US 2010O261934A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0261934 A1 FISCHER et al. (43) Pub. Date: Oct. 14, 2010

(54) METHOD FOR PREPARING (30) Foreign Application Priority Data 2,6-DIETHYL-4-METHYLPHENYLACETIC ACD Nov. 4, 2004 (DE) ...... 1020040531919 (75) Inventors: Reiner FISCHER, Monheim (DE); Publication Classification SEWA his (DE): (51) Int. Cl. ark winem Urewes, C07C 5 L/09 (2006.01) Langenfeld (DE); Dieter Feucht, C07C 5 L/08 (2006.01) Eschborn (DE): Olga Malsam, Rosrath (DE); Guido Bojack, (52) U.S. Cl...... 562/496 Wiesbaden (DE); Christian Arnold, Langenfeld (DE). Thomas (57) ABSTRACT Auler, Leichlingen (DE); Jeffrey Marin Hills, Idstein (DE); Heinz The invention relates to novel 2,6-diethyl-4-methylphenyl Kehne, Hofheim (DE); Chris substituted tetramic acid derivatives of the formula (I) Rosinger, Hofheim (DE) Correspondence Address: G (I) STERNE, KESSLER, GOLDSTEIN & FOX P.L. V L.C. A O CHs 1100 NEW YORKAVENUE, N.W. B WASHINGTON, DC 20005 (US) \ -N CH3 (73) Assignee: Bayer CropScience AG, Monheim (DE) O C2H5 (21) Appl. No.: 12/821,831 in which A, B, D and Gare as defined above, to a plurality of (22) Filed: Jun. 23, 2010 processes and intermediates for their preparation and to their O O use as pesticides and/or herbicides, and also to selectively Related U.S. Application Data herbicidal compositions comprising, firstly, the 2,6-diethyl (62) Division of application No. 1 1/666,870, filed on Mar. 4-methylphenyl-substituted tetramic acid derivatives of the 24, 2008, filed as application No. PCT/EP2005/ formula (I) and, secondly, at least one crop plant tolerance 011343 on Oct. 21, 2005. promoter compound. US 2010/0261934 A1 Oct. 14, 2010

METHOD FOR PREPARING in which 2,6-DIETHYL-4-METHYLPHENYLACETIC 0007. A represents hydrogen, represents in each case ACD optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl or alkylthioalkyl or represents optionally substituted cycloalkyl, 0008 B represents hydrogen, alkyl or alkoxyalkyl, or 0001. The invention relates to novel 2,6-diethyl-4-meth 0009. A and B together with the carbonatom to which they ylphenyl-substituted tetramic acid derivatives, to a plurality are attached represent a saturated or unsaturated C-Cs of processes for their preparation and to their use as pesticides ring which optionally contains at least one heteroatom and and/or herbicides. Moreover, the invention relates to novel which is optionally substituted and selective herbicidal active compound combinations compris 0010 D represents hydrogen, ing, firstly, the 2,6-diethyl-4-methylphenyl-substituted tetra O mic acid derivatives and, secondly, a crop plant tolerance 0011. A represents hydrogen or alkyl, promoter compound, which combinations can be used with 0012 B represents hydrogen and 0013 D represents an optionally substituted radical from particularly good results for the selective control of weeds in the group consisting of alkyl, alkenyl, alkynyl, alkoxy various crops of useful plants. alkyl, alkylthioalkyl or optionally cycloalkyl, or 0002 Pharmaceutical properties of 3-acylpyrrolidine-2,4- 0014) A and D together with the atoms to which they are diones are described in the prior art (S. Suzuki et al. Chem. attached represent a saturated or unsaturated cycle which Pharm. Bull. 151120 (1967)). Furthermore, R. Schmierer and optionally contains at least one oxygen or Sulfur atom in the H. Mildenberger (Liebigs Ann. Chem. 1985, 1095) synthe A.D moiety or which is optionally substituted by alkyl, size N-phenylpyrrolidine-2,4-diones. A biological activity of alkoxy or haloalkyl and these compounds has not been described. 00.15 G represents one of the groups 0003 EP-A-0262399 and GB-A-2266 888 disclose com pounds of a similar structure (3-arylpyrrolidine-2,4-diones); however, a herbicidal, insecticidal or acaricidal action of (b) these compounds is not known. Known to have a herbicidal, insecticidal or acaricidal action are unsubstituted, bicyclic 3-arylpyrroli-dine-2,4-dione derivatives (EP-A-355 599 and EP-A-415 211), and also substituted monocyclic 3-arylpyr (c) rolidine-2,4-dione derivatives (EP-A-377.893 and EP-A-442 077). 0004 Also known are polycyclic 3-arylpyrrolidine-2,4- dione derivatives (EP-A-442 073), and also 1H-arylpyrroli (d) dine dione derivatives (EP-A-456 063, EP-A-521334, EP-A- 596.298, EP-A-613 884, EP-A-613885, WO 94/01997, WO 95/26954, WO95/20572, EP-A 0 668 267, WO 96/25395, (e) WO 96 35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO/98/05638, WO 98/06721, WO 98/25928, WO 99/16748, WO 99/24437, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/09092, WO 01/17972, WO (f) 01/23354, WO 01/74770, WO 03/013249, WO 2004/007448, DE-A-10 239 479, WO 04/065336, WO 04/080962, WO (g) 04/111042, WO 05/044791, WO 05/044796, WO 05/048710, WO 05/049569, DE-A-04 001433). 0005. However, the efficacy and activity spectrum of these compounds, in particular at low application rates and concen trations, are not always satisfactory. Furthermore, the com patibility of these compounds with crops is not always Suffi 0016 in which cient. 0017 E represents a metal ion equivalent or an ammo nium ion, 0006. This invention now provides novel compounds of 0.018 L represents oxygen or sulfur, the formula (I). 0.019 M represents oxygen or sulfur, I0020) R' represents in each case optionally substituted primary or secondary alkyl, alkenyl, alkoxy-alkyl, alkylth (I) ioalkyl or polyalkoxyalkyl or represents in each case optionally halogen-, alkyl- or alkoxy-Substituted cycloalkyl or heterocyclyl or represents in each case optionally substituted phenyl or hetaryl, N \ CH3 (0021) R' represents in each case optionally halogen-sub stituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents in each case optionally Substituted cycloalkyl, phenyl or benzyl, I0022 R, R and Rindependently of one another repre sent in each case optionally halogen-substituted alkyl, US 2010/0261934 A1 Oct. 14, 2010

alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent in each case optionally Substi -continued tuted phenyl, benzyl, phenoxy or phenylthio. (1-e): 0023 R and R7 independently of one another represent hydrogen, represent in each case optionally halogen-Sub stituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent in each case optionally Substituted phenyl or benzyl or together with the N atom to which they are attached form an optionally substituted cycle which optionally contains oxygen or Sulfur. 0024 Depending inter alia on the nature of the substi tutents, the compounds of the formula (I) can be present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if appropriate, may be separated in a customary manner. The present invention provides both (1-f): the pure isomers and the isomer mixtures, their preparation and use, and compositions comprising them. However, for the sake of simplicity, hereinbelow only compounds of the for mula (I) are referred to, although what is meant are both the pure compounds and, if appropriate, also mixtures having varying proportions of isomeric compounds. 0.025 Including the meanings (b), (c), (d), (e), (f) and (g) of group G, the following principal structures (I-b) to (I-g) result:

(1-b): (1-g):

(1-c):

in which A, B, D, E, L. M. R. R. R. R. R. RandR areas defined above. 0026. Furthermore, it has been found that the novel com pounds of the formula (I) are obtained by one of the processes described below: 0027 (A) compounds of the formula (I-b) shown above in which A, B, D and R' are as defined above are obtained when compounds of the formula (I-a) (1-d):

(I-a) US 2010/0261934 A1 Oct. 14, 2010

0028 in which 0056 (E) Compounds of the formula (I-d) shown above in 0029) A, B and Dare as defined above which A, B, D and R are as defined above are obtained 0.030 are reacted when compounds of the formula (I-a) shown above in 0.031 O) with acid halides of the formula (II) which A, B and D are as defined above are in each case reacted 0057 with sulfonyl chlorides of the formula (VII) (II) R SO, Cl (VII) "S RI 0058 in which O 0059 R is as defined above, 0060 if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder. 0032 in which 0061 (F) Compounds of the formula (I-e) shown above in 0033 R' is as defined above and which A, B, D, L. R. and R are as defined above are 0034 Hal represents halogen (in particular chlorine or obtained when compounds of the formula (I-a) shown bromine) above in which A, B and Dareas defined above are in each 0035 or case reacted 0036 B) with carboxylic anhydrides of the formula (III) 0062 with phosphorus compounds of the formula R" CO-O CO-R' (III) (VIII) 0037 in which 0038) R' is as defined above, 4 (VIII) 0039) if appropriate in the presence of a diluent and if R appropriate in the presence of an acid binder. 0040 (C) Compounds of the formula (I-c) shown above in Half which A, B, D, R and M are as defined above and L Ys represents oxygen are obtained when compounds of the formula (I-a) shown above in which A, B and D are as 0063 in which defined above are in each case reacted 0064. L. R* and Rare as defined above and 0041 with chloroformic esters or chloroformic 0065 Hal represents halogen (in particular chlorine or thioesters of the formula (IV) bromine), R’ M. CO Cl (IV) 0.066 if appropriate in the presence of a diluent and if 0042 in which appropriate in the presence of an acid binder. 0043. Rand Mare as defined above, 0067 (G) Compounds of the formula (I-f) shown above in 0044) if appropriate in the presence of a diluent and if which A, B, D and E are as defined above are obtained appropriate in the presence of an acid binder. when compounds of the formulae (I-a) in which A, B and D 0045 (D) Compounds of the formula (I-c) shown above in are as defined above are in each case reacted which A, B, D, R and M are as defined above and L 0068 with metal compounds oramines of the formulae represents sulfur are obtained when compounds of the (IX) or (X) formula (I-a) shown above in which A, B and D are as Me(OR), (DX) defined above are in each case 0046 CE) reacted with chloromonothioformic esters or chlorodithioformic esters of the formula (V) RIQ R11 (X) n N1 st (V) s S 0069 in which 0070 Me represents a mono- or divalent metal (prefer 0047 in which ably an alkali metal or alkaline earth metal. Such as 0048 M and Rare as defined above, lithium, Sodium, potassium, magnesium or calcium), 0049 if appropriate in the presence of a diluent and if 0071 t represents the number 1 or 2 and appropriate in the presence of an acid binder, 0072 R', R'', R' independently of one another rep resent hydrogen or alkyl (preferably C-Cs-alkyl). 0050 or 0.073 if appropriate in the presence of a diluent. 0051 B) reacted with carbon disulfide and then with com 0074 (H) Compounds of the formula (I-g) shown above in pounds of the formula (VI) which A, B, D, L. R. and R are as defined above are R°-Hal (VI) obtained when compounds of the formula (I-a) shown 0052 in which above in which A, B and Dareas defined above are in each 0053 R’ is as defined above and CaSC 0054 Hal represents chlorine, bromine or iodine, 0075 C.) reacted with isocyanates or isothiocyanates of the 0055 if appropriate in the presence of a diluent and if formula (XI) appropriate in the presence of a base. US 2010/0261934 A1 Oct. 14, 2010

0076 in which 0093. D represents an optionally substituted radical from (0077 R and L are as defined above, the group consisting of C-Co-alkyl, alkenyl, alkynyl, 0078 if appropriate in the presence of a diluent and if alkoxyalkyl, alkylthioalkyl or optionally substituted appropriate in the presence of a catalyst, or cycloalkyl, or 0079 f) reacted with carbamoyl chlorides or thiocarbam 0094) A and D together with the atoms to which they are oyl chlorides of the formula (XII) attached represent a saturated or unsaturated cycle which optionally contains at least one oxygen or Sulfur atom in the A.D-moiety or which is optionally substituted by alkyl, (XII) alkoxy or haloalkyl, and 0.095 (c) at least one crop plant tolerance promoter com R6 SN ls C pound from the following group of compounds: R7 4-dichloroacetyl-1-Oxa-4-azaspiro4.5 decane (AD-67, MON-4660), 1-dichloroacetylhexahydro-3,3,8a-trimeth ylpyrrolo 1,2-alpyrimidin-6(2H)-one (dicyclonon, BAS 0080 in which 145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4- I0081 L, Rand R7 areas defined above, benzoxazine (benoxacor), 1-methylhexyl 5-chloroquinoline I0082) if appropriate in the presence of a diluent and if 8-oxy-acetate (cloquintocet-mexyl-cf. also related appropriate in the presence of an acid binder. compounds in EP-A-86750, EP-A-94349, EP-A-191736, 0083. Furthermore, it has been found that the novel com EP-A-492366), 3-(2-chlorobenzyl)-1-(1-methyl-1-phenyl pounds of the formula (I) have very good activity as pesti ethyl)urea (cumyluron), C-(cyanomethoximino)phenylac cides, preferably as insecticides and/or acaricides, and/or as etonitrile (cyometrinil), 2,4-dichlorophenoxyacetic acid (2,4- herbicides. D), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), 1-(1- 0084 Surprisingly, it has now been found that certain sub methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron, stituted cyclic ketoenols, when employed together with the dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba), crop plant tolerance promoter compounds (Safeners/anti S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate dotes) described later on, are extremely good at preventing (dimepiperate), 2.2-dichloro-N-(2-oxo-2-(2-propenylamino) damage to the crop plants and can be used with particular ethyl)-N-(2-propenyl)acetamide (DKA-24), 2,2-dichloro-N. advantage as broad-spectrum combination products for the N-di-2-propenylacetamide (dichlormid), 4,6-dichloro-2- selective control of unwanted plants in crops of useful plants, phenylpyrimidine (fenclorim), ethyl 1-(2,4-dichlorophenyl)- Such as, for example, in cereals, but also in maize, soybeans 5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate and rice. (fenchlorazole-ethyl-cf. also related compounds in EP-A- 0085. The invention also provides selective herbidical 174562 and EP-A-346620), phenylmethyl 2-chloro-4-trif compositions comprising an effective amount of an active luoromethylthiazole-5-carboxylate (flurazole), 4-chloro-N- compound combination comprising, as components, (1,3-dioxolan-2-ylmethoxy)-O-trifluoroacetophenone oxime a') at least one substituted cyclic ketoenol of the formula (I) in (fluxofenim), 3-dichloro-acetyl-5-(2-furanyl)-2,2-dimethy which A, B, D and G are as defined above loxazolidine (furilazole, MON-13900), ethyl 4,5-dihydro-5, O 5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl-cf. b') at least one substituted cyclic ketoenol of the formula (I-a) also related compounds in WO-A-95/07897), 1-(ethoxycar bonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor), (I-a) (4-chloro-o-tolyloxy)acetic acid (MCPA), 2-(4-chloro-o- OH CH5 tolyloxy)propionic acid (mecoprop), diethyl 1-(2,4-di chorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicar A boxylate (mefenpyr-diethyl-cf. also related compounds in N CH3 WO-A-91/07874), 2-dichloromethyl-2-methyl-1,3-diox B olane (MG-191), 2-propenyl-1-oxa-4-azaspiro4.5 decane / 4-carbodithioate (MG-838), 1.8-naphthalic anhydride, C-(1, D O C2H5 3-dioxolan-2-ylmethoximino)phenylacetonitrile (oxabetrinil), 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N- 0086 in which (2-propenyl)acetamide (PPG-1292), 3-dichloroacetyl-2.2- 0087. A represents hydrogen, C-Co-alkyl, C-C-ha dimethyloxazolidine (R-28725), 3-dichloroacetyl-2.2.5-tri loalkyl, represents in each case optionally halogen-Substi methyloxazolidine (R-29148), 4-(4-chloro-o-tolyl)butyric tuted alkenyl, alkoxyalkyl or alkylthioalkyl or represents acid, 4-(4-chlorophenoxy)butyric acid, diphenylmethoxy optionally Substituted cycloalkyl, acetic acid, methyl diphenylmethoxyacetate, ethyl diphenyl 0088 B represents hydrogen, alkyl or alkoxyalkyl, or methoxyacetate, methyl 1-(2-chlorophenyl)-5-phenyl-1H 0089 A and B together with the carbonatom to which they pyrazole-3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5- are attached represent a saturated or unsaturated C-Cs methyl-1H-pyrazole-3-carboxylate, ethyl 1-(2,4- ring which is substituted by alkyl, alkoxy or haloalkyl or dichlorophenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, representa Cs-Cs-ring which contains at least one heteroa ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)-1H tom and which is optionally Substituted, and pyrazole-3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5-phe 0090 D represents hydrogen nyl-1H-pyrazole-3-carboxylate (cf. also related compounds in EP-A-269806 and EP-A-333131), ethyl 5-(2,4-dichlo Or robenzyl)-2-isoxazoline-3-carboxylate, ethyl 5-phenyl-2- 0091. A represents hydrogen or alkyl, isoxazoline-3-carboxylate, ethyl 5-(4-fluorophenyl)-5-phe 0092 B represents hydrogen and nyl-2-isoxazoline-3-carboxylate (cf. also related compounds US 2010/0261934 A1 Oct. 14, 2010 in WO-A-91/08202), 1,3-dimethylbut-1-yl 5-chloroquino line-8-oxyacetate, 4-allyloxybutyl 5-chloro-quinoline-8- -continued oxyacetate, 1-allyloxyprop-2-yl 5-chloroquinoline-8- -(Can oxyacetate, methyl 5-chloroquinoxaline-8-oxyacetate, ethyl 5-chloroquinoline-8-oxyacetate, allyl 5-chloroquinoxaline Sry 8-oxyacetate, 2-oxoprop-1-yl 5-chloroquinoline-8-oxyac O-N etate, diethyl 5-chloroquinoline-8-oxymalonate, diallyl 0.098 in represents a number 0, 1, 2, 3, 4 or 5, 5-chloroquinoxaline-8-oxymalonate, diethyl 5-chloroquino I0099. A represents optionally C-C-alkyl- and/or C-C-alkoxy-carbonyl- and/or C-C-alkenyloxy-carbo line-8-oxy-malonate (cf. also related compounds in EP-A- nyl-substituted alkanediyl having 1 or 2 carbon atoms, 582198), 4-carboxychroman-4-ylacetic acid (AC-304415, cf. 10100) R' represents hydroxyl, mercapto, amino, C-C- EP-A-613618), 4-chlorophenoxyacetic acid, 3,3'-dimethyl alkoxy, C-C-alkylthio, C-C-alkylamino or di(C-C- 4-methoxy-benzophenone, 1-bromo-4-chloromethylsulfo alkyl)amino, nylbenzene, 1-4-(N-2-methoxybenzoylsulfamoyl)-phenyl 10101) R' represents hydroxyl, mercapto, amino, C-C,- 3-methylurea (also known as N-(2-methoxybenzoyl)-4- alkoxy, C-C-alkenyloxy, C-C-alkenyloxy-C-C- (methylaminocarbonyl)-aminobenzenesulfonamide), 1-4- alkoxy, C-C-alkylthio, C-C-alkylamino or di(C-C- (N-2-methoxybenzoylsulfamoyl)phenyl-3,3-dimethylurea, alkyl)amino, 1-4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl-3-methy I0102) R' represents in each case optionally fluorine-, lurea, 1-4-(N-naphthylsulfamoyl)phenyl)-3,3-dimethy chlorine-and/or bromine-substituted C-C-alkyl, lurea, N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylami (0103 R'7 represents hydrogen, in each case optionally fluorine-, chlorine- and/or bromine-substituted C-C- nocarbonyl)benzenesulfonamide, alkyl, C-C-alkenyl or C-C-alkynyl, dioxolanyl-C-C- and/or one of the following compounds, defined by general alkyl, furyl, furyl-C-C-alkyl, thienyl, thiazolyl, piperidi formulae, nyl, or optionally fluorine-, chlorine- and/or bromine- or of the general formula (IIa) C Catallyl-substituted phenyl, (0.104) R' represents hydrogen, in each case optionally fluorine-, chlorine- and/or bromine-substituted C-C- alkyl, C-C-alkenyl or C-C-alkynyl, C-C-alkoxy-C- (IIa) C-alkyl, dioxolanyl-C-C-alkyl, furyl, furyl-C-C- 1N O alkyl, thienyl, thiazolyl, piperidinyl, or optionally (X) + ls fluorine-, chlorine- and/or bromine- or C-C-alkyl-substi 21 Al R14 tuted phenyl, I0105) R'' and R' also together represent C-C-al kanediyl or C-C-Oxaalkanediyl, each of which is option or of the general formula (IIb) ally substituted by C-C-alkyl, phenyl, furyl, a fused ben Zenering or by two substituents which, together with the C atom to which they are attached, form a 5- or 6-membered carboxycle, (IIb) I0106) R' represents hydrogen, cyano, halogen, or repre sents in each case optionally fluorine-, chlorine- and/or bromine-Substituted C-C-alkyl, C-C-cycloalkyl or phenyl, (0.107) R' represents hydrogen, optionally hydroxyl-, cyano-, halogen- or C-C-alkoxy-substituted C-C alkyl, C-C-cycloalkyl or tri(C-C-alkyl)silyl, I0108) R' represents hydrogen, cyano, halogen, or repre sents in each case optionally fluorine-, chlorine- and/or bromine-Substituted C-C-alkyl, C-C-cycloalkyl or or of the formula (IIc) phenyl, (IIc) I0109) X' represents nitro, cyano, halogen, C-C-alkyl, O C-Ca-haloalkyl, C-C-alkoxy or C-C-haloalkoxy, 10110 X represents hydrogen, cyano, nitro, halogen, R17 C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-ha loalkoxy, . 10111 X represents hydrogen, cyano, nitro, halogen, R18 C-C-alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Ca-ha loalkoxy, where and/or the following compounds, defined by general formu 0096 m represents a number 0, 1, 2, 3, 4 or 5, lae, 0097. A represents one of the divalent heterocyclic of the general formula (IId) groupings shown below (IId) R23 N N N (X) NY N r NY Y O N N SA R22 21 o )=N R24 l -H(X'), R19 OR20 R19 R 19 2 SO, S O US 2010/0261934 A1 Oct. 14, 2010

