BRPI0920543B1 - The invention relates to a bicyclic 1,3-dioxane derivative substituted by phenyl alcohol, its intermediates, its preparation processes and their uses, compositions and method of preparation thereof, and methods for controlling pests and / or undesirable vegetation, and for increasing the activity of pesticides and / OR HERBICIDES - Google Patents

Description

Report of the Invention Patent for "CYCLO-OCTANE-1,3-DIONA DERIVATIVES SUBSTITUTED BY PHENYL, ITS INTERMEDIARIES, THEIR PREPARATION PROCESSES AND THEIR USES, COMPOSITIONS, AND THEIR PREPARATION PROCESS, AND METHODS FOR CONTROLING OR PICKING UNDESIRED, AND TO INCREASE ACTIVITY OF PESTICIDES AND / OR HERBICIDES ". The present invention relates to novel phenyl substituted bicyclooctane-1,3-dione derivatives, various processes for their preparation and their use as pesticides and / or herbicides. The invention further relates to novel combinations of selective herbicidal active substances which contain, on the one hand, phenyl-substituted bicyclooctane-1,3-dione derivatives and, on the other hand, at least one compound which enhances compatibility with crop plants, and can be used with success particularly good for selective weed control in various useful plant crops. The present invention further relates to enhancing the effect of plant protection agents which contain, in particular, phenyl-substituted bicyclooctane-1,3-dione derivatives by the addition of ammonium or phosphonium salts and, optionally penetrating agents, the corresponding agents, processes for preparing them and applying them to plant protection as a pest control agent and / or to prevent the growth of undesirable plants.

Certain substituted 2-arylcyclopetandions are known to have herbicidal, insecticidal and acaricidal properties (comp. For example, US-4 283 348; 4,338 122; 4,436,666; 4,526,723; 4,551,547; 4,632,698; WO 96/01 798, WO 96/03 366, WO 97/14 667 and also WO 98/39281, WO 99/43649, WO99 / 48869, WO 99/55673, WO 01/17972, WO 01/74770, WO 03 / 062244, WO 04/080962, WO04 / 111042, WO05 / 092897, WO06 / 029799, W007 / 080066, W007 / 096058, WO 09/019005 and WO 09/019015). Also similar compounds are known to be substituted: 3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1-one from the publication of Micklefield et. al., Tetrahedron, (1992), 7519-26 and Following is sheet 1a / 215 the natural product Involution (-) - cis-5- (3,4-dihydroxyphenyl) -3,4-dihydroxy- 2- (4-hydroxyphenyl) -cyclopent-2-en-one from Edwards et al., J. Chem. Soc. S, (1967), 405-9. No insecticidal or acari-acidic action is described. In addition, 2- (2,4,6-trimethylphenyl) -1,3-indandione is known from J. Economic Entomology publication, 66 (1973), 584 and DE-A 2,361,084. indication of herbicidal and acaricidal activities.

But the efficiency and spectrum of action of these compounds are not always fully satisfactory, particularly at low application rates and concentrations. Moreover, plant compatibility of these compounds is not always sufficient.

Novel compounds of formula (I) have now been found wherein X represents alkyl, cycloalkyl or alkoxy, Y represents hydrogen, alkyl or alkoxy, Z represents hydrogen, alkyl or cycloalkyl, where A and B together with the carbon atom to which they are attached represent a saturated or unsaturated, unsubstituted or substituted cycle optionally containing at least one heteroatom, or A and B together with the carbon atom to which they are attached represent a carbonyl group, a C1 -C4 group. alkylene or a group = N-OR9, G represents hydrogen (a) or represents one of the groups in which E represents a metal ion equivalent or an ammonium ion, L represents oxygen or sulfur, M represents oxygen or sulfur, R1 represents alkyl alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, in each case optionally substituted by halogen, or cycloalkyl, optionally substituted by halogen, alkyl or alkoxy, which may be r is interrupted by at least one heteroatom, phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, in each case optionally substituted, 2 R represents alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, in each case optionally substituted by halogen, or represents cycloalkyl, phenyl or benzyl, in each case optionally substituted, 3. R, R and R independently of one another represent alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio in each case optionally substituted by halogen, or represent phenyl, benzyl, phenoxy or phenylthio in each case optionally substituted, R 7 and R 7 independently of each other represent hydrogen, in each case represent alkyl, cycloalkyl, alkenyl, alkoxy, optionally halogen substituted alkoxy, represent phenyl in each case optionally substituted by benzyl, or together with the N atom to which they are attached represent a cycle optionally substituted by oxygen or sulfur, R 9 represents hydrogen, in each case optionally substituted by alkyl, cycloalkyl, CH 2 -cycloalkyl, alkenyl, alkynyl, arylalkyl or hetarylalkyl.

