 Dec. 9, 2010 47

6 nonane-7,9-dione and ethyl chloroformate as starting com- starting materials, the course of reaction can be illustrated by pounds, the course of the method according to the invention the following reaction scheme: can be illustrated by the following reaction scheme:

OH CH3

\ O /CFs Hess"CI-SO,-CH, Base

HCO-C-CI Base O-SOCH

0704. Using, for example, according to method (P), 3-(2, 6-dimethyl-4-trifluoroethoxyphenyl)-4-hydroxy-5,5-dim ethylpyrrolidine-2,4-dione and 2.2.2-trifluoroethyl meth anethiophosphonyl chloride as starting materials, the course of reaction can be illustrated by the following reaction scheme:

CH3 OH CH3 i OCHCF, H3C "CI-PC 0702. Using, for example, according to method (N), 3-(2, \ o1\ CH3 6-dimethyl-4-trifluoroethoxyphenyl)-4-hydroxy-5-methyl- HN CF Base 6-(phenyl)pyrone and methyl chloromonothioformate as starting materials, the course of reaction can be illustrated as O CH follows: p-ki OCHCF 2V-13 CH CH, CH3

M CH CF S 0705. Using, for example, according to method (O), 3-(2- ethyl-4-trifluoroethoxy-6-methylphenyl-5-cyclopropyl-5- OCH methylpyrrolidine-2,4-dione and NaOH as components, the O CH course of the method according to the invention can be illus CH / \ ( ) trated by the following reaction scheme:

O O O OH C2H5 W CH CF NaOH H3C N o1 Ner, s HN 0703. Using, for example, according to method (O), 3-(2, 6-dimethyl-4-trifluoroethoxyphenyl)-5,5-penta-methyl enepyrrolidine-2,4-dione and methanesulphonyl chloride as US 2010/03 11593 A1 Dec. 9, 2010 48

dione and trifluoroethanol as starting materials, the course of -continued reaction can be illustrated by the following scheme: Na(+) O (-) C2H5 OH CH3 H3C H3C N o1 Ner, HN 1HN N B -FC C OH - O CH O CH OH CH 0706. Using, for example, according to method(R) variant H3C C. 3-(2,6-dimethyl-4-trifluoroethoxyphenyl)-4-hydroxy-5,5- tetramethylene-A-dihydrofuran-2-one and ethyl isocyanate H3C N o1 Ner, as starting materials, the course of reaction can be illustrated HN by the following reaction scheme: O CH

OH CH 0709. The compounds of the formula (II) required as start \ o1 Ner, HeCHs-N=C=O ing materials in the process according to the invention (a) O (II) O CH COR O H X | / B O-C- N N D1 N -HZ

1. \ o1 Ner, W -N-xY O O CH in which 0710 A, B, D, WX,Y,Z and Rare each as defined above, 0707 Using, for example, according to method(R) variant 0711 are novel. B, 3-(2-methyl-4-trifluoroethoxy-6-ethylphenyl)-5-meth 0712. The acylamino acid esters of the formula (II) are ylpyrrolidine-2,4-dione and dimethylcarbamyl chloride as obtained, for example, when amino acid derivatives of the starting materials, the course of reaction can be illustrated by formula (XXVII) the following scheme: (XXVII) O ADr COR OH CH3 C --ch H3C D1 NH N o1 Nep, —S - HN -HCI in which O C2H5 0713 A, B, Rand Dare each as defined above, t 0714 are acylated with substituted phenylacetic acid ON N YCH, derivatives of the formula (XXVIII) O CH3 (XXVIII) HC X N o1 Ner, HN Zn/7 X1 \ O CHs Y VE COU2 W 0708. Using, for example, according to method (S), 3-(4- bromine-2,6-dimethylphenyl)-5,5-di-methylpyrrolidine-2,4- US 2010/03 11593 A1 Dec. 9, 2010 49 in which in which 0715 W, X, Y and Z are each as defined above and 0727 W, X, Y and Z are each as defined above and 0716. U is a leaving group introduced by carboxylic acid 0728 U is as defined above, activating reagents such as carbonyldiimidazole, carbon 0729 for example according to Schotten-Baumann (Or yldiimides (for example dicyclohexylcarbodiimide), phos ganikum, VEB Deutscher Verlag der Wissen-schaften, phorylating reagents (for example POCl, BOP Cl), Berlin 1977, p. 505). (0730. The compounds of the formula (XXVIII) are novel. halogenating agents, e.g. thionyl chloride, oxalyl chloride, They can be prepared by processes known in principle (see, phosgene or chloroformic esters, for example, H. Henecka, Houben-Weyl, Methoden der 0717 (Chem. Reviews 52,237-416 (1953); Bhattacharya, Organischen Chemie, Vol. 8, p. 467-469 (1952) WO Indian J. Chem. 6,341-5, 1968) 97/02243, WO 99/43699), or are obtained in situ with the 0718 or when acylamino acids of the formula (XXIX) above-specified reagents. (0731. The compounds of the formula (XXVIII) are (XXIX) obtained, for example, by reacting Substituted phenylacetic A CO2H acids of the formula (XXXI) X B N (XXXI) D1 21 X -HZ O w1s x Y 'gM y 1X / CO2H in which 0719 A, B, D, W, X, Y and Z are each as defined above, W 0720 are esterified (Chem. Ind. (London) 1568 (1968)). 0721 The compounds of the formula (XXIX) in which 0732 W, X, Y and Z are each as defined above, with halogenating agents (e.g. thionyl chloride, thionyl bro (XXIX) mide, oxalyl chloride, phosgene, phosphorus trichloride, A CO2H phosphorus tribromide or phosphorus pentachloride), phos X phonylating reagents (for example POCl, BOP Cl), carbo B nyldiimidazole, carbonyldiimides (e.g. dicyclohexylcarbon D1 N 21 yldiimide), optionally in the presence of a diluent (for -HZ example optionally chlorinated aliphatic or aromatic hydro O S x carbons such as toluene or methylene chloride or ethers, e.g. W Y tetrahydrofuran, dioxane, methyl tert-butyl ether) attempera tures of -20°C. to 150° C., preferably of -10°C. to 100° C. (0733 Some of the compounds of the formula (XXVII)and in which (XXX) are known from the patent literature cited at the outset 0722 A, B, D, W, X, Y and Z are each as defined above and/or can be prepared by known processes (see, for example, 0723 are novel. Compagnon, Miocque Ann. Chim. (Paris) 145, p. 11-22, 0724. The compounds of the formula (XXIX) are obtained 23-27 (1970)). when amino acids of the formula (XXX) 0734 The substituted cyclic amino carboxylic acids of the formula (XXX) in which A and B form a ring are generally obtainable by the Bucherer-Bergs synthesis or by the Strecker (XXX) synthesis and are obtained in different isomeric forms in each A CO2H case. Thus, under the conditions of the Bucherer-Bergs syn Dr thesis, predominantly the isomers (for the sake of simplicity NH referred to hereinafter as B) in which the R radicals and the D1 carboxyl group are in equatorial positions are obtained, whereas, under the conditions of the Strecker synthesis, pre dominantly the isomers (for the sake of simplicity, referred to in which hereinafter as C.) in which the amino group and the R radicals 0725 A, B and Dare each as defined above, are in equatorial positions are obtained. 0726 are acylated with substituted phenylacetic acid derivatives of the formula (XXVIII) R H NH R H CO2H (XXVIII) CO2H NH2 X 'g H H XM Bucherer-Bergs synthesis Strecker synthesis y1V / COU2 (f isomer) (C. isomer) W (0735 (L. Munday, J. Chem. Soc. 4372 (1961); J.T. Eward, C. Jitrangeri, Can. J. Chem. 53,3339 (1975). US 2010/03 11593 A1 Dec. 9, 2010 50

0736. In addition, the starting materials of the formula (II) 0746 The compounds of the formula (III) required as used in the above method (A) starting materials in the method (B) according to the inven tion

(II) A COR (III) X B X N B D1 N O HZ -n-x1. rs-HZ W Y 1. W -NeeY in which 0737 A, B, D, W, X,Y,Z and Rare each as defined above, in which 0747 A, B, W, X,Y,Z and Ware each as defined above, are 0738 can be prepared when aminonitriles of the formula novel. (XXXII) 0748. They can be prepared by methods known in prin ciple. (XXXII) 0749 For example, the compounds of the formula (III) are A B obtained when 0750 2-hydroxycarboxylic esters of the formula H- * - N (XXXIV-A) D (XXXIV-A) A COR in which Dr 0739 A, B and Dare each as defined above, OH 0740 are reacted with substituted phenylacetic acid derivatives of the formula (XXVIII) in which (0751 A, B and Rare each as defined above, (XXVIII) 0752 are acylated with substituted phenylacetic acid X derivatives of the formula (XXVIII) Zn/ X1 \ (XXVIII) Y VE COU2 X W Zn/ X1 \ in which Y VE COU2 0741 W, X, Y, Z and U are each as defined above, W 0742 to give compounds of the formula (XXXIII)) in which (XXXIII) (0753 W, X, Y, Z and U are each as defined above, X (0754 (Chem. Reviews 52,237-416 (1953)). 0755. In addition, compounds of the formula (HI) are Zn/? y obtained when Y* -/ y 0756 substituted phenylacetic acids of the formula CN (XXXI)

W O X B A (XXXI) X in which Zn/ CO2H 0743 A, B, D, W, X, Y and Z are each as defined above, \ 0744 and the latter are subsequently subjected to an acidic Y( - alcoholysis. W 0745. The compounds of the formula (XXXIII) are like wise novel. US 2010/03 11593 A1 Dec. 9, 2010

in which in which W, X, Y and Z are each as defined above, are alkylated with C.-halocarboxylic esters of the formula 0768 W, X, Y, Z and Rare each as defined above, are obtained by the method analogous to method (S) (XXXIV-B) described in the examples, when phenylacetic esters of the formula (XXXV-a) (XXXIV-B) AX" (XXXV-a) B Hal in which COR 0757 A, B and Rare each as defined above and 0758 Hal is chlorine or bromine. (0759. Some of the compounds of the formula (XXXIV-A) are commercially available or known from the disclosures mentioned at the outset. in which 0760. The compounds of the formula (XXXIV-B) are commercially available. 0769 R. W. X and Y are each as defined above 0761 The compounds of the formula (XXXI) are novel. (0770 and Z is bromine or iodine, 0762. For example, the compounds of the formula (XXXI) are converted in the presence of haloalkyl alcohols (e.g. trif are obtained luoroethanol, in the presence of a base and optionally in the presence of a copper salt (preferably Cu(I) I). (XXXI) (0771. The phenylacetic esters of the formula (XXXV-a) X are known in principle, for example, from publications WO 96/35664, WO 97/02243, WO 97/01535, WO 98/05638 and Zn/ CO2H DE-A-10 301 804, and can be prepared by the processes \ described there. Y( - 0772. The compounds of the formula (IV) required as W starting materials in the above method (C) in which (IV) 0763 W, X, Y and Z are each as defined above, 0764 when phenylacetic esters of the formula (XXXV)

(XXXV) X

Z SC( \ COR Y( - W in which (0773) A, B, V, W, X,Y,Z and Rare each as defined above, in which are novel. 0765 W, X, Y, Z and are each as defined above, are hydrolysed in the presence of acids or bases, in the pres 0774 They can be prepared by methods known in prin ence of a solvent, under commonly known standard condi ciple. tions. (0775. The compounds of the formula (IV) are obtained, 0766 The compounds of the formula (XXXV) are novel. for example, when substituted phenylacetic esters of the for 0767 The compounds of the formula (XXXV) mula (XXXV)

(XXXV) X (XXXV) X

Z Z COR SQ( \ COR YG = {o\ W US 2010/03 11593 A1 Dec. 9, 2010 52 in which Deutscher Verlag der Wissenschaften, Berlin 1977, p. 517 ff. (0776 W, X, Y, Z and Rare each as defined above, EP-A-528 156, WO 96/35 664, WO 97/02 243, WO are acylated with 2-benzylthiocarbonylhalides of the formula 97/01535, WO 97/36868 and WO 98/05638). (XXXVI) 0785 For instance, phenylmalonic acids of the formula (XXXVII) (XXXVI) A B (XXXVII) ( ) X. X W. V. Hal Z/ CO2H X1 \ in which Y VE CO2H 0777 A, B and V are each as defined above and W 0778 Hal is halogen (especially chlorine or bromine), in the presence of strong bases (see, for example, M. S. Chambers, E.J. Thomas, D.J. Williams, J. Chem. Soc. Chem. in which Commun., (1987), 1228). 0786 W, X, Y and Z are each as defined above, (0779. Some of the benzylthiocarbonyl halides of the for mula (XXXVI) are known and/or can be prepared by known are obtained when phenylmalonic esters of the formula (XI) processes (J. Antibiotics (1983), 26, 1589). 0780. The halocarbonyl ketenes of the formula (VI) (XI) required as starting materials in the above methods (D), (E) X and (H-C.) are novel. They can be prepared by methods known in principle (cf., for example, Org. Prep. Proced. Int., 7, (4), Z COUl 155-158, 1975 and DE 1945 703). For example, the com \ pounds of the formula (VI) YG COUl W (VI) in which 0787 W, X, Y and Z are each as defined above, 0788 and U" is OR, 0789 where R is as defined above, are first hydrolysed in the presence of a base and a solvent and in which then acidified cautiously (see, for example, EP-A-528 156, 0781 W, X, Y and Z are each as defined above and WO 96/35664, WO 97/02 243). 0782 Hal is chlorine or bromine 0790 The malonic esters of the formula (XI) are obtained when substituted phenylmalonic acids of the formula (XXXVII) (XI)

(XXXVII) X

o COOH

V y1\(X /) i? COOH

W in which in which 0791) W, X, Y and Z are each as defined above, 0783 W, X, Y and Z are each as defined above, 0792 and U' is OR, are reacted with acid halides, for example thionyl chloride, 0793 where R is as defined above phosphorus(V) chloride, phosphorus(III) chloride, oxalyl are novel. chloride, phosgene or thionyl bromide, optionally in the pres ence of catalysts, for example dimethylformamide, methyl 0794. They can be prepared by commonly known methods Stearylformamide or triphenylphosphine, and optionally in of organic chemistry (cf., for example, Tetrahedron Lett. 27. the presence of bases, for example pyridine or triethylamine. 2763 (1986), Organikum VEB Deutscher Verlag der Wissen 0784 The substituted phenylmalonic acids of the formula schaften, Berlin 1977, p. 587 ff., WO 96/35664, WO (XXXVII) are novel. They can be prepared in a simple man 97/02243, WO 97/01535, WO 97/36868, WO 98/05638 and ner by known processes (cf., for example, Organikum, VEB WO 99/47525). US 2010/03 11593 A1 Dec. 9, 2010

0795. The carbonyl compounds of the formula (V) 0803. The 5-aryl-4-ketocarboxylic esters of the formula required as starting materials for the method (D) according to (VIII) are obtained, for example, when 5-aryl-4-ketocarboxy the invention lic acids of the formula (XXXVIII)

(V) (XXXVIII) --O in which 0796 A and Dare each as defined above, or the silyl enol ethers thereof, of the formula (Va) in which 0804 W, X, Y, Z. A, B, Q' and Q are each as defined (Va) CHA above, | are esterified (cf., for example, Organikum, 15th edition, Berlin, 1977, page 499) or alkylated (see preparation example). in which 0805. The 5-aryl-4-ketocarboxylic acids of the formula 0797 A, D and Rare each as defined above, (XXXVIII) are commercially available, commonly known compounds, or compounds obtainable by known processes. (XXXVIII) 0798. The principle of preparation of the ketenyl chlorides of the formula (VI) required as starting materials to perform the method (E) according to the invention has already been described in connection with method D. The thioamides of the formula (VII) required to perform the method (E) accord ing to the invention

(VII) in which HN Y-A 0806 A, B, Q', Q, W, X, Y and Z are each as defined M above, S are novel, but can be prepared by methods known in principle (WO 96/01798, WO 97/14667, WO 98/39281). in which 0807. The 5-aryl-4-ketocarboxylic acids of the formula 0799 A is as defined above, (XXXVIII) are obtained, for example, when 2-phenyl-3- are compounds which are common knowledge in organic oxoadipicesters of the formula (XXXIX) chemistry.

0800 The compounds of the formula (VIII) required as (XXXIX) starting materials in the above method (F)

(VIII) Q Q2 ROC CO X A B in which (0808 A, B, Q, Q, W, X, Y and Z are each as defined above and (0809 R and Rare each alkyl (especially C-C-alkyl) and in which when the compound of the formula (XLI-a) is used, R is 0801) A, B, Q, Q, W, X, Y, Z and Rare each as defined hydrogen, above, are decarboxylated, optionally in the presence of a diluent and are novel. optionally in the presence of a base or acid (cf., for example, 0802. They can be prepared by methods known in prin Organikum, 15th edition, Berlin, 1977, page 519 to 521, WO ciple. 96/01798, WO 97/14667, WO 98/39281). US 2010/03 11593 A1 Dec. 9, 2010 54

0810. The compounds of the formula (XXXIX) 0817. Some of the compounds of the formulae (XL) and (XLI-a) are known compounds in organic chemistry and/or can be prepared in a simple manner by methods known in (XXXIX) principle. 0818. The compounds of the formula (IX) required as starting materials in the above method (G)

(IX) So U in which ROC 0811 A, B, Q, Q, W, X, Y, Z, R and R are each as X CO X defined above and A B when the compound of the formula (XLI-a) is used, R is 21 hydrogen, -HZ are novel. 0812. The compounds of the formula (XXXIX) are -N-x obtained, for example, when dicarboxylic monoester chlorides of the formula (XL) in which 0819 A, B, Q, Q, U, W, X, Y, Z and R are each as 2 (XL) defined above, Q 'B are novel. 0820. They can be prepared by methods known in prin ORC COR8 ciple. V Hal 0821) 6-aryl-5-ketocarboxylic esters of the formula (IX) are obtained, for example, when 6-aryl-5-ketocarboxylic in which acids of the formula (XLII) 0813 A, B, Q, Q and Rare each as defined above and 0814 Hal is chlorine or bromine, or carboxylic anhydrides of the formula (XLI-a) (XLII)

(XLI-a) A O

B O Q2 Q O in which 0822 A, B, Q, Q, U, W, X, Y and Z are each as defined in which above, 0815) A, B, Q' and Q are each as defined above, are esterified (cf., for example, Organikum, 15th edition, are acylated with a phenylacetic ester of the formula (XXXV) Berlin, 1977, page 499, WO 99/43649, WO 99/48869). 0823 The 6-aryl-5-ketocarboxylic acids of the formula (XXXV) X (XLII) Z/ \ OR 8 (XLII) X Y V. O W in which 0816 W, X, Y, Z and Rare each as defined above, in the presence of a diluent and in the presence of a base (cf. for example, M.S. Chambers, E.J. Thomas, D.J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228; cf. also the preparation examples). US 2010/03 11593 A1 Dec. 9, 2010

in which in which 0824 A, B, Q, Q, U, W, X, Y and Z are each as defined 0829 A, B, Q, Q, U and Rare each as defined above, above, or carboxylic anhydrides of the formula (XLI-b) are novel. They can be prepared by methods known in prin ciple (WO 99/43649, WO99/48869), for example when sub stituted 2-phenyl-3-oxoheptanedioic esters of the formula (XLI-b) (XLIII)

(XLIII)

in which A, B, Q, Q and U are each as defined above are condensed with a substituted phenylacetic ester of the for mula (XXXV)

(XXXV) in which X 0825 A, B, Q, Q, U, W, X and Z are each as defined above and Zn/ \ OR 8 0826. Rand Rare each alkyl (preferably C-C-alkyl). X1 and, Y VE O when the compound of the formula (XLI-b) is used, R is W hydrogen, are hydrolysed and decarboxylated, optionally in the pres in which ence of a diluent and optionally in the presence of a base or 0830 W, X, Y, Z and R' are each as defined above, acid (cf., for example, Organikum, 15th edition, Berlin, 1977, in the presence of a diluent and in the presence of a base. page 519 to 521, WO99/43649, WO 99/48869). 0831. Some of the compounds of the formula (XLIV) are 0827. The compounds of the formula (XLIII) known and/or can be prepared by known processes. 0832. Some of the hydrazines of the formula (X) required as starting materials for the method (H-C) and (H-B) accord (XLIII) ing to the invention A-NH NH-D (X) in which 0833 A and Dare each as defined above, are known and/or preparable by literature methods (cf., for example, Liebigs Ann. Chem. 585, 6 (1954); Reaktionen der organischen Synthese, C. Ferri, page 212,513; Georg Thieme Verlag Stuttgart, 1978; Liebigs Ann. Chem. 443,242 (1925); Chem. Ber. 98, 2551 (1965), EP-A-508 126, WO 92/16510, in which WO 99/47525, WO 01/17972). 0828 A, B, Q, Q, U, W, X, Y, Z, Rand Rare each as 0834. The compounds of the formula (XII) required for defined above, the method (H-Y) according to the invention are novel and are obtainable, when dicarboxylic esters of the formula (XLIV) (XII) D (XLIV) 7-6( \ nN.1 COR82 X1 Y VE O A W

in which 0835 A, D, W, X, Y, Z and Rare each as defined above, are novel. US 2010/03 11593 A1 Dec. 9, 2010 56

0836. The acyl carbazates of the formula (XII) are in which obtained, for example, when carbazates of the formula (XLV) 10844) A, B, Q', Q, Rand Dare each as defined above, are acylated with substituted hetarylacetic acid derivatives of the formula (XXVIII) (XLV) A n COR N1 (XXVIII) X D1 NH 21 --z in which 0837 A. Rand Dare each as defined above, O w-sy are acylated with substituted phenylacetic acid derivatives of Y the formula (XXVIII) in which 0845 W, X, Y, Z and U are each as defined above (XXVIII) 0846 (Chem. Reviews 52,237-416 (1953); Bhattacharya, X Indian J. Chem. 6,341-5, 1968) Zn/ or when acylamino acids of the formula (XLVII) X1 \ Y VE COU2 (XLVII) W A CO2H B X in which 0838 W, X,Y,Z, and U are each as defined above (Chem. N Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Q: D1 21 Chem. 6,341-5, 1968). -HZ 0839. Some of the carbazates of the formula (XLV) are -sy commercially available and some are known compounds or W y can be, prepared by methods of organic chemistry known in principle. 0840. The compounds of the formula (XXVIII) have in which already been described for the precursors for methods (A) and 0847 A, B, D, Q, Q, W, X, Y and Z are each as defined (B). above, 0841. The compounds of the formula (XIII) required as are esterified (Chem. Ind. (London) 1568 (1968)). starting materials in the method (I) according to the invention 0848. The compounds of the formula (XLVII)

(XIII) (XLVII) A A CO2H B COR B Q X X

2 N Q D1 21 Q Q? D1. N 21 --z -HZ O N x W -'six Y W Y in which in which 0842) A, B, D, Q, Q, W, X, Y, Z and R are each as 0849 A, B, D, Q, Q, W, X, Y and Z are each as defined defined above are novel. above, 0843. The acylamino acid esters of the formula (XIII) are are novel. obtained, for example, when amino acid derivatives of the 0850. The compounds of the formula (XLVII) are formula (XLVI) obtained when B-amino acids of the formula (XLVIII)