or of the general formula (IIe) ene group is replaced by oxygen or Sulfur and which is optionally Substituted by C-C-alkyl, C-Ca-haloalkyl or C-C-alkoxy, and (IIe) I012.5 D preferably represents hydrogen, O O I0126. A preferably represents hydrogen or C-C-alkyl, R2 (X), I0127 B preferably represents hydrogen and NN SS R22 21 I0128 D preferably represents C-C-alkyl, C-C-alk k l +-(X'), enyl, C-C-alkoxy-C-C-alkyl or C-C-alkylthio-C- 2 SO, S C-alkyl, each of which is optionally mono- to pentasub stituted by halogen, represents C-C-cycloalkyl which is O optionally mono- to trisubstituted by halogen, C-C-alkyl, C-C-alkoxy or C-C-haloalkyl, or where I0129. A and D together preferably represent a C-C-al kanediyl or C-C-alkenediyl group in which in each case 0112 t represents a number 0, 1, 2, 3, 4 or 5, optionally one methylene group is replaced by oxygen or 0113 V represents a number 0, 1, 2, 3, 4 or 5, sulfur and which is in each case mono- to disubstituted by I0114) R' represents hydrogen or C-C-alkyl, C-C-alkyl, C-C-alkoxy or C-Ca-haloalkyl or by a fur I0115I R' represents hydrogen or C-C-alkyl, ther C-C-alkanediyl, C-C-alkenediyl or C-C-alkane I0116) R' represents hydrogen, in each case optionally dienediyl group which forms a fused-on ring, cyano-, halogen- or C-Calkoxy-Substituted C-C-alkyl, 0.130 G preferably represents one of the groups C-C-alkoxy, C-C-alkylthio, C-C-alkylamino or di(C-C-alkyl)amino, or in each case optionally cyano halogen- or C-C-alkyl-substituted C-C-cycloalkyl, (b) C-C-cycloalkyloxy, C-C-cycloalkylthio or C-C-cy cloalkylamino, I0117 R represents hydrogen, optionally cyano-, hydroxyl-, halogen- or C-C-alkoxy-substituted C-C- (c) alkyl, in each case optionally cyano- or halogen-substi tuted C-C-alkenyl or C-C-alkynyl, or optionally cyano-, halogen- or C-C-alkyl-substituted C-C-cy cloalkyl, (d) I0118 R represents hydrogen, optionally cyano-, hydroxyl-, halogen- or C-C-alkoxy-substituted C-C- (e) alkyl, in each case optionally cyano- or halogen-Substi tuted C-C-alkenyl or C-C-alkynyl, optionally cyano halogen- or C-C-alkyl-substituted C-C-cycloalkyl, or optionally nitro-, cyano-, halogen-, C-C-alkyl-, C-C- alkoxy- or C-Ca-haloalkoxy-Substituted phenyl, or (f) together with R represents in each case optionally C-C- (g) alkyl-substituted C-C-alkanediyl or C-Cs-Oxaal kanediyl. I0119) X' represents nitro, cyano, carboxyl, carbamoyl, formyl, Sulfamoyl, hydroxyl, amino, halogen, C-C alkyl, C-Ca-haloalkyl, C-C-alkoxy or C-Chaloalkoxy, and I0120 X represents nitro, cyano, carboxyl, carbamoyl, 0.131 in which formyl, sulfamoyl, hydroxyl, amino, halogen, C-C-alkyl, 0.132 E represents a metal ion equivalent or an ammo C-Ca-haloalkyl, C-C-alkoxy or C-Chaloalkoxy. nium ion, 0121 The formula (I) provides a general definition of the 0.133 L represents oxygen or sulfur and compounds according to the invention. Preferred Substituents 0.134 M represents oxygen or sulfur, or ranges of the radicals listed in the formulae given above I0135) R' preferably represents primary or secondary and below are illustrated below: C-Co-alkyl, C-Co-alkenyl, C-C-alkoxy-C-C-alkyl, 0122) A preferably represents hydrogen, represents C-C-alkylthio-C-C-alkyl or poly-C-C-alkoxy-C- C-Cs-alkyl, C-C-alkenyl, C-Cs-alkoxy-C-C-alkyl or C-alkyl, each of which is optionally mono- to heptasub C-C-alkylthio-C-C-alkyl, each of which is optionally stituted by halogen, mono- to disubstituted by cyano, mono- to trisubstituted by halogen, represents C-C-cy monosubstituted by COR', C=N OR, COR' or cloalkyl which is optionally mono- to trisubstituted by halogen, C-C-alkyl or C-C-alkoxy, 0123 B preferably represents hydrogen, C-C-alkyl or C-C-alkoxy-C-C-alkyl or 0.124 A, B and the carbonatom to which they are attached preferably represent Saturated C-Cs-cycloalkyl or unsat urated C5-C8-cycloalkyl in which optionally one methyl US 2010/0261934 A1 Oct. 14, 2010

or represents C-Cs-cycloalkyl which is optionally mono- to 0146 In the radical definitions mentioned as being pre trisubstituted by halogen, C-C-alkyl or C-C-alkoxy and in ferred, halogen represents fluorine, chlorine, bromine and which optionally one or two not directly adjacent methylene iodine, in particular fluorine, chlorine and bromine. groups are replaced by oxygen and/or Sulfur, 0147 A particularly preferably represents hydrogen, rep 0.136 represents phenyl, phenyl-C-C-alkyl or phenyl resents C-C-alkyl, C-C-alkenyl, C-C-alkoxy-C-C- C-C2-alkenyl, each of which is optionally mono- to alkyl or C-C-alkylthio-C-C-alkyl, each of which is trisubstituted by halogen, cyano, nitro, C-C-alkyl, optionally mono- to trisubstituted by fluorine or chlorine, C-C-alkoxy, C-C-haloalkyl, C-C-haloalkoxy, or represents C-C-cycloalkyl which is optionally mono to disubstituted by fluorine, chlorine, C-C-alkyl or C-C-alkylthio, C-C-alkylsulfinyl or C-C-alkylsul C-C2-alkoxy, fonyl, 0.148 B particularly preferably represents hydrogen, 0.137 represents 5- or 6-membered hetaryl which is C-C-alkyl or C-C-alkoxy-C-C-alkyl, optionally mono- to disubstituted by halogen or C-C- O alkyl and which has one or two heteroatoms from the 0149 A, B and the carbonatom to which they are attached group consisting of oxygen, Sulfur and nitrogen, particularly preferably represent Saturated C-C7-cy I0138 R preferably represents C1-Co-alkyl, C-Co-alk cloalkyl in which optionally one methylene group is enyl, C-C-alkoxy-C-C-alkyl or poly-C-C-alkoxy replaced by oxygen and which is optionally mono- to dis C-C-alkyl, each of which is optionally mono- to trisub ubstituted by C-C-alkyl, C-C-haloalkyl or C-C- stituted by halogen, alkoxy, and 0.139 represents C-C-cycloalkyl which is optionally 0150 D particularly preferably represents hydrogen, mono- to disubstituted by halogen, C-C-alkyl or O C-C-alkoxy or 0151. A particularly preferably represents hydrogen or 0140 represents phenyl or benzyl, each of which is C-C-alkyl, optionally mono- to trisubstituted by halogen, cyano, 0152 B particularly preferably represents hydrogen and nitro, C-C-alkyl, C-C-alkoxy, C-C-haloalkyl or 0153 D particularly preferably represents C-C-alkyl, C-C-haloalkoxy, C-C-alkenyl, C-C-alkoxy-C-C-alkyl or C-C-alky I0141 R preferably represents C-Cs-alkyl which is lthio-C-C-alkyl, each of which is optionally mono- to optionally mono- to poly Substituted by halogen or repre trisubstituted by fluorine or chlorine, represents C-C- sents phenyl or benzyl, each of which is optionally mono cycloalkyl which is optionally mono- to disubstituted by to disubstituted by halogen, C-C-alkyl, C-C-alkoxy, fluorine, chlorine, C-C-alkyl, C-C-alkoxy or trifluo C-Ca-haloalkyl, C-C-haloalkoxy, cyano or nitro, romethyl, or I0142 R and Rindependently of one another preferably 0154) A and D together particularly preferably represent a represent C-Cs-alkyl, C-Cs-alkoxy, C-Cs-alkyl-amino, C-C-alkanediyl group in which optionally one methyl di (C-Cs-alkylamino, C-Cs-alkylthio or C-Cs-alk ene group is replaced by oxygen or Sulfur and which is enylthio, each of which is optionally mono- to trisubsti optionally mono- to disubstituted by C-C-alkyl, C-C- tuted by halogen, or represent phenyl, phenoxy or phe alkoxy or trifluoromethyl, nylthio, each of which is optionally mono- to trisubstituted or A and D together with the atoms to which they are attached by halogen, nitro, cyano, C-C-alkoxy, C-C-haloalkoxy, represent one of the groups AD-1 to AD 10 C-C-alkylthio, C-Ca-haloalkylthio, C-C-alkyl or C-Ca-haloalkyl, 0143 Rand R7 independently of one another preferably AD-1 represent hydrogen, represent C-Cs-alkyl, C-C-cy cloalkyl, C-Cs-alkoxy, C-C-alkenyl or C-Cs-alkoxy C-C-alkyl, each of which is optionally mono- to trisub N X stituted by halogen, represent phenyl or benzyl, each of which is optionally mono- to trisubstituted by halogen, C-Cs-alkyl, C-C-haloalkyl or C-Cs-alkoxy, or together AD-2 represent a C-C-alkylene radical which is optionally mono- to disubstituted by C-C-alkyl in which optionally one methylene group is replaced by oxygen or Sulfur, I0144) R' preferably represents C-C-alkyl, C-C-alk enyl, C-C-alkynyl or C-C-alkoxy-C-C-alkyl, each of which is optionally mono- to trisubstituted by halogen, or AD-3 represents C-C-cycloalkyl which is optionally mono- to disubstituted by halogen, C-C2-alkyl or C-C2-alkoxy and in which optionally one or two not directly adjacent meth ylene groups are replaced by oxygen or represents phenyl N X or phenyl-C-C-alkyl, each of which is optionally mono to disubstituted by fluorine, chlorine, bromine, C-C- AD-4 alkyl, C-C-alkoxy, C-C-haloalkyl, C-C-haloalkoxy, cyano or nitro, (0145) R' preferably represents hydrogen, C-C-alkyl or OOCN C-C-alkenyl. US 2010/0261934 A1 Oct. 14, 2010

0156 in which -continued 0157 E represents a metal ion equivalent or an ammo AD-5 nium ion, 0158 L represents oxygen or sulfur and 0159 M represents oxygen or sulfur, N (0160) R' particularly preferably represents primary or sec N ondary C-Co-alkyl, C-Co-alkenyl, C-C-alkoxy-C- AD-6 C2-alkyl, C-C-alkylthio-C-C-alkyl or poly-C-C- alkoxy-C-C-alkyl, each of which is optionally mono- to pentasubstituted by fluorine or chlorine, monosubstituted by cyano or monosubstituted by CO R', C=N OR' N or COR', or represents C-C-cycloalkyl which is optionally mono- to disubstituted by fluorine, chlorine, AD-7 C-C-alkyl or alkoxy and in which optionally one or two not directly adjacent methylene groups are replaced by OXygen, N 0.161 represents phenyl or benzyl, each of which is optionally mono- to disubstituted by fluorine, chlorine, bromine, cyano, nitro, C-C-alkyl, C-C-alkylthio. AD-8 C-C-alkylsulfinyl, C-C-alkylsulfonyl, C-C- alkoxy, C-C-haloalkyl or C-C-haloalkoxy, N 0162 represents pyrazolyl, thiazolyl, pyridyl, pyrim N idyl, furanyl or thienyl, each of which is optionally mono- to disubstituted by fluorine, chlorine, bromine or C-C2-alkyl, AD-9 (0163 R’ particularly preferably represents C-Co-alkyl, C-Co-alkenyl, C-C-alkoxy-C-C-alkyl or poly-C- N C-alkoxy-C-C-alkyl, each of which is optionally mono C N to trisubstituted by fluorine or chlorine, 0.164 represents C-C7-cycloalkyl which is optionally AD-10 monosubstituted by C-C-alkyl or C-C-alkoxy or 0.165 represents phenyl or benzyl, each of which is optionally mono- to disubstituted by fluorine, chlorine, bromine, cyano, nitro, C-C-alkyl, methoxy, trifluo romethyl or trifluoromethoxy, Cl (0166 R particularly preferably represents C-C-alkyl which is optionally mono- to trisubstituted by fluorine or chlorine or represents phenyl or benzyl, each of which is 0155 G particularly preferably represents one of the optionally monosubstituted by fluorine, chlorine, bromine, groups C-C-alkyl, C-C-alkoxy, trifluoromethyl, trifluo romethoxy, cyano or nitro, (0167 RandR independently of one another particularly (b) preferably represent C-C-alkyl, C-C-alkoxy, C-C- alkylamino, di(C-C-alkyl)amino, C-C-alkylthio or C-C-alkenylthio, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represent phenyl, (c) phenoxy or phenylthio, each of which is optionally mono to disubstituted by fluorine, chlorine, bromine, nitro, cyano, C-C-alkoxy, trifluoromethoxy, C-C-alkylthio. C-C-alkyl or trifluoromethyl, (d) (0168 RandR independently of one another particularly preferably represent hydrogen, represent C-C-alkyl, C-C-cycloalkyl, C-C-alkoxy, C-C-alkenyl or C-C- (e) alkoxy-C-C-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, represent phenyl which is optionally mono- to disubstituted by fluorine, chlorine, bromine, trifluoromethyl, C-C-alkyl or C-C- (f) alkoxy, or together represent a C-C-alkylene radical which is optionally mono- to disubstituted by methyl in (g) which optionally one methylene group is replaced by oxy gen, (0169) R' particularly preferably represents C-C-alkyl, C-C-alkenyl, C-C-alkynyl, or C-C-alkoxy-C-C- alkyl or represents C-C-cycloalkyl in each optionally one methylene group is replaced by oxygen. US 2010/0261934 A1 Oct. 14, 2010

0170 In the radical definitions mentioned as being pre ferred, halogen represents fluorine, chlorine, bromine and -continued iodine, in particular fluorine, chlorine and bromine. (e) 0171 A very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, sec butyl, tert-butyl, trifluoromethyl, methoxymethyl, ethoxymethyl, cyclopropyl, cyclopentyl or cyclohexyl, (g) 0172 B very particularly preferably represents hydrogen, methyl or ethyl, or 0173 A, B and the carbonatom to which they are attached very particularly preferably represent Saturated C-cy cloalkyl in which optionally one methylene group is 0181 L represents oxygen and replaced by oxygen and which is optionally Substituted by 0182 M represents oxygen or sulfur, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, n-pro 0183 R' very particularly preferably represents primary poxy, n-butyoxy or isobutoxy, and or secondary C-C-alkyl, C-C-alkenyl, C-C2-alkoxy 0.174 D very particularly preferably represents hydrogen, C-C2-alkyl, C-C2-alkylthio-C-C-alkyl or poly-C-C- O alkoxy-C-C-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represents cyclo 0.175. A very particularly preferably represents hydrogen, propyl, cyclopentyl or cyclohexyl, each of which is option methyl or ethyl, ally monosubstituted by fluorine, chlorine, methyl, ethyl or 0176 B very particularly preferably represents hydrogen, methoxy, and 0.184 represents phenyl which is optionally monosub 0177 D very particularly preferably represents methyl, stituted by fluorine, chlorine, bromine, cyano, nitro, ethyl, n-propyl, isopropyl. n-butyl, sec-butyl, isobutyl, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, cyclopropyl, cyclopentyl or cyclohexyl, or methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl or trif 0.178 A and D together very particularly preferably rep luoro-methoxy, resent a C-C-alkanediyl group in which in each case 0185 represents furanyl, thienyl or pyridyl, each of optionally one methylene group is replaced by oxygen or which is optionally monosubstituted by chlorine, bro sulfur and which is optionally mono- to disubstituted by mine or methyl, methyl or methoxy, or 0186 R very particularly preferably represents C-C- 0179 A and D together with the atoms to which they are alkyl, C-C-alkenyl or C-C-alkoxy-C-C-alkyl, cyclo attached very particularly preferably represent the groups pentyl or cyclohexyl, below: 0187 or represents phenyl or benzyl, each of which is optionally monosubstituted by fluorine, chlorine, bro mine, cyano, nitro, methyl, methoxy, trifluoromethyl or AD-1 trifluoromethoxy, 0188 R very particularly preferably represents C-C- alkoxy, (0189 R very particularly preferably represents C-C- N w alkoxy, (0190. R very particularly preferably represents hydrogen, AD-2 represents C-C-alkyl, C-C-cycloalkyl or allyl, repre sents phenyl which is in each case optionally monosubsti tuted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, (0191) R' very particularly preferably represents methyl, ethyl, n-propyl, isopropyl or allyl, \ (0192 RandR together very particularly preferably rep resent a C-C-alkylene radical in which optionally one 0180 G very particularly preferably represents one of the methylene group is replaced by oxygen. groups 0193 A especially preferably represents methyl, ethyl or cyclopropyl. 0194 B especially preferably represents methyl or ethyl, (b) 0.195 A, B and the carbonatom to which they are attached especially preferably represent Saturated C-cycloalkyl which is optionally substituted by methyl or methoxy, 0196. Despecially preferably represents hydrogen, (c) O 0.197 A especially preferably represents methyl or ethyl, 0198 B especially preferably represents hydrogen, 0199. Despecially preferably represents methyl, ethyl or cyclopropyl. US 2010/0261934 A1 Oct. 14, 2010

0200 A and D together especially preferably represent a 0213 Very particular preference according to the inven C-C-alkanediyl group which is optionally monosubsti tion is given to the compounds of the formula (I) which tuted by methoxy, contain a combination of the meanings given above as being 0201 A and D together with the atoms to which they are very particularly preferred. attached especially preferably represent the groups AD-1 0214 Special preference according to the invention is and AD-2, given to the compounds of the formula (I) which contain a 0202 Gespecially preferably represents one of the groups combination of the meanings given above as being especially preferred. 0215 Saturated or unsaturated hydrocarbon radicals, such (b) as alkyl, alkanediyl or alkenyl, can in each case be straight chain or branched as far as this is possible, including in the combination with heteroatoms. Such as, for example, in alkoxy. (c) 0216. Unless indicated otherwise, optionally substituted radicals can be mono- or poly Substituted, where in the case of polysubstitution the substituents can be identical or different. 0217. In addition to the compounds mentioned in the (e) preparation examples, particular mention may be made of the following compounds of the formulae (I-b) and (I-c):

TABLE 1

(0203 R' especially preferably represents primary or sec G ondary C-C-alkyl, C-C-alkenyl, C-C2-alkoxy-C-C- Y CH5 alkyl, C-C-alkylthio-C-C-alkyl or poly-C-C-alkoxy A C-C2-alkyl, each of which is optionally mono- to B N CH3 trisubstituted by fluorine or chlorine, or represents cyclo HN propyl, cyclopentyl or cyclohexyl, each of which is option ally monosubstituted by fluorine, chlorine, methyl, ethyl or methoxy, O H5C2 G = CH3-S-CO 0204 represents phenyl which is optionally monosub A. B stituted by fluorine, chlorine, bromine, cyano, nitro, —(CH2)2— methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, -(CH2) - methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, —(CH2)5 - methylsulfonyl, ethylsulfonyl, trifluoromethyl or trif —(CH2)6 - luoro-methoxy, —(CH2)7 - -(CH2)2 O-(CH2)2— 0205 represents furanyl, thienyl or pyridyl, each of —CH2—O—(CH2)— which is optionally monosubstituted by chlorine, bro —(CH2)2—S—(CH2)2— mine or methyl, (and represents in particular primary or —CH2—CHCH-(CH2) - secondary C-C-alkyl or C-C2-alkoxy-C-C-alkyl). -(CH2). CHCH -(CH2)— —(CH2)2—CHOCH2—(CH2)2— (0206 R especially preferably represents C-Cs-alkyl, —(CH2)2—CHOCHS (CH2)2— C-C-alkenyl or C-C-alkoxy-C-C-alkyl, cyclopentyl —(CH2)2—CHOCH7 -(CH2)2— or cyclohexyl, -(CH2)2 CHO CH-(CH2)2— —(CH2)2—CH-O-i-C4H9—(CH2)2— 0207 or represents phenyl or benzyl, each of which is —(CH2)2—C(CH3)2—(CH2)2— optionally monosubstituted by fluorine, chlorine, bro —CH2—(CHCH3)2—(CH2)2— mine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy, (and represents in particular C-Cs alkyl or C-C-alkenyl), 0218. A and B as defined in table 1, 0208 Respecially preferably represents C-Calkoxy, 0219. Table 2 G=CH, CO (0209 Respecially preferably represents C1-Co-alkoxy. 0220 Table 3 G=CH-CO 0210. The general or preferred radical definitions or illus 0221 Table 4 G=CH-CO trations given above can be combined with one another as 0222 Table 5 G=i-CH, CO desired, i.e. including combinations between the respective 0223 Table 6 G=CH-CO ranges and preferred ranges. They apply both to the end 0224) Table 7 G=i-CH CO products and, correspondingly, to precursors and intermedi 0225. Table 8 G=S-CH CO ates. 0226 Table 9 G=t-CH CO 0211 Preference according to the invention is given to the 0227 Table 10 compounds of the formula (I) which contain a combination of the meanings given above as being preferred (preferably). 0212 Particular preference according to the invention is G = D-co given to the compounds of the formula (I) which contain a combination of the meanings given above as being particu larly preferred. 0228 Table 11 G=HC O CH-CO US 2010/0261934 A1 Oct. 14, 2010 11