Depending on the type of the substituents, the compounds of formula (I) may also be presented as geometric and / or optical isomers or mixtures of isomers, in different composition, which optionally may be separated in the usual manner. Both pure isomers as well as mixtures of isomers, the production and use thereof, and the agents containing them, are the object of the present invention. However, for the sake of simplicity, the following are always referred to as compounds of formula (I), although optionally pure compounds may also mean mixtures with different fractions of isomeric compounds.

Depending on the position of substituent G, the compounds of formula (I) may be in the two isomeric forms of formulas (1-A) and (1-B), which shall be shown by the dashed line in formula (I).

The compounds of formulas (1-A) and (1-B) may be presented as mixtures as well as in their pure isomers. Mixtures of the compounds of formulas (1-A) and (1-B) optionally may also be separated by physical methods, for example by chromatographic methods.

For the sake of clarity, hereinafter only one of the possible isomers is described in each case. This does not exclude the fact that the compounds may optionally be in the form of isomer mixtures or, in each case, in the other isomeric form.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (la) to (lg) result: which 1 2 3 4 5 6 7 A, B, E, L, Μ, X, Y, Z, R, R, R, R, R, R and R have the meanings indicated above.

Another form of stereoisomer results from the cis-bonding of the two five-membered carbocyclic rings, namely, especially where the two substituents A and B in formula (Ia) are not identical.

The isomers found in this case are hereinafter referred to as "sin" and "anti" depending on whether the substituent A or B to be prioritized according to Cahn-Ingold-Prelog rules is in the anti or sin position. cyclopentandione ring. Two examples of such isomeric forms in the compounds of formula (Ia) are mentioned below: anti-isomer synisomer In addition, it has been found that the new compounds of formula (I) are obtained according to one of the processes described below: (A) Compounds of formula (la) in which A, Β, X, Y and Z have the meaning given above are obtained when intramolecularly cyclizing esters of ketocarboxylic acid of formula (II) in which A, Β, X, Y and Z have the meaning given above, and R 8 represents alkyl (particularly C 1 -C 8 alkyl) optionally in the presence of a diluent and in the presence of a base. In addition, it has been found that (B) compounds of the formula (1b) shown above are obtained, wherein A, B, R 1, X, Y and Z have the meanings indicated above, when reacting compounds of the formula (la) shown above. where A, Β, X, Y and Z have the meaning given above, in each case (a) with acid halides of formula (III) wherein R1 has the meaning given above and Hal represents halogen or (β) with carboxylic anhydrides of formula (IV) wherein R 1 has the meaning given above, optionally in the presence of a diluent and optionally in the presence of an acid binder; (C) that the compounds of formula (1c) shown above are obtained, in which A, B, R, Μ, X, Y and Z have the meaning indicated above and L represents oxygen when compounds are reacted. of formula (la) shown above, wherein A, B, X, Y and Z have the meaning given above in each case with chloroform acid esters or chloroform acid thioesters of formula (V) R2-M-CO- CI (V) wherein 2 R and M have the meaning given above, optionally in the presence of a diluent and optionally in the presence of an acid binder; (D) which are obtained compounds of formula (1c) shown at -2 above, wherein A, B, R, Μ, X, Y and Z have the meaning given above and L represents sulfur when compounds of formula (1) are reacted. la) shown above, in which A, B, X, Y and Z have the meaning given above, in each case with chloromonothioformic acid esters or chlorodithioformic acid esters of formula (VI) wherein 2 M and R have the meaning given above, optionally in the presence of a diluent and optionally in the presence of an acid binder; (E) which compounds of formula (1d) shown above are obtained, wherein A, B, R, X, Y and Z have the meaning indicated above when reacting compounds of formula (1a) shown above, wherein A , B, X, Y and Z have the meaning given above in each case with sulfonyl chlorides of the formula (VII) R3-SO2-Cl (VII) wherein 3 R has the meaning indicated above, optionally in the presence of a diluent and optionally in the presence of an acid binder, (F) compounds of formula (le) are shown above, wherein A, B, L, R, R, X, Y and Z have the meaning given above when reacting compounds of the formula (1a) shown above, wherein A, B, X, Y and Z have the meaning indicated above in each case with phosphorus compounds of the formula (VIII) in which . L, R and R have the meaning given above, and Hal represents halogen, optionally in the presence of a diluent and optionally in the presence of an acid binder, (G) which compounds of formula (If) shown above are obtained. wherein A, B, E, X, Y and Z have the meaning given above when and react compounds of formula (la), wherein A, B, X, Y and Z have the meaning given above in each case with metal or amine compounds in each case of formulas (IX) and (X) wherein Me represents a mono- or divalent metal (preferably an alkaline or alkaline earth metal such as lithium, sodium, potassium magnesium or calcium), t is 1 or 2, and 10-12 R, R, R independently of one another are hydrogen or alkyl (preferably C1 -C6 alkyl), optionally in the presence of a diluent (H) which are obtained compounds of the formula (lg) shown above, R 7 wherein A, B, L, R, R, X, Y and Z have the meaning indicated above, which The compounds of formula (Ia) shown above are reacted wherein A, B, X, Y and Z have the meanings indicated above, in each case (a) with isocyanates or isothiocyanates of formula (XI) R 6 -N = C = L (XI) wherein R6 and L have the meanings indicated above, optionally in the presence of a diluent and optionally in the presence of a catalyst, or (β) with carbamide chlorides or thiocarbamide chlorides of formula (XII) wherein R1 and R2 have the meaning indicated above, optionally in the presence of a diluent and optionally in the presence of an acid binder.