(XLVI) (XLVIII) A 8 B COR B CO2H Q! 2 Q NH M D US 2010/03 11593 A1 Dec. 9, 2010 57 in which in which 0851 A, B, Q, Q and D are each as defined above, 0858 W, X, Y, Z and U are each as defined above are acylated with substituted phenylacetic acid derivatives of (see preparation examples of the formula (II)). the formula (XXVIII) 0859. Some of the compounds of the formula (XLIX) are known from WO 01/98288 or can be prepared by methods known in principle, for example by Reformatsky synthesis (XXVIII) (Organikum, VEB Deutscher Verlag der Wissenschaften, X Berlin 1990, 18th ed. p. 501 ff.) 0860. The compounds of the formula (XV) required as Zn/ starting materials in the method (K) according to the inven tion X1 \ Y VE COU2 W (XV) A in which COR X 0852 W, X, Y, Z and U are each as defined above, B for example according to Schotten-Baumann (Organikum, R N VEB Deutscher Verlag der Wissen-schaften, Berlin 1977, p. N -HY 505). O e 0853 Some of the compounds of the formulae (XLVI) and l W eX (XLVIII) are known from WO 01/79204 or can be prepared Z by the method known in principle specified there. 0854. The compounds of the formula (XIV) required as in which starting materials in the method (J) according to the invention 0861) A, B, D, W, X,Y,Z and Rare each as defined above, are novel. 0862 The acylhydroxylamino acid esters of the formula (XIV) (XV) are obtained, for example, when amino acid derivatives A of the formula (L) B COR Q! X (L) A COR Q2 O 21 Dr O S Xj-Z o- -H W Y D in which in which 0855 A, B, Q, Q, W, X, Y, Z and Rare each as defined 0863 A, B, Rand Dare each as defined above, above, are acylated with substituted phenylacetic acid derivatives of are novel. the formula (XXVIII) 0856. The acylhydroxycarboxylic esters of the formula (XIV) are obtained, for example, when hydroxycarboxylic esters of the formula (XLIX) (XXVIII)

(XLIX) A B COR COU2 Q! 2 Q OH in which 0864 W, X, Y, Z and U are each as defined above in which 0865 (Chem. Reviews 52,237-416 (1953); Bhattacharya, 0857 A, B, Q, Q and Rare each as defined above, Indian J. Chem. 6,341-5, 1968). are acylated with substituted phenylacetic acid derivatives of 0866. Some of the hydroxylamino acid esters of the for the formula (XXVIII) mula (L.) required as starting materials to prepare compounds of the formula (H) (XXVIII) X (L) Z * \ A B Y( - COU2 *so NH2 US 2010/03 11593 A1 Dec. 9, 2010

in which 0875. In addition, for example, acylhydroxylamino acid 0867 A, B and Rare each as defined above are novel and esters of the formula (XV) can be prepared by known processes (N. A. Porteret. al. J. Org. Chem. 635547 (1998), WO 03/048138). (XV) 0868 For example, hydroxylamino acid esters of the for mula (L)

(L) A B

O COR NH2 in which 0876 A, B, D, W, X,Y,Z and Rare each as defined above, in which but D is preferably not hydrogen, are obtained when, for example, phenylacetic acid derivatives 0869 A, B and Rare each as defined above are obtained of the formula (XXVIII) when N-hydroxyphthalimide of the formula (LI)

(XXVIII) (LI) W Y. SC( \ COU2 N-OH Z 31 o

X

in which 0877 W, X, Y, Z and U are each as defined above is reacted with haloalkyl esters of the formula (LII) are reacted with hydroxylamines of the formula (LIV)

(LII) A B OH (LIV) ^o D H in which in which 0870 A, B and Rare each as defined above and 0878 D is as defined above, but is preferably not hydro gen, 0871 Hal is chlorine, bromine or iodine, preferably bro to give compounds of the formula (LV) mine, 0872 to give O-alkoxyphthalimides of the formula

(LIII), (LV)

(LIII) O -*soA B in which O 0879 D. W, X, Y and Z are each as defined above, and the latter are alkylated with haloalkyl esters of the for in which mula (LII), 0873 A, B and Rare each as defined above, (LII) and then the compounds of the formula (L) are released, for A B example by hydrazinolysis. 0874. The compounds of the formula (LII) and (LI) are Hal COR likewise known and can be prepared by known processes (N. A. Porter et. al. J. Org. Chem. 63,5547-5554, 1998). US 2010/03 11593 A1 Dec. 9, 2010 59 in which lacetic acids of the formula (XXXI) required to prepare the 0880 A, B and Rare each as defined above compounds of the formula (I-1'-a) and 0881 Hal is chlorine, bromine and iodine, preferably bro (XXXI) mine, X to give compounds of the formula (XV) (E. K. Ryo et al., Bull. Korean Chem. Soc. 20965 (1999)). 0882. Some of the compounds of the formula (LIV) are r:M commercially available. Some are known, and can be pre 2K / CO2H pared by known methods. 0883 Moreover, compounds of the formula (XV) in which W D is not hydrogen are obtained when compounds of the for mula (XV-a) in which W, X, Y and Z are each as defined above are novel. Compounds of the formula (XXXI) in which Z is in the 3 position and Y is hydrogen are novel. 0892 Method (A) is characterized in that compounds of the formula (II) in which A, B, W, X, Y, Z and Rare each as defined above are Subjected to an intramolecular condensa tion in the presence of a base. 0893. The diluents used in method (A) according to the invention may be any inert organic solvent. Preference is given to using hydrocarbons, such as toluene and Xylene, and also ethers, such as dibutyl ether, tetrahydrofuran, dioxane, in which glycol dimethyl ether and diglycol dimethyl ether, and addi 0884 A, B, W, X, Y, Z and Rare each as defined above tionally polar solvents, such as dimethyl Sulphoxide, Sul are alkylated with compounds of the formula (LVI) pholane, dimethylformamide and N-methylpyrrolidone, and also alcohols, such as methanol, ethanol, propanol, isopro D-LG (LVI) panol, butanol, isobutanol and tert-butanol. in which 0894. The bases (deprotonating agents) used in the perfor 0885 D is as defined above, but is not hydrogen, mance of method (A) according to the invention may be any and customary proton acceptor. Preference is given to using alkali 0886 LG is a leaving group, for example chlorine, bro metal and alkaline earth metal oxides, hydroxides and car mine, iodine, mesylate, tosylate or triflate bonates, such as Sodium hydroxide, potassium hydroxide, to give compounds of the formula (XV) (WO 03/048138). magnesium oxide, calcium oxide, Sodium carbonate, potas 0887. Some of the compounds of the formula (LVI) are sium carbonate and calcium carbonate, which may also be commercially available. Some are known, and can be pre used in the presence of phase transfer catalysts, for example pared by known methods. triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium 0888. The compounds of the formulae (LIII) and (LV) are chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is known and are preparable according to the literature cited at additionally possible to use alkali metals, such as sodium or the outset. potassium. It is also possible to employ alkali metal and 0889. The acid halides of the formula (XVI), carboxylic alkaline earth metal amides and hydrides, such as Sodium anhydrides of the formula (XVII), chloroformic esters or amide, sodium hydride and calcium hydride, and additionally chloroformic thioesters of the formula (XVIII), chloromono thioformic esters or chlorodi-thioformic esters of the formula also alkali metal alkoxides, such as sodium methoxide, (XIX), sulphonyl chlorides of the formula (XX), phosphorus Sodium ethoxide and potassium tert-butoxide. compounds of the formula (XXI) and metal hydroxides, 0895. When performing method (A) according to the metal alkoxides or amines of the formula (XXII) and (XXIII) invention, the reaction temperatures may be varied within a and isocyanates of the formula (XXIV) and carbamyl chlo relatively wide range. In general, the temperatures employed rides of the formula (XXV) and haloalkanols of the formula are between 0° C. and 250° C., preferably between 50° C. and (XXVI) also required as starting materials to perform the 1500 C. methods (L), (M), (N), (O), (P), (O), (R) and (S) according to 0896 Method (A) according to the invention is generally the invention are commonly known compounds in organic or performed under atmospheric pressure. inorganic chemistry. 0897. When performing method (A) according to the (0890. The compounds of the formulae (V), (VII), (X), invention, the reaction components of the formula (II) and the (XXVII), (XXX), (XXXII), (XXXIV-A), (XXXIV-B), deprotonating bases are generally employed in about double (XXXVI), (XL), (XLI-a), (XLI-b), (XLIV), (XLV), (XLVI), the equimolaramounts. However, it is also possible to use one (XLVIII), (XLIX), (LI), (LII), (LIV) and (LVI) are addition component or the other in a greater excess (up to 3 mol). ally known from the patent applications cited at the outset 0898 Method (B) is characterized in that compounds of and/or can be prepared by the methods specified there. the formula (III) in which A, B, W, X,Y,Z and Rare each as 0891. The compounds of the formulae (I-1'-I-11) can be defined above are Subjected to an intramolecular condensa prepared analogously to the methods A to R described and tion in the presence of a diluent and in the presence of a base. some are novel. The compounds of the formula (I-1'-a) are 0899. The diluents used for the method (B) according to novel and can be prepared by method A. Some of the pheny the invention may be any inert organic solvent. US 2010/03 11593 A1 Dec. 9, 2010 60

0900 Preference is given to using hydrocarbons, such as 0910 Method (C) according to the invention is generally toluene and Xylene, and also ethers, such as dibutyl ether, performed under atmospheric pressure. tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol 0911. When performing method (C) according to the dimethyl ether, and additionally polar solvents, such as dim invention, the reaction components of the formula (IV) and ethylsulphoxide, sulpholane, dimethylformamide and N-me the acid are used, for example, in equimolar amounts. How thylpyrrolidone. It is also possible to use alcohols, such as ever, it is also possible in Some cases to use the acid as the methanol, ethanol, propanol, isopropanol, butanol, isobu Solvent or as the catalyst. tanol and tert-butanol. 0912 Method (D) according to the invention is character 0901. The bases (deprotonating agents) used when per ized in that carbonyl compounds of the formula (V) or the forming method (B) according to the invention may be any enol ether thereof, of the formula (V-a), is reacted with customary proton acceptor. Preference is given to using alkali ketenoyl halides of the formula (VI) in the presence of a metal and alkaline earth metal oxides, hydroxides and car diluent and optionally in the presence of an acid acceptor. bonates, such as sodium hydroxide, potassium hydroxide, 0913. The diluents used in method (D) according to the magnesium oxide, calcium oxide, Sodium carbonate, potas invention may be any inert organic solvent. Preference is sium carbonate and calcium carbonate, which may also be given to using optionally halogenated hydrocarbons. Such as used in the presence of phase transfer catalysts, such as, for toluene, Xylene, mesitylene, chlorobenzene and dichloroben example, triethylbenzylammonium chloride, tetrabutylam Zene, and also ethers, such as dibutyl ether, glycol dimethyl monium bromide, Adogen 464 ( methyltrialkyl(Cs-Co)am ether, diglycol dimethyl ether and diphenyl ether, and also monium chloride) or TDA 1 (tris(methoxyethoxyethyl) polar solvents, such as dimethyl Sulphoxide, Sulpholane, dim amine). It is also possible to use alkali metals, such as sodium ethylformamide or N-methylpyrrolidone. or potassium. In addition, it is possible to employ alkali metal 0914. The acid acceptors used when performing method and alkaline earth metal amides and hydrides, such as sodium variant (D) according to the invention may be any customary amide, sodium hydride and calcium hydride, and additionally acid acceptor. also alkali metal alkoxides, such as sodium methoxide, 0915 Preference is given to using tertiary amines, such as Sodium ethoxide and potassium tert-butoxide. triethylamine, pyridine, diazabicyclooctane (DABCO), diaz 0902. When performing method (B) according to the abicycloundecane (DBU), diazabicyclononene (DBN), invention, the reaction temperatures may be varied within a Hünig's base and N,N-dimethylaniline. relatively wide range. In general, the temperatures employed 0916. The reaction temperatures when performing are between 0° C. and 250° C., preferably between 50° C. and method variant (D) according to the invention can be varied 15OO C. within a relatively wide range. It is appropriate to work at 0903 Method (B) according to the invention is generally temperatures between 0° C. and 250° C., preferably between performed under atmospheric pressure. 50° C. and 220° C. 0904. When performing method (B) according to the 0917 Method (D) according to the invention is appropri invention, the reaction components of the formula (III) and ately performed under atmospheric pressure. the deprotonating bases are generally employed in about 0918 When performing method (D) according to the equimolar amounts. However, it is also possible to use one invention, the reaction components of the formulae (V) and component or the other in a greater excess (up to 3 mol). (VI) in which A, D, W, X, Y and Z are each as defined above 0905 Method (C) is characterized in that compounds of and Hal is halogen, and optionally the acid acceptors, are the formula (IV) in which A, B, V, W, X,Y,Z and Rare each generally used in about equimolar amounts. However, it is as defined above are intramolecularly cyclized in the presence also possible to use one or the other component in a greater of an acid and optionally in the presence of a diluent. excess (up to 5 mol). 0919 Method (E) according to the invention is character 0906. The diluents used in method (C) according to the ized in that thioamides of the formula (VII) are reacted with invention may be any inert organic solvent. Preference is ketenoyl halides of the formula (VI) in the presence of a given to using hydrocarbons, such as toluene and Xylene, and diluent and optionally in the presence of an acid acceptor. also halogenated hydrocarbons, such as dichloromethane, 0920. The diluents used in method variant (E) according to chloroform, ethylene chloride, chlorobenzene, dichloroben the invention may be any inert organic solvent. Preference is Zene, and also polar solvents, such as dimethyl Sulphoxide, given to using hydrocarbons, such as toluene and Xylene, and sulpholane, dimethylformamide and N-methylpyrrolidone. It also ethers, such as dibutyl ether, glycol dimethyl ether and is additionally possible to use alcohols such as methanol, diglycol dimethyl ether, and also polar solvents, such as dim ethanol, propanol, isopropanol, butanol, isobutanol, tert-bu ethylsulphoxide, sulpholane, dimethylformamide and N-me tanol. thylpyrrolidone. 0907 The acid used may optionally also serve as the dilu 0921. The acid acceptors used when performing method ent (E) according to the invention may be any customary acid 0908. The acid used in method (C) according to the inven acceptor. tion may be any customary inorganic or organic acid, for 0922 Preference is given to using tertiary amines, such as example hydrohalic acids, Sulphuric acid, alkyl-, aryl- and triethylamine, pyridine, diazabicyclooctane (DABCO), diaz haloalkylsulphonic acids, especially halogenated alkylcar abicycloundecane (DBU), diazabicyclononene (DBN), boxylic acids, for example trifluoroacetic acid. Hünig's base and N,N-dimethylaniline. 0909. The reaction temperatures when performing 0923. The reaction temperatures when performing method (C) according to the invention may be varied within a method (E) according to the invention can be varied within a relatively wide range. In general, the temperatures employed relatively wide range. It is appropriate to work at tempera are between 0° C. and 250° C., preferably between 50° C. and tures between 0° C. and 250° C., preferably between 20° C. 15OO C. and 220° C. US 2010/03 11593 A1 Dec. 9, 2010