0229 Table 12 G=H.C.. O CH-CO C-C-alkoxy-C-C-alkyl or C-C-alkylthio-C-C- 0230 Table 13 G=HC S CH-CO alkyl, each of which is optionally mono- to trisubstituted 0231 Table 14 G=H.C. S CH-CO by fluorine or chlorine, or represents C-C-cycloalkyl 0232 Table 15 G=CH, O, CO which is optionally mono- to disubstituted by fluorine, 0233 Table 16 G=CHs O CO chlorine, C-C2-alkyl or C-C-alkoxy, 0234 Table 17 G=CH-O-CO 0265 B particularly preferably represents hydrogen, 0235 Table 18 G=i-CH, O CO C-C-alkyl or C-C-alkoxy-C-C-alkyl, or 0236 Table 19 G=CH, O CO 0266 A, B and the carbonatom to which they are attached 0237) Table 20 G=i-CH, O CO particularly preferably represent Saturated C-C7-cy 0238 Table 21 G=S-CH-O-CO cloalkyl which is substituted by C-C-alkyl, C-C- 0239) Table 22 G=t-CH, O CO alkoxy or C-C-haloalkyl or represent unsaturated C-C- 0240 Table 23 G=t-CH, CH, O CO cycloalkyl or represent Cs-Cs-cycloalkyl in which one 0241 Table 24 G=CH-CH O CO methylene group is replaced by oxygen or Sulfur and which 0242 Table 25 G=CHs O CO is optionally mono- to disubstituted by C-C-alkyl, 0243 Table 26 G=CH, S CO 0267 D particularly preferably represents hydrogen, 0244 Table 27 G=CH, S CO 0245 Table 28 G=CH, S CO O 0246 Table 29 G=i-CH, S CO 0268 A particularly preferably represents hydrogen or 0247 Table 30 G=CH, S CO C-C-alkyl, 0248 Table 31 G=i-CH, S CO 0269 B particularly preferably represents hydrogen, 0249 Table 32 G=S-CH, S CO 0270 D particularly preferably represents C-C-alkyl, 0250 Table 33 G=t-CH, S CO C-C-alkenyl, C-C-alkoxy-C-C-alkyl or C-C-alky 0251 Table 34 G=t-CH, CH, S CO lthio-C-C-alkyl, each of which is optionally mono- to 0252 Table 35 G=CH-CH S CO trisubstituted by fluorine or chlorine, represents C-C- 0253 Preferred meanings of the cyclic ketoenols, men cycloalkyl which is optionally mono- to disubstituted by tioned above as active compounds in combination with the fluorine, chlorine, C-C-alkyl, C-C-alkoxy or trifluo crop plant tolerance promoter compounds (herbicide Safen romethyl, ers), of the formula (I-a) are defined below. 0271 A and D together particularly preferably represent a 0254 G preferably represents hydrogen, C-C-alkanediyl group in which optionally one methyl 0255. A preferably represents hydrogen, C-C-alkyl, ene group is replaced by oxygen or Sulfur and which is C-Ca-haloalkyl, represents C-C-alkenyl, C-C- optionally mono- to disubstituted by C-C-alkyl, C-C- alkoxy-C-C-alkyl or C-C-alkylthio-C-C-alkyl, each alkoxy or trifluoromethyl, of which is optionally mono- to trisubstituted by halogen, represents C-Cs-cycloalkyl which is optionally mono- to 0272 or A and D together with the atoms to which they are trisubstituted by halogen, C-C-alkyl or C-C-alkoxy, attached represent one of the groups AD-1 to AD-10 0256 B preferably represents hydrogen, C-C-alkyl or C-C-alkoxy-C-C-alkyl, or AD-1 0257 A, B and the carbonatom to which they are attached preferably represent C-C-alkyl-, C-C-alkoxy- or C-Ca-haloalkyl-substituted saturated C-C-cycloalkyl or represent unsaturated Cs-Cs-cycloalkyl or represent N a Cs-Cs-cycloalkyl in which one methylene group is replaced by oxygen or Sulfur and which is optionally AD-2 mono- to disubstituted by C-C-alkyl, 0258 D preferably represents hydrogen, or 0259. A preferably represents hydrogen or C-C-alkyl, 0260 B preferably represents hydrogen, 0261) D preferably represents C-C-alkyl, C-C-alk enyl, C-C-alkoxy-C-C-alkyl or C-C-alkylthio-C- C-alkyl, each of which is optionally mono- to pentasub AD-3 stituted by halogen, represents C-Cs-cycloalkyl which is optionally mono- to trisubstituted by halogen, C-C-alkyl, C-C-alkoxy or C-C-haloalkyl. N a 0262 A and D together preferably represent a C-C-al kanediyl group or C-C-alkenediyl group in which in each case optionally one methylene group is replaced by oxygen AD-4 or Sulfur and which are in each case optionally mono- to disubstituted by C-C-alkyl, C-C-alkoxy or C-Ca-ha N loalkyl or by a further C-C-alkanediyl, C-C-alkenediyl N or C-C-alkanedienediyl group which forms a fused-on AD-5 ring, 0263 G particularly preferably represents hydrogen, 0264. A particularly preferably represents hydrogen, N N C-C-alkyl, C-C-haloalkyl, represents C-C-alkenyl, US 2010/0261934 A1 Oct. 14, 2010

0282 A and D together with the atoms to which they are -continued attached represent the group below: AD-6

AD-1

N

AD-7

N 0283 Special preference is given to the compounds of the formula (I-a) listed in the table below: AD-8

(I-a) O NQ OH C2H5 A AD-9 B N CH 1N C NQ O C2H5 A. B D AD-10

0273 G very particularly preferably represents hydrogen, 0274) A very particularly preferably represents hydrogen, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, sec-butyl, tert butyl, trifluoromethyl, methoxymethyl, ethoxymethyl, cyclopropyl, cyclopentyl or cyclohexyl, 0275 B very particularly preferably represents hydrogen, methyl or ethyl, or 0276 A, B and the carbonatom to which they are attached very particularly preferably represent Saturated C-cy cloalkyl which is substituted by methyl, ethyl, trifluorom ethyl, methoxy, ethoxy, n-propoxy, n-butoxy or isobutoxy or represent Co-cycloalkyl in which one methylene group is replaced by oxygen and which is optionally monosub stituted by methyl or ethyl,

0277 D very particularly preferably represents hydrogen C 13 O A 0278 A very particularly preferably represents hydrogen, methyl or ethyl, 0279 B very particularly preferably represents hydrogen, 0280 D very particularly preferably represents ethyl, n-propyl, isopropyl. n-butyl, sec-butyl, isobutyl, cyclopro pyl, cyclopentyl or cyclohexyl, 0281 A and D together very particularly preferably rep resent a C-C-alkanediyl group in which in each case A. D B optionally one methylene group is replaced by oxygen or H C2H5 H sulfur and which is optionally mono- to disubstituted by H CH7 H methyl or US 2010/0261934 A1 Oct. 14, 2010 13

propynyl or butynyl, methoxymethyl, ethoxymethyl, -continued methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furyl-methyl, thienyl, thiazolyl, piperidinyl, or optionally H i-CH7 H H CHg H fluorine-, chlorine-, methyl-, ethyl-, n- ori-propyl-, n-, s- or H i-CAHg H t-butyl-substituted phenyl. CH C2H5 H (0293 R' preferably represents hydrogen, in each case C2H5 C2H5 H optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl. n-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furyl-methyl, thienyl, thiazolyl, piperidinyl, or optionally fluorine-, chlorine-, methyl-, ethyl-, n- ori-propyl-, n-, s- or H Cl H t-butyl-substituted phenyl, or together with R' represents one of the radicals —CH2—O—CH2—CH2— and CH-CH O—CH2—CH2— which are optionally substituted by methyl, ethyl, furyl, phenyl, a fused benzene ring or by two substituents which, together with the Catom to which they are attached, form a 5- or 6-membered car —(CH2)— H bocycle. —(CH2)— H (0294) R' preferably represents hydrogen, cyano, fluorine, —CH2—S—(CH2)— H chlorine, bromine, or represents in each case optionally fluorine-, chlorine- and/or bromine-substituted methyl, —ci-fil- H ethyl, n- or i-propyl, cyclo-propyl, cyclobutyl, cyclopentyl, (CH2)3 cyclohexyl or phenyl. (0295) R' preferably represents hydrogen, optionally 0284 Preferred meanings of the groups listed above in hydroxyl-, cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, connection with the crop plant tolerance promoter com n- ori-propoxy-Substituted methyl, ethyl, n- ori-propyl. n-, pounds (“herbicide safeners’) of the formulae (IIa), (IIb). s- or t-butyl. (Ic), (IId) and (IIe) are defined below. (0296) R' preferably represents hydrogen, cyano, fluorine, 0285 m preferably represents the numbers 0, 1, 2, 3 or 4. chlorine, bromine, or represents in each case optionally 0286 A' preferably represents one of the divalent hetero fluorine-, chlorine- and/or bromine-substituted methyl, cyclic groupings shown below ethyl, n- or i-propyl. n-, s- ort-butyl, cyclopropyl, cyclobu tyl, cyclopentyl, cyclohexyl or phenyl. (0297 X' preferably represents nitro, cyano, fluorine, chlo NYN NYN NY rine, bromine, methyl, ethyl, n- ori-propyl. n-, s- ort-butyl, o )=N difluoromethyl, dichloromethyl, trifluoromethyl, trichlo romethyl, chloro-difluoromethyl, fluorodichloromethyl, R19 OR20 R19 R19 methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or tri O fluoromethoxy. 1 (C H2) 0298 X preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl. n-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluo romethyl, trichloromethyl, chlorodifluoromethyl, fluorod 0287 in preferably represents the numbers 0, 1, 2, 3 or 4. ichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoro (0288. A preferably represents in each case optionally methoxy or trifluoromethoxy. methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl- or (0299 X preferably represents hydrogen, nitro, cyano, allyloxycarbonyl-substituted methylene or ethylene. fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl. 0289 R'' preferably represents hydroxyl, mercapto, n-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluo amino, methoxy, ethoxy, n- or i-propoxy, n-, s- ort-butoxy, romethyl, trichloromethyl, chlorodifluoromethyl, fluorod methylthio, ethylthio, n- or i-propylthio, n-, s- or t-bu ichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoro tylthio, methylamino, ethylamino, n- or i-propylamino, n-, methoxy or trifluoromethoxy. s-ort-butylamino, dimethylamino or diethylamino. 0300 t preferably represents the numbers 0, 1, 2, 3 or 4. 0290 R" preferably represents hydroxyl, mercapto, 0301 v preferably represents the numbers 0, 1, 2, or 3. amino, methoxy, ethoxy, n- or i-propoxy, n-, s- ort-butoxy, 0302) R' preferably represents hydrogen, methyl, ethyl, 1-methylhexyloxy, allyloxy, 1-allyloxymethylethoxy, n- or i-propyl. methylthio, ethylthio, n- or i-propylthio, n-, s- or t-bu 0303 R’ preferably represents hydrogen, methyl, ethyl, tylthio, methylamino, ethylamino, n- or i-propylamino, n-, n- or i-propyl. s-ort-butylamino, dimethylamino or diethylamino. (0304) R' preferably represents hydrogen, in each case 0291) R' preferably represents in each case optionally optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, fluorine-, chlorine-, and/or bromine-substituted methyl, n- ori-propoxy-Substituted methyl, ethyl, n- ori-propyl. n-, ethyl, n- or i-propyl. S- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, s- or 0292) R' preferably represents hydrogen, in each case t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, s- or optionally fluorine- and/or chlorine-substituted methyl, t-butylthio, methylamino, ethylamino, n- or i-propy ethyl, n- or i-propyl. n-, s- or t-butyl, propenyl, butenyl, lamino, n-, s- or t-butylamino, dimethylamino or diethy US 2010/0261934 A1 Oct. 14, 2010 14

lamino, or in each case optionally cyano-, fluorine-, chlo rine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted TABLE-continued cyclopropyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cyclo propyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclo-propylthio, cyclobutylthio, cyclopentylthio, cyclo Examples of the compounds of the formula (IIa) hexylthio, cyclopropylamino, cyclobutyl-amino, cyclo pentylamino or cyclohexylamino. (IIa) (0305 R preferably represents hydrogen, in each case optionally cyano-, hydroxyl-, fluorine-, chlorine-, meth oxy-, ethoxy-, n- ori-propoxy-Substituted methyl, ethyl, n or i-propyl. n-, i- or S-butyl, in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted propenyl, bute nyl, propynyl or butynyl, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-pro Example (Positions) pyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or No. (X"), R14 cyclohexyl. (0306 R preferably represents hydrogen, in each case IIa-2 (2) Cl, (4) Cl OCH optionally cyano-, hydroxyl-, fluorine-, chlorine-, meth oxy-, ethoxy-, n- ori-propoxy-Substituted methyl, ethyl, n or i-propyl. n-, i- or S-butyl, in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted propenyl, bute nyl, propynyl or butynyl, in each case optionally cyano-, OCH5 fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-pro pyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or optionally nitro-, cyano-, fluorine-, chlo IIa-3 (2) Cl, (4) Cl OCHs rine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-pro poxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl, or together with R represents in each case option ally methyl- or ethyl-substituted butane-1,4-diyl (trimeth ylene), pentane-1,5-diyl, 1-oxabutane-1,4-diyl or 3-oxap entane-1,5-diyl. (0307 Xpreferably represents nitro, cyano, carboxyl, car IIa-4 (2) Cl, (4) Cl OCH, bamoyl, formyl, Sulfamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl. n-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy. 0308) Xpreferably represents nitro, cyano, carboxyl, car bamoyl, formyl, Sulfamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl. n-, s- or IIa-5 (2) Cl OCH t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy. 0309 Examples of the compounds of the formula (IIa) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.

TABLE Examples of the compounds of the formula (IIa IIa-6 (2) Cl, (4) Cl OCH (IIa) 3 4 N2 O

(X) + 2 Al ls R 14

Example (Positions) No. (X), Al R 14 IIa-7 (2) F OCH N/ N IIa-1 (2) Cl, (4) Cl N OCH NY N

HC OCH O US 2010/0261934 A1 Oct. 14, 2010

TABLE-continued TABLE-continued

Examples of the compounds of the formula (IIa) Examples of the compounds of the formula (IIa)

(IIa) (IIa) 3 4 N 2 O 4. N2 O

(X) + 2 Al ls R 14 (X) + 21 Al ls R 14

Example (Positions) Example (Positions) No. (X"), Al R14 No. (X"), A. R14

IIa-8 (2) F N OCH, IIa-13 NY N (2) Cl, (4) Cl y OCDs

HC CI

IIa-14 (2) Cl, (4) Cl N OCH NY N 2115 IIa-9 (2) Cl, (4) Cl OCHs C3H7-i

IIa-15 (2) Cl, (4) Cl N OCH NY N 2115 IIa-10 (2) Cl, (4) CF OCH C4H9-t

IIa-16 (2) Cl, (4) Cl 1"--- OCHs O-N

IIa-11 (2) Cl N OCH IIa-17 (2) Cl, (4) Cl Y- OCHs O-N

IIa-18 - OH

o1 N IIa-12 - OCHs

0310 Examples of the compounds of the formula (IIb) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.

US 2010/0261934 A1 Oct. 14, 2010 17

0311 Examples of the compounds of the formula (IIc) 0312 Examples of the compounds of the formula (IId) which are very particularly preferred as herbicide safeners which are very particularly preferred as herbicide safeners according to the invention are listed in the table below. according to the invention are listed in the table below.

TABLE TABLE

Examples of the compounds of the formula (IIc Examples of the compounds of the formula (IId

(IIc) R23 (IId) O (X), R17 O N N SA R22 21 . l -H(X'), R18 21 So, N Example No. R 16 N(R17, R18) O IIc-1 CHCl, N(CH-CH=CH-), Ex ample (Positions) (Positions) 22 23 24 4 5 IIc-2 CHCl, H3C CH3 No. R. R R (X"), (X), IId-1. H H CH (2) OCH N O IId-2 H H C2H5 (2) OCH IId-3 H H C3H7-n (2) OCH \ / IId-4 H H C3H7-i (2) OCH IIc-3 CHCl, "y" II-S H H (2) OCH NN O \- IId-6 H H CH (2) OCH, CH (5) CH 3 II-7 H H C2H5 (2) OCH (5) CH IIc-4 CHCl, IId-8 H H C3H7-n (2) OCH (5) CH IId-9 H H C3H7-i (2) OCH (5) CH N O IId-10 H H (2) OCH \- (5) CH

IIc-5 CHCl, H3C CH3 N X -11 H OCH (2) OCH N O (5) CH, -12. H OCHs (2) OCH (5) CH C6Hs -13 H OCH7-i (2) OCH (5) CH -14 H SCH (2) OCH IIc-6 CHCl, CH (5) CH -1S H SC2H5 (2) OCH N (5) CH Id-6 SCH7-i (2) OCH O (5) CH -17 H NHCH (2) OCH (5) CH -18 H NHC-Hs (2) OCH (5) CH -19 H NHCH7-i (2) OCH IIc-7 CHCl, H3C CH3 (5) CH N X -20 H N (2) OCH N O NH (5) CH

/ O 21 IId-21 H H NHCH, (2) OCH, IId-22 H H NHCH7-i (2) OCH IId-23 H H N(CH), (2) OCH US 2010/0261934 A1 Oct. 14, 2010

razole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole, TABLE-continued fenclorim, cumyluron, dymron, dimepiperate and the com pounds IIe-5 and IIe-11, and particular emphasis is given to Examples of the compounds of the formula (IId cloquintocet-mexyl and mefenpyr-diethyl. (IId) 0315 Examples of the selective-herbicidal combinations R23 according to the invention comprising in each case one active (X) compound of the formula (I) and one of the safeners defined ON N S/S R22 21 above are listed in the table below. R24 2 N +-(X'), TABLE SO, Examples of the combinations according to the invention O Active compounds Ex of the formula (I) Safeners ample (Positions) (Positions) No. R22 R23 R24 (X), (X), -8 cloquintocet-mexyl -8 enchlorazole-ethyl IId-24 H H N(CH3)2 (3) CH -8 isoxadifen-ethyl (4) CH -8 mefenpyr-diethyl IId-2S H H CH-O-CH (2) OCH -8 furiazole -8 enclorim -8 cumyluron 0313 Examples of the compounds of the formula (IIe) -8 daimuron dymron which are very particularly preferred as herbicide safeners -8 dimepiperate -8 Ie-11 according to the invention are listed in the table below. -8 Ie-5 -b cloquintocet-mexyl TABLE -b enchlorazole-ethyl -b isoxadifen-ethyl Examples of the compounds of the formula (IIe -b mefenpyr-diethyl -b furiazole -b enclorim (IIe) -b cumyluron -b daimuron dymron R2 -b dimepiperate R22 21 -b Ie-11 -H(X'), -b Ie-5 N -C cloquintocet-mexyl -C enchlorazole-ethyl -C isoxadifen-ethyl O -C mefenpyr-diethyl -C furiazole Ex -C enclorim ample (Positions) (Positions) -C cumyluron No. R22 R25 R26 (X), (X), -C daimuron dymron -C dimepiperate IIe-1 H H CH (2) OCH, -C Ie-5 IIe-2 H H C2H5 (2) OCH -C Ie-11 IIe-3 H H C3H7-n (2) OCH -d cloquintocet-mexyl IIe-4 H H C3H7-i (2) OCH -d enchlorazole-ethyl -d isoxadifen-ethyl IIe-5 H H (2) OCH -d mefenpyr-diethyl -d furiazole -d enclorim -d cumyluron -d daimuron dymron IIe-6 H CH CH (2) OCH -d dimepiperate IIe-7 H H CH (2) OCH, -d Ie-11 (5) CH -d Ie-5 IIe-8 H H C2H5 (2) OCH -e cloquintocet-mexyl (5) CH -e enchlorazole-ethyl IIe-9 H H CH7-n (2) OCH, -e isoxadifen-ethyl (5) CH -e mefenpyr-diethyl IIe-10 H H C3H7-i (2) OCH -e furiazole (5) CH, -e enclorim -e cumyluron IIe-11 H H (2) OCH -e daimuron dymron (5) CH -e dimepiperate -e Ie-5 -e Ie-11 -f cloquintocet-mexyl IIe-12 H CH CH (2) OCH -f enchlorazole-ethyl (5) CH -f isoxadifen-ethyl -f mefenpyr-diethyl -f furiazole 0314. Most preferred as crop plant tolerance promoter -f enclorim compound component (c) are cloquintocet-mexyl, fenchlo US 2010/0261934 A1 Oct. 14, 2010