Furthermore, it has been found that the novel compounds of formula (I) have very good efficiency as pesticides, preferably as insecticides, acaricides and herbicides.

Surprisingly it has now also been found that certain substituted cyclic ketoenols, in conjunction with the crop enhancing compound (antidote) compounds described below, very effectively prevent damage to crop plants and can be used particularly well. It is advantageous as broad-effective combination preparations for the selective control of undesirable plants in useful plant crops, such as, for example, cereals, but also maize, potatoes, soybeans and rice.

Selective herbicides, which contain an efficient content of a combination of active substances, comprising as components (a ') at least one compound of formula (I), wherein A, B, G, X, Y and Z have the meaning given above, and (b ') at least one compound which enhances compatibility with crop plants (antidote).

Antidotes are preferably selected from the group consisting of symbols and indices having the following meanings: nA is a natural number from 0 to 5, preferably 0 to 3;

Ra1 is halogen, (C1-C4) alkyl, (C1-C4) alkoxy, nitro or (C1-C4) haloalkyl; WA is a divalent, unsubstituted or substituted heterocyclic radical of the group of partially unsaturated or aromatic five-membered heterocycles having 1 to 3 ring heteroatoms of the group N and O, with at least one atom of N and, in the at most one O atom is contained in the ring, preferably a radical of the group (WA1) to (WA4) mA is 0 or 1;

Ra2 is ORa3, SRa3 or NRa3Ra4 or a 3 to 7 membered saturated or unsaturated heterocycle with at least one N atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is bonded by nitrogen atom to the carbonyl group in (S1) and which is unsubstituted or substituted by radicals of the group consisting of (C1 -C4) alkyl, (C1 -C4) alkoxy and phenyl, optionally substituted, preferably a radical of the formula ORA3, NHRA4 or N (CH3) 2, particularly of formula O-Ra3;

Ra3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably 1 to 18 C atoms, Ra4 is hydrogen, substituted or unsubstituted (C1 -C6) alkyl, (C1 -C6) alkoxy phenyl ;

Ra5 is H, (C1 -C8 alkyl), (C1 -C8) haloalkyl, (C1 -C4) alkoxy (C1 -C8) alkyl, cyano or COORA9, where RA9 is hydrogen, (C1 -C8) - (C 1 -C 8) alkylhaloalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, (C 1 -C 4 hydroxyalkyl, (C 3 -C 12) cycloalkyl or tri- (C 1 -C 4) alkylsilyl;