0924 Method (E) according to the invention is appropri thylpyrrolidone. It is additionally possible to use alcohols ately performed under atmospheric pressure. Such as methanol, ethanol, propanol, isopropanol, butanol, 0925. When performing method (E) according to the isobutanol, tert-butanol. invention, the reaction components of the formulae (VII) and 0934. The bases (deprotonating agents) used when per (VI) in which A, W, X,Y and Z are each as defined above and forming method (G) according to the invention may be any Hal is halogen and optionally the acid acceptors are generally customary proton acceptor. used in about equimolar amounts. However, it is also possible 0935 Preference is given to using alkali metal and alkaline to use one or the other component in a greater excess (up to 5 earth metal oxides, hydroxides and carbonates, such as mol). Sodium hydroxide, potassium hydroxide, magnesium oxide, 0926 Method (F) is characterized in that compounds of calcium oxide, Sodium carbonate, potassium carbonate and the formula (VIII) in which A, B, Q, Q, W, X,Y,Z and Rare calcium carbonate, which can also be used in the presence of each as defined above are subjected to an intramolecular phase transfer catalysts, for example triethylbenzylammo condensation in the presence of a base. nium chloride, tetrabutylammonium bromide, Adogen 464 0927. The diluents used in method (F) according to the (methyltrialkyl (C-C)ammonium chloride) or TDA 1 (tris invention may be any organic Solvent inert toward the reac (methoxyethoxyethyl)amine). In addition, alkali metals such tion participants. Preference is given to using hydrocarbons, as sodium or potassium can be used. Additionally usable are Such as toluene and Xylene, and also ethers. Such as dibutyl alkali metal and alkaline earth metal amides and hydrides, ether, tetrahydrofuran, dioxane, glycol dimethyl ether and Such as Sodium amide, sodium hydride and calcium hydride, diglycol dimethyl ether, and also polar solvents. Such as col and additionally also alkali metal alkoxides Such as Sodium lidine, dimethylsulphoxide: sulpholane, dimethylformamide methoxide, Sodium ethoxide and potassium tert-butoxide. and N-methylpyrrolidone. It is additionally possible to use 0936. The reaction temperatures when performing alcohols such as methanol, ethanol, propanol, isopropanol, method (G) according to the invention can be varied within a butanol, isobutanol, tert-butanol. relatively wide range. In general, the temperatures employed 0928 The bases (deprotonating agents) used when per are between 0° C. and 250° C., preferably between 50° C. and forming method (F) according to the invention may be any 1500 C. customary proton acceptor. Preference is given to using alkali 0937 Method (G) according to the invention is generally metal and alkaline earth metal oxides, hydroxides and car performed under atmospheric pressure. bonates, such as sodium hydroxide, potassium hydroxide, 0938 When performing method (G) according to the magnesium oxide, calcium oxide, Sodium carbonate, potas invention, the reaction components of the formula (IX) and sium carbonate and calcium carbonate, which can also be the depronating bases are generally used in about equimolar used in the presence of phase transfer catalysts, for example amounts. However, it is also possible to use one or the other triethylbenzylammonium chloride, tetrabutylammonium component in a greater excess (up to 3 mol). bromide, Adogen 464 (methyltrialkyl (Cs-Co)ammonium 0939 Method (H-O.) according to the invention is charac chloride) or TDA 1 (tris(methoxyethoxyethyl)amine). In terized in that hydrazines of the formula (X) or salts of these addition, alkali metals such as sodium or potassium can be compounds are reacted with ketenoyl halides of the formula used. Additionally usable are alkali metal and alkaline earth (VI) in the presence of a diluent and optionally in the presence metal amides and hydrides, such as sodium amide, sodium of an acid acceptor. hydride and calcium hydride, and additionally also alkali 0940. The diluents used in method (H-C) according to the metal alkoxides such as Sodium methoxide, sodium ethoxide invention may be any inert organic solvent. Preference is and potassium tert-butoxide. given to using optionally chlorinated hydrocarbons, for 0929. The reaction temperatures when performing example mesitylene, chlorobenzene and dichlorobenzene, method (F) according to the invention can be varied within a toluene, Xylene, and also ethers, such as dibutyl ether, glycol relatively wide range. In general, the temperatures employed dimethyl ether, diglycol dimethyl ether and diphenylethane, are between -75° C. and 250° C., preferably between -50° C. and also polar solvents, such as dimethyl Sulphoxide, Sul and 150° C. pholane, dimethylformamide or N-methylpyrrolidone. 0930 Method (F) according to the invention is generally 0941 The acid acceptors used when performing method performed under atmospheric pressure. variant (H-C) according to the invention may be any custom 0931. When performing method (F) according to the ary acid acceptor. invention, the reaction components of the formula (VIII) and 0942 Preference is given to using tertiary amines, such as the depronating bases are generally used in about equimolar triethylamine, pyridine, diazabicyclooctane (DABCO), diaz amounts. However, it is also possible to use one or the other abicycloundecane (DBU), diazabicyclononene (DBN), component in a greater excess (up to 3 mol). Hünig's base and N,N-dimethylaniline. 0932 Method (G) is characterized in that compounds of 0943. The reaction temperatures when performing the formula (IX) in which A, B, Q, Q, U, W, X, Y, Z and R' method variant (H-C) according to the invention may be are each as defined above are subjected to an intramolecular varied within a relatively wide range. It is appropriate to work condensation in the presence of bases. at temperatures between 0° C. and 250° C., preferably 0933. The diluents used in method (G) according to the between 50° C. and 220° C. invention may be any organic Solvent inert toward the reac 0944 Method (H-C) according to the invention is appro tion participants. Preference is given to using hydrocarbons, priately performed under atmospheric pressure. Such as toluene and Xylene, and also ethers. Such as dibutyl 0945. When performing method (H-O.) according to the ether, tetrahydrofuran, dioxane, glycol dimethyl ether and invention, the reaction components of the formulae (VI) and diglycol dimethyl ether, and also polar solvents, such as dim (X) in which A, D, W, X, Y and Z are each as defined above ethylsulphoxide, sulpholane, dimethylformamide and N-me and Hal is halogen, and optionally the acid acceptors, are US 2010/03 11593 A1 Dec. 9, 2010 62 generally used in about equimolar amounts. However, it is ethylformamide and N-methylpyrrolidone, and also alcohols, also possible to use one or the other component in a greater Such as methanol, ethanol, propanol, isopropanol, butanol, excess (up to 5 mol). isobutanol and tert-butanol. 0946 Method (H-B) is characterized in that hydrazines of 0955. The bases (deprotonating agents) used when per the formula (X) or salts of this compound, in which A and D forming method (H-Y) according to the invention may be any are each as defined above, are subjected to a condensation customary proton acceptor. Preference is given to using alkali with malonic esters or malonamides of the formula (XI) in metal and alkaline earth metal oxides, hydroxides and car which U", W, X,Y,Z and Rare each as defined above, in the bonates, such as Sodium hydroxide, potassium hydroxide, presence of a base. magnesium oxide, calcium oxide, Sodium carbonate, potas 0947 The diluents used in method (H-B) according to the sium carbonate and calcium carbonate, which can also be invention may be any inert organic solvent. Preference is used in the presence of phase transfer catalysts, for example given to using optionally halogenated hydrocarbons. Such as triethylbenzylammonium chloride, tetrabutylammonium toluene, Xylene, mesitylene, chlorobenzene and dichloroben bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium Zene, and also ethers. Such as dibutyl ether, tetrahydrofuran, chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is dioxane, diphenyl ether, glycol dimethyl ether and diglycol additionally possible to use alkali metals such as sodium or dimethyl ether, and also polar solvents, such as dimethyl potassium. It is also possible to use alkali metal and alkaline Sulphoxide, Sulpholane, dimethylformamide, dimethylaceta earth metal amides and hydrides, such as Sodium amide, mide and N-methylpyrrolidone, and also alcohols such as Sodium hydride and calcium hydride, and additionally also methanol, ethanol, propanol, isopropanol, butanol, isobu alkali metal alkoxides, such as Sodium methoxide, Sodium tanol and tert-butanol. ethoxide and potassium tert-butoxide. 0948. The bases (deprotonating agents) used when per 0956. The reaction temperatures when performing forming method (H-B) according to the invention may be any method (H-Y) according to the invention can be varied within customary proton acceptor. Preference is given to using alkali a relatively wide range. In general, the temperatures metal and alkaline earth metal oxides, hydroxides and car employed are between 0°C. and 250°C., preferably between bonates, such as sodium hydroxide, potassium hydroxide, 50° C. and 150° C. magnesium oxide, calcium oxide, Sodium carbonate, potas 0957 Method (H-Y) according to the invention is gener sium carbonate and calcium carbonate, which can also be ally performed under atmospheric pressure. used in the presence of phase transfer catalysts, for example 0958. When performing method (H-Y) according to the triethylbenzylammonium chloride, tetrabutylammonium invention, the reaction components of the formula (XII) and bromide, Adogen 464 (methyltrialkyl (Cs-Co)ammonium the deprotonating bases are generally used in about double chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is the equimolaramounts. However, it is also possible to use one additionally possible to use alkali metals such as sodium or or the other component in a greater excess (up to 3 mol). potassium. It is also possible to use alkali metal and alkaline 0959 Method (I) is characterized in that compounds of the earth metal amides and hydrides, such as Sodium amide, formula (XIII) in which A, B, D, Q, Q, W, X,Y,Z and Rare Sodium hydride and calcium hydride, and additionally also each as defined above are subjected to an intramolecular alkali metal alkoxides, such as Sodium methoxide, sodium condensation in the presence of a base. ethoxide and potassium tert-butoxide. 0960. The diluents used in method (I) according to the 0949. It is also possible to use tertiary amines, such as invention may be any inert organic solvent. Preference is triethylamine, pyridine, diazabicyclooctane (DABCO), diaz given to using hydrocarbons, such as toluene and Xylene, and abicycloundecane (DBU), diazabicyclononene (DBN), also ethers, such as dibutyl ether, tetrahydrofuran, dioxane, Hünig's base and N,N-dimethylaniline. glycol dimethyl ether and diglycol dimethyl ether, and also 0950 The reaction temperatures when performing polar solvents, such as dimethyl Sulphoxide, Sulpholane, dim method (H-B) according to the invention can be varied within ethylformamide and N-methylpyrrolidone, and also alcohols, a relatively wide range. In general, the temperatures Such as methanol, ethanol, propanol, isopropanol, butanol, employed are between 0°C. and 280°C., preferably between isobutanol and tert-butanol. 50° C. and 180° C. 0961. The bases (deprotonating agents) used when per 0951. The method (H-B) according to the invention is gen forming method (I) according to the invention may be any erally performed under atmospheric pressure. customary proton acceptor. Preference is given to using alkali metal and alkaline earth metal oxides, hydroxides and car 0952. When performing method (H-B) according to the bonates, such as Sodium hydroxide, potassium hydroxide, invention, the reaction components of the formulae (XI) and magnesium oxide, calcium oxide, Sodium carbonate, potas (X) are generally used in about equimolaramounts. However, sium carbonate and calcium carbonate, which can also be it is also possible to use one or the other component in a used in the presence of phase transfer catalysts, for example greater excess (up to 3 mol). triethylbenzylammonium chloride, tetrabutylammonium 0953 Method (H-Y) is characterized in that compounds of bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium the formula (XII)in which A, D, W, X,Y,Z and Rare each as chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is defined above are Subjected to an intramolecular condensa additionally possible to use alkali metals such as sodium or tion in the presence of a base. potassium. It is also possible to use alkali metal and alkaline 0954. The diluents used in method (H-Y) according to the earth metal amides and hydrides, such as Sodium amide, invention may be any inert organic solvent. Preference is Sodium hydride and calcium hydride, and additionally also given to using hydrocarbons, such as toluene and Xylene, and alkali metal alkoxides, such as Sodium methoxide, Sodium also ethers, such as dibutyl ether, tetrahydrofuran, dioxane, ethoxide and potassium tert-butoxide. glycol dimethyl ether and diglycol dimethyl ether, and also 0962. The reaction temperatures when performing polar solvents, such as dimethyl Sulphoxide, Sulpholane, dim method (I) according to the invention can be varied within a US 2010/03 11593 A1 Dec. 9, 2010 relatively wide range. In general, the temperatures employed ethylformamide and N-methylpyrrolidone, and also alcohols, are between -80° C. and 180°C., preferably between -50° C. Such as methanol, ethanol, propanol, isopropanol, butanol, and 120° C. isobutanol and tert-butanol. 0963 Method (I) according to the invention is generally 0973. The bases (deprotonating agents) used when per performed under atmospheric pressure. forming method (K) according to the invention may be any customary proton acceptor. Preference is given to using alkali 0964. When performing method (I) according to the metal and alkaline earth metal oxides, hydroxides and car invention, the reaction components of the formula (XIII) and bonates, such as Sodium hydroxide, potassium hydroxide, the deprotonating bases are generally used in about double magnesium oxide, calcium oxide, Sodium carbonate, potas the equimolar amounts. However, it is also possible to use one sium carbonate and calcium carbonate, which can also be or the other component in a greater excess (up to 3 mol). used in the presence of phase transfer catalysts, for example 0965 Method (J) is characterized in that compounds of the triethylbenzylammonium chloride, tetrabutylammonium formula (XIV) in which A, B, Q, Q, W, X, Y, Z and Rare bromide, Adogen 464 ( methyltrialkyl (Cs-Co)ammonium each as defined above are subjected to an intramolecular chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is condensation in the presence of a base. additionally possible to use alkali metals such as sodium or 0966. The diluents used in method (J) according to the potassium. It is also possible to use alkali metal and alkaline invention may be any inert organic solvent. Preference is earth metal amides and hydrides, such as Sodium amide, given to using hydrocarbons, such as toluene and Xylene, and Sodium hydride and calcium hydride, and additionally also also ethers, such as dibutyl ether, tetrahydrofuran, dioxane, alkali metal alkoxides, such as Sodium methoxide, Sodium glycol dimethyl ether and diglycol dimethyl ether, and also ethoxide and potassium tert-butoxide. polar solvents, such as dimethyl Sulphoxide, Sulpholane, dim 0974. When performing method (K) according to the ethylformamide and N-methylpyrrolidone, and also alcohols, invention, the reaction temperatures can be varied within a Such as methanol, ethanol, propanol, isopropanol, butanol, relatively wide range. In general, the temperatures employed isobutanol and tert-butanol. are between -78° C. and 250° C., preferably between 0° C. 0967. The bases (deprotonating agents) used when per and 150° C. forming method (J) according to the invention may be any 0975 Method (K) according to the invention is generally customary proton acceptor. Preference is given to using alkali performed under atmospheric pressure. metal and alkaline earth metal oxides, hydroxides and car 0976. When performing method (K) according to the bonates, such as sodium hydroxide, potassium hydroxide, invention, the reaction components of the formula (XV) and magnesium oxide, calcium oxide, Sodium carbonate, potas the deprotonating bases are generally used in about double sium carbonate and calcium carbonate, which can also be the equimolaramounts. However, it is also possible to use one used in the presence of phase transfer catalysts, for example or the other component in a greater excess (up to 3 mol). triethylbenzylammonium chloride, tetrabutylammonium 0977 Method (L-C.) is characterized in that compounds of bromide, Adogen 464 (methyltrialkyl (Cs-Co)ammonium the formulae (I-1-a) to (I-11-a) are each reacted with carbonyl chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is halides of the formula (XVI), optionally in the presence of a additionally possible to use alkali metals such as sodium or diluent and optionally in the presence of an acid binder. potassium. It is also possible to use alkali metal and alkaline 0978. The diluents used in method (L-C) according to the earth metal amides and hydrides, such as Sodium amide, invention may be all solvents inert toward the acid halides. Sodium hydride and calcium hydride, and additionally also Preference is given to using hydrocarbons, such as benzine, alkali metal alkoxides, such as Sodium methoxide, sodium benzene, toluene, Xylene and tetralin, and also halohydrocar ethoxide and potassium tert-butoxide. bons, such as methylene chloride, chloroform, carbon tetra 0968. The reaction temperatures when performing chloride, chlorobenzene and o-dichlorobenzene, and also method (J) according to the invention may be varied within a ketones, such as acetone and methyl isopropyl ketone, and relatively wide range. In general, temperatures between 0°C. additionally ethers, such as diethyl ether, tetrahydrofuran and and 250° C., preferably between 50° C. and 150° C., are dioxane, and additionally carboxylic esters, such as ethyl employed. acetate, and also strongly polar solvents, such as dimethyl sulphoxide and sulpholane. If the hydrolysis stability of the 0969 Method (J) according to the invention is generally acid halide permits it, the reaction can also be performed in performed under atmospheric pressure. the presence of water. 0970. When performing method (J) according to the 0979 Useful acide binders in the reaction in the process invention, the reaction components of the formula (XIV) and according to the invention (L-C.) are any customary acid the deprotonating bases are generally used in about double acceptor. Preference is given to using tertiary amines, such as the equimolar amounts. However, it is also possible to use one triethylamine, pyridine, diazabicyclooctane (DABCO), diaz or the other component in a greater excess (up to 3 mol). abicycloundecene (DBU), diazabicyclononene (DBN), 0971 Method (K) is characterized in that compounds of Hünig's base and N,N-dimethylaniline, and also alkaline the formula (XV) in which A, B, D, W, X,Y,Z and Rare each earth metal oxides, such as magnesium and calcium oxide, as defined above are Subjected to an intramolecular conden and also alkali metal and alkaline earth metal carbonates, sation in the presence of a base. Such as Sodium carbonate, potassium carbonate and calcium 0972. The diluents used in method (K) according to the carbonate, and also alkali metal hydroxides such as Sodium invention may be any inert organic solvent. Preference is hydroxide and potassium hydroxide. given to using hydrocarbons, such as toluene and Xylene, and 0980. The reaction temperatures in method (L-C.) accord also ethers, such as dibutyl ether, tetrahydrofuran, dioxane, ing to the invention may be varied within a relatively wide glycol dimethyl ether and diglycol dimethyl ether, and also range. In general, the temperatures employed are between polar solvents, such as dimethyl Sulphoxide, Sulpholane, dim –20° C. and +150° C., preferably between 0° C. and 100° C. US 2010/03 11593 A1 Dec. 9, 2010 64

0981. When performing method (L-C.) according to the ence of a diluent and an acid binder, the reaction temperatures invention, the starting materials of the formulae (I-1-a) to are generally between -20° C. and +100° C., preferably (I-11-a) and the carbonyl halide of the formula (XVI) are between 0° C. and 50° C. generally used each in approximately equivalent amounts. 0992 Method (M) according to the invention is generally However, it is also possible to use the carbonyl halide in a performed under atmospheric pressure. greater excess (up to 5 mol). The workup is effected by 0993 When performing method (M) according to the customary methods. invention, the starting materials of the formulae (I-1-a) to 0982 Method (L-R) is characterized in that compounds of (I-11-a) and the appropriate chloroformic ester or chlorofor the formulae (I-1-a) to (I-11-a) are reacted with carboxylic mic thioester of the formula (XVIII) are generally each anhydrides of the formula (XVII), optionally in the presence employed in approximately equivalent amounts. However, it of a diluent and optionally in the presence of an acid binder. is also possible to use one component or the other in a greater 0983. The diluents used in method (L-B) according to the excess (up to 2 mol). Workup is performed by customary invention are preferably those diluents which are also prefer methods. In general, precipitated salts are removed and the ably considered when acid halides are used. Otherwise, a reaction mixture that remains is concentrated by removing carboxylic anhydride used in excess may function simulta the diluent under reduced pressure. neously as a diluent. 0994 Method (N) according to the invention is character 0984. Useful acid binders optionally added in method ized in that compounds of the formulae (I-1-a) to (I-11-a) are (L-R) are preferably those acid binders which are preferably in each case reacted with compounds of the formula (XIX) in also considered when acid halides are used. the presence of a diluent and optionally in the presence of an 0985. The reaction temperatures in method (L-B) accord acid binder. ing to the invention can be varied within a relatively wide 0995. In preparation method (N), about 1 mol of chlo range. In general, the temperatures employed are between romonothioformic ester or chlorodithioformic ester of the –20° C. and +150° C., preferably between 0° C. and 100° C. formula (XIX) is reacted per mole of the starting compound 0986. When performing method (L-B) according to the of the formulae (I-1-a) to (I-11-a) at from 0 to 120° C. invention, the starting materials of the formulae (I-1-a) to preferably from 20 to 60° C. (I-11-a) and the carboxylic anhydride of the formula (XVII) 0996 Suitable diluents which are added optionally are any are generally each used inapproximately equivalent amounts. inert polar organic solvent, such as ethers, amides, Sulphones, However, it is also possible to use the carboxylic anhydride in Sulphoxides, and also halogenated alkanes. a greater excess (up to 5 mol). The workup is effected by 0997 Preference is given to using dimethyl sulphoxide, customary methods. tetrahydrofuran, dimethylformamide or methylene chloride. 0987. In general, diluent and excess carboxylic anhydride 0998 If, in a preferred embodiment, the enolate salt of the and the carboxylic acid formed are removed by distillation or compounds (I-1-a) to (I-11-a) is prepared by addition of by washing with an organic solvent or with water. strong deprotonating agents, for example Sodium hydride or 0988 Method (M) is characterized in that compounds of potassium tert-butoxide, the further addition of acid binders the formulae (I-1-a) to (I-11-a) are in each case reacted with may be dispensed with. chloroformic esters or chloroformic thioesters of the formula 0999 If acid binders are used, these are customary inor (XVIII), optionally in the presence of a diluent and optionally ganic or organic bases; examples include Sodium hydroxide, in the presence of an acid binder. Sodium carbonate, potassium carbonate, pyridine and triethy 0989 Suitable acid binders for the reaction in method (M) lamine. according to the invention are any customary acid acceptor. 1000 The reaction may be performed at atmospheric pres Preference is given to using tertiary amines, such as triethy Sure or under elevated pressure, preference being given to lamine, pyridine, DABCO, DBU, DBA, Hinig's base and working at atmospheric pressure. Workup is performed by N,N-dimethylaniline, and also alkaline earth metal oxides, customary methods. Such as magnesium oxide and calcium oxide, and also alkali 1001 Method (O) according to the invention is character metal and alkaline earth metal carbonates, such as sodium ized in that compounds of the formulae (I-1-a) to (I-11-a) are carbonate, potassium carbonate and calcium carbonate, and in each case reacted with sulphonyl chlorides of the formula also alkali metal hydroxides, such as Sodium hydroxide and (XX), optionally in the presence of a diluent and optionally in potassium hydroxide. the presence of an acid binder. 0990 Suitable diluents for use in method (M) according to 1002. In preparation method (O), about 1 mol of sulphonyl the invention are any solvents which are inert towards the chloride of the formula (XX) is reacted per mole of the start chloroformic esters or chloroformic thioesters. Preference is ing compound of the formulae (I-1-a) to (I-11-a) at from -20 given to using hydrocarbons, such as benzine, benzene, tolu to 150° C., preferably from 20 to 70° C. ene, Xylene and tetralin, and also halogenated hydrocarbons, 1003 Useful diluents which are optionally added are any such as methylene chloride, chloroform, carbon tetrachlo inert polar organic solvent, such as ethers, amides, nitriles, ride, chlorobenzene and o-dichlorobenzene, and also Sulphones, Sulphoxides or halogenated hydrocarbons, such as ketones, such as acetone and methyl isopropyl ketone, and methylene chloride. also ethers, such as diethyl ether, tetrahydrofuran and diox 1004 Preference is given to using dimethyl sulphoxide, ane, and additionally carboxylic esters, such as ethyl acetate, tetrahydrofuran, dimethylformamide, methylene chloride. and also strongly polar solvents, such as dimethyl Sulphoxide 1005 If, in a preferred embodiment, the enolate salt of the and Sulpholane. compounds (I-1-a) to (I-11-a) is prepared by addition of 0991. When performing method (M) according to the strong deprotonating agents (for example Sodium hydride or invention, the reaction temperatures can be varied within a potassium tert-butoxide), the further addition of acid binders relatively wide range. If the method is performed in the pres may be dispensed with. US 2010/03 11593 A1 Dec. 9, 2010

1006. If acid binders are used, these are customary inor 1021 Optionally, catalysts may be added to accelerate the ganic or organic bases, for example sodium hydroxide, reaction. Suitable for use as catalysts are, very advanta Sodium carbonate, potassium carbonate, pyridine and triethy geously, organotin compounds, for example dibutyltin dilau lamine. rate. The reaction is preferably performed at atmospheric 1007. The reaction may be performed at atmospheric pres pressure. sure or under elevated pressure and is preferably performed at 1022. In preparation method (R-B), about 1 mol of car atmospheric pressure. Workup is performed by customary bamoyl chloride of the formula (XXV) is reacted per mole of methods. starting compound of the formulae (I-1-a) to (I-11-a), at from 1008 Method (P) according to the invention is character -20 to 150° C., preferably at from 0 to 70° C. ized in that compounds of the formulae (I-1-a) to (I-11-a) are 1023 Suitable diluents which are added optionally are any reacted with phosphorus compounds of the formula (XXI). inert polar organic solvent, such as ethers, amides, Sulphones, optionally in the presence of a diluent and optionally in the Sulphoxides or halogenated hydrocarbons. presence of an acid binder. 1024 Preference is given to using dimethyl sulphoxide, 1009. In preparation method (P), to obtain compounds of tetrahydrofuran, dimethylformamide or methylene chloride. the formulae (I-1-e) to (I-11-e), from 1 to 2, preferably from 1025) If, in a preferred embodiment, the enolate salt of the 1 to 1.3, mol of the phosphorus compound of the formula compounds (I-1-a) to (I-11-a) is prepared by addition of (XXI) are reacted per mole of the compounds (I-1-a) to (I-11 strong deprotonating agents (for example Sodium hydride or a), attemperatures between -40°C. and 150° C., preferably potassium tert-butoxide), the further addition of acid binders between -10 and 110° C. may be dispensed with. 1010 Suitable diluents which are added optionally are any 1026 If acid binders are used, they are customary inor inert polar organic solvent, Such as ethers, amides, nitriles, ganic or organic bases, for example sodium hydroxide, alcohols, Sulphides, Sulphones, Sulphoxides, etc. Sodium carbonate, potassium carbonate, triethylamine or 1011 Preference is given to using acetonitrile, dimethyl pyridine. sulphoxide, tetrahydrofuran, dimethyl-formamide, methyl 1027. The reaction can be performed at atmospheric pres ene chloride. sure or under elevated pressure and is preferably performed at 1012 Suitable acid binders which are optionally added are atmospheric pressure. Workup is performed by customary customary inorganic or organic bases, such as hydroxides, methods. carbonates or amines. Examples include Sodium hydroxide, 1028 Method (S) is characterized in that compounds of sodium carbonate, potassium carbonate, pyridine and triethy the formulae (I-1') to (I-11") in which A, B, D, G, Q, Q, U, lamine. Q, Q, W, X and Y are each as defined above and Z is 1013 The reaction can be performed at atmospheric pres preferably bromine or iodine are reacted with alcohols of the sure or under elevated pressure and is preferably performed at formula ZOH in which Z is as defined above, in the presence atmospheric pressure. Workup is performed by customary of a base and of a Cu(I) salt (e.g. CuBr or Cul). methods of organic chemistry. The resulting end products are 1029. The diluents used in method (S) according to the preferably purified by crystallization, chromatographic puri invention may be any organic Solvent inert toward the reac fication or “incipient distillation’, i.e. removal of the volatile tion participants. Preference is given to using hydrocarbons, components under reduced pressure. Such as toluene and Xylene, and also ethers. Such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and 1014 Method (Q) is characterized in that compounds of diglycol dimethyl ether, and also polar solvents, such as col the formulae (I-1-a) to (I-11-a) are reacted with metal hydrox lidine, dimethyl Sulphoxide, Sulpholane, dimethyl-forma ides or metal alkoxides of the formula (XXII) or amines of the mide, dimethylacetamide and N-methylpyrrolidone, esters formula (XXII), optionally in the presence of a diluent. Such as methyl acetate, ethyl acetate, propyl acetate, and 1015 Suitable diluents for use in method (Q) according to alcohols of the formula WOH, for example methanol, etha the invention are, preferably, ethers, such as tetrahydrofuran, nol, propanol, isopropanol, butanol and isobutanol. dioxane, diethyl ether, or else alcohols, such as methanol, 1030 The bases (deprotonating agents) used when per ethanol, isopropanol, and also water. forming method (S) according to the invention may be any 1016 Method (Q) according to the invention is generally customary proton acceptor. Preference is given to using alkali performed under atmospheric pressure. metals such as sodium or potassium. It is additionally pos 1017. The reaction temperatures are generally between sible to use alkali metal and alkaline earth metal amides and –20° C. and 100° C., preferably between 0° C. and 50° C. hydrides, such as sodium amide, Sodium hydride and calcium 1018 Method (R) according to the invention is character hydride, and preferably also alkali metal alkoxides such as ized in that compounds of the formulae (I-1-a) to (I-11-a) are Sodium methoxide, Sodium ethoxide, Sodium isopropoxide, reacted in each case with (R-C) compounds of the formula Sodium tert-butoxide and potassium tert-butoxide. (XXIV), optionally in the presence of a diluent and optionally 1031. The reaction temperature when performing method in the presence of a catalyst, or (R-B) with compounds of the (S) according to the invention may be varied within a rela formula (XXV), optionally in the presence of a diluent and tively wide range. In general, the temperatures employed are optionally in the presence of an acid binder. between 0° C. and 250° C., preferably between 50° C. and 1019. In preparation method (R-O.), about 1 mol of isocy 1500 C. anate of the formula (XXIV) is reacted per mole of starting 1032 Method (S) according to the invention is generally compound of the formulae (I-1-a) to (I-11-a), at from 0 to performed under atmospheric pressure. 100° C., preferably from 20 to 50° C. 1033. When performing method (S) according to the 1020 Suitable diluents which are added optionally are any invention, the reaction component of the formula (I-1') to inert organic solvent, such as ethers, amides, nitrites, Sul (I-11") is generally reacted with excesses of the alcohols ZOH phones or Sulphoxides. and of the bases of up to 20 mol, preferably 3 to 5 mol. The US 2010/03 11593 A1 Dec. 9, 2010 66 copper(I) salts are generally used in catalytic amounts; 0.001 lectularius, Collaria spp., Creontiades dilutus, Dasynus pip to 0.5 mol, preferably 0.01 to 0.2 mol. However, it is also eris, Dichelops fircatus, Diconocoris hewetti, Dysdercus possible to use them in equimolar amounts. spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Hor 1034 The inventive active ingredients are suitable, given cias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, good plant compatibility, favourable toxicity to warm Lygus spp., Macropes excavatus, Miridae, Monal onion atra blooded animals and good environmental compatibility, for tum, Nezara spp., Oebalus spp., Pentomidae, Piesma protecting plants and plant organs; for increasing harvest quadrata, Piezodorus spp., Psallus spp., Pseudacy.sta persea, yields, improving the quality of the harvest and for control Rhodnius spp., Sahlbergella singularis, Scaptocoris Casta ling animal pests, especially insects, aracnids, helminthes, nea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Tri nematodes and molluscs, which are encountered in agricul atoma spp. ture, in horticulture, in animal breeding, in forests, in gardens 1047. From the order of the Anoplura (Phthiraptera), for and leisure facilities, in the protection of stored products and example Damalinia spp., Haematopinus spp., Linognathus materials, and in the hygiene sector. They can preferably be spp., Pediculus spp., Ptirus pubis, Trichodectes spp. used as crop protection compositions. They are active against 1048. From the order of the Homoptera, for example normally sensitive and resistant species, and against all or Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Ago Some stages of development. The abovementioned pests noscena spp., Aleurodes spp., Aleurolobus barodensis, Aleu include: rothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella 1035. From the phylum Mollusca, for example from the spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, class of the Lamellibranchiata, for example Dreissena spp. Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum 1036 From the class of the Gastropoda, for example Arion Solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Brevicoryne brassicae, Calligypona marginata, Car spp., Lynnaea spp., Oncomelania spp., Pomacea spp., Suc neocephala filgida, Ceratovacuna lanigera, Cercopidae, Cinea spp. Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tega 1037. From the phylum Arthropoda, for example from the lensis, Chlorita Onuki, Chromaphis juglandicola, Chry order of the Isopoda, for example Armadillidium vulgare, somphalus ficus, Cocadulina mbila, Coccomytilus halli, Coc Oniscus asellus, Porcellio Scaber. cus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., 1038. From the class of the Arachnida, for example Acarus Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp., spp., Aceria Sheldoni, Aculops spp., Aculus spp., Amblyomma Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythro spp., Amphitetranychus viennensis, Argas spp., Boophilus neura spp., Euscelis bilobatus, Ferrisia spp., Geococcus cof spp., Brevipalpus spp., Bryobia praetiosa, Centruroides spp., feae, Hieroglyphus spp., Homalodisca coagulata, Hva Chorioptes spp., Dermanyssus gallinae, Dermatophagoides lopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus pteronyssius, Dermatophagoides farinae, Dermacentor spp., spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp., Eriophyes spp., Halotydeus destructor; Hemitarisonemus Melanaphis sacchari, Metcalfiella spp., Metopolophium spp., Hvalomma spp., Ixodes spp., Latrodectus spp., LOXOsce dirhodium, Monellia Costalis, Monelliopsis pecanis, Myzus les spp., Metatetranychus spp., Nuphersa spp., Oligonychus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata spp., Ornithodorus spp., Ornithonyssus spp., Panonychus lugens, Oncometopia spp., Orthezia praelonga, Parabemisia spp., Phylocoptruta oleivora, Polyphagotarisonemus latus, myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sar Peregrinus maidis, Phenacoccus spp., Phloeomyzus passeri coptes spp., Scorpio maurus, Stenotarisonemus spp., Tarson nii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidis emus spp., Tetranychus spp., Vaejovis spp., Vasates lycoper trae, Planococcus spp., Protopulvinaria pyriformis, Pseu SC. daulacaspis pentagona, Pseudococcus spp., Psylla spp., 1039 From the order of the Symphyla, for example Scuti Pteromalus spp., Pyrilla spp., Ouadraspidiotus spp., Oue gerella spp. Sada gigas, Rastrococcus spp., Rhopalosiphum spp., Saisse 1040 From the order of the Chilopoda, for example Geo tia spp., Scaphoides titanus, Schizaphis graminum, Selena philus spp., Scutigera spp. spidus articulatus, Sogata spp., Sogatella fircifera, 1041. From the order of the Collembola, for example Ony Sogatodes spp., Stictocephala festina, Tenalaphara malayen chiurus armatus. sis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., 1042. From the order of the Diplopoda, for example Bla Trialeurodes spp., Trioza spp., Tiphlocyba spp., Unaspis niulus guttulatus. spp., Viteus vitifolii, Zygina spp. 1043. From the order of the Zygentoma, for example Lepi 1049 From the order of the Coleoptera, for example Aca sma saccharina, Thermobia domestica. lymma vittatum, Acanthoscelides Obtectus, Adoretus spp., 1044. From the order of the Orthoptera, for example Agelastica alni, Agriotes spp., Alphitobius diaperinus, Acheta domesticus, Blatta Orientalis, Blattella germanica, Amphimallon solstitialis, Anobium punctatum, Anoplophora Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia Locusta spp., Melanoplus spp., Periplaneta spp., Pulex irri spp., Atomaria spp., Attagenus spp., Bruchidius Obtectus, tans, Schistocerca gregaria, Supella longipalpa. Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutor 1045. From the order of the Isoptera, for example Copto rhynchus spp., Chaetocnema spp., Cleonus mendicus, Con termes spp., Cornitermes cumulans, Cryptotermes spp., oderus spp., Cosmopolites spp., Costelytra zealandica, Cten Incisitermes spp., Microtermes Obesi, Odontotermes spp., icera spp., Curculio spp., Cryptorhynchus lapathi, Reticulitermes spp., Cylindrocopturus spp., Dermestes spp., Diabrotica spp., 1046. From the order of the Heteroptera, for example Dichocrocis spp., Diloboderus spp., Epilachna spp., Epitrix Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., spp., Faustinus spp., Gibbium psylloides, Hellula undalis, Calocoris spp., Campylomma livida, Cavelerius spp., Cimex Heteronychus arator, Heteronyx spp., Hylamorpha elegans, US 2010/03 11593 A1 Dec. 9, 2010 67

Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Dasy neura spp., Delia spp., Dermatobia hominis, Droso Lachnosterna Consanguinea, Lema spp., Leptinotarsa phila spp., Echinocnemus spp., Fannia spp., Gasterophilus decemlineata, Leucoptera spp., Lisso-rhoptrus Oryzophilus, spp., Glossina spp., Haematopota spp., Hydrellia spp., Hyl Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., envia spp., Hippobosca spp., Hypoderma spp., Liriomyza Melanotus spp., Melligethes aeneus, Melolontha spp., Migdo spp. Lucilia spp., Lutzomia spp., Mansonia spp., Musca spp., lus spp., Monochamus spp., Naupactus xanthographus, Nip Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., tus hololeucus, Oryctes rhinoceros, Oryzaephilus surina Phlebotomus spp., Phorbia spp., Phormia spp., Prodiplosis mensis, Oryzaphagus Oryzae, Otiorrhynchus spp., spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simu Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga lium spp., Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Phyllotreta spp., Popillia japonica, Premnotrypes spp., spp., Tipula spp. ProStephanus truncatus, Psylliodes spp., Ptinus spp., Rhizo 1053 From the order of the Thysanoptera, for example bius ventralis, Rhizopertha dominica, Sitophilus spp., Sphe Anaphothrips obscurus, Baliothrips biformis, Drepanothris nophorus spp., Stegobium paniceum, Sternechus spp., Sym reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips phyletes spp., Tanymecus spp., Tenebrio molitor; Tribolium spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, spp., Trogoderma spp., Tichius spp., Xylotrechus spp., Scirtothrips spp., Taeniothrips cardanoni, Thrips spp. Zabrus spp. 1054 From the order of the Siphonaptera, for example 1050 From the order of the Hymenoptera, for example Ceratophyllus spp., Ctenocephalides spp., Tunga penetrans, Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hop Xenopsylla cheopis. locampa spp., Lasius spp., Monomorium pharaonic, Sole 1055. From the phyla of the Plathelminthes and Nema nopsis invicta, Tapinoma spp., Vespa spp. todes as animal parasites, for example from the class of the 1051. From the order of the Lepidoptera, for example Helminthes, for example Ancylostoma duodenale, Ancylos Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis toma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Alabama spp., Amyelois transitella, Anarsia spp., Anti spp., Ascaris spp., Brugia malayi, Brugia timori, Bunosto carsia spp., Argyroploce spp., Barathra brassicae, Borbo mum spp., Chabertia spp., Clonorchis spp., Cooperia spp., cinnara, Bucculatrix thurberiella, Bupalus piniarius, Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium Busseola spp., Cacoecia spp., Caloptilia theivora, Capua latum, Dracunculus medimensis, Echinococcus granulosus, reticulana, Carpocapsa pomonella, Carposina niponensis, Echinococcus multilocularis, Enterobius vermicularis, Chematobia brumata, Chilo spp., Choristoneura spp., Clysia Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis ambiguella, Cnaphalocerus spp., Cnephasia spp., Conopo nana, Hvostrongulus spp., Loa Loa, Nematodirus spp., morpha spp., Conotrachelus spp., Copitarsia spp., Cydia Oesophagostomum spp. Opisthorchis spp., Onchocerca vol spp., Dallaca noctuides, Diaphania spp., Diatraea sacchara vulus, Ostertagia spp., Paragonimus spp., Schistosomen spp. lis, Earias spp., Ecdytolopha aurantium, Elasmopalpus Strongyloides fuelleborni, Strongyloides Stercoralis, Strony lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., loides spp., Taenia Saginati, Taenia solium, Trichinella spi Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ralis, Trichinella nativa, Trichinella britovi, Trichinella nel ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria soni, Trichinella pseudopsiralis, Tricho strongulus spp., mellonella, Gracillaria spp., Grapholitha spp., Hedylepta Trichuris trichuria, Wuchereria bancrofti. spp., Helicoverpa spp., Heliothis spp., Hofinannophila pseu 1056 From the phylum of the Nematodes as plant pests, dospretella, Homoeosoma spp., Homona spp., Hyponomeuta for example Aphelenchoides spp., Bursaphelenchus spp., padella, Kakivoria flavofasciata, Laphygma spp., Laspeyre Dity lenchus spp., Globodera spp., Heterodera spp., Longi sia molesta, Leucinodes Orbonalis, Leucoptera spp., Lithoc dorus spp., Meloidogyne spp., Pratylenchus spp., Radopho Olletis spp., Lithophane antennata, Lobesia spp., Loxagrotis lus similis, Trichodorus spp., Tilenchulus semipenetrans, albicosta, Lymantria spp., Lyonetia spp., Malacosoma neus Xiphinema spp. tria, Maruca testulalis, Mamestra brassicae, Mocis spp., 1057. From the subphylum of the Protozoa, for example Mythinna separata, Nymphula spp., Oiketicus spp., Oria Eineria. spp., Orthaga spp., Ostrinia spp., Oulema Oryzae, Panolis 1058 If appropriate, the inventive compounds can, at cer flammea, Parnara spp., Pectinophora spp., Perileucoptera tain concentrations or application rates, also be used as her spp., Phthorimaea spp., Phyllocnistis citrella, Phyllono bicides, safeners, growth regulators or agents to improve rycter spp., Pieris spp., Platynota Stultana, Plodia interpunc plant properties, or as microbicides, for example as fungi tella, Plusia spp., Plutella xylostella, Prays spp., Prodenia cides, antimycotics, bactericides, viricides (including agents spp., Protoparce spp., Pseudaletia spp., Pseudoplusia against Viroids) or as agents against MLO (Mycoplasma-like includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius organisms) and RLO (Rickettsia-like organisms). If appropri spp., Scirpophaga spp., Scotia Segetum, Sesamia spp., Spar ate, they can also be employed as intermediates or precursors ganothis spp., Spodoptera spp., Stathmopoda spp., Stomop for the synthesis of other active ingredients. teryx subsecivella, Synanthedon spp., Tecia Solanivora, Ther 1059 All plants and plant parts can be treated in accor mesia gemmatalis, Tinea pellionella, Tineola bisselliella, dance with the invention. Plants should be understood to Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., Tiuta mean, in the present context, all plants and plant populations absoluta, Virachola spp. Such as desired and undesired wild plants or crop plants 1052 From the order of the Diptera, for example Aedes (including naturally occurring crop plants). Crop plants can spp., Agromyza spp., Anastrepha spp., Anopheles spp., be plants which can be obtained by conventional plant breed Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calli ing and optimization methods or by biotechnological and phora erythrocephala, Ceratitis capitata, Chironomus spp., genetic engineering methods or by combinations of these Chrysomyia spp., Chrysops spp., Cochliomyia spp., Con methods, including the transgenic plants and including the tarinia spp., Cordylobia anthropophaga, Culex spp., Culi plant cultivars protectable or not protectable by plant breed coides spp., Culiseta spp., Cuterebra spp., Dacus oleae, ers’ rights. Plant parts should be understood to mean all parts US 2010/03 11593 A1 Dec. 9, 2010 and organs of plants above and below the ground, such as to plants or plant parts. The solid or liquid carrier is generally shoot, leaf flower and root, examples which may be men inert and should be usable in agriculture. tioned being leaves, needles, stalks, stems, flowers, fruit bod 1067 Useful solid carriers are: ies, fruits, seeds, roots, tubers and rhizomes. The plant parts for example, ammonium salts and ground natural minerals also include harvested material, and vegetative and generative Such as kaolins, clays, talc, chalk, quartz, attapulgite, mont propagation material, for example cuttings, tubers, rhizomes, morillonite or diatomaceous earth, and ground synthetic min offshoots and seeds. erals, such as finely divided silica, alumina and silicates; 1060 Inventive treatment of the plants and plant parts with Suitable Solid carriers for granules are: for example, crushed the active ingredients is effected directly or by allowing the and fractionated natural rocks such as calcite, marble, pum compounds to act on their Surroundings, habitat or storage ice, Sepiolite and dolomite, and also synthetic granules of space by the customary treatment methods, for example by inorganic and organic meals, and granules of organic material immersion, spraying, evaporation, fogging, scattering, paint Such as paper, sawdust, coconut shells, maize cobs and ing on, injection and, in the case of propagation material, in tobacco stalks; suitable emulsifiers and/or foam-formers are: particular in the case of seeds, also by applying one or more for example, nonionic and anionic emulsifiers, such as poly oxyethylene fatty acid esters, polyoxyethylene fatty alcohol COats. ethers, for example alkylaryl polyglycol ethers, alkylsulpho 1061. The active ingredients can be converted to the cus nates, alkyl Sulphates, arylsulphonates and also protein tomary formulations, such as solutions, emulsions, wettable hydrolysates; Suitable dispersants are nonionic and/or ionic powders, water- and oil-based suspensions, powders, dusts, substances, for example from the classes of the alcohol-POE pastes, soluble powders, soluble granules, granules for broad and/or -POP ethers, acid and/or POP-POE esters, alkylaryl casting, Suspension-emulsion concentrates, natural materials and/or POP-POE ethers, fat- and/or POP-POE adducts, POE impregnated with active ingredient, synthetic materials and/or POP-polyol derivatives, POE- and/or POP-sorbitan impregnated with active ingredient, fertilizers and microen or -Sugar adducts, alkyl or aryl Sulphates, alkyl- or arylsul capsulations in polymeric Substances. phonates and alkyl or aryl phosphates or the corresponding 1062. These formulations are produced in a known man PO-ether adducts. Furthermore, suitable oligo- or polymers, ner, for example by mixing the active ingredients with extend for example those derived from vinylic monomers, from ers, that is liquid solvents and/or solid carriers, optionally acrylic acid, from EO and/or PO alone or in combination with the use of surfactants, that is emulsifiers and/or dispers with, for example, (poly)alcohols or (poly)amines. It is also ants and/or foam-formers. The formulations are prepared possible to employ lignin and its sulphonic acid derivatives, either in suitable plants or else before or during the applica unmodified and modified celluloses, aromatic and/or ali tion. phatic sulphonic acids and their adducts with formaldehyde. 1063 Suitable for use as auxiliaries are substances which 1068 Tackifiers such as carboxymethylcellulose and are Suitable for imparting to the composition itself and/or to natural and synthetic polymers in the form of powders, gran preparations derived therefrom (for example spray liquors, ules or latices, such as gum arabic, polyvinyl alcohol and seed dressings) particular properties such as certain technical polyvinyl acetate, as well as natural phospholipids such as properties and/or also particular biological properties. Typi cephalins and lecithins, and synthetic phospholipids, can be cal suitable auxiliaries are: extenders, solvents and carriers. used in the formulations. 1064 Suitable extenders are, for example, water, polar and 1069. It is possible to use dyes Such as inorganic pigments, nonpolar organic chemical liquids, for example from the for example iron oxide, titanium oxide and Prussian Blue, and classes of the aromatic and nonaromatic hydrocarbons (such organic dyes, such as alizarin dyes, azo dyes and metal phtha as paraffins, alkylbenzenes, alkylnaphthalenes, chloroben locyanine dyes, and trace nutrients such as salts of iron, Zenes), the alcohols and polyols (which, if appropriate, may manganese, boron, copper, cobalt, molybdenum and zinc. also be substituted, etherified and/or esterified), the ketones 1070. Other possible additives are perfumes, mineral or (such as acetone, cyclohexanone), esters (including fats and Vegetable, optionally modified oils, waxes and nutrients (in oils) and (poly)ethers, the unsubstituted and substituted cluding trace nutrients). Such as salts of iron, manganese, amines, amides, lactams (such as N-alkylpyrrolidones) and boron, copper, cobalt, molybdenum and zinc. lactones, the Sulphones and Sulphoxides (such as dimethyl 1071 Stabilizers, such as low-temperature stabilizers, Sulphoxide). preservatives, antioxidants, light stabilizers or other agents 1065. If the extender used is water, it is also possible to which improve chemical and/or physical stability may also be employ, for example, organic solvents as auxiliary Solvents. present. Essentially, Suitable liquid solvents are: aromatics such as 1072. The formulations generally contain between 0.01 Xylene, toluene or alkylnaphthalenes, chlorinated aromatics and 98% by weight of active ingredient, preferably between and chlorinated aliphatic hydrocarbons such as chloroben 0.5 and 90%. Zenes, chloroethylenes or methylene chloride, aliphatic 1073. The inventive active ingredient can be used in its hydrocarbons such as cyclohexane or paraffins, for example commercially available formulations and in the use forms, petroleum fractions, mineral and vegetable oils, alcohols prepared from these formulations, as a mixture with other Such as butanol or glycol and also their ethers and esters, active ingredients, such as insecticides, attractants, sterilizing ketones such as acetone, methyl ethylketone, methyl isobutyl agents, bactericides, acaricides, nematicides, fungicides, ketone or cyclohexanone, strongly polar solvents such as growth-regulating Substances, herbicides, Safeners, fertiliz dimethyl Sulphoxide, and also water. ers or semiochemicals. 1066. According to the invention, “carrier means a natu 1074. A mixture with other known active ingredients, such ral or synthetic, organic or inorganic Substance which may be as herbicides, fertilizers, growth regulators, Safeners, semio solid or liquid, with which the active ingredients are mixed or chemicals, or else with agents for improving the plant prop combined for better applicability, especially for application erties, is also possible. US 2010/03 11593 A1 Dec. 9, 2010 69

1075. When used as insecticides, the inventive active spp., Demodex spp., Trombicula spp., Listrophorus spp., ingredients may additionally be present in their commercially Acarus spp., Tvrophagus spp., Caloglyphus spp., Hypodectes available formulations and in the use forms, prepared from spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Oto these formulations, as a mixture with Synergistic agents. Syn dectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes ergistic agents are compounds which increase the action of spp., Cytodites spp., Laminosioptes spp. the active ingredients, without it being necessary for the Syn 1088. The inventive active ingredients of the formula (I) ergistic agent added to be active itself. are also Suitable for controlling arthropods which infest agri 1076. When used as insecticides, the inventive active ingredients can furthermore be present in their commercially cultural productive livestock, for example cattle, sheep,goats, available formulations and in the use forms, prepared from horses, pigs, donkeys, camels, buffalo, rabbits, chickens, tur these formulations, as a mixture with inhibitors which reduce keys, ducks, geese and bees, other pets, for example dogs, degradation of the active ingredient after use in the environ cats, caged birds and aquarium fish, and also so-called test ment of the plant, on the Surface of parts of plants or in plant animals, for example hamsters, guinea pigs, rats and mice. By tissues. controlling these arthropods, cases of death and reductions in 1077. The active ingredient content of the use forms pre productivity (for meat, milk, wool, hides, eggs, honey etc.) pared from the commercially available formulations can vary should be diminished, so that more economic and easier within wide limits. The active ingredient concentration of the animal husbandry is possible by use of the inventive active use forms can be from 0.00000001 to 95% by weight of active ingredients. ingredient, preferably between 0.00001 and 1% by weight. 1089. The inventive active ingredients are used in the vet 1078. The compounds are employed in a customary man erinary sector and in animal husbandry in a known manner by ner appropriate for the use forms. enteral administration in the form of, for example, tablets, 1079. The inventive active ingredients act not only against capsules, portions, drenches, granules, pastes, boluses, the plant, hygiene and stored product pests, but also in the vet feed-through process and Suppositories, by parenteral admin erinary medicine sector against animal parasites (ecto- and istration, for example by injection (intramuscular, Subcutane endoparasites). Such as hard ticks, soft ticks, mange mites, ous, intravenous, intraperitoneal and the like), implants, by leaf mites, flies (biting and licking), parasitic fly larvae, lice, nasal administration, by dermal use in the form, for example, hair lice, feather lice and fleas. These parasites include: of dipping or bathing, spraying, pouring on and spotting on, 1080 From the order of the Anoplurida, for example, Hae washing and powdering, and also with the aid of moulded matopinus spp., Linognathus spp., Pediculus spp., Phtirus articles containing the active ingredient, Such as collars, ear spp., Solenopotes spp. marks, tail marks, limb bands, halters, marking devices and 1081 From the order of the Mallophagida and the subor the like. ders Amblycerina and Ischnocerina, for example, Trime 1090 When used for cattle, poultry, pets and the like, the nopon spp., Menopon spp., Trinoton spp., Bovicola spp., Wer active ingredients of the formula (I) can be used as formula neckiella spp., Lepikentron spp., Damalina spp., tions (for example powders, emulsions, free-flowing compo Trichodectes spp., Felicola spp. sitions), which comprise the active ingredients in an amount 1082 From the order of the Diptera and the suborders of 1 to 80% by weight, directly or after 100- to 10 000-fold Nematocerina and Brachycerina, for example, Aedes spp., dilution, or they can be used as a chemical bath. Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., 1091. It has additionally been found that the inventive Phlebotomus spp., Lutzomyia spp., Culicoides spp., compounds have a strong insecticidal action against insects Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., which destroy industrial materials. Haematopota spp., Philipomyia spp., Braula spp., Musca 1092. The following insects may be mentioned as spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., examples and as preferred—but without any limitation: Morelia spp., Fannia spp., Glossina spp., Caliphora spp., 1093 Beetles, such as Hylotrupes bajulus, Chlorophorus Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga pilosis, Anobium punctatum, Xestobium rufo villosum, Ptili spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hip nuspecticornis, Dendrobium pertinex, Ernobius mollis, Prio pobosca spp., Lipoptena spp., Melophagus spp. bium carpini, Lyctus brunneus, Lyctus africanus, Lyctus pla 1083. From the order of the Siphonapterida, for example, nicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon Pulex spp., Ctenocephalides spp., Xenopsylla spp., Cerato aequale, Minthes rugicollis, Xvleborus spec. Tryptodendron phyllus spp. spec. Apate monachus, Bostrychus capucins, Heterobostry 1084. From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp. chus brunneus, Sinoxylon spec. Dinoderus minutus, 1085. From the order of the Blattarida, for example, Blatta 1094) Hymenopterons, such as Sirex juvencus, Urocerus Orientalis, Periplaneta americana, Blattela germanica, gigas, Urocerus gigas taignus, Urocerus augur, Supella spp. 1095 Termites, such as Kalotermes flavicollis, Cryptoter 1086. From the subclass of the Acari (Acarina) and the mes brevis, Heterotermes indicola, Reticulitermes flavipes, orders of the Meta- and Mesostigmata, for example, Argas Reticulitermes Santonensis, Reticulitermes lucifugus, Masto spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblvo termes darwiniensis, Zootermopsis nevadensis, Coptotermes mma spp., Boophilus spp., Dermacentor spp., Haemophysa formosanus, lis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus 1096 Bristletails, such as Lepisma saccharina. spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., 1097 Industrial materials in the present connection Varroa spp. should be understood to mean non-living materials, such as, 1087. From the order of the Actinedida (Prostigmata) and preferably, plastics, adhesives, sizes, papers and cardboards, Acaridida (Astigmata), for example, Acarapis spp., Cheyle leather, wood and processed wood products and coating com tiella spp., Ornithochevletia spp., Myobia spp., Psorergates positions. US 2010/03 11593 A1 Dec. 9, 2010 70