0324. Using, for example, according to process (BC) TABLE-continued 8-methyl-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4.5 decane-2,4-dione and isobutyl chloride as starting materials, Examples of the combinations according to the invention the course of the process according to the invention can be Active compounds represented by the reaction scheme below: of the formula (I) Safeners cumyluron daimuron dymron dimepiperate CH IIe-5 OH IIe-11 H5C2 CH3 H-Hcoc cloquintocet-mexyl CH3 N CH3 fenchlorazole-ethyl He isoxadifen-ethyl HN base mefenpyr-diethyl furiazole O C2H5 fenclorim cumyluron daimuron dymron dimepiperate IIe-5 CH IIe-11 H O 0316 The compounds of the general formula (IIa) to be CH C.H., used as Safeners according to the invention are known and/or O CH3 can be prepared by processes known per se (cf. WO-A-91/ 07874, WO-A-95/07897). HC N 0317. The compounds of the general formula (IIb) to be HN used as Safeners according to the invention are known and/or can be prepared by processes known per se (cf. EP-A- O C2H5 191736). 0318. The compounds of the general formula (IIc) to be used as Safeners according to the invention are known and/or 0325 Using, for example, according to process (B) (vari can be prepared by processes known per se (cf. DE-A- ant B) 8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-aza 2218097, DE-A-2350547). spiro4.5 decane-2,4-dione and acetic anhydride as starting 0319. The compounds of the general formula (IId) to be materials, the course of the process according to the invention used as Safeners according to the invention are known and/or can be represented by the reaction scheme below: can be prepared by processes known per se (cf. DE-A- 19621522/U.S. Pat. No. 6,235,680). HC-CO 0320. The compounds of the general formula (IIe) to be CH3 3 V used as safeners according to the invention are known and can O be prepared by processes known perse (cf. WO-A-99/66795/ / HC-CO U.S. Pat. No. 6,251,827). --- 0321. It has now surprisingly been found that the above HCO base defined active-compound combinations of Substituted ketoenols of the general formula (I) and (I-a) and Safeners (antidotes) from the component (c) set out above combine very good useful plant tolerance with a high herbicidal activ ity and can be used in various crops, in particular in cereals (especially wheat), but also in Soybeans, potatoes, maize and rice, for selective weed control. 0322. In this context it is considered surprising that, from a multiplicity of known Safeners or antidotes capable of antagonizing the damaging effect of a herbicide on the crop plants, it is specifically the compounds of component (c) set out above which are Suitable for compensating—almost com pletely—the damaging effect of Substituted cyclic ketoenols on the crop plants, without at the same time having any critical adverse effect on the herbicidal activity against the weeds. 0323 Emphasis may be given here to the particularly advantageous effect of the particularly preferred and most 0326 Using, for example, according to process (C) preferred combination partners from component (c'), particu 8-methoxy 3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4.5 larly with regard to the gentle treatment of cereal plants. Such decane-2,4-dione and ethyl chloraformate as starting materi as wheat, barley and rye, for example, but also maize and rice, als, the course of the process according to the invention can be as crop plants. represented by the reaction scheme below: US 2010/0261934 A1 Oct. 14, 2010 20

OCH OH H3C C2H5

/ He+CS +CHI HsC-O-C-CI +base He NH base C2H5 O

OCH

OCH

O CH-O-C-O

0329. Using, for example, according to process (E) 8-me thyl-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4.5 decane 2,4-dione and methanesulfonyl chloride as starting material, the course of the reaction can be represented by the reaction OCH scheme below: 0327 Using, for example, according to process (D), vari anta 8-methyl 3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4. OH C2H5 5decane-2,4-dione and methyl chloromonothioformate as HC starting materials, the course of the reaction can be repre \ CH3 +CI-SO-CH sented as follows: base HN

O CH5

O-SOCH C2H5 HC \ CH HN O CHs

0330. Using, for example, according to process (F) 8-methoxy 3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4.5 CH3 decane-2,4-dione and (2.2.2-trifluoroethyl)methanethio phosphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:

CH5 OH S CH5 OCH2CF3 CI-PC 0328. Using, for example, according to process (D), Vari \ -- CH3 HCO CH" -->base ant B 8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro HN 4.5 decane-2,4-dione, carbon disulfide and methyl iodide as starting components, the course of the reaction can be repre O CH5 sented as follows: US 2010/0261934 A1 Oct. 14, 2010 21

-continued O OH C2H5 CH3 H3CO M C N N CH3 - CH3 - HN -HCI

HCO

O

0331 Using, for example, according to process (G) H3CO 8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4.5 decane-2,4-dione and NaOH as components, the course of the process according to the invention can be represented by the reaction scheme below: O CHs

OH C2H5 0334 Some of the compounds, required as starting mate rials in the process (A) according to the invention, of the HCO N NaOH CH -- formula (Ia) HN

O CHs (I-a) Na(+) O(-) C2H5 HCO N CH3 HN

O CHs

0332 Using, for example, according to process (H) variant in which C. 8-methoxy 3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4. 0335 A, B and Dare as defined above 5decane-2,4-dione and ethyl isocyanate as starting materi are novel (WO 01/17972, WO 01/74770) or they can be als, the course of the reaction can be represented by the prepared by the processes described therein in principle. reaction scheme below: 0336. The acid halides of the formula (II), carboxylic anhydrides of the formula (III), chloroformic esters or chlo roformic thioesters of the formula (IV), chloromonothiofor OH CH5 mic esters or chlorodithioformic esters of the formula (V), HC alkyl halides of the formula (VI), sulfonyl chlorides of the \ CH3 -CHs-N=C=O - - formula (VII), phosphorus compounds of the formula (VIII) and metal hydroxides, metal alkoxides or amines of the for HN mula (IX) and (X) and isocyanates of the formula (XI) and O CH5 carbamoyl chlorides of the formula (XII) furthermore O H required as starting materials for carrying out the processes / (A), (B), (C), (D), (E), (F) and (G) according to the invention -CNCH are generally known compounds of organic or inorganic H3C 215 CH5 chemistry. 0337 The process (AC) is characterized in that com \ CH pounds of the formula (I-a) are in each case reacted with HN carbonyl halides of the formula (II), if appropriate in the presence of a diluent and if appropriate in the presence of an O CH5 acid binder. 0338 Suitable diluents for use in the process (AC.) accord 0333. Using, for example, according to process (H) variant ing to the invention are all solvents which are inert to the acid B 8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro4. halides. Preference is given to using hydrocarbons, such as 5decane-2,4-dione and dimethylcarbamoyl chloride as start benzine, benzene, toluene, Xylene and tetraline, furthermore ing materials, the course of the reaction can be represented by halogenated hydrocarbons, such as methylene chloride, chlo the scheme below: roform, carbon tetrachloride, chlorobenzene and o-dichlo US 2010/0261934 A1 Oct. 14, 2010 22 robenzene, moreover ketones, such as acetone and methyl 0349 Suitable acid binders for the process (B) according isopropyl ketone, furthermore ethers, such as diethyl ether, to the invention are all customary acid acceptors. tetrahydrofuran and dioxane, additionally carboxylic esters, 0350 Preference is given to using tertiary amines, such as Such as ethyl acetate, and also strongly polar solvents, such as triethylamine, pyridine, DABCO, DBU, DBA, Hünig base dimethylsulfoxide and sulfolane. The hydrolytic stability of and N,N-dimethylaniline, furthermore, alkaline earth metal the acid halide permitting, the reaction can also be carried out oxides, such as magnesium oxide and calcium oxide, more in the presence of water. over alkali metal and alkaline earth metal carbonates, such as 0339 Suitable acid binders for the reaction according to process (AC) according to the invention are all customary Sodium carbonate, potassium carbonate and calcium carbon acid acceptors. Preference is given to using tertiary amines, ate, and also alkali metal hydroxides, such as Sodium hydrox Such as triethylamine, pyridine, diazabicyclooctane ide and potassium hydroxide. (DABCO), diazabicycloundecene (DBU), diazabicyclonon 0351 Suitable diluents for use in the process (B) accord ene (DBN), Hünig base and N,N-dimethylaniline, further ing to the invention are all solvents which are inert to the more alkaline earth metal oxides, such as magnesium oxide chloroformic esters or chloroformic thioesters. Preference is and calcium oxide, moreover alkali metal and alkaline earth given to using hydrocarbons, such as benzine, benzenes, tolu metal carbonates, such as sodium carbonate, potassium car ene, Xylene and tetraline, furthermore halogenated hydrocar bonate and calcium carbonate, and also alkali metal hydrox bons, such as methylene chloride, chloroform, carbon tetra ides, such as Sodium hydroxide and potassium hydroxide. chloride, chlorobenzene and o-dichlorobenzene, moreover 0340. The reaction temperature in the process (AC.) ketones, such as acetone and methyl isopropyl ketone, fur according to the invention may be varied within a relatively thermore ethers, such as diethyl ether, tetrahydrofuran and wide range. In general, the process is carried out attempera dioxane, additional carboxylic esters, such as ethyl acetate, tures between -20° C. and +150° C., preferably between 0°C. and also strongly polar solvents, such as dimethyl Sulfoxide and 100° C. and Sulfolane. 0341 When carrying out the process (AC.) according to 0352. When carrying out the process (B) according to the the invention, the starting materials of the formula (I-a) and invention, the reaction temperature may be varied within a the carbonyl halide of the formula (II) are generally each relatively wide range. In general, the reaction temperature is employed in approximately equivalent amounts. However, it between -20° C. and +100° C., preferably between 0° C. and is also possible to use a relatively large excess (up to 5 mol) of 500 C. the carbonyl halide. Work-up is carried out by customary 0353. The process (B) according to the invention is gen methods. erally carried out under atmospheric pressure. 0342. The process (AB) is characterized in that com 0354 When carrying out the process (B) according to the pounds of the formula (I-a) are in each case reacted with invention, the starting materials of the formula (I-a) and the carboxylic anhydrides of the formula (III), if appropriate in appropriate chloroformic ester or chloroformic thioester of the presence of a diluent and if appropriate in the presence of the formula (IV) are generally each employed in approxi an acid binder. mately equivalent amounts. However, it is also possible to use 0343 Suitable diluents for use in the process (ABB a relatively large excess (up to 20 mol) of one component or according to the invention are, preferably, those diluents the other. Work-up is carried out by customary methods. In which are also preferred when acid halides are used. Besides, general, precipitated salts are removed and the reaction mix it is also possible for excess carboxylic anhydride to act ture that remains is concentrated by removing the diluent simultaneously as diluent. under reduced pressure. 0344 Suitable optional binders in the process (AB) are, 0355 The process (C) according to the invention is char preferably, those acid binders which are also preferred when acterized in that compounds of the formula (I-a) are in each acid halides are used. case reacted with (CC) compounds of the formula (V) in the 0345 The reaction temperature in the process (AB) presence of a diluent and, if appropriate, in the presence of an according to the invention can be varied within a relatively acid binder or (CB) carbon disulfide and subsequently with wide range. In general, the process is carried out attempera alkyl halides of the formula (VI), if appropriate in the pres tures between -20° C. and +150° C., preferably between 0°C. ence of a diluent and if appropriate in the presence of a base. and 100° C. 0356. In preparation process (CC), about 1 mol of chlo 0346 When carrying out the process (AB) according to the romonothioformic ester or chlorodithioformic ester of the invention, the starting materials of the formula (I-a) and the formula (VI) is reacted per mole of the starting material of the carboxylic anhydride of the formula (III) are generally each formula (I-a), at from 0 to 120° C., preferably from 20 to 60° employed in approximately equivalent amounts. However, it C is also possible to use a relatively large excess (up to 5 mol) of 0357 Suitable diluents which are added, if appropriate, the carboxylic anhydride. Work-up is carried out by custom are all inert polar organic solvents, such as ethers, esters, ary methods. amides, Sulfones, Sulfoxides, and also halogenated alkanes. 0347 In general, diluent and excess carboxylic anhydride 0358 Preference is given to using dimethyl sulfoxide, and also the carboxylic acid formed are removed by distilla ethyl acetate, tetrahydrofuran, dimethylformamide or meth tion or by washing with an organic solvent or with water. ylene chloride. 0348. The process (B) is characterized in that compounds 0359. If, in a preferred embodiment, the enolate salt of the of the formula (I-a) are in each case reacted with chloroformic compound (I-a) is prepared by adding strong deprotonating esters orchloroformic thioesters of the formula (IV), if appro agents, such as, for example, sodium hydride or potassium priate in the presence of a diluent and if appropriate in the tert-butoxide, the further addition of acid binders may be presence of an acid binder. dispensed with. US 2010/0261934 A1 Oct. 14, 2010

0360. If acid binders are used, these are customary inor agents (such as, for example, sodium hydride or potassium ganic or organic bases, for example sodium hydroxide, tert-butoxide), the further addition of acid binders may be Sodium carbonate, potassium carbonate, pyridine and triethy dispensed with. lamine. 0376. If acid binders are used, these are customary inor 0361. The reaction can be carried out at atmospheric pres ganic or organic bases, for example Sodium hydride, sodium sure or under elevated pressure and is preferably carried out at carbonate, potassium carbonate, pyridine and triethylamine. atmospheric pressure. Work-up is carried out by customary 0377 The reaction can be carried out at atmospheric pres methods. sure or under elevated pressure and is preferably carried out at 0362. In preparation process (CB), in each case an aquimo atmospheric pressure. Work-up is carried out by customary lar amount of in excess of carbon disulfide is added per mole methods. of starting materials of the formula (I-a). Here, the process is 0378. The process (E) according to the invention is char preferably carried out attemperatures of from 0 to 50° C. and acterized in that compounds of the formula (I-a) are in each in particular at from 20 to 30° C. case reacted with phosphorus compounds of the formula 0363 Frequently, it is expedient to prepare initially the (VIII), if appropriate in the presence of a diluent and if appro corresponding salt from the compounds of the formula (I-a) priate in the presence of an acid binder. by adding a base (such as, for example, potassium tert-butox 0379. In preparation process (E), to obtain compounds of ide or sodium hydride). In each case, the compound (I-a) is the formula (I-e), from 1 to 2, preferably from 1 to 1.3 mol of reacted with carbon disulfide until the formation of the inter the phosphorus compound of the formula (VIII) are reacted mediate has ended, for example after stirring for a number of per mole of the compound (I-a), at temperatures between hours at room temperature. –40° C. and 150° C., preferably between -10 and 110° C. 0364 Suitable bases for use in the process (CB) are all 0380. The process (E) is preferably carried out in the pres customary proton acceptors. Preference is given to using ence of a diluent. alkali metal hydrides, alkali metal alkoxides, alkali metal or 0381 Suitable diluents are all inert polar organic solvents, alkaline earth metal carbonates or bicarbonates or nitrogen Such as ethers, esters, amides, nitriles, Sulfides, Sulfones, Sul bases. Sodium hydride, Sodium methoxide, sodium hydrox foxides, etc. ide, calcium hydroxide, potassium carbonate, Sodium bicar 0382 Preference is given to using acetonitrile, ethyl bonate, triethylamine, dibenzylamine, diisopropylethy acetate, dimethyl sulfoxide, tetrahydrofuran, dimethyl-for lamine, pyridine, quinoline, diazabicyclooctane (DABCO), mamide, methylene chloride. diazabicyclonone (DBN) and diazabicycloundecene (DBU) 0383 Suitable acid binders which are added, if appropri may be mentioned by way of example. ate, are customary inorganic or organic bases, such as hydrox 0365 Suitable diluents for use in this process are all cus ides, carbonates or amines. Sodium hydroxide, Sodium car tomary solvents. bonate, potassium carbonate, pyridine and triethylamine may 0366 Preference is given to using aromatic hydrocarbons, be mentioned by way of example. Such as benzene or toluene, alcohols, such as methanol, etha 0384 The reaction can be carried out at atmospheric pres nol, isopropanol or ethylene glycol, nitriles, such as acetoni sure or under elevated pressure and is preferably carried out at trile, ethers, such as tetrahydrofuran and dioxane, amides, atmospheric pressure. Work-up is carried out by customary Such as dimethylformamide, or other polar solvents, such as methods of organic chemistry. The end products are prefer dimethylsulfoxide or sulfonane. ably purified by crystallization, chromatographic purification 0367 The further reaction with the alkyl halide of the or by “insipient distillation’, i.e. the removal of the volatile formula (VI) is preferably carried out at from 0 to 70° C. and components under reduced pressure. in particular at from 20 to 50° C. Here, at least an aquimolar 0385. The process (F) is characterized in that compounds amount of alkyl halide is used. of the formula (I-a) are in each case reacted with metal 0368. The process is carried out at atmospheric pressure or hydroxides or metal alkoxides of the formula (IX) or amines under elevated pressure, preferably at atmospheric pressure. of the formula (X), if appropriate in the presence of a diluent. 0369 Work-up is again carried out by customary methods. 0386 Suitable diluents for use in the process (F) according 0370. The process (D) according to the invention is char to the invention are, preferably, ethers, such as tetrahydrofu acterized in that compounds of the formula (I-a) are in each ran, dioxane, diethyl ether, or else alcohols, such as methanol, case reacted with sulfonyl chlorides of the formula (VII), if ethanol, isopropanol, but also water. The process (F) accord appropriate in the presence of a diluent and if appropriate in ing to the invention is generally carried out under atmospheric the presence of an acid binder. pressure. The reaction temperatures are generally between 0371. In preparation process (D), about 1 mol of sulfonyl –20° C. and 100° C., preferably between 0° C. and 50° C. chloride of the formula (VII) is reacted per mole of starting 0387. The process (G) according to the invention is char material of the formula (I-a), at from -20 to 150° C., prefer acterized in that compounds of the formula (I-a) are in each ably from 20 to 70° C. case reacted with (GC) compounds of the formula (XI), if 0372. The process (D) is preferably carried out in the appropriate in the presence of a diluent and if appropriate in presence of a diluent. the presence of a catalyst, or (GB) with compounds of the 0373 Suitable diluents are all inert polar organic solvents, formula (XII), if appropriate in the presence of a diluent and Such as ethers, esters, amides, nitriles, Sulfones, Sulfoxides or if appropriate in the presence of an acid binder. halogenated hydrocarbons, such as methylene chloride. 0388. In preparation process (GC.), about 1 mol of isocy 0374 Preference is given to using dimethylsulfoxide, tet anate of the formula (XI) is reacted per mole of starting rahydrofuran, ethyl acetate, dimethylformamide, methylene material of the formula (I-a), at from 0 to 100° C., preferably chloride. from 20 to 50° C. 0375. If, in a preferred embodiment, the enolate salt of the 0389. The process (GC.) is preferably carried out in the compound (I-a) is prepared by adding strong deprotonating presence of a diluent. US 2010/0261934 A1 Oct. 14, 2010 24

0390 Suitable diluents are all inert organic solvents, such 04.09 From the order of the Isoptera, for example, Reticu as ethers, esters, amides, nitriles, Sulfones or Sulfoxides. litermes spp. 0391) If appropriate, catalysts may be added to promote 0410. From the order of the Phthiraptera, for example, the reaction. Suitable for use as catalysts are, very advanta Pediculus humanus corporis, Haematopinus spp., Linog geously, organotin compounds. Such as, for example, dibu nathus spp., Trichodectes spp., Damalinia spp. tyltin dilaurate. 0411. From the order of the Thysanoptera, for example, 0392 The process is preferably carried out at atmospheric Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Fran pressure. kliniella accidentalis. 0393. In preparation process (G.B), about 1 mol of carbam 0412. From the order of the Heteroptera, for example, oyl chloride of the formula (XII) is reacted per mole of start Eurygaster spp., Dysdercus intermedius, Piesma quadrata, ing material of the formula (I-a), at from 0 to 150°C., pref Cimex lectularius, Rhodnius prolixus and Triatoma spp. erably from 20 to 70° C. 0413 From the order of the Homoptera, for example, 0394 Suitable diluents which are added, if appropriate, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporari are all inert polar organic solvents, such as ethers, esters, orum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus amides, Sulfones, Sulfoxides or halogenated hydrocarbons. ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hva 0395 Preference is given to using dimethyl sulfoxide, lopterus arundinis, Phylloxera vastatrix, Pemphigus spp., ethyl acetate, tetrahydrofuran, dimethylformamide or meth Macrosiphum avenae, Myzus spp., Phorodon humuli, Rho ylene chloride. palosiphumpadi, Empoasca spp., Euscelis bilobatus, Nepho 0396. If, in a preferred embodiment, the enolate salt of the tettix cincticeps, Lecanium corni, Saissetia oleae, Laodel compound (I-a) is prepared by adding strong deprotonating phax striatellus, Nilaparvata lugens, Aonidiella aurantii, agents (such as, for example, Sodium hydride or potassium Aspidiotus hederae, Pseudococcus spp. and Psylla spp. tert-butoxide), the further addition of acid binders may be 0414. From the order of the Lepidoptera, for example, dispensed with. Pectinophora gossypiella, Bupalus piniarius, Chematobia 0397) If acid binders are used, these are customary inor brumata, Lithocolletis blancardella, Hyponomeuta padella, ganic or organic bases, for example sodium hydroxide, Plutella xylostella, Malacosoma neustria, Euproctis chrysor Sodium carbonate, potassium carbonate, triethylamine or rhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnis pyridine. tis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insu 0398. The reaction can be carried out atmospheric pres lana, Heliothis spp., Mamestra brassicae, Panolis flammea, sure or under elevated pressure and is preferably carried out at Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, atmospheric pressure. Work-up is carried out by customary Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kueh methods. niella, Galleria mellonella, Tineola bisselliella, Tinea pel 0399. The active compounds are well tolerated by plants, lionella, Hofmannophila pseudospretella, Cacoecia podana, have favorable homeotherm toxicity and are environmentally Capua reticulana, Choristoneura filmiferana, Clysia ambig friendly; they are suitable for protecting plants and plant uella, Homona magnanima, Tortrix viridana, Cnaphalocerus organs, for increasing harvest yields, for improving the qual spp. and Oulema oryzae. ity of the harvested material and for controlling animal pests, 0415. From the order of the Coleoptera, for example, Ano in particularinsects, arachnids and nematodes encountered in bium punctatum, Rhizopertha dominica, Bruchidius Obtec agriculture, in forests, in gardens and leisure facilities, in the tus, Acanthoscelides Obtectus, Hylotrupes bajulus, Agellas protection of stored products and materials and in the hygiene tica alni, Leptinotarsa decemlineata, Phaedon cochleariae, sector. They are preferably used as crop protection agents. Diabrotica spp., Psylliodes chrysocephala, Epillachna They are active against normally sensitive and resistant spe varivestis, Atomaria spp., Oryzaephilus surinamensis, cies and against all or some stages of development. The Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, abovementioned pests include: Cosmopolites Sordidus, Ceuthorrhynchus assimilis, Hypera 0400 From the order of the Isopoda, for example, Oniscus postica, Dermestes spp., Trogoderma spp., Anthrenus spp., asellus, Armadillidium vulgare and Porcellio scaber: Attagenus spp., Lyctus spp., Melligethes aeneus, Ptinus spp., 04.01. From the order of the Diplopoda, for example, Bla Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tene niulus guttulatus. brio molitor; Agriotes spp., Conoderus spp., Melolontha 0402 From the order of the Chilopoda, for example, Geo melolontha, Amphimallon solstitialis, Costelytra zealandica philus carpophagus and Scutigera spp. and Lissorhoptrus Oryzophilus. 0403. From the order of the Symphyla, for example, Scuti 0416) From the order of the Hymenoptera, for example, gerella immaculata. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium 0404 From the order of the Thysanura, for example, Lepi pharaonis and Vespa spp. sma saccharina. 0417. From the order of the Diptera, for example, Aedes 04.05 From the order of the Collembola, for example, spp., Anopheles spp., CulexO spp., Drosophila melanogaster, Onychiurus armatus. Musca spp., Fannia spp., Caliphora erythrocephala, Lucilia 0406. From the order of the Orthoptera, for example, spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Acheta domesticus, Gryllotalpa spp., Locusta migratoria Hippobosca spp., Stomoxys spp., Oestrus spp., Hypoderma migratorioides, Melanoplus spp. and Schistocerca gregaria. spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella 0407. From the order of the Blattaria, for example, Blatta frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Orientalis, Periplaneta americana, Leucophaea maderae and Dacus oleae, Tipula paludosa, Hyllemyia spp. and Liriomyza Blattella germanica. spp. 0408. From the order of the Dermaptera, for example, 0418 From the order of the Siphonaptera, for example, Forficula auricularia. Xenopsylla cheopis and Ceratophyllus spp. US 2010/0261934 A1 Oct. 14, 2010 25

0419 From the class of the Arachnida, for example, Scor mineral oil fractions, mineral and vegetable oils, alcohols pio maurus, Latrodectus mactans, Acarus Siro, Argas spp., Such as butanol or glycol and their ethers and esters, ketones Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Such as acetone, methyl ethyl ketone, methyl isobutyl ketone Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., or cyclohexanone, strongly polar solvents such as dimethyl Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes formamide and dimethyl sulfoxide, or else water. spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., 0427 Suitable solid carriers are: Bryobia praetiosa, Panonychus spp., Tetranychus spp., for example ammonium salts and ground natural minerals Hemitarisonemus spp. and Brevipalpus spp. Such as kaolins, clays, talc, chalk, quartz, attapulgite, mont 0420. The plant-parasitic nematodes include, for example. morillonite or diatomaceous earth, and ground synthetic min Pratylenchus spp., Radopholus similis, Dity lenchus dipsaci, erals such as highly disperse silica, alumina and silicates; Tvlenchulus semipenetrans, Heterodera spp., Globodera Suitable Solid carriers for granules are: for example crushed spp., Meloidogyne spp., Aphelen.choides spp., Longidorus and fractionated natural rocks such as calcite, marble, pum spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchus ice, Sepiolite and dolomite, or else synthetic granules of inor spp. ganic and organic meals, and granules of organic material 0421. If appropriate, the compounds according to the Such as sawdust, coconut shells, maize cobs and tobacco invention may also be used in certain concentrations or appli stalks; suitable emulsifiers and/or foam formers are: for cation rates to act as herbicides and microbicides, for example example nonionic and anionic emulsifiers such as polyoxy as fungicides, antimycoties and bactericides. If appropriate, ethylene fatty acid esters, polyoxyethylene fatty alcohol they can also be employed as intermediates or precursors for ethers, for example alkylaryl polyglycol ethers, alkylsul the synthesis of further active compounds. fonates, alkylsulfates, arylsulfonates, or else protein hydroly 0422 All plants and plant parts can be treated in accor sates; Suitable dispersants are: for example lignoSulfite waste dance with the invention. Plants are to be understood as liquors and methylcellulose. meaning in the present context all plants and plant popula 0428 Tackifiers such as carboxymethylcellulose and tions such as desired and undesired wild plants or crop plants natural and synthetic polymers in the form of powders, gran (including naturally occurring crop plants). Crop plants can ules or latices, such as gum arabic, polyvinyl alcohol and be plants which can be obtained by conventional plant breed polyvinyl acetate, or else natural phospholipids such as ing and optimization methods or by biotechnological and cephalins and lecithins and synthetic phospholipids can be recombinant methods or by combinations of these methods, used in the formulations. Other additives can be mineral and including the transgenic plants and inclusive of the plant Vegetable oils. cultivars protectable or not protectable by plant breeders 0429. It is possible to use colorants such as inorganic rights. Plant parts are to be understood as meaning all parts pigments, for example iron oxide, titanium oxide and Prus and organs of plants above and below the ground, such as sian Blue, and organic colorants such as alizarin colorants, shoot, leaf flower and root, examples which may be men aZo colorants and metal phthalocyanine colorants, and trace tioned being leaves, needles, stalks, stems, flowers, fruit bod nutrients such as salts of iron, manganese, boron, copper, ies, fruits, seeds, roots, tubers and rhizomes. The plant parts cobalt, molybdenum and zinc. also include harvested material, and vegetative and generative 0430. The formulations generally comprise between 0.1 propagation material, for example cuttings, tubers, rhizomes, and 95% by weight of active compound, preferably between offsets and seeds. 0.5 and 90%. 0423. The treatment according to the invention of the 0431. The active compounds according to the invention, as plants and plant parts with the active compounds is carried out Such or in their formulations, can also be used as a mixture directly or by allowing the compounds to act on their Sur with known fungicides, bactericides, acaricides, nematicides roundings, habitat or storage space by the customary treat or insecticides, for example in order to widen the spectrum of ment methods, for example by immersion, spraying, evapo action or to prevent the development of resistances in this ration, fogging, Scattering, painting on, injecting and, in the way. In many cases, synergistic effects result, i.e. the activity case of propagation material, in particular in the case of seeds, of the mixture exceeds the activity of the individual compo also by applying one or more coats. nentS. 0424 The active compounds can be converted into the 0432 Compounds which are suitable as mixing partners customary formulations such as Solutions, emulsions, wet are, for example, the following: table powders, Suspensions, powders, dusts, pastes, soluble powders, granules, Suspension-emulsion concentrates, natu Fungicides: ral and synthetic materials impregnated with active com 0433 2-phenylphenol; 8-hydroxyquinoline sulfate; pound, and microencapsulations in polymeric materials. acilbenzolar-5-methyl; aldimorph; amidoflumet, ampropyl 0425 These formulations are produced in a known man fos; ampropylfos-potassium; andoprim; anilazine; azacona ner, for example by mixing the active compounds with Zole; azoxystrobin; benalaxyl; benodanil; benomyl; benthia extenders, that is, liquid solvents and/or Solid carriers, option valicarb-isopropyl; benzamacril; benzamacril-isobutyl, ally with the use of surfactants, that is, emulsifiers and/or bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S; dispersants, and/or foam formers. bromuconazole; bupirimate; buthiobate; butylamine; cal 0426 If the extender used is water, it is also possible, for cium polysulfide; capsimycin; captafol; captan; carbenda example, to use organic solvents as cosolvents. The following Zim; carboxin; carpropamid; carvone; chinomethionat, chlo are essentially suitable as liquid solvents: aromatics such as benthiazone; chlorfenazole; chloroneb; chlorothalonil; Xylene, toluene or alkylnaphthalenes, chlorinated aromatics chloZolinate; cloZylacon; cyaZofamid; cyflufenamid; and chlorinated aliphatic hydrocarbons such as chloroben cymoxanil; cyproconazole, cyprodinil; cyprofuram; Dagger Zenes, chloroethylenes or methylene chloride, aliphatic G; debacarb; dichlofluanid; dichlone; dichlorophen; diclo hydrocarbons such as cyclohexane or paraffins, for example cymet; diclomeZine; dicloran; diethofencarb; difenocona US 2010/0261934 A1 Oct. 14, 2010 26

Zole; diflumetorim; dimethirimol; dimethomorph; dimox butocarboxim, butoxycarboxim, carbaryl, carbofuran, ystrobin: diniconazole; diniconazole-M; dinocap: carbosulfan, cloethocarb, dimetilan, ethiofencarb, diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; fenobucarb, fenothiocarb, formetanate, furathiocarb, draZOXolon; edifenphos; epoxiconazole; ethaboxam, ethiri isoprocarb, metam-Sodium, methiocarb, methomyl, mol; etridiazole; famoxadone; fenamidone; fenapanil; fena metolcarb, oxamyl, pirimicarb, promecarb, propoXur, rimol; fenbuconazole; fenfuram; fenhexamid; fenitropan: thiodicarb, thiofanox, trimethacarb. XMC, xylylcarb fenoxanil; fenpiclonil; fempropidin; fempropimorph, ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; 0437 Triazamates fluoromide; fluoxastrobin: fluguinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl 1.2 Organophosphates, for Example Al; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; fur 0438 acephate, azamethiphos, azinphos (-methyl, carbanil; furmecyclox, guazatline; hexachlorobenzene: hexa conazole; hymexazole; imazalil; imibenconazole; -ethyl), bromophos-ethyl, brom-fenvinfos (-methyl), iminoctadine triacetate; iminoctadine tris(albesilate); butathiofos, cadusafos, carbophenothion, chlorethoxy iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; fos, chlorfenvinphos, chlormephos, chlorpyrifos (-me irumamycin; isoprothiolane; isovaledione; kasugamycin; thyl/-ethyl), coumaphos, cyanofenphos, cyanophos, kresoxim-methyl; mancoZeb; maneb, meferimZone; mepa chlorfenvinphos, demeton-S-methyl, demeton-S-meth nipyrim, mepronil; metalaxyl; metalaxyl-M; metconazole; ylsulfone, dialifos, diazinon, dichlofenthion, dichlor methasulfocarb; methfuroxam; metiram; metominostrobin; vos/DDVP, dicrotophos, dimethoate, dimethylvinphos, metSulfoVax; mildiomycin; myclobutanil; mycloZolin; nata dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, mycin; nicobifen, nitrothal-isopropyl; noviflumuron; nuari etrimfos, famphur, fenamiphos, fenitrothion, fensul mol; ofurace; orysastrobin, oxadixyl; oXolinic acid; Oxpo fothion, fenthion, flupyrazofos, fonofos, formothion, conazole; oxycarboxin; oxyfenthiin, paclobutrazole; foSmethilan, fosthiazate, heptenophos, iodofenphos, pefurazoate; penconazole; pencycuron; phosdiphen; phtha iprobenfos, isaZofos, isofenphos, isopropyl O-Salicy lide, picoxystrobin; piperalin; polyoxins; polyoxorim; late, isoxathion, malathion, mecarbam, methacrifos, probenazole; prochloraz; procymidone; propamocarb; pro methamidophos, methidathion, mevinphos, monocroto panosine-Sodium; propiconazole; propineb; produinazid; phos, naled, omethoate, oxydemeton-methyl, parathion prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; (-methyl/-ethyl), phenthoate, phorate, phosalone, phos pyrimethanil; pyroquilon; pyroxyfur, pyrrollenitrine; quin met, phosphamidon, phosphocarb, phoxim, pirimiphos conazole; quinoxyfen; quintoZene; Simeconazole; spiroXam (-methyl/-ethyl), profenofos, propaphos, propetamphos, ine; sulfur, tebuconazole; tecloftalam, tecnazene: tetcyclacis; prothiofos, prothoate, pyraclofos, pyridaphenthion, tetraconazole; thiabendazole; thicyofen; thifluzamide: pyridathion, quinallphos, Sebufos, Sulfotep, Sulprofos, thiophanate-methyl; thiram, tioxymid; tolclofoS-methyl; tebupirimfos, temephos, terbufos, tetrachlorvinphos, tolylfluanid; triadimefon: triadimenol; triazbutil; triazoxide: tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflu thiometon, triaZophos, triclorfon, Vamidothion mizole; triforine; triticonazole; uniconazole; validamycin A; 2. Sodium Channel Modulators/Voltage-Dependent Sodium Vinclozolin; Zineb; Ziram; Zoxamide: (2 S) N-2-4-3-(4- chlorophenyl)-2-propynyloxy-3-methoxyphenylethyl-3- Channel Blockers methyl-2-(methylsulfonyl)aminobutanamide: 1-(1-naph 2.1 Pyrethroids, for Example thalenyl)-1H-pyrrole-2,5-dione: 2,3,5,6-tetrachloro-4- (methylsulfonyl)pyridine: 2-amino-4-methyl-N-phenyl-5- 0439 acrinathrin, allethrin (d-cis-trans, d-trans), beta thiazolecarboxamide: 2-chloro-N-(2,3-dihydro-1,1,3- cyfluthrin, bifenthrin, bioallethrin, bioallethrin-Scyclo trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide: 3,4,5- pentyl isomer, bioethanomethrin, biopermethrin, trichloro-2,6-pyridinedicarbonitrile; actinovate; cis-1-(4- bioresmethrin, chlovaporthrin, cis-cypermethrin, cis chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol: resmethrin, cis-permethrin, clocythrin, cycloprothrin, methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, imidazole-5-carboxylate; monopotassium carbonate, N-(6- theta-, Zeta-), cyphenothrin, deltamethrin, empenthrin methoxy-3-pyridinyl)cyclopropanecarboxamide: N-butyl-8- (1R isomer), esfenvalerate, etofemprox, fenfluthrin, fen (1,1-dimethylethyl)-1-oxaspiro4.5 decane-3-amine; propathrin, fenpyrithrin, fenvalerate, flubrocythrinate, Sodium tetrathiocarbonate; flucythrinate, flufenprox, flumethrin, fluvalinate, and copper salts and preparations, such as Bordeaux mixture; fubfenproX, gamma-cyhalothrin, imiprothrin, kade copper hydroxide; copper naphthenate; copper oxychloride; thrin, lambda-cyhalothrin, metofluthrin, permethrin copper Sulfate; cufraneb, cuprous oxide; mancopper, OXine (cis-, trans-), phenothrin (1R trans-isomer), prallethrin, copper. profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, tau-fluvalinate, tefluthrin, teral Bactericides: lethrin, tetramethrin (1R isomer), tralomethrin, trans 0434 bronopol, dichlorophen, nitrapyrin, nickel dimeth fluthrin, ZXI 8901, pyrethrins (pyrethrum) yldithiocarbamate, kasugamycin, octhillinone, furancarboxy 0440 DDT lic acid, oxytetracyclin, probenazole, Streptomycin, teclofta lam, copper Sulfate and other copper preparations. 2.2 Oxadiazines, for Example Indoxacarb Insecticides/Acaricides/Nematicides: 3. Acetylcholine Receptor Agonists/Antagonists 0435 1. Acetylcholine esterase (AChE) inhibitors 1.1 Carbamates, for Example 3.1 Chloronicotinyls, for Example 0436 alanycarb, aldicarb, aldoxycarb, allyxycarb, ami 0441 acetamiprid, clothianidin, dinotefuran, imidaclo nocarb, bendiocarb, benfuracarb, bufencarb, butacarb, prid, nitenpyram, nithiazine, thiacloprid, thiamethoxam US 2010/0261934 A1 Oct. 14, 2010 27