1098. The ready-to-use compositions may, if appropriate, 1117. From the order of the Diptera, for example, Aedes comprise further insecticides and, if appropriate, one or more aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles fungicides. spp., Caliphora erythrocephala, Chrysozona pluvialis, 1099 With respect to possible additional additives, refer Culex quinquefasciatus, Culex pipiens, Culex tarsalis, ence may be made to the insecticides and fungicides men Drosophila spp., Fannia canicularis, Musca domestica, Phle tioned above. botomus spp., Sarcophaga carnaria, Simulium spp., Sto 1100 The inventive compounds can likewise be employed moxys calcitrans, Tipula paludosa. for protecting objects which come into contact with Saltwater 1118 From the order of the Lepidoptera, for example, or brackish water, in particular hulls, Screens, nets, buildings, Achroia grisella, Galleria mellonella, Plodia interpunctella, moorings and signalling systems, against fouling. Tinea cloacella, Tinea pellionella, Tineola bisselliella. 1101 Furthermore, the inventive compounds, alone or in 1119 From the order of the Siphonaptera, for example, combinations with other active ingredients, may be employed Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, as antifouling agents. Tunga penetrans, Xenopsylla cheopis. 1102. In domestic, hygiene and stored-product protection, 1120. From the order of the Hymenoptera, for example, the active ingredients are also suitable for controlling animal Camponotus herculeanus, Lasius fuliginosus, Lasius niger, pests, in particular insects, arachnids and mites, which are Lasius umbratus, Monomorium pharaonis, Paravespula spp., found in enclosed spaces for example dwellings, factory Tetramorium caespitum. halls, offices, vehicle cabins and the like. They can be 1121. From the order of the Anoplura, for example, employed alone or in combination with other active ingredi Pediculus humanus capitis, Pediculus humanus corporis, ents and auxiliaries in domestic insecticide products for con Pemphigus spp., Phylloera vastatrix, Phthirus pubis. trolling these pests. They are active against sensitive and 1122. From the order of the Heteroptera, for example, resistant species and against all developmental stages. These Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Tri pests include: atoma infestans. 1103 From the order of the Scorpionidea, for example, 1123. In the field of household insecticides, they are used Buthus Occitanus. alone or in combination with other Suitable active ingredients, 1104 From the order of the Acarina, for example, Argas Such as phosphoric esters, carbamates, pyrethroids, neonico persicus, Argas reflexus, Bryobia ssp., Dermanyssus galli tinoids, growth regulators or active ingredients from other nae, Glyciphagus domesticus, Ornithodorus moubat, Rhipi known classes of insecticides. cephalus sanguineus, Trombicula alfreddugesi, Neutrom 1124. They are used in aerosols, pressure-free spray prod bicula autumnalis, Dermatophagoides pteronissimus, ucts, for example pump and atomizer sprays, automatic fog Dermatophagoides forinae. ging systems, foggers, foams, gels, evaporator products with 1105 From the order of the Araneae, for example, Avicu evaporator tablets made of cellulose or polymer, liquid evapo lariidae, Araneidae. rators, gel and membrane evaporators, propeller-driven 1106 From the order of the Opiliones, for example, Pseu evaporators, energy-free, or passive, evaporation systems, doscorpiones chelifer, Pseudoscorpiones cheiridium, Opil moth papers, moth bags and moth gels, as granules or dusts, iones phalangium. in baits for spreading or in bait stations. 1107 From the order of the Isopoda, for example, Oniscus 1125. The inventive compounds of the formula (I) (active asellus, Porcellio scaber. ingredients) have marked herbicidal activity against a broad 1108 From the order of the Diplopoda, for example, Bla spectrum of economically important mono- and dicotyledon niulus guttulatus, Polydesmus spp. ous annual harmful plants. Even perennial harmful plants which are difficult to control, which produce shoots from 1109 From the order of the Chilopoda, for example, Geo rhizomes, rootstocks or other permanent organs, are well philus spp. controlled by the active ingredients. 1110 From the order of the Zygentoma, for example, 1126. The application rate of active ingredient can vary Ctenolepisma spp., Lepisma saccharina, Lepismodes inquili within a relatively wide range. Essentially, it depends on the S. nature of the desired effect. In general, the application rates 1111. From the order of the Blattaria, for example, Blatta are between 1 g and 10 kg of active ingredient per hectare of Orientalies, Blattella germanica, Blattella asahinai, Leu soil area, preferably between 5g and 5 kg per ha. cophaea maderae, Panchlora spp., Parcoblatta spp., 1127. The advantageous effect of the compatibility with Periplaneta australasiae, Periplaneta americana, Periplan crop plants of the inventive active ingredient combinations is eta brunnea, Periplaneta fuliginosa, Supella longipalpa. particularly pronounced at certain concentration ratios. How 1112. From the order of the Saltatoria, for example, ever, the weight ratios of the active ingredients in the active Acheta domesticus. ingredient combinations can be varied within relatively wide 1113 From the order of the Dermaptera, for example, ranges. In general, from 0.001 to 1000 parts by weight, pref Forficula auricularia. erably from 0.01 to 100 parts by weight, particularly prefer 1114. From the order of the Isoptera, for example, Kalo ably 0.05 to 20 parts by weight, of one of the compounds termes spp., Reticulitermes spp. which improves crop plant compatibility (antidotes/safeners) 1115. From the order of the Psocoptera, for example, Lepi mentioned above under (b") are present per part by weight of natus spp., LipOscelis spp. active ingredient of the formula (I). 1116. From the order of the Coleoptera, for example, 1128. The inventive active ingredient combinations are Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus generally applied in the form of finished formulations. How Oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, ever, the active ingredients present in the active ingredient Sitophilus granarius, Sitophilus Oryzae, Sitophilus zeanais, combinations can, as individual formulations, also be mixed Stegobium paniceum. during use, i.e. be applied in the form of tank mixes. US 2010/03 11593 A1 Dec. 9, 2010

1129. For certain applications, in particular in the post or shoot parts with buds) or to the area on which the plants emergence method, it may furthermore be advantageous to grow (for example the area under cultivation). In this context, include, as further additives in the formulations, mineral or the inventive compounds can be applied for example pre vegetable oils which are tolerated by plants (for example the planting (if appropriate also by incorporation into the soil), commercial preparation "Rako Binol”), or ammonium salts, pre-emergence or post-emergence. Examples of individual Such as, for example, ammonium Sulphate or ammonium representatives of the monocotyledonous and dicotyledonous thiocyanate. weed flora which can be controlled by the inventive com 1130. The novel active ingredient combinations can be pounds will be mentioned, though there is no intention to used as such, in the form of their formulations or the use forms impose a restriction to particular species mentioned. prepared therefrom by further dilution, such as ready-to-use Solutions, Suspensions, emulsions, powders, pastes and gran 1137 Monocotyledonous harmful plants of the genera: ules. Application is in the customary manner, for example by Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, watering, spraying, atomizing, dusting or scattering. Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cype 1131. The application rates of the active ingredient com rus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, binations according to the invention can be varied within a Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Het certain range; they depend, interalia, on the weather and on eranthera, Imperata, Ischaemum, Leptochloa, Lolium, soil factors. In general, the application rates are between Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, 0.001 and 5 kg perha, preferably between 0.005 and 2 kg per Rottboelia, Sagittaria, Scirpus, Setaria, Sorghum. ha, particularly preferably between 0.01 and 0.5 kg per ha. 1138. Dicotyledonous weeds of the genera: Abutilon, 1132) Depending on their properties, the safeners for use Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemi in accordance with the invention can be used to pretreat the sia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Cen seed of the crop plant (seed dressing) or can be introduced taurea, Chenopodium, Cirsium, Convolvulus, Datura, Des into the seed furrows prior to Sowing or be used separately modium, Emex, Erysimum, Euphorbia, Galeopsis, prior to the herbicide or together with the herbicide, before or Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, after emergence of the plants. Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mul 1133 Examples of plants include important crop plants, lugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Such as cereals (wheat, barley, rice), maize, soya beans, pota Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, toes, cotton, oilseed rape, beet, Sugarcane and also fruit plants Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, (with the fruits apples, pears, citrus fruits and grapevines), Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, greater emphasis being given to cereals, maize, Soya beans, Urtica, Veronica, Viola, Xanthium. potatoes, cotton and oilseed rape. 1139. The plants listed can be treated in accordance with 1134 All plants and plant parts can be treated with the the invention in a particularly advantageous manner with the inventive active ingredients. In this context, plants should be compounds of the general formula I or the inventive active understood to mean all plants and plant populations such as ingredient mixtures. The preferred ranges stated above for the wanted and undesired wild plants or crop plants (including active ingredients or mixtures also apply to the treatment of naturally occurring crop plants). Crop plants can be plants these plants. Particular emphasis is given to the treatment of which can be obtained by conventional plant breeding and plants with the compounds or mixtures specifically men optimization methods or by biotechnological and recombi tioned in the present text. nant methods or by combinations of these methods, including 1140 If the inventive compounds are applied to the soil the transgenic plants and inclusive of the plant cultivars pro Surface before germination, either the emergence of the weed tectable or not protectable by plant breeders’ rights. Plant seedlings is prevented completely or the weeds grow until parts should be understood to mean all parts and organs of they have reached the cotyledon stage, but then stop their plants above and below the ground, such as shoot, leaf, flower growth and, finally, die completely after three to four weeks and root, examples which may be mentioned being leaves, have elapsed. needles, stalks, stems, flowers, fruit bodies, fruits and seed 1141. When the active ingredients are applied post-emer and also roots, tubers and rhizomes. The plant parts also gence to the green plant parts, growth stops after the treat include harvested material, and also vegetative and generative ment, and the harmful plants remain in the growth stage of the propagation material, for example cuttings, tubers, rhizomes, time of application or die fully after a certain period of time, offshoots and seeds. so that competition by weeds, which is harmful to the crop 1135 The inventive treatment of the plants and plant parts plants, is thus eliminated at an early point in time and in a with the active ingredients is effected directly or by allowing Sustained manner. the compounds to act on their Surroundings, habitat or storage 1142 Although the inventive compounds display an out space by the customary treatment methods, for example by standing herbicidal activity against monocotyledonous and immersion, spraying, evaporation, fogging, broadcasting, dicotyledonous weeds, crop plants of economically impor painting on or injection and, in the case of propagation mate tant crops, for example dicotyledonous crops of the genera rial, especially in the case of seed, also by applying one or Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, more COatS. Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, 1136. The present invention therefore also provides a Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, method of controlling undesired plants or for regulating the Solanum, Vicia, or monocotyledonous crops of the genera growth of plants, preferably in crops of plants, wherein one or Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Pani more inventive compound(s) is/are applied to the plants (for cum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea. example harmful plants such as monocotyledonous ordicoty are damaged only to an insignificant extent, or not at all, ledonous weeds or undesired crop plants), to the seeds (for depending on the structure of the respective inventive com example grains, seeds or vegetative propagules such as tubers pound and its application rate. This is why the present com US 2010/03 11593 A1 Dec. 9, 2010 72 pounds are highly suitable for the selective control of undes Furtherparticular properties may be tolerance or resistance to ired vegetation in plant crops such as agriculturally useful abiotic stresses, for example heat, cold, drought, salt and plants or ornamentals. ultraviolet radiation. The active ingredients can also be used 1143 Moreover, the inventive compounds (depending on in transgenic plants which are notable for higher yields, for their respective structure and the application rate applied) example for improved photosynthesis performance or have outstanding growth-regulatory properties in crop plants. improved nutrient uptake. They engage in the plant metabolism in a regulatory fashion 1148. It is preferred to use the inventive compounds of the and can therefore be employed for the influencing, in a tar formula (I) or salts thereof in economically important trans geted manner, of plant constituents and for facilitating har genic crops of useful plants and ornamentals, for example of vesting, Such as, for example, by triggering desiccation and cereals such as wheat, barley, rye, oats, Sorghum and millet, stunted growth. Moreover, they are also suitable for generally rice, cassaya and maize or else crops of Sugar beet, cotton, controlling and inhibiting undesired vegetative growth with Soya bean, oilseed rape, potato, tomato, peas and other veg out destroying the plants in the process. Inhibiting the Veg etables. etative growth plays an important role in many monocotyle 1149. It is preferred to employ the compounds of the for donous and dicotyledonous crops since for example lodging mula (I) as herbicides in crops of useful plants which are can be reduced, or prevented completely, hereby. resistant, or have been made resistant by recombinant means, 1144. As already mentioned above, it is possible to treat all to the phytotoxic effects of the herbicides. plants and their parts according to the invention. In a preferred 1150 Conventional ways of generating novel plants embodiment, wild plant species and plant cultivars, or those which, in comparison with existing plants, have modified obtained by conventional biological breeding methods, Such properties are, for example, traditional breeding methods and as crossing or protoplast fusion, and parts thereof, are treated. the generation of mutants. Alternatively, novel plants with In a further preferred embodiment, transgenic plants and modified properties can be generated with the aid of recom plant cultivars obtained by genetic engineering methods, if binant methods (see, for example, EP 0221044, EP 0131624). appropriate in combination with conventional methods (Ge For example, the following have been described in several netically Modified Organisms), and parts thereof are treated. CaSCS The terms “parts”, “parts of plants' and “plant parts” have 1151 recombinant modifications of crop plants for the been explained above. purpose of modifying the starch synthesized in the 1145 Particularly preferably, plants of the plant cultivars plants (for example WO92/011376 A. WO92/14827A, which are in each case commercially available or in use are WO 91/19806A), treated in accordance with the invention. Plant cultivars 1152 transgenic crop plants which are resistant to cer should be understood to mean plants having novel properties tain herbicides of the glufosinate type (cf., for example, (“traits”) which have been obtained by conventional breed EP 0242236A, EP242246A) or of the glyphosate type ing, by mutagenesis or by recombinant DNA techniques. (WO 92/000377 A) or of the sulphonylurea type (EP These can be cultivars, bio- or genotypes. 0257993 A, U.S. Pat. No. 5,013,659), or are resistant to 1146. Depending on the plant species or plant cultivars, combinations or mixtures of these herbicides by virtue their location and growth conditions (soils, climate, vegeta of "gene Stacking'. Such as transgenic crop plants, for tion period, diet), the treatment according to the invention example maize or Soya with the trade name or the des may also result in superadditive (“synergistic) effects. Thus, ignation OptimumTM GATTM (Glyphosate ALS Toler for example, reduced application rates and/or a widening of ant). Additionally described have been transgenic plants the activity spectrum and/or an increase in the activity of the which are resistant to synthetic auxins (e.g. 2.4 D), Substances and compositions which can be used according to HRAC mode of action Class O and aryloxy-phenoxy the invention, better plant growth, increased tolerance to high propionate (fops, HRAC, Class A) (DHT, Dow Agro or low temperatures, increased tolerance to drought or to science Herbicide Tolerance. Trait) water or soil salt content, increased flowering performance, 1153 transgenic crop plants, for example cotton which easier harvesting, accelerated maturation, higher harvest is capable of producing Bacillus thuringiensis toxins (Bt yields, higher quality and/or a higher nutritional value of the toxins), which make the plants resistant to certain pests harvested products, better storage stability and/or process (EP 0142924A, EP 0193259A), ability of the harvested products are possible, which exceed 1154 transgenic crop plants with a modified fatty acid the effects which were actually to be expected. composition (WO 91/13972 A), 1147. Owing to their herbicidal and plant-growth-regula 1155 genetically modified plants which have new tory properties, the active ingredients can also be employed insect resistances, for example based on the expression for controlling harmful plants in crops of known genetically of toxins from Photorhabdus, Xenorhabdus symbionts modified plants or genetically modified plants which are yet from entomopathogenic nematodes and toxins from Spi to be developed. As a rule, the transgenic plants are distin ders, Scorpions, ants, parasitic wasps, guished by especially advantageous properties, for example 1156 genetically modified crop plants with novel con by resistances to certain pesticides, mainly certain herbicides, stituents or secondary metabolites, for example novel resistances to plant diseases or causative organisms of plant phytoalexins, which bring about an increased disease diseases, such as certain insects, nematodes or microorgan resistance (EP309862 A, EP0464461 A), isms such as fungi, bacteria or viruses. Other special proper 1157 genetically modified plants with reduced photo ties relate for example to the harvested material with regard to respiration which feature higher yields and higher stress quantity, quality, storability, composition and specific con tolerance (EP 0305398 A), stituents. Thus, transgenic plants with an increased starch 1158 transgenic crop plants which produce pharma content or a modified starch quality or those with a different ceutically or diagnostically important proteins (“mo fatty acid composition of the harvested material are known. lecular pharming), US 2010/03 11593 A1 Dec. 9, 2010 73