3.2 Nicotine, Bensultap, Cartap 14. Site-III Electron Transport Inhibitors 4. Acetylcholine Receptor Modulators 0449 Acequinocyl, fluacrypyrim 4.1 Spinosyns, for Example Spinosad 15. Microbial Disruptors of the Insect Gut Membrane 5. GABA-Controlled Chloride Channel Antagonists 0450 Bacillus thuringiensis strains 5.1 Cyclodiene Organochlorines, for Example 0442 camphechlor, chlordane, endosulfan, gamma 16. Fat Synthesis Inhibitors HCH, HCH, heptachlor, lindane, methoxychlor 0451 Tetronic acids, for example 0452 spirodiclofen, spiromesi?en 5.2 Fiproles, for Example 0453 Tetramic acids, for example 0443 acetoprole, ethiprole, fipronil, vaniliprole 0454) spirotetramat 6. Chloride Channel Activators 17. Carboxamides, for Example Flonicamid 6.1 Mectins, for Example 18. Octopaminergic Agonists, for Example Amitraz 0444 avermectin, emamectin, emamectin-benzoate, 19. Inhibitors of Magnesium-Stimulated ATPase, for ivermectin, milbemycin Example Propargite 0455 20. BDCAs, for example N2-1,1-dimethyl-2-(me 7. Juvenile Hormone Mimetics, for Example thylsulfonyl)ethyl-3-iodo-N-1-2-methyl-4-1.2.2.2-tet 0445 diofenolan, epofenonane, fenoxycarb, hydro rafluoro-1-(trifluoromethyl)ethylphenyl-1,2-benzenedi prene, kinoprene, methoprene, pyriproxifen, triprene carboxamide (CAS-Reg-No. 272451-65-7) 8. Ecdyson Agonists/Disruptors 21. Nereistoxin Analogs, for Example Thiocyclam Hydrogen 8.1 Diacylhydrazines, for Example Oxalate. Thiosultap-Sodium 0446 chromafenozide, halofenozide, methoxy 22. Biologicals, Hormones or Pheromones, for Example fenozide, tebufenozide 0456 azadirachtin, Bacillus spec. Beauveria spec. codilemone, Metarrhizium spec. Paecilomyces spec. 9. Chitin Biosynthesis Inhibitors thuringiensin, Verticillium spec. 9.1 Benzoylureas, for Example 23. Active Compounds with Unknown or Unspecific Mecha nisms of Action 0447 bistrifluoron, chlofluaZuron, diflubenzuron, flua Zuron, flucycloXuron, flufenoXuron, hexaflumuron, 23.1 Fumigants, for Example lufenuron, novaluron, noviflumuron, penfluoron, teflubenzuron, triflumuron 0457 aluminum phosphide, methyl bromide, sulfuryl fluoride 9.2 Buprofezin 9.3 Cyromazine 23.2 Selective Antifeedants, for Example 10. Oxidative Phosphorylation Inhibitors, ATP Disruptors 0458 cryolite, flonicamid, pymetrozine 10.1 Diafenthiuron 23.3 Mite Growth Inhibitors, for Example 10.2 Organotins, for Example Azocyclotin, Cyhexatin, Fen 0459 clofentezine, etoxazole, hexythiazox butatin-Oxide 23.4 Amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, quino-methionate, chlordime 11. Oxidative Phosphorylation Decouplers Acting by Inter form, chlorobenzilate, chloropicrin, clothiazoben, cyclo rupting the H-Proton Gradient prene, di-cyclanil, fenoxacrim, fentrifanil, flubenzimine, 11.1 Pyrroles, for Example Chlorfenapyr flufenerim, flutenzin, gossyplure, hydra-methylnone, japoni lure, metoxadiaZone, petroleum, piperonyl butoxide, potas 11.2 Dinitrophenols, for Example Binapacyrl, Dinobuton, sium oleate, pyridalyl, Sulfluramid, tetradifon, tetraSul, triara Dinocap, DNOC thene, verbutin, 12. Site-I Electron Transport Inhibitors and also products which comprise insecticidal plant extracts, nematodes, fungi or viruses. 12.1 METIs, for Example Fenazaquin, Fenpyroximate, Pyri 0460 A mixture with other known active compounds, midifen, Pyridaben, Tebufenpyrad, Tolfenpyrad Such as herbicides, or with fertilizers and growth regulators, 12.2 Hydramethylnon safeners and/or semiochemicals is also possible. 0461) When used as insecticides in their commercially 12.3 Dicofol available formulations and in the use forms prepared with 13. Site-II Electron Transport Inhibitors these formulations, the active compounds according to the invention can furthermore be present in the form of a mixture 0448 Rotenone with synergists. Synergists are compounds by which the US 2010/0261934 A1 Oct. 14, 2010 28 activity of the active compounds is increased without it being harvesting, accelerated maturation, higher yields, higher necessary for the synergist added to be active itself. quality and/or higher nutritional value of the harvested prod 0462. When used as insecticides in their commercially ucts, better storage characteristics and/or better processabil available formulations and in the use forms prepared with ity of the harvested products. Further examples of such traits, these formulations, the active compounds according to the examples which must be mentioned especially, are better invention can furthermore be present in the form of a mixture defense of the plants against animal and microbial pests. Such with inhibitors which reduce the degradation of the active as against insects, mites, phytopathogenic fungi, bacteria compound after application in the habitat of the plant, on the and/or viruses and an increased tolerance of the plants to Surface of parts of plants or in plant tissues. certain herbicidal active compounds. Examples of transgenic 0463. The active compound content of the use forms pre plants which may be mentioned are the important crop plants, pared from the commercially available formulations can vary Such as cereals (wheat, rice), maize, soybeans, potato, cotton, within broad ranges. The active compound concentration of tobacco, oilseed rape and fruit plants (with the fruits apples, the use forms can be from 0.0000001 up to 95% by weight of pears, citrus fruits and grapes), with particular emphasis on active compound, preferably between 0.0001 and 1% by maize, soybeans, potatoes, cotton, tobacco, and oilseed rape. weight. Traits which are especially emphasized are the increased 0464. They are applied in a customary manner adapted to defense of the plants against insects, arachnids, nematodes Suit the use forms. and slugs and Snails, owing to toxins being formed in the 0465. When used against hygiene pests and pests of stored plants, in particular toxins which are generated in the plants products, the active compound is distinguished by excellent by the genetic material of Bacillus thuringiensis (for example residual action on wood and clay as well as good stability to by the genes CryIA(a), CryIA(b), CryIA(c), Cry IIA, CryIIIA, alkali on limed substrates. CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their com 0466 As already mentioned above, it is possible to treat all binations; hereinbelow “Bt plants'). Other traits which are plants and their parts in accordance with the invention. In a particularly emphasized are the increased defense of plants preferred embodiment, wild plant species or plant varieties against fungi, bacteria and viruses by the systemic acquired and plant cultivars which have been obtained by traditional resistance (SAR), systemin, phytoalexins, elicitors and resis biological breeding methods, such as hybridization or proto tance genes and correspondingly expressed proteins and tox plast fusion, and the parts of these varieties and cultivars are ins. Other traits which are especially emphasized are the treated. In a further preferred embodiment, transgenic plants increased tolerance of the plants to certain herbicidal active and plant cultivars which have been obtained by recombinant compounds, for example imidazolinones, Sulfonylureas, gly methods, if appropriate in combination with conventional phosate or phosphinotricin (for example "PAT gene). The methods (genetic modified organisms), and their parts are genes which confer the desired traits in each case may also be treated. The term “parts” or “parts of plants' or “plant parts” present in the transgenic plants in combination with one has been explained above. another. Examples of “Bt plants” which may be mentioned 0467 Plants which are treated particularly preferably in are maize cultivars, cotton cultivars, soybean cultivars and accordance with the invention are those of the plant cultivars potato cultivars which are commercially available under the which are in each case commercially available or in use. Plant trade names YIELD GARDR (for example maize, cotton, cultivars are understood as meaning plants with new traits soybeans), KnockCutR) (for example maize), StarLink R. (for which have been bred either by conventional breeding, by example maize), Bollgard(R) (cotton), Nucotnir (cotton) and mutagenesis or by recombinant DNA techniques. They may New LeafR (potato). take the form of cultivars, biotypes and genotypes. 0470 Examples of herbicide-tolerant plants which may be 0468. Depending on the plant species or plant cultivars, mentioned are maize cultivars, cotton cultivars and Soybean their location and growth conditions (soils, climate, vegeta cultivars which are commercially available under the trade tion period, nutrition), the treatment according to the inven names Roundup Ready R (tolerance to glyphosate, for tion may also result in superadditive (“synergistic) effects. example maize, cotton, soybean), Liberty Link. R (tolerance Thus, for example, reduced application rates and/or a wid to phosphinotricin, for example oilseed rape), IMIR (toler ened activity spectrum and/oran increase in the activity of the ance to imidazolinones) and STSR) (tolerance to sulfony Substances and compositions which can be used in accor lureas, for example maize). Herbicide-resistant plants (plants dance with the invention, better plant growth, increased tol bred in a conventional manner for herbicide tolerance) which erance to high or low temperatures, increased tolerance to may be mentioned also include the varieties commercially drought or to Salinity in the water or soil, increased flowering available under the name Clearfield(R) (for example maize). performance, facilitated harvesting, accelerated maturation, Naturally, these statements also apply to plant cultivars hav higher yields, higher quality and/or better nutritional value of ing these genetic traits or genetic traits still to be developed, the harvested products, better storage characteristics and/or which plant cultivars will be developed and/or marketed in processability of the harvested products are possible which the future. exceed the effects which were actually to be expected. 0471. The plants listed can be treated particularly advan 0469. The preferred transgenic plants or plant cultivars tageously according to the invention with the compounds of (those obtained by recombinant methods) to be treated in the general formula I or the active compound mixtures accordance with the invention include all those plants which, according to the invention. The preferred ranges stated above owing to the process of recombinant modification, were given for the active compounds and mixtures also apply to the genetic material which confers particular, advantageous, treatment of these plants. Particular emphasis may be given to valuable traits to these plants. Examples of Such properties the treatment of plants with the compounds or mixtures spe are better plant growth, increased tolerance to high or low cifically mentioned in the present text. temperatures, increased tolerance to drought or to Salinity in 0472. The active compounds according to the invention the water or soil, increased flowering performance, facilitated are not only active against plant, hygiene and stored-product US 2010/0261934 A1 Oct. 14, 2010 29 pests, but also, in the veterinary medicine sector, against capsules, drinks, drenches, granules, pastes, boli, the feed animal parasites (ectoparasites). Such as ixodid ticks, argasid through method, Suppositories, by parenteral administration, ticks, Scab mites, trombi-culid mites, flies (stinging and Suck Such as, for example, by means of injections (intramuscular, ing), parasitic fly larvae, lice, hair lice, bird lice and fleas. Subcutaneous, intravenous, intraperitoneal and the like), These parasites include: implants, by nasal application, by dermal administration, for 0473. From the order of the Anoplurida, for example, Hae example in the form of dipping or bathing, spraying, pouring matopinus spp., Linognathus spp., Pediculus spp., Phtirus on and spotting-on, washing, dusting, and with the aid of spp., Solenopotes spp. shaped articles which comprise active compound. Such as 0474 From the order of the Mallophagida and the sub collars, ear tags, tail marks, limb bands, halters, marking orders Amblycerina and Ischnocerina, for example, Trime devices and the like. nopon spp., Menopon spp., Trinoton spp., Bovicola spp., Wer 0483 When administered to livestock, poultry, domestic neckiella spp., Lepikentron spp., Damalina spp., animals and the like, the active compounds of the formula (I) Trichodectes spp., Felicola spp. can be used as formulations (for example powders, emul 0475. From the order of the Diptera and the sub-orders sions, flowables) which comprise the active compounds in an Nematocerina and Brachycerina, for example, Aedes spp., amount of 1 to 80% by weight, either directly or after dilution Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., by a factor of 100 to 10 000, or they may be used in the form Phlebotomus spp., Lutzomyia spp., Culicoides spp., of a chemical bath. Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., 0484 Furthermore, it has been found that the compounds Haematopota spp., Philipomyia spp., Braula spp., Musca according to the invention have a potent insecticidal action spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., against insects which destroy industrial materials. Morelia spp., Fannia spp., Glossina spp., Caliphora spp., 0485 The following insects may be mentioned by way of Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga example and as being preferred, but without any limitation: spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hip Beetles, such as pobosca spp., Lipoptena spp. and Mellophagus spp. 0486 Hylotrupes bajulus, Chlorophorus pilosis, Anobium 0476. From the order of the Siphonapterida, for example, punctatum, Xestobium rufo villosum, Ptilinus pecticornis, Pulex spp., Ctenocephalides spp., Xenopysla spp. and Cer Dendrobium pertinex, Emobius mollis, Priobium carpini, atophyllus spp. Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus 0477. From the order of the Heteropterida, for example, linearis, Lyctus pubescens, Trogoxylon aequale, Minthes Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus rugicollis, Xvleborus spec. Tryptodendron spec. Apate spp. monachus, Bostrychus capucins, Heterobostrychus brun 0478 From the order of the Blattarida, for example, Blatta neus, Sinoxylon spec., Dinoderus minutus. Orientalis, Periplaneta americana, Blattela germanica and Dermapterans, such as Supella spp. 0487 Sirex juvencus, Urocerus gigas, Urocerus gigas 0479. From the sub-class of the Acaria (Acarina) and the taignus, Urocerus augur: orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblvo Termites, such as mma spp., Boophilus spp., Dermacentor spp., Haemophysa 0488 Kalotermes flavicollis, Cryptotermes brevis, Het lis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus erotermes indicola, Reticulitermes flavipes, Reticulitermes spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. Santonensis, Reticulitermes lucifigus, Mastotermes darwin and Varroa spp. iensis, Zootermopsis nevadensis, Coptotermes formosanus. 0480. From the order of the Actinedida (Prostigmata) and Bristletails, such as Lepisma saccharina. Acaridida (Astigmata), for example, Acarapis spp., Cheyle 0489 Industrial materials are to be understood as mean tiella spp., Ornithochevletia spp., Myobia spp., Psorergates ing, in the present context, non-live materials. Such as, pref spp., Demodex spp., Trombicula spp., Listrophorus spp., erably, synthetic materials, glues, sizes, paper and board, Acarus spp., Tvrophagus spp., Caloglyphus spp., Hypodectes leather, wood and timber products, and paint. spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Oto 0490 The materials to be very particularly preferably pro dectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes tected against attack by insects are wood and timber products. spp., Cytodites spp. and Laminosioptes spp. 0491 Wood and timber products which can be protected 0481. The active compounds of the formula (I) according by the composition according to the invention or mixtures to the invention are also suitable for controlling arthropods comprising Such a composition are to be understood as mean which attack agricultural livestock, such as, for example, ing, for example: construction timber, wooden beams, rail cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, way sleepers, bridge components, jetties, wooden vehicles, rabbits, chickens, turkeys, ducks, geese, honeybees, other boxes, pallets, containers, telephone poles, wood cladding, domestic animals, such as, for example, dogs, cats, cage windows and doors made of wood, plywood, particle board, birds, aquarium fish, and so-called experimental animals, joiner's articles, or wood products which, quite generally, are Such as, for example, hamsters, guinea-pigs, rats and mice. used in the construction of houses or in joinery. By combating these arthropods, it is intended to reduce deaths 0492. The active compounds can be used as such, in the and decreased performances (in meat, milk, wool, hides, form of concentrates or generally customary formulations, eggs, honey and the like), so that more economical and sim Such as powders, granules, Solutions, Suspensions, emulsions pler animal keeping is made possible by using the active or pastes. compounds according to the invention. 0493. The formulations mentioned can be prepared in a 0482 In the veterinary sector, the active compounds manner known per se, for example by mixing the active according to the invention are used in a known manner by compounds with at least one solvent or diluent, emulsifier, enteral administration, for example in the form of tablets, dispersant and/or binder or fixative, water repellent, if appro US 2010/0261934 A1 Oct. 14, 2010 30 priate desiccants and UV stabilizers and, if appropriate, colo and/or drying oils and/or physically drying binders based on rants and pigments and other processing auxiliaries. a natural and/or synthetic resin. 0494 The insecticidal compositions or concentrates used 0503. The synthetic resin used as the binder can be for the protection of wood and wooden materials comprise the employed in the form of an emulsion, dispersion or solution. active compound according to the invention in a concentra Up to 10% by weight of bitumen orbituminous substances tion of 0.0001 to 95% by weight, in particular 0.001 to 60% by can also be used as binders. In addition, colorants, pigments, weight. water repellents, odor-masking Substances and inhibitors or 0495. The amount of the compositions or concentrates anticorrosives known per se and the like can also be employed depends on the species and the occurrence of the employed. insects and on the medium. The optimum rate of application 0504 The composition or the concentrate preferably com can be determined upon use in each case by a test series. prises, in accordance with the invention, at least one alkyd However, in general, it suffices to employ 0.0001 to 20% by resin or modified alkyd resin and/or a drying vegetable oil as weight, preferably 0.001 to 10% by weight, of the active the organochemical binder. Preferably used according to the compound, based on the material to be protected. invention are alkyd resins with an oil content of over 45% by 0496 The solvent and/or diluent used is an organochemi weight, preferably 50 to 68% by weight. cal solvent or solvent mixture and/oran oily or oil-type orga 0505 All or some of the abovementioned binder can be nochemical solvent or solvent mixture of low volatility and/or replaced by a fixative (mixture) or a plasticizer (mixture). a polar organochemical solvent or solvent mixture and/or These additives are intended to prevent volatilization of the water and, if appropriate, an emulsifier and/or wetting agent. active compounds and crystallization or precipitation. They 0497 Organochemical solvents which are preferably preferably replace0.01 to 30% of the binder (based on 100% employed are oily or oil-type solvents having an evaporation of binder employed). 0506. The plasticizers are from the chemical classes of the number of above 35 and a flashpoint of above 30°C., prefer phthalic esters, such as dibutyl phthalate, dioctyl phthalate or ably above 45° C. Substances which are used as such oily and benzylbutyl phthalate, the phosphoric esters, such as tributyl oil-type solvents which have low volatility and are insoluble phosphate, the adipicesters, such as di(2-ethylhexyl) adipate, in water are suitable mineral oils or their aromatic fractions, the Stearates. Such as butyl Stearate or amyl Stearate, the or mineral-oil-containing solvent mixtures, preferably white oleates, such as butyl oleate, the glycerol ethers or relatively spirit, petroleum and/or allylbenzene. high-molecular-weight glycol ethers, glycerol esters and 0498. Substances which are advantageously used are min p-toluenesulfonic esters. eral oils with a boiling range of 170 to 220° C., white spirit 0507 Fixatives are chemically based on polyvinyl alkyl with a boiling range of 170 to 220° C., spindle oil with a ethers, such as, for example, polyvinyl methyl ether, or boiling range of 250 to 350° C., petroleum or aromatics of ketones, such as benzophenone or ethylenebenzophenone. boiling range 160 to 280° C., essence of terpentine and the 0508 Particularly suitable as a solvent or diluent is also like. water, if appropriate as a mixture with one or more of the 0499. In a preferred embodiment, liquid aliphatic hydro abovementioned organochemical solvents or diluents, emul carbons with a boiling range of 180 to 210°C. or high-boiling sifiers and dispersants. mixtures of aromatic and aliphatic hydrocarbons with a boil (0509 Particularly effective protection of wood is achieved ing range of 180 to 220° C. and/or spindle oil and/or by large-scale industrial impregnation processes, for example monochloronaphthalene, preferably C-monochloronaphtha vacuum, double-vacuum or pressure processes. lene, are used. 0510) If appropriate, the ready-to-use compositions can 0500. The organic oily or oil-type solvents of low volatil additionally comprise other insecticides and, if appropriate, ity having an evaporation number of above 35 and a flashpoint additionally one or more fungicides. of above 30° C., preferably above 45° C. can be partially 0511 Suitable additional components which may be replaced by organochemical Solvents of high or medium Vola admixed are, preferably, the insecticides and fungicides men tility, with the proviso that the solvent mixture also has an tioned in WO94/29 268. The compounds mentioned in that evaporation number of above 35 and a flashpoint of above 30° document are expressly part of the present application. C., preferably above 45°C., and that the insecticide/fungicide 0512 Very particularly preferred components which may mixture is soluble or emulsifiable in this solvent mixture. be admixed are insecticides, such as chlorpyriphos, phoxim, 0501. In a preferred embodiment, part of the orga Silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta nochemical Solvent or solvent mixture or an aliphatic polar methrin, permethrin, imidacloprid, NI-25, flufenoxuron, organochemical Solvent or solvent mixture is replaced. Sub hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxid, stances which are preferably used are aliphatic organochemi triflumuron, chlothianidin, spinosad, tefluthrin, cal Solvents having hydroxyland/or ester and/or ether groups, and fungicides, such as epoxyconazole, hexaconazole, aza Such as, for example, glycol ethers, esters and the like. conazole, propiconazole, tebuconazole, cyproconazole, met 0502. The organochemical binders used within the scope conazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2- of the present invention are the synthetic resins and/or bind propynylbutyl carbamate, N-octyl-isothiazolin-3-one and ing drying oils which are known perse and can be diluted with 4,5-dichloro-N-octylisothiazolin-3-one. water and/or are soluble or dispersible or emulsifiable in the 0513. The compounds according to the invention can at organochemical solvents employed, in particular binders the same time be employed for protecting objects which come composed of, or comprising, an acrylate resin, a vinyl resin, into contact with salt water or brackish water, in particular for example polyvinyl acetate, polyester resin, polyconden hulls, screens, nets, buildings, moorings and signaling sys sation or polyaddition resin, polyurethane resin, alkyd resin tems, against fouling. or modified alkyd resin, phenol resin, hydrocarbon resin, Such 0514 Fouling by sessile Oligochaeta, such as Serpulidae, as indenefcoumarone resin, silicone resin, drying vegetable and by shells and species from the Ledamorpha group (goose US 2010/0261934 A1 Oct. 14, 2010 barnacles). Such as various Lepas and Scalpellum species, or for example, those described in Ungerer, Chem. Ind. 1985, by species from the Balanomorpha group (acorn barnacles), 37, 730-732 and Williams, Antifouling Marine Coatings, Such as Balanus or Policipes species, increases the frictional Noyes, Park Ridge, 1973. drag of ships and, as a consequence, leads to a marked 0522 Besides the algicidal, fungicidal, molluscicidal increase in operation costs owing to higher energy consump active compounds and insecticidal active compounds accord tion and additionally frequent residence in the dry dock. ing to the invention, antifouling paints comprise, in particular, 0515 Apart from fouling by algae, for example Ectocar binders. pus sp. and Ceramium sp., fouling by sessile Entomostraka 0523 Examples of recognized binders are polyvinyl chlo groups, which come under the generic term Cirripedia (cir ride in a solvent system, chlorinated rubber in a solvent sys riped crustaceans), is of particular importance. tem, acrylic resins in a solvent system, in particular in an 0516 Surprisingly, it has now been found that the com aqueous system, vinyl chloride/vinyl acetate copolymer sys pounds according to the invention, alone or in combination tems in the form of aqueous dispersions or in the form of with other active compounds, have an outstanding antifouling organic solvent systems, butadiene/styrenefacrylonitrile rub action. bers, drying oils such as linseed oil, resin esters or modified 0517. Using the compounds according to the invention, hardened resins in combination with tar orbitumens, asphalt alone or in combination with other active compounds, allows and epoxy compounds, Small amounts of chlorine rubber, the use of heavy metals such as, for example, in bis(trialkyl chlorinated polypropylene and vinyl resins. tin) sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, 0524. If appropriate, paints also comprise inorganic pig copper(I) oxide, triethyltin chloride, tri-n-butyl-(2-phenyl-4- ments, organic pigments or colorants which are preferably chlorophenoxy)tin, tributyltin oxide, molybdenum disulfide, insoluble in salt water. Paints may furthermore comprise antimony oxide, polymeric butyl titanate, phenyl-(bispyri materials such as rosin to allow controlled release of the dine)-bismuth chloride, tri-n-butyltin fluoride, manganese active compounds. Furthermore, the paints may comprise ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, plasticizers, modifiers which affect the rheological properties Zinc ethylenebisthiocarbamate, Zinc salts and copper salts of and other conventional constituents. The compounds accord 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc ing to the invention or the abovementioned mixtures may also ethylenebisthiocarbamate, zinc oxide, copper(I) ethylenebi be incorporated into self-polishing antifouling systems. Sdithiocarbamate, copper thiocyanate, copper naphthenate 0525. The active compounds are also suitable for control and tri-butyltin halides to be dispensed with, or the concen ling animal pests, in particular insects, arachnids and mites, tration of these compounds to be substantially reduced. which are found in enclosed spaces such as, for example, 0518) If appropriate, the ready-to-use antifouling paints dwellings, factory halls, offices, vehicle cabins and the like. can additionally comprise other active compounds, prefer They can be employed in domestic insecticide products for ably algicides, fungicides, herbicides, molluscicides, or other controlling these pests alone or in combination with other antifouling active compounds. active compounds and auxiliaries. They are active against 0519 Preferably suitable components in combination sensitive and resistant species and against all development with the antifouling compositions according to the invention stages. These pests include: a. 0526. From the order of the Scorpionidea, for example, algicides such as Buthus Occitanus. 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5- 0527. From the order of the Acarina, for example, Argas triazine, dichlorophen, diuron, endothal, fentin acetate, iso persicus, Argas reflexus, Bryobia ssp., Dermanyssus galli proturon, methabenzthiaZuron, oxyfluorfen, quinoclamine nae, Glyciphagus domesticus, Ornithodorus moubat, Rhipi and terbutryn; cephalus sanguineus, Trombicula alfreddugesi, Neutron fungicides such as bicula autumnalis, Dermatophagoides pteronissimus, benzobthiophenecarboxylic acid cyclohexylamide S.S.-di Dermatophagoides forinae. oxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynylbutylcar 0528. From the order of the Araneae, for example, Avicu bamate, tolylfluanid and azoles such as lariidae, Araneidae. aZaconazole, cyproconazole, epoxyconazole, hexaconazole, 0529. From the order of the Opiliones, for example, Pseu metconazole, propiconazole and tebuconazole; doscorpiones chelifer, Pseudoscorpiones cheiridium, Opil molluscicides such as iones phalangium. fentin acetate, metaldehyde, methiocarb, niclosamid, thiodi 0530. From the order of the Isopoda, for example, Oniscus carb and trimethacarb. Fechelates: asellus, Porcellio Scaber: or conventional antifouling active compounds Such as 0531. From the order of the Diplopoda, for example, Bla 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodometh niulus guttulatus, Polydesmus spp. ylparatryl sulfone, 2-(N,N-dimethyl-thiocarbamoylthio)-5- 0532. From the order of the Chilopoda, for example, Geo nitrothiaZyl, potassium, copper, Sodium and Zinc salts of philus spp. 2-pyridinethiol 1-oxide, pyridine/triphenylborane, tetrabu 0533. From the order of the Zygentoma, for example, tyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-py Ctenolepisma spp., Lepisma saccharina, Lepismodes inquili ridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthi S. uram disulfide and 2,4,6-trichlorophenylmaleimide. 0534. From the order of the Blattaria, for example, Blatta 0520. The antifouling compositions used comprise the Orientalies, Blattella germanica, Blattella asahinai, Leu active compound according to the invention of the com cophaea maderae, Panchlora spp., Parcoblatta spp., pounds according to the invention in a concentration of 0.001 Periplaneta australasiae, Periplaneta americana, Periplan to 50% by weight, in particular 0.01 to 20% by weight. eta brunnea, Periplaneta fuliginosa, Supella longipalpa. 0521. Moreover, the antifouling compositions according 0535. From the order of the Saltatoria, for example, to the invention comprise the customary components such as, Acheta domesticus. US 2010/0261934 A1 Oct. 14, 2010 32

0536 From the order of the Dermaptera, for example, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesba Forficula auricularia. nia, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, 0537 From the order of the Isoptera, for example, Kalo Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, termes spp., Reticulitermes spp. Xanthium. 0538 From the order of the Psocoptera, for example, Lepi 0550 Dicotyledonous crops of the genera: Arachis, Beta, natus spp., LipOscelis spp. Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, 0539 From the order of the Coleptera, for example, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicoti Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus ana, Phaseolus, Pisum, Solanum, Vicia. Oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, 0551 Monocotyledonous weeds of the genera: Aegilops, Sitophilus granarius, Sitophilus Oryzae, Sitophilus zeanais, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Stegobium paniceum. Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dacty 0540 From the order of the Diptera, for example, Aedes loctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, spp., Caliphora erythrocephala, Chrysozona pluvialis, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboelia, Drosophila spp., Fannia canicularis, Musca domestica, Phle Sagittaria, Scirpus, Setaria, Sorghum. botomus spp., Sarcophaga carnaria, Simulium spp., Sto 0552 Monocotyledonous crops of the genera: Allium, moxys calcitrans, Tipula paludosa. Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Sac 0541. From the order of the Lepidoptera, for example, charum, Secale, Sorghum, Triticale, Triticum, Zea. Achroia grisella, Galleria mellonella, Plodia interpunctella, 0553. However, the use of the active compounds accord Tinea cloacella, Tinea pellionella, Tineola bisselliella. ing to the invention is in no way restricted to these genera, but 0542. From the order of the Siphonaptera, for example, extends in the same manner to other plants. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, 0554. Depending on the concentration, the active com Tunga penetrans, Xenopsylla cheopis. pounds according to the invention are Suitable for the nonse 0543. From the order of the Hymenoptera, for example, lective weed control on, for example, industrial terrains and Camponotus herculeanus, Lasius fitliginosus Lasius niger, railway tracks and on paths and locations with and without Lasius umbratus, Monomorium pharaonis, Paravespula spp., trees. Likewise the active compounds according to the inven Tetramorium caespitum. tion can be employed for controlling weeds in perennial (0544. From the order of the Anoplura, for example, crops, for example forests, ornamental tree plantings, Pediculus humanus capitis, Pediculus humanus corporis, orchards, vineyards, citrus groves, nut orchards, banana plan Phthirus pubis. tations, coffee plantations, teaplantations, rubber plantations, 0545 From the order of the Heteroptera, for example, oil palm plantations, cocoa plantations, soft fruit plantings Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Tri and hop fields, on lawns, turf and pastureland, and for the atoma infestans. selective control of weeds in annual crops. 0546. They are used in the household insecticides sector 0555. The compounds of the formula (I) according to the alone or in combination with other suitable active compounds invention have strong herbicidal activity and a broad activity Such as phosphoric esters, carbamates, pyrethroids, neonico spectrum when used on the Soil and on aerial plant parts. To a tinoids, growth regulators or active compounds from other certain extent, they are also suitable for the selective control known classes of insecticides. of monocotyledonous and dicotyledonous weeds in mono 0547. They are used in aerosols, pressure-free spray prod cotyledonous and dicotyledonous crops, both pre- and post ucts, for example pump and atomizer sprays, automatic fog emergence. ging systems, foggers, foams, gels, evaporator products with 0556. At certain concentrations or application rates, the evaporator tablets made of cellulose or polymer, liquid evapo active compounds according to the invention can also be rators, gel and membrane evaporators, propeller-driven employed for controlling animal pests and fungal or bacterial evaporators, energy-free, or passive, evaporation systems, plant diseases. If appropriate, they can also be used as inter moth papers, moth bags and moth gels, as granules or dusts, mediates or precursors for the synthesis of other active com in baits for spreading or in bait stations. pounds. The active compounds can be converted into the 0548. The active compounds according to the invention customary formulations, such as Solutions, emulsions, wet can also be used as defoliants, desiccants, haulm killers and, table powders, Suspensions, powders, dusting agents, pastes, in particular, as weedkillers. Weeds in the broadest sense are soluble powders, granules, Suspoemulsion concentrates, understood as meaning all plants which grow at locations natural and synthetic materials impregnated with active com where they are undesired. Whether the substances according pound, and very fine capsules in polymeric Substances. to the invention act as nonselective or selective herbicides 0557. These formulations are produced in a known man depends essentially on the application rate. ner, for example by mixing the active compounds with 0549. The active compounds according to the invention extenders, that is liquid solvents and/or solid carriers, option can be used, for example, in the following plants: ally with the use of surfactants, that is emulsifiers and/or Dicotyledonous weeds of the genera: Abutilon, Amaranthus, dispersants and/or foam-formers. Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, 0558 If the extender used is water, it is also possible to Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopo use, for example, organic solvents as auxiliary solvents. Suit dium, Cirsium, Convolvulus, Datura, Desmodium, Emex, able liquid solvents are essentially: aromatics, such as Xylene, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibis toluene or alkylnaphthalenes, chlorinated aromatics and cus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matri chlorinated aliphatic hydrocarbons, such as chlorobenzenes, caria, Mentha, Mercurialis, Mulugo, Myosotis, Papaver; chloroethylenes or methylene chloride, aliphatic hydrocar Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, bons, such as cyclohexane or paraffins, for example petro US 2010/0261934 A1 Oct. 14, 2010

leum fractions, mineral and vegetable oils, alcohols, such as Sulam, diethatyl (-ethyl), difenZoquat, diflufenican, butanol or glycol, and also their ethers and esters, ketones, diflufenZopyr, dimefuron, dimepiperate, dimethachlor, Such as acetone, methyl ethyl ketone, methyl isobutyl ketone dimethametryn, dimethenamid, dimexyflam, dinitramine, or cyclohexanone, strongly polar solvents, such as dimethyl diphenamid, diduat, dithiopyr, diuron, dymron, epropodan, formamide and dimethyl sulfoxide, and also water. EPTC, esprocarb, ethal fluralin, ethametsulfuron (-methyl), 0559 Suitable solid carriers are: for example ammonium ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, salts and ground natural minerals, such as kaolins, clays, talc, fenoxaprop (-P-ethyl), fentraZamide, flamprop (-isopropyl. chalk, quartz, attapulgite, montmorillonite or diatomaceous -isopropyl-L, -methyl), flaZaSulfuron, florasulam, fluazifop earth, and ground synthetic minerals, such as finely divided (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flu silica, alumina and silicates, Suitable solid carriers for gran cetosulfuron, flumetSulam, flumiclorac (-pentyl), flumiox ules are: for example crushed and fractionated natural rocks azin, flumipropyn, flumetSulam, fluometuron, fluorochlori Such as calcite, marble, pumice, Sepiolite and dolomite, and done, fluoroglycofen (-ethyl), flupoxam, flupropacil, also synthetic granules of inorganic and organic meals, and flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluri granules of organic material Such as sawdust, coconut shells, done, fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol. maize cobs and tobacco stalks; suitable emulsifiers and/or flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foam-formers are: for example non-ionic and anionic emul foramsulfuron, glufosinate (-ammonium), glyphosate (-iso sifiers, such as polyoxyethylene fatty acid esters, polyoxyeth propylammonium), halosafen, haloxyflop (-ethoxyethyl, -P- ylene fatty alcohol ethers, for example alkylaryl polyglycol methyl), hexazinone, HOK-201, imazamethabenz (-methyl), ethers, alkylsulfonates, alkyl Sulfates, arylsulfonates and pro imaZamethapyr, imaZamox, imaZapic, imazapyr, imaZaquin, tein hydrolysates; Suitable dispersants are: for example ligno imazethapyr, imaZosulfuron, iodosulfuron (-methyl, -so Sulfite waste liquors and methylcellulose. dium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, 0560 Tackifiers such as carboxymethylcellulose and isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, natural and synthetic polymers in the form of powders, gran linuron, MCPA, mecoprop, mefenacet, mesosulfurone, ules or latices, such as gum arabic, polyvinyl alcohol and mesotrione, metamifop, metamitron, metaZachlor, metha polyvinyl acetate, and also natural phospholipids, Such as benzthiaZuron, metobenzuron, metobromuron, (alpha-) cephalins and lecithins, and synthetic phospholipids, can be metolachlor, metoSulam, metoxuron, metribuzin, metSulfu used in the formulations. Other possible additives are mineral ron (-methyl), molinate, monolinuron, naproanilide, and vegetable oils. napropamide, neburon, nicosulfuron, norflurazon, orbencarb, 0561. It is possible to use colorants such as inorganic orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfu pigments, for example iron oxide, titanium oxide and ron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, 0562 Prussian Blue, and organic colorants, such as pendimethalin, pendralin, penoXSulam, pentoxaZone, phen alizarin colorants, azo colorants and metal phthalocyanine medipham, picolinafen, pinoxaden, piperophos, pretilachlor, colorants, and trace nutrients such as salts of iron, manganese, primisulfuron (-methyl), profluaZol, prometryn, propachlor, boron, copper, cobalt, molybdenum and zinc. propanil, propaquizafop, propisochlor, propoxycarbazone (-Sodium), propyZamide, prosulfocarb, prosulfuron, 0563 The formulations generally comprise between 0.1 pyraflufen (-ethyl), pyrasulfotole, pyrazogyl, pyrazolate, and 95 percent by weight of active compound, preferably pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyribu between 0.5 and 90%. ticarb, pyridate, pyridatol, pyriftalide, pyriminobac (-me 0564. The active compounds according to the invention, as thyl), pyrithiobac (-Sodium), pyrimisulfan, quinchlorac, such or in their formulations, can also be used for weed quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), control purposes as a mixture with known herbicides and/or rimsulfuron, Sethoxydim, simazine, simetryn, Sulcotrione, with Substances which improve crop plant tolerance (“safen SulfentraZone, Sulfometuron (-methyl), Sulfosate, Sulfosulfu ers'), ready mixes or tank mixes being possible. Mixtures ron, tebutam, tebuthiuron, tembotrione, tepraloxydim, ter with herbicide products which contain one or more known buthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr. herbicides and a safener are hence also possible. thidiazimin, thiencarbazone-methyl, thifensulfuron (-me Herbicides which are Suitable for the Mixtures are Known thyl), thiobencarb, tiocarbazil, toprameZone, tralkoxydim, Herbicides, for Example triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiph acetochlor, acifluorfen (-Sodium), aclonifen, alachlor, alloxy ane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tri dim (-Sodium), ametryne, amicarb-aZone, amidochlor, ami tosulfuron, trifloSulam, dosulfuron, aminopyralid, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), bencarbazone, benfuresate, bensulfuron (-methyl), benta Zone, benzfendizone, benzobicyclon, benzofenap, benzoyl prop (-ethyl), bialaphos, bifenox, bispyribac (-Sodium), bro mobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentraZone (-ethyl), chlom ethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodin afop (-propargyl), clomaZone, clomeprop, clopyralid, clopy rasulfuron (-methyl), cloranSulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cycloSulfamuron, cycloxy KIH485 dim, cyhalofop (-butyl), 2,4-D, 2.4-DB, desmedipham, dial late, dicamba, dichlorprop (—P), diclofop (-methyl), diclo US 2010/0261934 A1 Oct. 14, 2010 34

0565. A mixture with other known active compounds, include, as further additives in the formulations, mineral or Such as fungicides, insecticides, acaricides, nematicides, bird vegetable oils which are tolerated by plants (for example the repellents, plant nutrients and Soil conditioners, is also pos commercial preparation "Rako Binol), or ammonium salts, sible. Such as, for example, ammonium sulfate or ammonium thio 0566. The active compounds or active compound combi cyanate. nations can be applied as such, in the form of their formula 0572 The novel active compound combinations can be tions or the use forms prepared therefrom by further dilution, used as such, in the form in of their formulations or the use Such as ready-to-use Solutions, Suspensions, emulsions, pow forms prepared therefrom by further dilution, such as ready ders, pastes and granules. They are applied in the customary to-use Solutions, Suspensions, emulsions, powders, pastes manner, for example by pouring, spraying, atomizing, and granules. Application is in the customary manner, for spreading. example by pouring, spraying, atomizing, dusting or scatter 0567 The active compounds or active compound combi 1ng. nations according to the invention can be applied both before 0573 The application rates of the active compound com and after plant emergence. They can also be incorporated into binations according to the invention can be varied within a the soil prior to planting. certain range; they depend, interalia, on the weather and on soil factors. In general, the application rates are between 0568. The application rate of active compound can vary 0.001 and 5 kg perha, preferably between 0.005 and 2 kg per within a substantial range. Essentially, it depends on the ha, particularly preferably between 0.01 and 0.5 kg per ha. nature of the desired effect. In general, the application rates 0574. The active compound combinations according to are between 1 g and 10 kg of active compound per hectare of the invention can be applied before and after emergence of the soil area, preferably between 5g and 5 kg per ha. plants, that is to say by the pre-emergence and post-emer 0569. The advantageous effect of the compatibility with gence method. crop plants of the active compound combinations according 0575 Depending on their properties, the safeners to be to the invention is particularly pronounced at certain concen used according to the invention can be used forpretreating the tration ratios. However, the weight ratios of the active com seed of the crop plant (seed dressing) or can be introduced pounds in the active compound combinations can be varied into the seed furrows prior to Sowing or be used separately within relatively wide ranges. In general, salts from 0.001 to prior to the herbicide or together with the herbicide, before or 1000 parts by weight, preferably from 0.01 to 100 parts by after emergence of the plants. weight, particularly preferably 0.05 to 20 parts by weight, of 0576 Examples of plants which may be mentioned are one of the compounds which improves crop plant compatibil important crop plants, such as cereals (wheat, barley, rice), ity (antidotes/safeners) mentioned above under (b") are maize, soybeans, potatoes, cotton, oilseed rape, beet, Sugar present perpart by weight of active compound of the formula cane and also fruit plants (with the fruits apples, pears, citrus (I). fruits and grapevines), greater emphasis being given to maize, 0570. The active compound combinations according to Soybeans, potatoes, cotton and oilseed rape. the invention are generally applied in the form of finished 0577. The term “active compounds' always also includes formulations. However, the active compounds contained in the active compound combinations mentioned here. the active compound combinations can, as individual formu 0578 Preparation and use of the active compounds lations, also be mixed during use, i.e. be applied in the form of according to the invention is illustrated by the examples tank mixes. below. 0571 For certain applications, in particular by the post- (0579 Compounds of the formula (I-a) known from WO emergence method, it may furthermore be advantageous to O 1/74. 770

(I-a) OH C2H5 A B N CH3 D1 N O CHs

Ex. No. D A. B m. p. Isomer I-a-1 H -(CH2)2 CHOCH -(CH2)2 - 244 B I-a-2 H —(CH2)2—CHOCHS (CH2)2— 212 B I-a-3 H a CH 227-229 -

I-a-4 H C2H5 CH 229-230 - I-a-5 CH C2H5 H 220-224 – I-a-6 D CH H 211-213 –

I-a-7 —(CH2)— H 195-198 I-a-8 —CH2—CHOCH-CH2— H 233 US 2010/0261934 A1 Oct. 14, 2010

-continued (I-a) OH C2H5 A B N CH D1 N O C2H5

Ex. No. D A. B . . Isomer

I-a-9 -CH-CH-CH- H *429 V / (dd. 1H, (CH2)4 Cs—H)— 6.84 (S, 2H, Ar–H) I-a-10 H —(CH2)2—CHCH -(CH2)2— *O.91 (d,3H, CH-B) Spiral cycle 6.84 (s, 2H, Ar–H) I-a-11 H —(CH2)2—CHCF-(CH2)2— Oi log P3.05 *H-NMR (400 MHz, d-DMSO): shifts & in ppm

PREPARATION EXAMPLES mmol) of the compound of preparation example I-a-1 and Example I-b-1 0.049 g (0.48 mmol) of triethylamine and 10 ml of ethyl acetate. The mixture is stirred under reflux for 20h, and the 0580 reaction is monitored by thin-layer chromatography. After the reaction has ended, 2 ml of saturated NaHO solution are added, and the mixture is stirred at room temperature for 10 min. HC 0582 The organic phase is separated off, the solvent is CH3 removed using a rotary evaporator and the precipitate is satu rated with n-heptane. The precipitate is filtered off with suc f isomer tion. 0583. Yield: 0.137 g (76% of theory) 0584) 'H-NMR (300 MHz, CDC1): 8 6.89 (s. 2H, O Ar H), 3.96 (s. 2H, CHOCH), 3.22 (m, 1H, CH-OCH) V ppm. CH3 0585 Analogously to example (I-b-1) and in accordance 0581. Under reflux, 0.052 g (0.48 mmol) of methoxyacetal with the general statements on the preparation, the following chloride in 2 ml of ethyl acetate is added to 0.15 g (0.437 compounds of the formula (I-b) are obtained

(I-b)

O C2H5

N CH3

D O C2H5

Ex. No D A. B RI m. p. C. Isomer I-b-2 H —(CH2)2—CHOCH2—(CH2)2— H5C2 O—CH2— 138-141 B I-b-3 H —(CH2)2—CHOCH2—(CH2)2— i-CH7 182-185 B

US 2010/0261934 A1 Oct. 14, 2010 37

Example I-c-1 Example I-e-1 0586 0590

f isomer

CH 0587 0.21 g (0.6 mmol) of the compound of preparation example (I-a-1) was suspended in 10 ml of dichloromethane, and 0.1 ml of triethylamine and 0.08 g (0.66 mmol) of allyl 0591 0.15 g (0.5 mmol) of the compound of example chloroformate were then added at room temperature. The 1-a-3 is initially charged inacetonitrile (10 ml), and 0.083 g of mixture was stirred over the weekend, and 10 ml of 5% potassium carbonate (1.2 eq) is added. After 30 min, dibu strength sodium carbonate solution was added. After 4 h of tylphosphoryl chloride (0.126 g, 1.1 eq) is added, and the stirring, the organic phase was separated off and concentrated mixture is stirred at TR for 48 h. The solid is filtered with to dryness. The residue obtained in this manner was taken up Suction and the organic solution is concentrated and purified in 1 ml of ethyl acetate, and 2 ml of n-heptane were added. by chromatography (n-heptane/ethyl acetate 9:1 to 1:4). This The solid is filtered off with suction. 0588 Yield: 84 mg (32.7% of theory) m.p.: 155-157° C. gives 82 mg of a colorless oil (yield 32% of theory). 0589 Analogously to example (I-c-1) and in accordance 0592 * 'H-NMR (300 MHz, CDC1): 8–0.21 (m,2H, CH, with the general statements on the preparation, the following from CycPr), compounds of the formula (I-c) are obtained 0593. 6.92 (d. 2H, Ar H)

(I-c) O

--- O C2H5 A B N CH D1 N O CHs

Ex. No D A. B M R2 m. p. C. Isomer c-2 H —(CH2)2—CHOCH -(CH2)2— O C2H5 149 B c-3 H CH CH O CHs 182-184 c-4 CH C2H5 H O CHs *3.03 (s.3H, NCH.) 4.18 (m, 2H, CH2—O) 6.92 (s, 2H, Ar–H) -c-5 C2H5 CH H O CHs *1.47 (d,3H, CHCH.) 4.18 (m, 2H,CH2—O) 6.91 (s, 2H, Ar–H) -c-6 -(CH2) - H O CHs *4.18 (m, 2H, CH-O) 4.74 (dd. 1H, C5-H) 6.92 (d. 2H, Ar–H) -c-7 —CH2—CHOCH-CH2— H O CHs *3.36 (s.3H, OCH) 4.18 (m, 2H, CH2—O) 6.92 (d. 2H, Ar–H) *H-NMR (300 MHz, CDCl3): shifts & in ppm US 2010/0261934 A1 Oct. 14, 2010 38

0594. The compounds of the formula (I-a) can be prepared by the processes described in WO 01/74770:

C2H5 D C2H5 A x C base A N B + HC -- B Y CH N-D O CN O C2H5 C2H5 A. route 1 B solo A CH2115 D CH2115 COAlk C A B + HC Pre- CH3 N-H B / O COAIk O CH5 CH5 Cl route 2 D'