1159 transgenic crop plants which are distinguished by tors, for example 2, 4 D, dicamba, or to herbicides which higher yields or better quality, inhibit essential plant enzymes, for example acetyl CoA car 1160 transgenic crop plants which are distinguished by boxylases, acetolactate synthases (ALS), EPSP synthases, increased tolerances to abiotic and biotic stresses, glutamine synthases (GS) or hydroxyphenylpyruvate dioxy 1161 transgenic crop plants which are distinguished by genases (HPPD), or to herbicides from the group of the FOPs, a combination, for example of the abovementioned Sulphonylureas, glyphosates, glufosinates or benzoylisox novel properties ('gene Stacking'). azoles and analogous active ingredients, or to any combina 1162. A large number of molecular biology techniques by tions of these active ingredients. means of which novel transgenic plants with modified prop 1170. It is particularly preferred to employ the inventive erties can be produced are known in principle; see, for compounds in transgenic crop plants which are resistant example, 1. Potrykus and G. Spangenberg (eds.) Gene Trans to a combination of glyphosates and glufosinates, gly fer to Plants, Springer Lab Manual (1995), Springer Verlag phosates and Sulphonylureas or imidazolinones. It is Berlin, Heidelberg. or Christou, “Trends in Plant Science 1 very particularly preferred to employ the inventive com (1996) 423-431). pounds in transgenic crop plants, for example maize or 1163 To carry out such recombinant manipulations, it is soya, with the trade name or the designation OptimumTM possible to introduce nucleic acid molecules into plasmids, GATTM (Glyphosate ALS Tolerant). In addition, it is which permit a mutagenesis or sequence modification by particularly preferred to employ the inventive com recombination of DNA sequences. For example, base substi pounds in transgenic plants which are resistant to syn tutions can be carried out, part-sequences can be removed, or thetic auxins (e.g. 2,4 D) with “HRAC mode of action natural or synthetic sequences may be added with the aid of Class O' and aryloxy-phenoxy propionate (fops) with standard methods. To link the DNA fragments with one “HRAC mode of action Class A (e.g. DHT, Dow Agro another, it is possible to add adapters or linkers to the frag science Herbicide Tolerance Trait). ments; see, for example, Sambrook et al., 1989, Molecular 1171 When the inventive active ingredients are used in Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor transgenic crops, effects are frequently observed —in addi Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker tion to the effects on harmful plants which can be observed in “Gene and Klone, VCH Weinheim 2nd ed., 1996 other crops—which are specific for the application in the 1164. The generation of plant cells with a reduced activity transgenic crop in question, for example a modified or spe for a gene product can beachieved for example by the expres cifically widened spectrum of weeds which can be controlled, Sion of at least one corresponding antisense RNA, a sense modified application rates which may be employed for appli RNA for achieving a cosuppression effect or by the expres cation, preferably good combinability with the herbicides to sion of at least one correspondingly constructed ribozyme, which the transgenic crop is resistant, and an effect on growth which specifically cleaves transcripts of the abovementioned and yield of the transgenic crop plants. gene product. 1172. The invention therefore also provides for the use of 1165. To this end, it is possible firstly to use DNA mol the inventive compounds of the formula (I) as herbicides for ecules which comprise all of the coding sequence of a gene controlling harmful plants in transgenic crop plants. product, including any flanking sequences which may be 1173. The inventive compounds can be used in the form of present, or else DNA molecules which only comprise parts of wettable powders, emulsifiable concentrates, sprayable solu the coding sequence, it being necessary for these parts to be tions, dusting products or granules in the customary formu long enough to bring about an antisense effect in the cells. It lations. The invention therefore also provides herbicidal and is also possible to use DNA sequences which have a high plant growth-regulating compositions which comprise the degree of homology with the coding sequences of a gene inventive compounds. product, but which are not entirely identical. 1174. The inventive compounds can beformulated in vari 1166 When expressing nucleic acid molecules in plants, ous ways according to which biological and/or physico the protein synthesized may be localized in any compartment chemical parameters are required. Possible formulations of the plant cell. In order to achieve localization in a particular include, for example: wettable powders (WP), water-soluble compartment, however, it is possible for example to link the powders (SP), water-soluble concentrates, emulsifiable con coding region to DNA sequences which ensure the localiza centrates (EC), emulsions (EW) such as oil-in-water and tion in a specific compartment. Such sequences are known to water-in-oil emulsions, sprayable solutions, Suspension con the skilled worker (see, for example, Braun et al., EMBO.J. 11 centrates (SC), oil- or water-based dispersions, oil-miscible (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA Solutions, capsule Suspensions (CS), dusting products (DP). 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), seed-dressing products, granules for scattering and soil appli 95-106). The nucleic acid molecules can also be expressed in cation, granules (GR) in the form of microgranules, spray the organelles of the plant cells. granules, coated granules and adsorption granules, water 1167. The transgenic plant cells can be regenerated by dispersible granules (WG), water-soluble granules (SG), known techniques to give intact plants. In principle, the trans ULV formulations, microcapsules and waxes. genic plants may be plants of any plant species, that is to say 1175. These individual formulation types are known in both monocotyledonous and dicotyledonous plants. principle and are described, for example, in: Winnacker 1168. Thus, transgenic plants can be obtained which fea Küchler, “Chemische Technologie” Chemical Technology, ture modified properties as the result of overexpression, Sup Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986: Wade van pression or inhibition of homologous (natural) genes or Valkenburg, “Pesticide Formulations’, Marcel Dekker, N.Y., gene sequences or expression of heterologous (foreign) 1973; K. Martens, “Spray Drying Handbook, 3rd Ed. 1979, genes or gene Sequences. G. Goodwin Ltd. London. 1169 It is preferred to employ the inventive compounds 1176. The necessary formulation assistants, such as inert (I) in transgenic crops which are resistant to growth regula materials, Surfactants, solvents and further additives, are like US 2010/03 11593 A1 Dec. 9, 2010 74 wise known and are described, for example, in: Watkins, by applying active ingredient concentrates by means of adhe “Handbook of Insecticide Dust Diluents and Carriers', 2nd sives, for example polyvinyl alcohol, Sodium polyacrylate or Ed., Darland Books, Caldwell N.J., H. V. Olphen, “Introduc else mineral oils, onto the Surface of carriers such as sand, tion to Clay Colloid Chemistry’: 2nd Ed., J. Wiley & Sons, kaolinites or of granulated inert material. It is also possible to N.Y.: C. Marsden, “Solvents Guide'; 2nd Ed., Interscience, granulate Suitable active ingredients in the manner customary N.Y. 1963; McCutcheon’s “Detergents and Emulsifiers for the production offertilizer granules if desired in a mix Annual, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, ture with fertilizers. “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. 1184 Water-dispersible granules are prepared generally Inc., N.Y. 1964: Schönfeldt, “Grenzflächenaktive Athyl by the customary processes such as spray-drying, fluidized enoxidaddukte' Interface-Active Ethylene Oxide Adducts, bed granulation, pan granulation, mixing with high-speed Wiss. Verlagsgesell. Stuttgart 1976: Winnacker-Kichler, mixers and extrusion without Solid inert material. “Chemische Technologie', Volume 7, C. Hanser Verlag 1185 For the preparation of pan, fluidized bed, extruder Munich, 4th Ed. 1986. and spray granules, see, for example, processes in "Spray 1177 Based on these formulations, it is also possible to Drying Handbook' 3rd ed. 1979, G. Goodwin Ltd., London; prepare combinations with other pesticidally active ingredi J. E. Browning, "Agglomeration’, Chemical and Engineering ents, such as, for example, insecticides, acaricides, berbi 1967, pages 147 ff.: “Perry's Chemical Engineer's Hand cides, fungicides, and also with safeners, fertilizers and/or book”, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. growth regulators, for example in the form of a finished 1186 For further details regarding the formulation of crop formulation or as a tank mix. protection compositions, see, for example, G. C. Klingman, 1178 Wettable powders are preparations which can be “Weed Control as a Science'. John Wiley and Sons, Inc., New dispersed uniformly in water and, as well as the active ingre York, 1961, pages 81-96 and J. D. Freyer, S.A. Evans, “Weed dient, apart from a diluent or inert Substance, also comprise Control Handbook’, 5th Ed., Blackwell Scientific Publica Surfactants of the ionic and/or nonionic type (wetting agents, tions, Oxford, 1968, pages 101-103. dispersants), for example polyoxyethylated alkylphenols, 1187. The agrochemical formulations contain generally polyoxyethylated fatty alcohols, polyoxyethylated fatty from 0.1 to 99% by weight, in particular from 0.1 to 95% by amines, fatty alcohol polyglycol ether Sulphates, alkane weight, of inventive compounds. Sulphonates, alkylbenzenesulphonates, sodium lignoSulpho 1188. In wettable powders, the active ingredient concen nate, Sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, tration is, for example, from about 10 to 90% by weight; the sodium dibutylnaphthalenesulphonate or else sodium oleyl remainder to 100% by weight consists of customary formu methyltauride. To prepare the wettable powders, the active lation constituents. In the case of emulsifiable concentrates, herbicidal ingredients are ground finely, for example in cus the active ingredient concentration may be from about 1 to tomary apparatus such as hammer mills, blower mills and 90% by weight, preferably from 5 to 80% by weight. Dust air-jet mills and simultaneously or Subsequently mixed with type formulations contain from 1 to 30% by weight of active the formulation assistants. ingredient, preferably usually from 5 to 20% by weight of 1179 Emulsifiable concentrates are prepared by dissolv active ingredient; sprayable solutions contain from about ing the active ingredient in an organic solvent, for example 0.05 to 80% by weight, preferably from 2 to 50% by weight of butanol, cyclohexanone, dimethylformamide, Xylene or else active ingredient. In water-dispersible granules, the active relatively high-boiling aromatics or hydrocarbons or mix ingredient content depends partly on whether the active com tures of the organic solvents with addition of one or more pound is present in Solid or liquid form and which granulation Surfactants of the ionic and/or nonionic type (emulsifiers). assistants, fillers, etc. are used. In the granules dispersible in The emulsifiers used may, for example, be: calcium alkylar water, the content of active ingredient is, for example, ylsulphonates such as calcium dodecylbenzenesulphonate, or between 1 and 95% by weight, preferably between 10 and nonionic emulsifiers such as fatty acid polyglycol esters, 80% by weight. alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, 1189. In addition, the active ingredient formulations men propylene oxide-ethylene oxide condensation products, alkyl tioned optionally comprise the respective customary adhe polyethers, Sorbitan esters, for example Sorbitan fatty acid sives, wetting agents, dispersants, emulsifiers, penetrants, esters, or polyoxyethylene Sorbitan esters, for example poly preservatives, antifreeze agents and solvents, fillers, carriers oxyethylene sorbitan fatty acid esters. and dyes, defoamers, evaporation inhibitors and agents which 1180 Dusting products are obtained by grinding the active influence the pH and the viscosity. ingredient with finely divided solid substances, for example 1190. The inventive treatment method is preferably used talc, natural clays such as kaolin, bentonite and pyrophyllite, on genetically modified organisms, for example plants or or diatomaceous earth. plant parts. 1181 Suspension concentrates may be water- or oil 1191 Genetically modified plants, known as transgenic based. They may be prepared, for example, by wet grinding plants, are plants in which a heterologous gene has been by means of commercial bead mills and optional addition of integrated Stably into the genome. surfactants as have, for example, already beenlisted above for 1192. The expression "heterologous gene' essentially the other formulation types. means a gene which is provided or assembled outside the 1182 Emulsions, for example oil-in-water emulsions plant and which, when introduced in the nuclear, chloroplas (EW), can be prepared, for example, by means of stirrers, tic or mitochondrial genome, gives the transformed plant new colloid mills and/or static mixers using aqueous organic Sol or improved agronomic or other properties by expressing a vents and optionally surfactants, as have, for example, protein or polypeptide of interest or by downregulating or already been listed above for the other formulation types. silencing other gene(s) which are present in the plant (using 1183 Granules can be produced either by spraying the for example antisense technology, coSuppression technology active ingredient onto adsorptive granulated inert material or or RNA interference RNAi technology). A heterologous US 2010/03 11593 A1 Dec. 9, 2010 gene that is located in the genome is also called a transgene. plants can be the result of for example, improved plant physi A transgene that is defined by its particular location in the ology, growth and development, such as water use efficiency, plant genome is called a transformation or transgenic event. water retention efficiency, improved nitrogen use, enhanced 1193 Depending on the plant species or plant varieties, carbon assimilation, improved photosynthesis, increasedger their location and growth conditions (soils, climate, vegeta mination efficiency and accelerated maturation. Yield can tion period, diet), the treatment according to the invention furthermore be affected by improved plant architecture (un may also result in superadditive (“synergistic) effects. Thus, der stress and non-stress conditions), including early flower for example, reduced application rates and/or a widening of ing, flowering control for hybrid seed production, seedling the activity spectrum and/or an increase in the activity of the vigour, plant size, internode number and distance, root active ingredients and compositions which can be used growth, seed size, fruit size, pod size, pod or ear number, seed according to the invention, better plant growth, increased number per pod or ear, seed mass, enhanced seed filling, tolerance to high or low temperatures, increased tolerance to reduced seed dispersal, reduced pod dehiscence and lodging drought or to water or soil salt content, increased flowering resistance. Further yield traits include seed composition, Such performance, easier harvesting, accelerated maturation, as carbohydrate content, protein content, oil content and com higher harvest yields, bigger fruits, larger plant height, position, nutritional value, reduction in anti-nutritional com greener leaf colour, earlier flowering, higher quality and/or a pounds, improved processability and better storage stability. higher nutritional value of the harvested products, higher 1199 Plants that may be treated in accordance with the Sugar concentration within the fruits, better storage stability invention are hybrid plants that already express the charac and/or processability of the harvested products are possible, teristics of heterosis, or hybrid vigour, which results in gen which exceed the effects which were actually to be expected. erally higher yield, vigour, health and resistance towards 1194. At certain application rates, the active ingredient biotic and abiotic stress factors. Such plants are typically combinations according to formula (I) may also have a made by crossing an inbred male-sterile parent line (the strengthening effect in plants. Accordingly, they are suitable female parent) with another inbred male-fertile parent line for mobilizing the defense system of the plant against attack (the male parent). Hybrid seed is typically harvested from the by unwanted phytopathogenic fungi and/or microorganisms malesterile plants and sold to growers. Malesterile plants can and/or viruses. This may, if appropriate, be one of the reasons Sometimes (e.g. in corn) be produced by detasseling (i.e. the for the enhanced activity of the combinations according to the mechanical removal of the male reproductive organs or male invention, for example against fungi. Plant-strengthening (re flowers) but, more typically, male sterility is the result of sistance-inducing) substances are understood as mean, in the genetic determinants in the plant genome. In that case, and present context, also those Substances or combinations of especially when seed is the desired product to be harvested Substances which are capable of stimulating the defense sys from the hybrid plants, it is typically useful to ensure that tem of plants in Such a way that, when Subsequently inocu male fertility in the hybrid plants, which contain the genetic lated with unwanted phytopathogenic fungi and/or microor determinants responsible for male sterility, is fully restored. ganisms and/or viruses, the treated plants display a This can be accomplished by ensuring that the male parents Substantial degree of resistance to these unwanted phyto have appropriate fertility restorer genes which are capable of pathogenic fungi and/or microorganisms and/or viruses. In restoring the male fertility in hybrid plants that contain the the present case, unwanted phytopathogenic fungi and/or genetic determinants responsible for male sterility. Genetic microorganisms and/or viruses are understood to mean phy determinants for male sterility may be located in the cyto topathogenic fungi, bacteria and viruses. Thus, the Substances plasm. Examples of cytoplasmic male sterility (CMS) were according to the invention can be employed for protecting for instance described for Brassica species. However, genetic plants against attack by the abovementioned pathogens determinants for male sterility can also be located in the within a certain period of time after the treatment. The period nuclear genome. Malesterile plants can also be obtained by of time within which protection is effected generally extends plant biotechnology methods such as genetic engineering. A from 1 to 10 days, preferably 1 to 7 days, after the treatment particularly useful means of obtaining male sterile plants is of the plants with the active ingredients. described in WO 89/10396 in which, for example, a ribonu 1195 Plants which are also preferably treated in accor clease Such as a barnase is selectively expressed in the tape dance with the invention are resistant to one or more biotic tum cells in the stamens. Fertility can then be restored by stress factors, i.e. said plants have an improved defense expression in the tapetum cells of a ribonuclease inhibitor against animal and microbial pests, such as nematodes, Such as barstar. insects, mites, phytopathogenic fungi, bacteria, viruses and/ 1200 Plants or plant cultivars (obtained by plant biotech or viroids. nology methods such as genetic engineering) which may be 1196. In addition to the aforementioned plants and plant treated in accordance with the invention are herbicide-toler varieties, it is also possible inaccordance with the invention to ant plants, i.e. plants made tolerant to one or more given treat those which are resistant to one or more abiotic stress herbicides. Such plants can be obtained either by genetic factors. transformation, or by selection of plants containing a muta 1197 Abiotic stress conditions may include, for example, tion imparting Such herbicide tolerance. drought, cold exposure, heat exposure, osmotic stress, water 1201. Herbicide-tolerant plants are for example glypho logging, increased soil salinity, increased exposure to miner sate-tolerant plants, i.e. plants made tolerant to the herbicide als, oZone conditions, strong light conditions, limited avail glyphosate or salts thereof. For example, glyphosate-tolerant ability of nitrogen nutrients, limited availability of plants can be obtained by transforming the plant with a gene phosphorus nutrients or shade avoidance. encoding the enzyme 5-enolpyruvylshikimate-3-phosphate 1198 Plants and plant varieties which may also be treated synthase (EPSPS). Examples of such, EPSPS genes are the in accordance with the invention are those plants character AroA gene (mutant CT7) of the bacterium Salmonella typh ized by enhanced yield characteristics. Enhanced yield in said imurium, the CP4 gene of the bacterium Agrobacterium sp., US 2010/03 11593 A1 Dec. 9, 2010 76 the genes encoding a petunia EPSPS, a tomato EPSPS, or an 1208. The term “insect-resistant transgenic plant, as used Eleusine EPSPS. It can also be a mutated EPSPS. Glypho herein, includes any plant containing at least one transgene sate-tolerant plants can also be obtained by expressing a gene comprising a coding sequence encoding: that encodes a glyphosate oxidoreductase enzyme. Glypho 1209 1) an insecticidal crystal protein from Bacillus sate-tolerant plants can also be obtained by expressing a gene thuringiensis or an insecticidal portion thereof. Such as that encodes a glyphosate acetyltransferase enzyme. Glypho the insecticidal crystal proteins listed online at: http:// sate-tolerant plants can also be obtained by selecting plants www.lifesci. Sussex.ac.uk/Home/Neil Crickmore/Bt/, containing naturally occurring mutations of the above-men or insecticidal portions thereof, e.g. proteins of the Cry tioned genes. protein classes Cry1Ab, Cry1Ac, Cry 1F, Cry2Ab, 1202. Other herbicide-resistant plants are for example Cry3Ae, or Cry3Bb or insecticidal portions thereof; or plants that are made tolerant to herbicides inhibiting the 1210 2) a crystal protein from Bacillus thuringiensis or enzyme glutamine synthase. Such as bialaphos, phosphino a portion thereof which is insecticidal in the presence of thricin or glufosinate. Such plants can be obtained by express a second other crystal protein from Bacillus thuringien ing an enzyme detoxifying the herbicide or a mutant sis or a portion thereof. Such as the binary toxin made up glutamine synthase enzyme that is resistant to inhibition. One of the Cy34 and Cy35 crystal proteins; or Such efficient detoxifying enzyme is, for example, an enzyme 1211 3) a hybrid insecticidal protein comprising parts encoding a phosphinothricin acetyltransferase (such as the of two different insecticidal crystal proteins from Bacil bar orpat protein from Streptomyces species). Plants express lus thuringiensis, such as a hybrid of the proteins of 1) ing an exogenous phosphinothricin acetyltransferase are above or a hybrid of the proteins of 2) above, e.g. the described. Cry1A.105 protein produced by corn event MON98034 1203. Further herbicide-tolerant plants are also plants that (WO 2007/027777); or are made tolerant to the herbicides inhibiting the enzyme 1212 4) a protein of any one of 1) to 3) above wherein hydroxyphenylpyruvatedioxygenase (HPPD). Hydroxyphe Some, particularly 1 to 10, amino acids have been nylpyruvatedioxygenases are enzymes that catalyze the reac replaced by anotheramino acid to obtain a higher insec tion in which para-hydroxyphenylpyruvate (HPP) is trans ticidal activity to a targetinsect species, and/or to expand formed into homogentisate. Plants tolerant to HPPD the range of target insect species affected, and/or inhibitors can be transformed with a gene encoding a natu because of changes induced into the encoding DNA rally occurring resistant HPPD enzyme, or a gene encoding a during cloning or transformation, such as the Cry3Bb1 mutated HPPD enzyme. Tolerance to HPPD inhibitors can protein in corn events MON863 or MON88017, or the also be obtained by transforming plants with genes encoding Cry3A protein in corn event MIR 604; certain enzymes enabling the formation of homogentisate 1213 5) an insecticidal secreted protein from Bacillus despite the inhibition of the native HPPD enzyme by the thuringiensis or Bacillus cereus, or an insecticidal por HPPD inhibitor. Tolerance of plants to HPPD inhibitors can tion thereof. Such as the vegetative insecticidal proteins also be improved by transforming plants with a gene encod (VIP) listed at: http://www.lifesci.sussex.ac.uk/Home/ ing an enzyme of prephenate dehydrogenase in addition to a Neil Crickmore/Bt/vip.html, e.g. proteins from the gene encoding an HPPD-tolerant enzyme. VIP3Aa protein class; or 1204 Further herbicide-resistant plants are plants that are 1214 6) a secreted protein from Bacillus thuringiensis made tolerant to acetolactate synthase (ALS) inhibitors. or Bacillus cereus which is insecticidal in the presence Known ALS inhibitors include, for example, sulphonylurea, of a second secreted protein from Bacillus thuringiensis imidazolinone, triazolopyrimidines, pyrimidinyloxy(thio) or B. cereus, such as the binary toxin made up of the benzoates, and/or Sulphonylaminocarbonyltriazolinone her VIP1A and VIP2A proteins; or bicides. Different mutations in the ALS enzyme (also known 1215. 7) a hybrid insecticidal protein comprising parts as acetohydroxyacid synthase, AHAS) are known to confer from different secreted proteins from Bacillus thuring tolerance to different herbicides and groups of herbicides. iensis or Bacillus cereus, such as a hybrid of the proteins The production of Sulphonylurea-tolerant plants and imida in 1) above or a hybrid of the proteins in 2) above; or Zolinone-tolerant plants has been described in the interna 1216 8) a protein of any one of 1) to 3) above wherein tional publication WO 1996/033270. Further sulphonylurea Some, particularly 1 to 10, amino acids have been and imidazolinone-tolerant plants have also been described, replaced by anotheramino acid to obtain a higher insec for example in WO 2007/024782. ticidal activity to a targetinsect species, and/or to expand 1205 Further herbicide-resistant plants are plants which the range of target insect species affected, and/or have been rendered tolerant to ACCase inhibitors. because of changes induced into the encoding DNA 1206 Further plants tolerant to imidazolinone and/or sul during cloning or transformation (while still encoding phonylurea can be obtained by induced mutagenesis, selec an insecticidal protein), such as the VIP3Aa protein in tion in cell cultures in the presence of the herbicide or muta cotton event COT 102. tion breeding. 1217 Ofcourse, insect-resistant transgenic plants, as used 1207 Plants or plant varieties (obtained by plant biotech herein, also include any plant comprising a combination of nology methods such as genetic engineering) which may also genes encoding the proteins of any one of the above classes 1 be treated in accordance with the invention are insect-resis to 8. In one embodiment, an insect-resistant plant contains tant transgenic plants, i.e. plants made resistant to attack by more than one transgene encoding a protein of any one of the certain target insects. Such plants can be obtained by genetic above classes 1 to 8, to expand the range of target insect transformation, or by selection of plants containing a muta species affected or to delay insect resistance development to tion imparting Such insect resistance. the plants, by using different proteins insecticidal to the same US 2010/03 11593 A1 Dec. 9, 2010 77 target insect species but having a different mode of action, 1228 b) plants, such as cotton plants, which contain an Such as binding to different receptor binding sites in the altered form of rSw2 or rSw3 homologous nucleic acids; insect. 1229 c) plants, such as cotton plants, with an increased 1218. Plants or plant varieties (obtained by plant biotech expression of Sucrose phosphate synthase; nology methods such as genetic engineering) which may also 1230 d) plants, such as cotton plants, with an increased be treated in accordance with the invention are tolerant to expression of Sucrose synthase; abiotic stresses. Such plants can be obtained by genetic trans formation, or by selection of plants containing a mutation 1231 e) plants, such as cotton plants, wherein the tim imparting Such stress resistance. Particularly useful stress ing of the plasmodesmatal gating at the basis of the fibre tolerance plants include: cell is altered, for example through downregulation of 1219 a. plants which contain a transgene capable of fibre-selective B-1,3-glucanase; reducing the expression and/or the activity of the poly 1232 f) plants, such as cotton plants, which have fibres (ADP-ribose)polymerase (PARP) gene in the plant cells with altered reactivity, for example through the expres or plants. sion of the N-acetylglucosaminetransferase gene 1220 b. plants which contain a stress tolerance-enhanc including nodC and chitin Synthase genes. ing transgene capable of reducing the expression and/or 1233 Plants or plant cultivars (that can be obtained by the activity of the PARG-encoding genes of the plants or plant biotechnology methods such as genetic engineering) plant cells; which may also be treated in accordance with the invention 1221 c. plants which contain a stress tolerance-enhanc are plants, such as oilseed rape or related Brassica plants, ing transgene coding for a plant-functional enzyme of with altered oil profile characteristics. Such plants can be the nicotinamide adenine dinucleotide Salvage biosyn obtained by genetic transformation or by selection of plants thesis pathway, including nicotinamidase, nicotinate containing a mutation imparting Such altered oil characteris phosphoribosyltransferase, nicotinic acid mononucle tics and include: otide adenyltransferase, nicotinamide adenine dinucle otide synthetase or nicotinamide phosphoribosyltrans 1234 a) plants, such as oilseed rape plants, which pro ferase. duce oil having a high oleic acid content; 1222 Plants or plant cultivars (obtained by plant biotech 1235 b) plants, such as oilseed rape plants, which pro nology methods such as genetic engineering) which may duce oil having a low linolenic acid content; likewise be treated in accordance with the invention have an 1236 c) plants, such as oilseed rape plants, which pro altered quantity, quality and/or storage stability of the har duce oil having a low level of saturated fatty acids. Vested product and/or altered properties of specific ingredi 1237 Particularly useful transgenic plants which may be ents of the harvested product, for example: treated in accordance with the invention are plants which 1223, 1) transgenic plants which synthesize a modified comprise one or more genes which encode one or more tox starch whose physicochemical characteristics, in par ins, are the following which are sold under the trade names: ticular the amylose content or the amylose/amylopectin YIELD GARDR (for example maize, cotton, soya beans), ratio, the degree of branching, the average chain length, KnockCut(R) (for example maize), BiteGard(R) (for example the side chain distribution, the viscosity behaviour, the maize), Bt-Xtra.R. (for example maize), StarLink R. (for gelling strength, the starch grain size and/or the starch example maize), Bolgard(R) (cotton), Nucotnir (cotton), grain morphology, is altered compared to the synthe Nucotn 33B(R) (cotton), NatureGard(R) (for example maize), sized starch in wild type plant cells or plants, such that ProtectaR) and New Leaf R (potato). Examples of herbicide this modified starch is better suited for certain applica tolerant plants which may be mentioned are maize varieties, tions. cotton varieties and soya bean varieties which are sold under 1224 2) transgenic plants which synthesize non-starch the trade names: Roundup Ready(R) (tolerance to glyphosate, carbohydrate polymers or which synthesize non-starch carbohydrate polymers with altered properties in com for example maize, cotton, soya beans), Liberty Link. R (tol parison to wildtype plants without genetic modification. erance to phosphinothricin, for example oilseed rape), IMIR) Examples are plants which produce polyfructose, espe (tolerance to imidazolinone) and SCSR) (tolerance to sulpho cially of the inulin and levan type, plants which produce nylurea, for example maize). Herbicide-resistant plants alpha-1,4-glucans, plants which produce alpha-1,6 (plants bred in a conventional manner for herbicide tolerance) branched alpha-1,4-glucans, and plants producing alter which may be mentioned include the varieties sold under the al name Clearfield(R) (for example maize). 1225 3) transgenic plants which produce hyaluronan. 1238 Particularly useful transgenic plants which may be 1226 Plants or plant cultivars (which can be obtained by treated in accordance with the invention are plants containing plant biotechnology methods such as genetic engineering) transformation events, or a combination of transformation which may likewise be treated in accordance with the inven events, that are listed for example in the databases for various tion are plants, such as cotton plants, with altered fibre char national or regional regulatory agencies (see for example acteristics. Such plants can be obtained by genetic transfor http://gmoinfo.jrc.it/gmp browse.aspx and http://www.ag mation, or by selection of plants containing a mutation bios.com/dbase.php). imparting Such altered fibre characteristics and include: 1239. The term “active ingredients’ or “compounds' 1227 a) plants, such as cotton plants, which contain an always also includes the active ingredient combinations men altered form of cellulose synthase genes; tioned here too. US 2010/03 11593 A1 Dec. 9, 2010 78

PREPARATION EXAMPLES Example I-1-a-2 Example (I-1-a-1) Method S Method A 1243 1240

O N CH3 S.

F OH F Y^ CH3 F F F 1244 0.5 g (1.55 mmol) of the compound (I-1-a-1") Yrs (known in generic terms from WO97/02243) is admixed with F 0.348 g (2 eq) of potassium t-butoxide and dissolved in 5 ml 3-isomer of DMA (solution 1). In addition, 0.296 g (1 eq) of copper(I) iodide and 1.35 g (6.7 eq) of 2.2.2-trifluoroethanol in 5 ml of DMA (dimethylacetamide) are Suspended underinert gas and admixed with 1.17 g (6.7 eq) of potassium t-butoxide. After 1241 0.41 g (0.58 mmol) of the compound according to the exothermic reaction has ended, the mixture is admixed example II-1-a-1 in a solution of 2 ml of DMF is added with solution 1 and stirred under microwave irradiation at dropwise at room temperature within 30 minto a solution of 145° C. for 2 h. The reaction mixture is freed of the solvent 5 ml of DMF and 164 mg (2.5 eq) of potassium t-butoxide, under reduced pressure and admixed with 200 ml of water, and stirred at this temperature for 18 h. The mixture is and the remaining residue is removed and discarded. The adjusted to pH=1 with 1N hydrochloric acid and the residue aqueous phase is adjusted to pH1 with 1N hydrochloric acid obtained is filtered off. Column chromatography purification and the residue formed is filtered off. Column chromatogra (RP-silica gel, acetonitrile/water gradient) gives the inventive phy purification (RP-Silica gel, waterfacetonitrile gradient) product (I-1-a-1)=200 mg (38% of theory). gives 0.13 g 24% of theory of inventive compound I-1-a-2 1242 "H NMR (400 MHz, d-DMSO): 8–6.75 (s. 2H, with an m.p. of 202-205° C. Ar–H), 4.70 (q,2H, CH, CFs), 3.57 (m. 1H, CH OCH), 1245. In analogy to example (I-1-a-1) and example (I-1- 3.45 (m,2H, OCHCH), 2.08 (d,3H, ArCH), 1.98 (m), 1.70 a-2), and according to the general information regarding (m), 1.29 (m, together 8H, cyclohexyl), 1.10 (t, 3H, CH) preparation, the following compounds of the formula (I-1-a) ppm. are obtained: US 2010/03 11593 A1 Dec. 9, 2010 79

(B-I-I)

SHÉO

US 2010/03 11593 A1 Dec. 9, 2010 80

(B-I-I)

ponu?uoo

if it

if it

if it

IO

US 2010/03 11593 A1 Dec. 9, 2010 83

(B-I-I)

ponu?uoo

US 2010/03 11593 A1 Dec. 9, 2010 84

Example (I-1-b-1) 1249. In analogy to example (I-1-b-1), example (I-1-b-2) is obtained.

1246 H CH3 N

HCO3 21 o1 Ner, O O H3C

HC CH 1250) M. p. 198-1999 C. Example (I-1-c-1) 1251

1247 0.15 g (0.36 mmol) of the compound according to example (I-1-a-3) is initially charged with 0.44 g (1.2 eq) of triethylamine and 1.5 mg of DMAP in 8ml of EtOAc"), and the mixture is stirred at 50° C. for 10 min. Subsequently 0.043 g (1.1 eq) of isobutyryl chloride in 2 ml of EtOAc) is added dropwise over 20 min and then the mixture is left to stir at 50° 1252 0.15 g (0.36 mmol) of the compound according to C. for 6 hand then at RT overnight. The mixture is admixed example (I-1-a-3) is initially charged with 0.44 g (1.2 eq) of triethylamine in 8ml ofdichloromethane and stirred at RT for with 10 ml of sodium hydrogencarbonate solution, the 5 min. Subsequently, 0.043 g (1.1 eq) of ethyl chloroformate organic phase is removed, the aqueous phase is reextracted is added dropwise over 20 min and then the mixture is left to with 20 ml of EtOAc', and the combined organic phases are stir at RT overnight. It is admixed with 5 ml of 10% sodium dried over sodium sulphate. The residue which remains after carbonate solution, and the organic phase is removed and dried. The residue which remained after the concentration the concentration is taken up in a mixture of EtOAc' and was purified by column chromatography (silica gel, EtOAc'/ n-heptane, and filtered again. This gives 0.07 g of inventive n-heptane gradient). This gives 0.12 g 68% of theory of compound (I-1-b-1)=40% of theory. inventive compound (I-1-c-1). 1253 'HNMR (400 MHz, CDC1): 8–6.66(pseudod, 2H, 1248 HNMR (400 MHz, CDC1): 8–6.61 (pseudod, 2H, Aryl-H), 6.37 (s, 1H, NH), 4.34 (q., 21-1, CH, CFs), 4.01 (q. Aryl-H), 6.37 (s, 1H, NH), 4.35 (q, 2H, CH, CFs), 3.37 (s, 2H, OCHCH), 3.40 (s, 3H, OCH), 3.25 (m, 1H, C 3H, OCH), 3.24 (m, 1H, CH OCH), 2.51 (m, 3H, CH H OCH), 2.49 (m. 2H, CH Ar), 2.21 (s.3H, ArylCH), 2.22, 1.96, 1.75, 1.40 (each m, together 8H cyclohexyl), 1.13 Arand CH(CH)), 2.20. (s, 3H, ArylCH), 2.19, 1.79, 1.38 (m, 6H, aryl CHCH and OCH2CH) ppm. (eachm, together 8H cyclohexyl), 1.13 (t,3H, Aryl CHCH), 1254. In analogy to example (I-1-c-1), and according to 1.00 (dd. 6H, (CH))ppm. the general information regarding preparation, the following 'Ethyl acetate compounds of the formula (I-1-c) are obtained:

US 2010/03 11593 A1 Dec. 9, 2010 86

Example II-1 1256 1.5 g (5.7 mmol) of the compound according to 1255 example (XXXI-1) are admixed with 3.4 g (5 eq) of thionyl chloride and one drop of DMF. The mixture is heated to boiling under reflux until the evolution of gas has ended, then the reaction Solution is concentrated and admixed with 4 ml of dichloromethane (Solution 1). 1.5 g (1.1 eq) of methyl trans O 3-ethoxy-1-aminocyclohexancarboxylate and 0.7 g (1.2 eq) w O of triethylamine are dissolved in 50 ml of dichloromethane, NW and solution 1 is added dropwise within 1 h. After stirring for 18 h, the mixture is admixed with 10 ml of water, and the CH3 CH3 organic phase is removed, concentrated and purified by col umn chromatography. This gives 0.56 g (23% of theory) of example II-a-1. O 1257, 1H NMR (400 MHz, CDC1): 8–4.36(q,2H, CH, > CF), 3.71 (s.3H, OCH), 3.40 (m, 2H, CH-OCH) ppm. F 1258. In analogy to example (II-1), and according to the F F general information regarding preparation, the following compounds of the formula (II) are obtained:

(II)

Ex. Iso No. W X Y 7 J1 J2 J3 D. A B R Analysis le

II- CH, CH, H 4- F F F H —CH2—CH(OCHo)—(CH2)3. CH H NMR (400 MHz, CDCl3): 4.34(q,trans 2H, CH2—CF), 3.70(s, 3H, OCH), 3.32(m,2H, CH OCH) II- CH, CH, H 4- F F F H -(CH), CH(CHOCH)–(CH) CH H NMR (300 MHz, CDC1): 4.34(q, B 2— 3 2H, CH2—CF), 3.70(s, 3H, OCH), 3.11(m, 2H, CH2—OCH) II- CH, CH H 4- F F F H –(CH) CH(OCH)–(CH) - CH H NMR (400 MHz, de-DMSO): cis .23(s, 6H, Ar—CH3), H), 3.23(s, 3H, OCH), 3.50(s, H, CH-CO), 3.52(s, 3H, COCH), .58-4.65 (q, 2H, O—CH2CF), .69(s, 2H, ArH) II- CH, CH, H 4- F F F H —(CH2)2—O—(CH2)2— CH. "H NMR (400 MHz, de-DMSO): – 5 1.84-1.97 (m, 4H, CH-), 2.23 (s, 6H, Ar—CH).3.51(s, 2H, CO-CH2), 3.55 (s, 3H, COCH), 4.58-4.65(q, 2H, ArH) US 2010/03 11593 A1 Dec. 9, 2010 87

1259. The following compounds of the formula (I-1'-a) 1266 1.36 g (34 mmol) of sodium hydride (60%) are which were used to prepare compounds of the formula (I-1-a) initially charged in 30 ml of THF, and 3.10 g (31 mmol) of are novel and can be prepared according to method A: trifluoroethanol are added dropwise, after the evolution of gas

Ex. No. W X Y A B M.p. Isomer I-1'-a-1 CH5, C2H5 H —(CH2)2—CHOCH -(CH2)2— 225-228 cis I-1'-a-2 CHS CHs H —(CH2)2—O—(CH2)2— 278

1260. The phenylacetic acids of the formula (XXXI) has ended 6.48 g (34 mmol) of copper(I) iodide are added, a required to prepare the compound (I-1'-a) are obtained, for solution of 2.00 g (6.18 mmol) of (I-2-a-1') (known in generic example, by bromination in glacial acetic acid. terms from WO 98/05638) dissolved in 20 ml of THF is Example (XXXI'-1) slowly added dropwise, and the mixture is boiled at reflux for 1261 2.5 h. (XXXI'-1) 1267 For workup, the cooled mixture is admixed with CH5 water, acidified with dil. HCl and extracted by shaking with ether and ethyl acetate, and the organic phase is dried, filtered and concentrated. 1268. This gives 1.57 g (70% of theory) of example (I-2- Br CO2H a-1): log P(HCOOH) 2.59. CH5 1269 1H NMR (CDCN): 8=1.80-2.20 (m, 8H), 2.15 (s, 1262. 3.85 g (20 mmol) of 2,6-diethylphenylacetic acid 3H), 3.35 (m, 2H), 7.15 (m. 1H), 7.30 (m, 1H), 7.35 (m, 1H) are initially charged in 40 ml of glacial acetic acid. At 10° C.-15° C., 3.2 g (20 mmol) of bromine in 12 ml of glacial ppm. acetic acid are added dropwise within approx. 40 min. After approx. 2 hours, another 1.1 g of bromine in 4 ml of glacial Example (I-2-a-2) acetic acid are added, and the mixture is stirred at room temperature overnight. After evaporating off the glacial acetic acid under reduced pressure, the residue is taken up in 40 ml 1270 of 2N sodium hydroxide solution and washed with MTB ether, and the aqueous phase is acidified, extracted with

dichloromethane, dried and concentrated under reduced pres SUC. 1263. This gives 4.3 g (72% of theory) of the compound (XXXI'-1). 1264) "H NMR (400 MHz, d-DMSO): 8=1.08, 1.12 (2t, each3H, CH, CH), 2.54-2.60 (q,2H, CHCH), 2.76-2.81 (q, 2H, CHCH), 3.70 (s. 2H, CHCO), 6.98, 7.41 (2d, each 1H, Ar—H) ppm. Example (I-2-a-1) 1265 (I-2-a-1) 1271 0.294 g (2.62 mmol) of potassium tert-butoxide is initially charged in 7 ml of DMF and cooled to 0°C., a OH solution of 0.732 g (1.75 mmol) of example (III-1) in 3 ml of DMF is added dropwise at 0-10° C., and the mixture is stirred at room temperature overnight. 1272 For workup, the DMF) is evaporated off by rotary evaporation, the residue is stirred in water, the alkaline phase is extracted with methyl tert-butyl ether, and the aqueous phase is acidified with hydrochloric acid, extracted with

US 2010/03 11593 A1 Dec. 9, 2010

Example I-6-a-1 Example I-6-c-1 1286 1293

O CH3 O CH O F F O b F y^. CH3 OCHs F O O CH F F 1294 69 mg (0.2 mmol) of the compound according to example (I-6-a-1) are dissolved in 5 ml of dichloromethane and admixed with 24 mg (0.22 mmol) of ethyl chloroformate 1287 300 mg (0.934 mmol) of the compound according to and 62 mg (0.6 mmol) of triethylamine. The mixture is left at example (I-6'-a-1) are dissolved in 5 ml of collidine and room temperature for 30 minutes. It is concentrated and puri fied by means of preparative HPLC (RP-18, acetonitrile/wa admixed with 702 mg (6.26 mmol) of potassium tert-butoxide ter gradient (1% trifluoroacetic acid)). (solution 1). In a separate flask, 178 mg (0.934 mmol) of 1295 Yield: 57 mg. copper(I) iodide, 841 mg (8.4 mmol) of trifluoroethanol and 1296) "H NMR (400 MHz CDC1): 1.21 (t,3H), 1.50 (mc, 210 mg (1.87 mmol) of potassium tert-butoxide are dissolved 1H), 1.65-1.88 (m,3H), 1.94 (mc, 1H), 2.06 and 2.09 (eachs, in 5 ml of collidine. Solution 1 is added dropwise thereto, the each 3H), 3.11 and 3.80 (each mc, each 1H), 4.12 (mc, 2H), vessel is rinsed with 2 ml of DMF and the reaction mixture is 4.30 (q, 2H), 6.62 (s. 2H) ppm. stirred at 145° C. in a microwave for 1 hour. The solvent is drawn off under reduced pressure, and the residue is taken up Example I-8-a-1 in water and filtered through Celite. 10 ml of ammonium 1297 chloride solution are added to the filtrate which is acidified with 2N hydrochloric acid. The solid which precipitates out is filtered off with suction and dried. 1288 Yield: 185 mg (58% of theory). H3C O Nr N 1289 H NMR, (400 MHz, CDC1): 1.38-148 (m, 1H), N 1.70 (mc,3H), 2.05 and 2.10 (eachs, each3H), 3.15 (mc, 2H), S. 4.31 (q, 2H), 6.65 (s. 2H) ppm. F OH 1290 The compound of the formula (I-6'-a-1) which is F used to prepare the compound of the formula (I-6-a-1) is y^ novel and can be prepared according to method F: F CH3

Example (I-6'-a-1) 1298 0.3 g of 8-(4-bromine-2,6-diethylphenyl)-9-hy droxy-1,2,4,5-tetrahydro-7H-pyrazolo 1,2-d1.4.5 oxadi 1291 azepin-7-one (known from WO99/047525 ex.: 1.087) is dis solved under a nitrogen atmosphere with 2 eq (0.176 g) of potassium t-butoxide in 5 ml of collidine (solution 1). 1299 Subsequently, 150 mg of copper(I) iodide, 0.69 g of 2.2.2-trifluoroethanol and 6.7 eq (0.591 g) of potassium t-bu O toxide are Suspended in 5 ml of collidine under a nitrogen atomsphere. Solution 1 is added thereto and the mixture is left CH3 O to stir at 145° C. for 1 h under microwave conditions. 1300. The solvent is removed under reduced pressure and OH the remaining residue is taken up in water. The remaining Br CH3 residue is filtered off and the mother liquor is adjusted to pH-1 with 1N hydrochloric acid. After extracting with ethyl acetate and drying over sodium Sulphate, the mixture is con centrated to obtain 0.275 g of inventive compound I-8-a-1. 1292 H NMR (400 MHz, CDC1): 1.43 (mc, 1H), 1.68 1301. In analogy to example (I-8-a-1), and according to (mc.3H), 2.08 and 2.11 (eachs, each 3H), 2.98 and 3.28 (each the general information regarding preparation, the following mc, each 1H), 7.18 (s. 2H) ppm. compounds of the formula (I-8-a) are obtained: US 2010/03 11593 A1 Dec. 9, 2010 90

(I-8-a) X OH An 1 % Wizy \ NX N W Y W D O J where Z = \/NoC / N

Ex. No. W X Z, Ji J2 J3 D Analysis

I-8-a-1 C2H5, C2H5 4- F F F —(CH2)2—O—(CH2)2— H NMR (400 M Z. DCl): 6.72(m, .32(m, 2H, CF CH2), .75(m, 2H, CH N) I-8-a-2 CHS CH 4- F F F —(CH2)2—O—(CH2)2— Z. H, Ar–H) H), 4.32 2), 3.80 (m,

I-8-a-3 CH, CH 4- F F F -(CH2)2 O-(CH2)2 - Z.

I-8-a-4 C-H CH 4- F F F —(CH2) - NMR (400 MHz DC1): 8 = 3.68 , 4H, CHN), s32(m,2H, OCHCF) I-8-a-5 C2H5, C2H5 4- F F F —(CH2) - s NMR (400 MHz DCl): 6.68(d, 2H, Ar–H),

I-8-a-6 CH, CH 4- F F F -(CH2) - NMR (400 MHz C DCl): 6.68(d, 2H, Ar–H),

3.

Example I-8-b-1 1303 0.05 g of the compound according to example I-8- a-4 is dissolved under a nitrogen atmosphere in 1 ml of 1302 dichloromethane. Subsequently, 17 mg of 2,2-dimethylpro panoyl chloride and 17 mg of triethylamine are added, and the mixture is stirred at room temperature overnight.

H3C O N 1304. The mixture is added to 5 ml of water and the phases M are separated by means of an extraction cartridge. The organic N S. phase is concentrated and then the residue is purified by O reverse phase HPL chromatography (acetonitrile/water gra F O dient, 0.05%TFA). This gives 0.024 g of inventive compound F O I-8-b-1. H3C CH3 F CH3 1305 H NMR (400 MHz, CDC1): 6.67 (s. 2H, Ar H), H3C 4.32(q,2H, OCHCF), 1.92 (m, 4H, CH), 1.05 (s.9H, t-Bu) 1306. In analogy to example (I-8-b-1), and according to the general information regarding preparation, the following compounds of the formula (I-8-b) are obtained:

US 2010/03 11593 A1 Dec. 9, 2010 92

(I-8-c)

O A Z Y-Z NN N W \ NX N Y M W D O

O where Z = J Y /N / N

Ex. No. W X Z, Ji J2 J3 A D R2 Analysis I-8-c-1 CHS CH -(CH2) -

d) H NMR (400M e) H NMR (400M f) H NMR (400 MHz CDCl); 6.65(d. 2H, Ar–H), 4.32(m,2H, CF CH), 4.16(m, 2H, CH-OC(=O))

2,6-Dimethyl-4-trifluoroethoxyphenylacetic acid with diethyl ether, and the ether phase is dried, filtered and (Example XXXI-1) concentrated: 1313 12.73 g of N,N-dimethyl-2,6-dimethyl-4-trifluoro ethoxyphenylacetamide. 1310 1314. The aqueous phase is acidified with hydrochloric acid and extracted repeatedly with dichloromethane, and the CH organic phase is dried and concentrated by rotary evapora tion: OH + 1315 7.66 g or arylacetic acid. 1316. The 12.73 g of N,N-dimethyl-2,6-dimethyl-4-trif F O luoroethoxyphenylacetamide are boiled in a solution of 58 g of potassium hydroxide in 165 ml of methanol and 43 ml of F>-so CH water for 36 h. For workup, the methanol is removed by rotary F evaporation, the residue is partitioned between water and CH3 CH3 dichloromethane, the aqueous phase is acidified with hydro N chloric acid and the precipitated crystals are filtered off with YCH, suction and dried. In this way, a further 11.6 g of the pheny lacetic acid (XXXI-1) are obtained. F O 1317| Total yield: 19.3 g (90% of theory) of 2,6-dimethyl F 4-trifluoroethoxyphenylacetic acid (XXXII). F |1318 H NMR (d-DMSO): 8–2.25 (s, 6H), 3.50 (s, 2H), 4.60 (m. 2H), 6.75 (s. 2H) ppm. 1311 18.05 g (451 mmol) of sodium hydride are initially 1319 log P(HCOOH)2.51. 1320. The log P values reported in the above tables and charged in 500 ml of DMF. 41.05 g (410 mmol) of trifluoro preparation examples are determined according to EEC ethanol are added dropwise, after the evolution of gas has Directive 79/831 Annex V.A8 by HPLC (High Performance ended 15.63 g (82 mmol) of copper(I) iodide are added, a Liquid Chromatography) on a reversed-phase column (C18). solution of 21.10 g (82 mmol) of methyl 2,6-dimethyl-4- Temperature: 43° C. bromophenylacetate in 100 ml of DMF is slowly added drop 1321. The determination is effected in the acidic range at wise and the mixture is boiled at reflux for 2.5 h. pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as 1312 For workup, the mixture is concentrated, the residue eluent; linear gradient from 10% acetonitrile to 95% aceto is admixed with water and extracted by shaking repeatedly nitrile. US 2010/03 11593 A1 Dec. 9, 2010