(I-a)

0595. Here, the substituents A, B and D are as defined 0601 A palladium (O) compound which may be men above and Alk represents C-C-alkyl, preferably methyl or tioned by way of example is bis-(dibenzylideneacetone)-pal ethyl. ladium. 0596 Analogously to G. C. Lloyd-Jones, Angew. Chem. 0602 Acids which may be mentioned are organic acids, Int. Ed. 2002, 41, 953-956; S. L. Buchwald, W. A. Moradi, for example formic acid, or inorganic acids, for example JACS 2001, 123, 7996-8002 and S. Lee, N. A. Beare, J. F. hydrochloric acid or sulfuric acid. Hartwig JACS 2001, 123, 8410-84.11, an improved process 0603 The reaction temperature in the process according to for preparing 2,6-diethyl-4-methylphenyl acetic acid was the invention may be varied within a relatively wide range. In found. general, the process is carried out at temperatures between 0597. The process is characterized in that 2,6-diethyl-4- -80° C. and +150° C., preferably between 0° C. and 100° C. methylbromobenzene is reacted with tert-butyl acetate, if 0604. When carrying out the process according to the invention, the starting materials are generally each employed appropriate in the presence of a diluent, if appropriate in the in approximately equivalent amounts. presence of a base, if appropriate in the presence of a phos 0605. A further process for preparing 2,6-diethyl-4-meth phine ligand and if appropriate in the presence of palladium ylphenylacetic acid comprises the reaction of 2,6-diethyl-4- (0) compounds, and then reacted with an acid. methylphenylmalodinitrile with acids, if appropriate in the 0598 Suitable diluents for use in the process according to presence of a diluent, and the Subsequent reaction with an the invention are all solvents which are inert to the reagents. acid. Preference is given to using hydrocarbons, such as benzine, 0606 Suitable acids are mineral acids, for example con benzene, toluene, Xylene and tetraline, furthermore ethers, centrated Sulfuric acid. such as diethyl ether, dimethoxyethane, tetrahydrofuran and 0607. The reaction temperature may be varied within a dioxane. relatively wide range. In general, the process is carried out at 0599 Suitable bases for the reaction according to the pro temperatures between 0 and 150° C. The starting materials cess according to the invention are lithium amide bases, pref are generally each employed in approximately equivalent erably lithium hexyldisilazide, lithium diisopropylamide, amountS. lithium dicyclohexylamide. 0608. By reacting 2,6-diethyl-4-methylphenylacetic acid 0600 Suitable phosphine ligands are, for example, in par with halogenating agents, if appropriate in the presence of a ticular tri-tert-butylphosphine and 2-dicyclohexylphosphino diluent, 2,6-diethyl-4-methylphenylacetyl chloride is (2'-N,N-dimethylamino)biphenyl. obtained (WO 01/74770). US 2010/0261934 A1 Oct. 14, 2010 39

Component D' Component D' Route 1 Route 2 0609 0615

H3C CH3 O CH3 RC CH O o1 3 f isomer O HN H3C OCH CH3 CH3 O O 0610 3.6 g (7.5 mmol) of component B' and 30 ml of HC1 dichloromethane are added dropwise to 2.32 ml of sulfuric acid. The mixture is stirred at 35° C. for 2 hours, and 3.25 ml 0616. At 20°C., 12 g (100.1 mmol) of thionyl chloride are of methanol are added. The mixture is stirred at 60° C. for 6 added to 4.13 g (20 mmol) of 2,6-diethyl-4-methylphenylace hours and left at room temperature overnight. The reaction tic acid in 20 ml of toluene. The mixture is stirred under reflux mixture is poured into water and extracted with dichlo for 2 hand the solvent is distilled off. The residue is dissolved romethane. The solvent is distilled off and the residue is taken in 20 ml of tetrahydrofuran and, at 0 to 5°C., added dropwise up in ethyl acetate/n-heptane 1:4. The residue is filtered off to a Suspension of 4.48 g of methyl 1-amino-4-methoxycy with suction through a frit, washed with ethyl acetate/n-hep clohexanecarboxylic hydrochloride (0.020 mol) and 6.1 ml tane 1:4, dried (0.5 g), and the solvent is removed using a (44 mmol) of triethylamine and 100 ml of tetrahydrofuran. rotary evaporator. The residue of the mother liquor is purified by column-chromatographic separation (silica gel, ethyl 0617 The mixture is stirred at 40°C. for 1 h (monitored by acetate/n-heptane 1:4-> 1:1. The fractions are concentrated TLC). The solvent is removed using a rotary evaporator. The using a concentrated evaporator, stirred with ethyl acetate/n- residue is purified by column chromatography on silica gel heptane 1:9 for 10 minutes and filtered off with suction (hexane:ethyl acetate, 2:1). through a frit, and the filter cake is washed with n-heptane and 0618. Yield: 5.9 g (72% of theory), m.p. 113°C. dried (0.85g). 0611 Total yield: 1.35 g (52% of theory), m.p. 95°C. Example I-a-1 Component B' 0619 0612

O CH HN H3C 21 RC f isomer & O OH HC1 CH3 O HC CH CH3 0620. At 60° C., 5.7g of component D' (route 2) in 15 ml 0613 1.3 g of 2-amino-2-cyclopropylpropionitrile and of dimethylactamide are added to 3.9 g of potassium tert 1.64 ml of triethylamine are initially charged in 50 ml of butoxide in 20 ml of dimethylacetamide. The mixture is tetrahydrofuran. With ice-cooling, 2.66 g of 2,6-diethyl-4- stirred at 80° C. and the reaction is monitored by TLC. The methylphenylacetyl chloride in 50 ml of tetrahydrofuran are reaction solution is added to 200 ml of ice-water, the pH is added, and the mixture is stirred for 3 days with monitoring adjusted to 2 using concentrated hydrochloric acid and the by thin-layer chromatography. The triethylamine hydrochlo precipitate is filtered off with suction. The precipitate is puri ride is filtered off with suction, the solvent is removed under fied using methyl tert-butyl ether/hexane. reduced pressure and the residue is used without further puri 0621. The product is purified by column chromatography fication for preparing the components D' (route 1). on silica gel (dichloromethane; ethyl acetate, 3:1). 0614 Yield: 3.65 g (58 of theory) 0622 Yield: 5 g (97% of theory) US 2010/0261934 A1 Oct. 14, 2010 40

Preparation of 2,6-Diethyl 4-MethylphenylAcetic Acid concentrated sulfuric acid and 48 ml of water at 140°C. for 24 h. After cooling, the mixture is repeatedly extracted with Component K dichloromethane and the extracts are washed twice with 0623 water, dried (sodium sulfate) and concentrated. This gives 18.8g of colorless crystals of melting point 116 to 117°C. (0628 'H-NMR (CDC1, 300 MHz): 8–1.19 (t, 6H), 2.28 CH3 (s, 3H), 2.60 (q, 4H), 3.73 (s. 2H), 6.90 (s. 2H) Methyl 2,6-diethyl-4-methylphenylacetate 0629 1 ml of concentrated sulfuric acid is added to 18.0 g HC CH (87.3 mmol) of 2,6-diethyl-4-methylphenylacetic acid and 300 ml of absolute methanol, and the mixture is heated at O reflux for 4 h. After cooling, the mixture is extracted with ethyl acetate, the extracts are washed with water in sodium carbonate solution and dried (magnesium Sulfate) and the HC O solvent is distilled off. This gives 18.37 g of (95%) of the desired product as a colorless oil. CHK. 0630 "H-NMR (CDC1, 300 MHz): 8–1.20 (t, 6H), 2.32 (s, 3H), 2.62 (1, 4H), 3.67 (s, 3H), 2.72 (s. 2H), 6.93 (s. 2H) 0624. At 15°C., 5.6 g of tert-butyl acetate were added to Use Examples 57.2 mmol of a freshly prepared lithium dicyclohexylamide Example A Solution. During the addition, the temperature increased from 15o C. to 250 C. 1. Herbicidal Pre-Emergence Action 0625. After 10 min, a degassed mixture of 10 g of 2.6- 0631 Seeds of monocotyledonous and dicotyledonous diethyl-4-methylbromobenzene and 0.253 g of bis(diben weed and crop plants are placed in Sandy loam in wood fiber Zylideneacetone)palladium and 0.089 g of tri-tert-butylphos pots and covered with soil. The test compounds, formulated phine as a 0.5 molar solution in toluene was added. Over a in the form of wettable powders (WP), are then, as an aqueous period of 30 min, the temperature increased to 35° C., and suspension with a water application rate of 600 l/ha (con over a period of half an hour, the temperature then cooled to verted), with 0.2% of wetting agent added, applied to the 28°C. The reaction mixture was put into a mixture of 10 ml Surface of the covering soil in various dosages. of hydrochloric acid and 200 ml of water, and 400 ml of 0632. After the treatment, the pots are placed in a green dichloromethane were added. After 30 min of stirring, the house and kept under good growth conditions for the test solid was separated off and washed with dichloromethane. plants. The visual assessment of the emergence damage on The organic phase was removed from the mother liquor and the test plants is carried out after a trial period of 3 weeks by dried with magnesium sulfate. Column filtration on silica gel comparison with untreated controls (herbicidal effect in per using ethyl acetate/n-heptane 1:6 gave 12.1 g of product. The cent (%): 100% effect—the plants have died, 0% effect—like viscous oil was reacted further without further purification. control plants). 0633. In addition to the examples explicitly mentioned, CH the following compounds, at an application rate of 320 g/ha, show an activity of 280% against Avena sativa, Lolium mul tiflorum and Setaria viridis: I-a-8, I-a-9, I-b-5, I-b-13, I-b-14, I-c-3. 2. Herbicidal Post-Emergence Action 0634. Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into Sandy loam in wood fiber pots, covered with soil and cultivated in a greenhouse under OH good growth conditions. Two-three weeks after Sowing, the 0626. At room temperature, 12 g of component K were test plants are treated at the one-leaf stage. The test com stirred in 100 ml of formic acid for 2 h. The mixture was then pounds, formulated as wettable powders (WP), are then, in poured into 400 ml of ice-water and stirred for 30 min, and the various dosages with a water application rate of 600 l/ha solid formed was filtered with suction. For drying, the residue (converted), with 0.2% of wetting agent added, sprayed onto was taken up in dichloromethane and this solution was dried the green parts of the plants. After the test plants have been with magnesium sulfate. After concentration, the residue was kept in the greenhouse under optimum growth conditions for digested in a little n-heptane and filtered off with suction. This about 3 weeks, the effect of the preparations is rated visually gave 8.2 g of 2,6-diethyl-4-methylphenylacetic acid, which in comparison to untreated controls (herbicidal effect in per corresponds to a total yield of 90% over all steps. M. p. 124° cent (%): 100% effect—the plants have died, 0% effect—like C. control plants). 0635. In addition to the examples explicitly mentioned, 2,6-Diethyl-4-methylphenylacetic acid the following compounds, at an application rate of 320 g/ha, show an activity of 280% against Avena sativa, Echinochloa 0627. Under an atmosphere of argon, 20.0 g of 2,6-di crus-galli, Lolium multiflorum and Setaria viridis: I-a-2, I-a- ethyl-4-methylphenylmalodinitrile (94.2 mmol), known 4, I-a-8, I-a-10, I-b-3, I-b-4, I-b-5, I-b-6, I-b-7, I-b-8, I-b-11, from WO 00/78712, are heated in a mixture of 128 g of I-b-13, I-b-14, I-c-3, I-c-4, I-c-5, I-c-6. US 2010/0261934 A1 Oct. 14, 2010

g of Greenhouse a.i./ha Alopect truts Avenafatua Loium Setaria Veronica

Ex. No. I-b-1 post-emergence 8O 100 100 100 100 8O g of Greenhouse a.i./ha Alopecurits Echinochloa Loium Setaria Veronica

Ex. No. I-c-2 pre-emergence 8O 90 100 100 90 post-emergence 8O 100 100 100 100 8O g of Greenhouse a.i./ha Alopect truts Avenafatua Echinochloa Lolium Setaria

Ex. No. pre-emergence 8O 100 60 100 100 100 I-c-1 post-emergence 8O 100 90 100 100 100 g of Greenhouse a.i./ha Alopect truts Avenafatua Loium Setaria Veronica

Ex. No. pre-emergence 32O 100 90 100 100 100 I-b-2 post-emergence 8O 100 100 100 100 70

Example B 2. Herbicidal Post-Emergence Action Container trials with cereal in a greenhouse 0636 Seeds of monocotyledonous and dicotyledonous Post-OSt-emergence 9. treatment weed and crop plants are placed into sandy loam in wood fiber Application Summer barley pots or in plastic pots, covered with soil and cultivated in a g of a.i./ha observed (%) greenhouse, during the vegetation period also outdoors out- Example 50 93 side of the greenhouse, under good growth conditions. Two- I-a-1 25 60 three weeks after sowing, the test plants are treated at the one- Example 5 oiOO 3. to three-leaf stage. The test compounds, formulated as wet- I-a-1 + 25 - 1 OO 2O table powders (WP) or liquid (EC) are, in various dosages mefenpyr 12.5 + 100 10 with a water application rate of 3001/ha (converted), with Example 25 60 wetting agent (0.2 to 0.3%)%) added,added sprayedd onto the plantsplant ExampleI-c-1 25 12.5- 1 OO 4035 and the surface of the soil. Three-four weeks after the treat- I-c-1 + 12.5 + 100 25 ment of the test plants, the effect of the preparations is rated mefenpyr visually in comparison to untreated controls (herbicidal effect in percent (%): 100% effect—the plants have died, 0% effect—like control plants). Use of Safeners Mefenpyr 1 day prior to herbicide application 28 days after application 0637. If it is additionally to be tested as to whether safeners can improve the plant compatibility of test Substances in the Application Summer wheat case of crop plants, the following options are used for apply- g of a.i./ha observed (%) ing the safener: Example 25 90 0638 seeds of the crop plants are, before sowing, I-b-1 dressed with the safener substance (the amount of Eple 25 - 1 OO 50 Safener stated in percent, based on the weight of the mefenpyr seed) 0639 before the application of the test substances, the 28 days after application crop plants are sprayed with the safener at a certain Application Summer barley Summer wheat application rate per hectare (usually 1 day before the g of a.i./ha observed (%) observed (%) application of the test Substances) Example 50 50 0640 the safener is applied together with the test sub- I-a-2 25 25 8O stance as a tank mix (the amount of safener is stated in 12.5 40 g/ha or as a ratio, based on the herbicide). Example SO - 100 2O I-a-2 + 25 - 100 10 40 0641 By comparing the effect of the test substances on mefenpyr 125 + 100 O crop plants without or with safener treatment, it is possible to assess the effect of the safener substance. US 2010/0261934 A1 Oct. 14, 2010 42

0650. After the desired period of time, the activity in % is -continued determined. 100% means that all spider mites have been killed, 0% means that none of the spider mites have been Mefenpyr 1 day prior to herbicide application killed. 28 days after application 0651. In this test, for example, the following compounds Application Summer wheat of the preparation examples, at application rates of 100 g/ha g of a.i./ha observed (%) ofa.i., show an activity of 270% after 5 d: I-a-4, I-b-1, I-b-2, I-c-3, I-c-4, I-c-7. Example 12.5 95 I-b-2 Example 12.5 + 100 30 Example E I-b-2 + mefenpyr Meloidogyne Test—(Spray Treatment)

Example C 0652 Myzus Test—(Spray Treatment) Solvent: 80 parts by weight of acetone 0642 0653) To produce a suitable preparation of active com pound, 1 part by weight of active compound is mixed with the Solvents: 78 parts by weight of acetone stated amounts of solvent, and the concentrate is diluted with 1.5 parts by weight of dimethylformamide water to the desired concentration. Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether 0654 Vessels are filled with sand, solution of active com pound, Meloidogyne incognita egg/larva Suspension and let 0643) To produce a suitable preparation of active com tuce seeds. The lettuce seeds germinate and the plants pound, 1 part by weight of active compound is mixed with the develop. On the roots, galls are formed. stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired con 0655. After the desired period of time, the nematicidal centration. activity is determined in % by the formation of galls. 100% 0644. Disks of Chinese cabbage (Brassica pekinensis) means that no galls have been found: 0% means that the which are infested by all stages of the green peach aphid number of galls on the treated plants corresponds to that of the (Myzus persicae) are sprayed with a preparation of active untreated control. compound of the desired concentration. 0656. In this test, for example, the following compounds 0645. After the desired period of time, the activity in % is of the preparation examples, at an application rate of 20 ppm determined. 100% means that all aphids have been killed, 0% ofa.i., show an activity of 270% after 14 d: I-b-2. means that none of the aphids have been killed. 0646. In this test, for example, the following compounds Example F of the preparation examples, at 500 g/ha of a.i... show an activity of 290% after 5 d: I-a-2, I-a-10, I-a-11, I-b-1, I-b-2. Phaedon Test (PHAECO Spray Treatment) Example D 0657 Tetranychus Test—(OP-Resistance/Spray Treatment) Solvents: 78 parts by weight of acetone (0647 1.5 parts by weight of dimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

Solvents: 78 parts by weight of acetone 0658. To produce a suitable preparation of active com 1.5 parts by weight of dimethylformamide pound, 1 part by weight of active compound is mixed with the Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired con 0648. To produce a suitable preparation of active com centration. pound, 1 part by weight of active compound is mixed with the 0659 Disks of Chinese cabbage (Brassica pekinensis) are stated amounts of solvents and emulsifier, and the concentrate sprayed with a preparation of active compound of the desired is diluted with emulsifier-containing water to the desired con concentration and, after drying, populated with larvae of the centration. mustard beetle (Phaedon cochleariae). 0649. Disks of bean leaves (Phaseolus vulgaris) infested 0660. After the desired period of time, the effect in % is by all stages of the greenhouse red spider mite (Tetranychus determined. 100% means that all beetle larvae have been urticae) are sprayed with a preparation of active compound of killed; =% means that none of the beetle larvae have been the desired concentration. killed. US 2010/0261934 A1 Oct. 14, 2010

0661. In this test, for example, the following compounds stated amount of solvent and the stated amount of emulsifier, of the preparation examples, at application rates of 500 g/ha and the concentrate is diluted with water to the desired con ofa.i., show an activity of 280% after 7 d: I-a-2, I-a-11, I-b-1, centration. I-b-2. 0668 Soybean shoots (Glycine max) of the cultivar Roundup Ready (trademark of Monsanto Comp. USA) are Example G treated by being dipped into the preparation of active com Critical Concentration Test/Soil Insects—Treatment pound of the desired concentration and are populated with the tobacco butterworm Heliothis virescens while the leaves are of Transgenic Plants still moist. 0662 0669. After the desired period of time, the kill of the insects is determined. 1-18. (canceled) Test insect: Diabiotica baiteata - larvae in the soil Solvent: 7 parts by weight of acetone 19. A method for preparing 2,6-diethyl-4-methylpheny Emulsifier: 1 part by weight of alkylaryl polyglycol ether lacetic acid, comprising reacting 2,6-diethyl-2-methylbro mobenzene with tert-butyl acetate, optionally in the presence of a base, a phosphine ligand, a palladium compound and a 0663 To produce a suitable preparation of active com diluent, and then reacting with an acid. pound, 1 part by weight of active compound is mixed with the 20. A process for preparing 2,6-diethyl-4-methylpheny stated amount of solvent, the stated amount of emulsifier is lacetic acid, comprising reacting 2,6-diethyl-4-methylphe added and the concentrate is diluted with water to the desired nylmalononitrile with an acid, optionally in the presence of a concentration. diluent. 0664. The preparation of active compound is poured onto 21. The method according to claim 19, wherein said base is the soil. Here, the concentration of active compound in the a lithium amide base. preparation is virtually immaterial; only the amount by 22. The method according to claim 21, wherein said base is weight of active compound per Volume unit of soil, which is lithium hexyldisilazide, lithium diisopropylamide or lithium stated in ppm (mg/l) matters. The soil is filled into 0.251 pots, dicyclohexylamide. and these are allowed to stand at 20° C. 23. The method according to claim 19, wherein said phos 0665 Immediately after the preparation, 5 pregerminated phine ligand is tri-tert-butylphosphine or 2-dicyclohexy maize corns of the cultivar YIELD GUARD (trademark of lphosphino (2'-N,N-dimethylamino)biphenyl. Monsanto Comp., USA) are placed into each pot. After 2 24. The method according to claim 19, wherein said palla days, the appropriate test insects are placed into the treated dium compound is bis(dibenzylideneacetone)palladium. soil. After a further 7 days, the efficacy of the active com pound is determined by counting the maize plants that have 25. The method according to claim 19, wherein said acid is emerged (1 plant=20% activity). an organic or inorganic acid. 26. The method according to claim 25, wherein said acid is Example H formic acid, hydrochloric acid or sulfuric acid. 27. The method according to claim 19, wherein said diluent Heliothis virescens Test Treatment of Transgenic is a hydrocarbon. Plants 28. The method according to claim 27, wherein said diluent 0666 is selected from the group consisting of benzine, benzene, toluene, Xylene, tetraline, diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane. 29. The method according to claim 20, wherein said acid is Solvent: 7 parts by weight of acetone a mineral acid acid. Emulsifier: 1 part by weight of alkylaryl polyglycol ether 30. The method according to claim 29, wherein said acid is concentrated Sulfuric acid. 0667 To produce a suitable preparation of active com pound, 1 part by weight of active compound is mixed with the c c c c c