1322 The determination by LC-MS in the acidic range is 1333 To prepare an appropriate active ingredient prepa effected at pH 2.7 with 0.1% aqueous formic acid and aceto ration, 1 part by weight of active ingredient is mixed with the nitrile (contains 0.1% formic acid) as the eluent; linear gra stated amounts of solvent and emulsifier, and the concentrate dient from 10% acetonitrile to 95% acetonitrile. is diluted with emulsifier-containing water to the desired con 1323. The determination by LC-MS in the neutral range is centration. effected at pH 7.8 with 0.001 molar aqueous ammonium 1334 Discs of Chinese cabbage (Brassica pekinensis) are hydrogen carbonate solution and acetonitrile as the eluent; sprayed with an active ingredient preparation of the desired linear gradient from 10% acetonitrile to 95% acetonitrile. 1324. The calibration is effected with unbranched alkane concentration and, after drying, populated with larvae of the 2-ones (with 3 to 16 carbon atoms), the log Pvalues of which mustard beetle (Phaedon cochleariae). are known (determination of log P values on the basis of the 1335. After the desired time, the effect in 96 is determined. retention times by linear interpolation between two Succes 100% means that all beetle larvae have been killed; 0% means sive alkanones). that none of the beetle larvae have been killed. 1325. The lambda-max values were determined using the 1336. In this test, for example, the following compounds UV spectra from 200 nm to 400 nm in the maxima of the of the preparation examples show, at an application rate of chromatographic signals. 500 g/ha, an effect of 280%: Application Examples Ex. No.: I-1-a-3, I-1-a-8, I-1-a-11, I-1-a-14, I-1-a-16, Example 1 I-1-a-28, I-1-a-30, I-1-a-31, I-1-a-32, I-1-a-33, I-1-c- 6, I-2-a-5 1326 Example 3 1337 Myzus test (MYZUPE spray treatment) Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide Tetranychus test: OP-resistant (TETRUR spray treatment) Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide 1327. To prepare an appropriate active ingredient prepa Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether ration, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate 1338. To prepare an appropriate active ingredient prepa is diluted with emulsifier-containing water to the desired con centration. ration, 1 part by weight of active ingredient is mixed with the 1328 Discs of Chinese cabbage (Brassica pekinensis) stated amounts of solvent and emulsifier, and the concentrate infected by all stages of the green peach aphid (Myzus persi is diluted to the desired concentration with emulsifier-con cae) are sprayed with an active ingredient preparation of the taining water. desired concentration. 1339 Discs of french bean leaves (Phaseolus vulgaris) 1329. After the desired time, the effect in 96 is determined. infested with all stages of the two-spotted spider mite (Tet 100% means that all of the aphids have been killed; 0% means ranychus urticae) are sprayed with a preparation of the active that none of the aphids have been killed. ingredient at the desired concentration. 1330. In this test, for example, the following compounds 1340. After the desired time, the effect in 96 is determined. from the preparation examples show, at an application rate of 100% means that all spider mites have been killed and 0% 500 g/ha, an effect of 280%: means that none of the spider mites have been killed. Ex. No.: I-1-a-1, I-1-a-3, I-1-a-4, I-1-a-5, I-1-a-6, 1341. In this test, for example, the following compounds I-1-a-7, I-1-a-8, I-1-a-10, I-1-a-12, I-1-a-13, I-1-a- from the preparation examples show an effect of 280% at an 14, I-1-a-15, I-1-a-17, I-1-a-18, I-1-a-19, I-1-a-23, application rate of 100 g/ha: I-1-a-24, I-1-a-25, I-1-a-26, I-1-a-27, I-1-a-28, I-1-a- 29, I-1-a-30, I-1-a-31, I-1-a-32, I-1-a-33, I-1-a-34, Ex. No.: I-1-a-4, I-1-a-5, I-1-a-6, I-1-a-7, I-1-a-8, I-1-a-35, I-1-a-36, I-1-a-37, I-1-a-38, I-1-a-39, I-1-a- I-1-a-10, I-1-a-14, I-1-a-17, I-1-a-2, I-1-a-25, I-1-a- 40, I-1-a-41, I-1-a-42, I-1-a-43, I-1-a-44, I-1-a-45, 28, I-1-a-3, I-1-a-30, I-1-a-31, I-1-a-32, I-1-b-1, I-1- I-1-a-46, I-1-a-48, I-1-b-1, I-1-c-1, I-1-c-2, I-1-c-3, c-2, I-1-c-3, I-1-c-4, I-1-c-5, I-1-c-6, I-2-a-5, I-2-a-6, I-1-c-4, I-1-c-5, I-1-c-6, I-2-a-1, I-2-a-2, I-2-a-3, I-2-a-4, I-2-a-5, I-2-a-6, I-8-a-2, I-8-b-3, I-8-b-5 I-2-b-1, I-8-c-1, I-8-a-2, I-8-b-3, I-8-b-5 1331. In this test, for example, the following compounds 1342. In this test, for example, the following compounds from the preparation examples show, at an application rate of from the preparation examples show an effect of 280% at an 20 g/ha, an effect of 280%: application rate of 20 g/ha: Ex. No.: I-1-a-20 Ex. No.: I-1-a-16, I-1-a-19 Example 2 Example 4 1332 1343

Phaedon test (PHAECO spray treatment) Spodoptera frugiperda test (SPODFR spray treatment) Solvent: 78.0 parts by weight of acetone Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide 1.5 parts by weight of dimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether US 2010/03 11593 A1 Dec. 9, 2010 94

1344. To prepare an appropriate active ingredient prepa 1356. After the desired time, the kill in % is determined. ration, 1 part by weight of active ingredient is mixed with the 100% means that all of the larvae have been killed; 0% means stated amounts of solvent and emulsifier, and the concentrate that none of the larvae have been killed. is diluted with emulsifier-containing water to the desired con 1357. In this test, for example, the following compounds centration. from the preparation examples show, at an application rate of 1345 Discs of maize leaves (Zea mays) are sprayed with 100 ppm, an effect of 2 80%: an active ingredient preparation of the desired concentration and, after drying, populated with caterpillars of the army worm (Spodoptera frugiperda). Ex. No.: I-1-a-25, I-1-a-3, I-2-a-5, I-2-a-6 1346. After the desired time, the effect in 96 is determined. Example 7 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed. 1358 1347. In this test, for example, the following compounds from the preparation examples show, at an application rate of 500 g/ha, an effect of 280%: Boophilus microplus test (BOOPMI injection) Ex. No.: I-1-a-27, I-1-a-28, I-1-a-32, I-1-a-36, I-1-a- Solvent: dimethylsulphoxide 39, I-1-c-1 Example 5 1359. To prepare an appropriate active ingredient prepa ration, 1 part by weight of active ingredient is mixed with the 1348 stated amount of solvent, and the concentrate is diluted to the desired concentration with water. The solution of active ingredient is injected into the abdomen (Boophilus microplus), and the animals are transferred into dishes and Meloidogyne incognita test (MELGIN) kept in a climate-controlled room. The activity is assessed by Solvent: 78.0 parts by weight of acetone laying offertile eggs. 1.5 parts by weight of dimethylformamide 1360. After the desired time, the effect in 96 is determined. Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether 100% means that none of the ticks has laid any fertile eggs. 1361. In this test, for example, the following compounds 1349 To prepare an appropriate active ingredient prepa from the preparation examples show, at an application rate of ration, 1 part by weight of active ingredient is mixed with the 20 ppm, an effect of 280%: stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water. Ex. No.: I-1-a-25, I-1-a-3, I-1-a-7, I-1-c-4, I-1-c-5, 1350 Vessels are filled with sand, solution of active ingre dient, Meloidogyne incognita egg/larvae Suspension and let I-2-a-5, I-2-a-6 tuce seeds. The lettuce seeds germinate and the plants Example 8 develop. On the roots, galls are formed. 1351. After: the desired time, the nematicidal effect is Enhancement of Activity by Ammonium/Phospho determined by the gall formation in %. 100% means that no nium Salts in Combination with Penetration Enhanc galls were found: 0% means that the number of galls on the CS treated plants corresponds to that of the untreated control. 1352. In this test, for example, the following compounds 1362 from the preparation examples show an effect of 280% at an application rate of 20 ppm. Myzus persicae test Ex. No.: I-1-a-25, I-1-c-6 Solvent: 7 parts by weight of dimethylformamide Example 6 Emulsifier: 1 part by weight of alkylaryl polyglycol ether 1353 1363 To prepare an appropriate active ingredient prepa ration, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate Lucilia cuprina test (LUCICU) is diluted to the desired concentration with water. For appli cation with ammonium orphosphonium salts and penetration Solvent: dimethylsulphoxide enhancer (rapeseed oil methyl ester 500 EW), these are each added to the spray liquor in a concentration of 1000 ppm. 1354. To prepare an appropriate active ingredient prepa 1364 Bell pepper plants (Capsicum annuum) heavily ration, 1 part by weight of active ingredient is mixed with the infested by the green peach aphid (Myzus persicae) are stated amount of solvent, and the concentrate is diluted to the treated by spraying to runoff point with the active ingredient desired concentration with water. preparation of the desired concentration. After the desired 1355 Vessels containing horse meat treated with the time, the kill in 96 is determined. 100% means that all animals active ingredient preparation of the desired concentration are have been killed; 0% means that none of the animals have populated with Lucilia cuprina larvae. been killed. US 2010/03 11593 A1 Dec. 9, 2010 95

weeks by comparison with the untreated controls (herbicidal TABLE effect in percent: 100% effect—the plants have died, 0% effect—like control plants). Kill rate/% after 6 days 1371. In addition to the aforementioned compounds, the --RME --RME-AS following compounds, applied by the pre-emergence method Active Concentration +AS (1000 (1000 at 320 g/ha a.i., show an effect of 280% against Alopecurus ingredient ppm (1000 ppm) ppm) ppm each) myosuroides, Echinocloa crus-galli, Lolium multiflorum and I-1-a-25 O.8 O O 40 55 Setaria viridis: I-1-a-6, I-1-a-7, I-1-a-9, I-1-a-12, I-1-a-13, I-1-a-14, I-1-a-16, I-1-a-19, I-1-a-22, I-1-a-33, I-1-a-34, I-1- a-35, I-1-a-37, I-1-a-38, I-1-a-39, I-1-a-40, I-1-a-41, I-1-b-2, I-1-c-2, I-1-c-3, I-1-c-6, I-2-a-5. Example 9 1372. In addition to the aforementioned compounds, the following compounds, applied by the pre-emergence method 1365 at 80 g/ha a.i., show an effect of 280% against Alopecurus myosuroides, Echinocloa crus-galli, Lolium multiflorum and Setaria viridis: I-1-a-1, I-1-a-2, I-1-a-3, I-1-a-4, I-1-a-5, I-1- Aphis gossypii test a-8, I-1-a-17, I-1-a-18, I-1-a-21, I-1-a-25, I-1-b-1, I-1-c-1, I-1-c-4, I-1-c-5. Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether 2. Herbicidal Post-Emergence Action 1366. To prepare an appropriate active ingredient prepa 1373. Seeds of monocotyledonous and dicotyledonous ration, 1 part by weight of active ingredient is mixed with the weed and crop plants are placed in Sandy loam in wood fibre stated amounts of solvent and emulsifier, and the concentrate pots, covered with soil and cultivated in a greenhouse under is diluted to the desired concentration with emulsifier-con good growth conditions. Two to three weeks after sowing, the taining water. For application with ammonium or phospho test plants are treated at the one-leaf stage. The test com nium salts and penetration enhancers (rapeseed oil methyl pounds, formulated as wettable powders (WP), are sprayed ester 500 EW), these are each added to the spray liquor in a onto the green parts of the plants in different dosages with a concentration of 1000 ppm. water application rate of 600 l/ha (converted), with 0.2% 1367 Cotton plants (Gossypium hirsutum) heavily added wetting agent. After the test plants have been kept in the infested by the cotton aphid (Aphis gossypii) are treated by greenhouse under optimal growth conditions for about three spraying to runoff point with the active ingredient preparation weeks, the effect of the preparations is assessed visually by of the desired concentration. comparison to untreated controls (herbicidal effect in per cent: 100% effect=the plants have died, 0% effect-like con 1368. After the desired time, the kill in % is determined. trol plants). 100% means that all the aphids have been killed; 0% means 1374. In addition to the aforementioned compounds, the that none of the aphids have been killed. following compounds, applied by the post-emergence method at 80 g/ha, show an effect of 280% against Alopecu TABLE rus myosuroides, Avena fatua, Echinocloa Crus-galli, Lolium Kill rate/% after 6 days multiflorum, Setaria viridis and Veronica persica: I-1-a-4, I-1-a-5, I-1-a-6, I-1-a-8, I-1-a-17, I-1-a-18, I-1-a-19, I-1-a- --RME --RME-AS Active Concentration +AS (1000 (1000 ppm 25, I-1-a-26, I-1-a-34, I-1-a-39, I-1-b-1, I-1-b-2, I-1-c-4, I-1- ingredient ppm (1000 ppm) ppm) each) c-5, I-2-a-5. 1375. In addition to the aforementioned compounds, the I-1-a-25 O.8 O 35 2O 85 following compounds, applied by the post-emergence I-1-a-29 4 10 15 8O 95 I-1-a-31 4 O 10 5 35 method at 80 g/ha, show an effect of 280% against Alopecu rus myosuroides, Avena fatua, Echinocloa Crus-galli, Lolium multiflorum and Setaria viridis: I-1-a-1, I-1-a-3, I-1-a-7, I-1- a-9, I-1-a-14, I-1-a-35, I-1-a-37, I-1-a-38, I-1-a-40, I-1-a-41, Example 10 I-1-c-1, I-8-a-1, I-8-c-1, I-8-c-3, I-8-c-5. 1. Herbicidal Pre-Emergence Action Use of Safeners: 1369. Seeds of monocotyledonous and dicotyledonous 1376. If there is to be an additional test as to whether weed and crop plants are placed in Sandy loam in wood fibre safeners can improve the plant compatibility of test Sub pots and covered with soil. The test compounds, formulated stances in the case of crop plants, the following options are in the form of wettable powders (WP), are then applied to the used for applying the safeners: Surface of the covering soil as an aqueous Suspension with a 1377 Seeds of the crop plants are, before sowing, water application rate of 600 l/ha (converted), with 0.2% dressed with safener substance (the amount of safener added wetting agent in different dosages. stated in percent, based on the weight of the seed) 1370. After the treatment, the pots are placed in a green 1378. Before the application of the test substances, the house and kept under good growth conditions for the test crop plants are sprayed with the safener at a certain plants. The visual assessment of the emergence damage on application rate per hectare (usually one day before the the test plants is effected after a test period of approx. three application of the test Substances) US 2010/03 11593 A1 Dec. 9, 2010 96

1379 The safener is applied together with the test sub stance as a tankmix (the amount of safener is stated in -continued g/ha or as a ratio, based on the herbicide). 28 days after application Application rate Summer barley Container Trials with Cereals in a Greenhouse ga.i./ha. observed (%) Ex. (I-1-a-17) 2OO 95 Mefenpyr 1 Day Before Herbicide Application 1OO 8O 50 40 Ex. (I-1-a-17) + 2OO -- SO 60 1380 mefenpyr 1OO -- SO 60 SO - SO 30 28 days after 28 days after 28 days after 28 days after application application application application Application rate Summer barley Summer wheat Application rate Summer barley Summer wheat ga.i./ha. observed (%) observed (%) ga.i./ha. observed (%) observed (%) Ex. (I-1-a-19) 100 85 Ex. (I-1-a-5) 25 95 50 70 12.5 65 65 25 70 2O Ex. (I-1-a-5) + 2S-- SO 75 12.5 10 mefenpyr 12.5 - SO 35 25 Ex. (I-1-a-19) + 100 - SO 70 mefenpyr SO - SO 50 28 days after application 2S-- SO 40 2O Application rate Summer wheat 12.5 - SO O ga.i./ha. observed (%) 10 days after 28 days after Ex. (I-1-a-6) 25 85 application application 12.5 70 Application rate Summer wheat Summer wheat Ex. (I-1-a-6) + 25 - SO 60 ga.i./ha. observed (%) observed (%) mefenpyr 12.5 - SO 50 Ex. (I-1-a-7) 1OO 70 Ex. (I-1-a-25) 12.5 40 70 50 70 Ex. (I-1-a-25) + 12.5 - SO 25 30 25 SO mefenpyr 12.5 50 Ex. (I-1-a-7) + 1OO -- SO 30 10 days after application mefenpyr SO - SO 2O Application rate Summer barley 25 - SO 2O ga.i./ha. observed (%) 12.5 - SO 10 Ex. (I-1-b-2) 12.5 50 10 days after 28 days after Ex. (I-1-b-2) + 12.5 - SO 2O application application mefenpyr Application rate Summer wheat Summer wheat ga.i./ha. observed (%) observed (%) 28 days after application Application rate Summer wheat Ex. (I-1-a-8) 12.5 65 98 ga.i./ha. observed (%) Ex. (I-1-a-8) + 12.5 - SO 50 50 mefenpyr Ex. (I-1-a-37) 12.5 70 Ex. (I-1-a-37) + 12.5 - SO 15 28 days after application mefenpyr Application rate Summer wheat ga.i./ha. observed (%) Ex. (I-1-a-14) 50 100 Container Tests with Maize-Soya-Cotton in a 25 99 Greenhouse 12.5 93 Ex. (I-1-a-14) + SO - SO 85 mefenpyr 25 - SO 85 Cyprosulfamide 1 Day Before Herbicide Application 12.5 - SO 40 28 days after 28 days after 1381 application application Application rate Summer barley Summer wheat ga.i./ha. observed (%) observed (%) 28 days after application Ex. (I-1-a-15) 1OO 60 Application rate Maize (Aventura) 50 97 40 ga.i./ha. observed (%) 25 85 30 Ex. (I-1-a-8) 50 70 12.5 70 10 25 60 Ex. (I-1-a-15) + 1OO -- SO 2O 12.5 35 mefenpyr SO - SO 8O 10 Ex. (I-1-a-8) + SO - 200 40 25 - SO 8O 5 cyprosulfamide 25 - 200 35 12.5 - SO 2O O 12.5 - 200 15 US 2010/03 11593 A1 Dec. 9, 2010 97

-continued -continued 28 days after 28 days after (2) application application Application rate Maize (Arsenal) Maize (Cecilia) ga.i./ha. observed (%) observed (%) Ex. (I-1-a-25) 1OO 100 35 50 75 2O 25 15 10 12.5 5 O Ex. (I-1-a-25) + 100 + 100 70 10 (3) cyprosulfamide 50 - 100 50 O 25 - 100 O O 125 + 100 O O Ex. (I-1-c-2) 1OO 25 75 50 2O 25 2O Ex. (I-1-c-2) + 100 - 200 15 25 cyprosulfamide SO - 200 O 25 - 200 O

(4)

1. Compounds of the formula (I)

(5) (I)

(6)

in which W is hydrogen, alkyl, halogen, haloalkyl, alkoxy or haloalkoxy, X is alkyl, alkenyl, alkynyl, halogen, alkoxy, haloalkyl, haloalkoxy or cyano, Y is hydrogen, alkyl, alkoxy or halogen, (7) Z is a group

(8) in which J and J are each independently hydrogen or halogen and J is halogen or a haloalkyl group, CKE is one of the groups

(1) (9) o1 G A - \ . D1 N US 2010/03 11593 A1 Dec. 9, 2010 98

A and Q' together are in each case optionally substituted -continued alkanediyl or alkenediyl, which may optionally be inter

(10) rupted by at least one heteroatom, a

O

CO /

(11) or substituted

group, or Band Q together with the atoms to which they are bonded in which are a saturated or unsaturated cycle which is unsubsti U is —S , —S(O)— —S(O) , —O—, tuted or substituted in the B. Q. moiety and optionally contains at least one heteroatom, or D and Q' together with the atoms to which they are bonded are a saturated or unsaturated cycle which is unsubsti tuted or substituted in the D. Q' moiety and optionally Y.1. contains at least one heteroatom, Q' is hydrogen, alkyl, alkoxyalkyl, optionally substituted cycloalkyl in which one methylene group is optionally an S=N , S(O)—N- or replaced by oxygen or sulphur, or is optionally substi tuted phenyl, Q, Q, Q and Q are each independently hydrogen or alkyl, CEN Q is hydrogen, in each case optionally substituted alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, or is optionally substituted cycloalkyl in which one or two group methylene groups are optionally replaced by oxygen or or is optionally Q- and Q-substituted C-C-alky Sulphur, or is optionally substituted phenyl, or lene which may optionally be interrupted by oxy Q' and Q together with the carbonatom to which they are gen, bonded are an unsubstituted or substituted cycle option A is hydrogen, in each case optionally halogen-substi ally containing one heteroatom, or tuted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, or is Q and Q together with the carbonatom to which they are saturated or unsaturated, optionally Substituted bonded are a saturated or unsaturated, unsubstituted or cycloalkyl in which at least one ring atom is option Substituted cycle optionally containing at least one het ally replaced by a heteroatom, or in each case option eroatom, or ally halogen-, alkyl-, haloalkyl-, alkoxy-, A and Q together with the carbonatom to which they are haloalkoxy-, cyano- or nitro-substituted aryl, aryla bonded are a saturated or unsaturated, unsubstituted or lkyl or hetaryl, Substituted cycle optionally containing at least one het eroatom, or B is hydrogen, alkyl or alkoxyalkyl, or A and Q together with the carbon atom to which they are A and B together with the carbon atom to which they are bonded are a saturated or unsaturated, unsubstituted or bonded are a saturated or unsaturated, unsubstituted or Substituted cycle optionally containing at least one het Substituted cycle optionally containing at least one het eroatom, eroatom, G is hydrogen (a) or one of the groups D is hydrogen oran optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxyalkyl, saturated or unsaturated cycloalkyl in which one or more ring (b) members are optionally replaced by heteroatoms, or in each case optionally Substituted arylalkyl, aryl, hetary lalkyl or hetaryl, or A and D together with the atoms to which they are bonded are a saturated or unsaturated cycle which is unsubsti tuted or substituted in the A, D moiety and optionally contains at least one (in the case of CKE-8 and 11 one further) heteroatom, or US 2010/03 11593 A1 Dec. 9, 2010 99

in which J and J are each independently hydrogen, fluo -continued rine or chlorine, and J is halogen or C-C-haloalkyl, (d) CKE is one of the groups

(e) G (1) o1 A (f) - \ . (g) D1 N O (2)

in which E is one metal ion equivalent or one ammonium ion, L is oxygen or Sulphur, M is oxygen or Sulphur, R" is in each case optionally halogen-substituted alkyl, (3) alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxy alkyl, or is optionally halogen-alkyl- or alkoxy-Sub stituted cycloalkyl which may be interrupted by at least one heteroatom, or is in each case optionally Substituted phenyl, phenylalkyl, hetaryl, phenoxy alkyl or hetaryloxyalkyl, R is in each case optionally halogen-substituted alkyl, (4) alkenyl, alkoxyalkyl, polyalkoxyalkyl, or in each case optionally substituted cycloalkyl, phenyl or benzyl, R. R. and R are each independently in each case optionally halogen-substituted alkyl, alkoxy, alky lamino, dialkylamino, alkylthio, alkenylthio. cycloalkylthio, or in each case optionally Substituted (5) phenyl, benzyl, phenoxy or phenylthio. RandR are each independently hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alk enyl, alkoxy, alkoxyalkyl, optionally Substituted phe nyl, optionally substituted benzyl, or, together with the nitrogen atom to which they are bonded, a cycle optionally interrupted by oxygen or Sulphur. (6) 2. Compounds of the formula (I) according to claim 1, in which W is hydrogen, C-C-alkyl, halogen, C-C-alkoxy, C-Ca-haloalkyl or C-Ca-haloalkoxy, X is halogen, C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C-alkoxy, C-Ca-halo-alkyl, C-Ca-haloalkoxy or (7) cyano, Y is hydrogen, halogen, C-C-alkyl or C-C-alkoxy, Z is a group