Ra6, Ra7, Ra8 are the same or different and are substituted or unsubstituted (C1 -C8) alkyl, (C1 -C8) haloalkyl, (C3 -C2) cycloalkyl or phenyl; preferably: a) dichlorophenylpyrazolin-3-carboxylic acid type compounds (S1a), preferably compounds such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-1-one 3-Carboxylic, 1- (2,4-Dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (S1-1) ("mefenpyridiethyl"), and compounds related, as described in WO-A-91/07874; b) dichlorophenylpyrazolecarboxylic acid derivatives (S1b), preferably compounds such as 1- (2,4-dichlorophenyl) -5-methylpyrazol-3-carboxylic acid ethyl ester (S1-2), ethyl acid ester 1 - (2,4-dichlorophenyl) -5-isopropylpyrazol-3-carboxylic acid (S1-3), 1- (2,4-dichlorophenyl) -5- (1,1-dimethylethyl) pyrazole acid ethyl ester -3-carboxylic acid (S1-4) and related compounds as described in EP-A-333 131 and EP-A-269 806; c) 1,5-diphenylpyrazol-3-carboxylic acid derivatives (S1c), preferably compounds such as 1- (2,4-dichlorophenyl) -5-phenylpyrazol-3-carboxylic acid ethyl ester (S1c) 5), 1- (2-chlorophenyl) -5-phenylpyrazol-3-carboxylic acid methyl ester (S1-6) and related compounds as described, for example, in EP-A-268554; d) triazolecarboxylic acid (S1d) -type compounds, preferably compounds such as phenochlorazole (-ethyl), ie 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1-ethyl ester 2,4-triazole-3-carboxylic acid (S1-7), and related compounds as described in EP-A-174,562 and EP-A-346,620; e) 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid-type compounds of 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (Si), preferably compounds such as 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-9) and related compounds as described in WO-A-91/08202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or 5,5-diphenyl-2-isoxazolinecarboxylic acid ethyl ester (S1-11) ("isoxadifen-ethyl") or 5-diphenyl-2-isoxazolinecarboxylic acid n-propyl ester (S1-12) or 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-ethyl ester -carboxylic (S1-13) as described in WO-A-95/07897. S2) Quinoline derivatives of formula (S2) wherein the symbols and indices have the following meanings: Rb1 is halogen, (C1 -C4) alkyl, (C1 -C4) alkoxy, nitro or (C1 -C4) haloalkyl ; nB is a natural number from 0 to 5, preferably from 0 to 3;

Rb2 is ORb3, SRb3 or NRb3Rb4 or a 3 to 7 membered saturated or unsaturated heterocycle, with at least one nitrogen atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is bonded via from the nitrogen atom to the carbonyl group in (S2) and which is unsubstituted or substituted by radicals from the group consisting of (C1 -C4) alkyl, (C1 -C4) alkoxy and phenyl, optionally substituted, preferably a radical of the formula ORb3, NHRb4 or N (CH3) 2, particularly of formula ORb3;

Rb3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms; Rb4 is hydrogen, substituted or unsubstituted (C1 -C6) alkyl, (C1 -C6) alkoxy or phenyl;

Tb is a (C 1 -C 2) alkandyl chain which is unsubstituted or substituted by one or two (C 1 -C 4) alkyl radicals or by [(C 1 -C 3) alkoxy] carbonyl radicals; preferably: a) 8-quinolinoxyacetic acid (S2a) type compounds, preferably (1-methylhexyl) (5-chloro-8-quinolinoxy) acetic acid ("cloquintocet-mexylic") ester (S2-1) (5-Chloro-8-quino-linoxy) acetic acid (1,3-dimethyl-but-1-yl) ester (S2-2), 4-allyloxy-butyl ester (5-chloro-8-yl) (5-chloro-8-quinolin-1-yl) acetic acid (S2-3), (5-chloro-8-quinoline-1-yl) acetic acid (S2-4), (5-chloro) 8-quinolinoxy) acetic acid (S2-5), (5-chloro-8-quinolinoxy) acetic acid methyl ester (S2-6), allyl (5-chloro-8-quinolinoxy) acetic acid ester (S2-7) (5-Chloro-8-quinolinoxy) acetic acid, 2- (2-propyliden-iminoxy) -1-ethyl ester (S-2-8), 2-oxo-prop-1-yl ester 8-quinolinoxy) acetic (S2-9) and related compounds as described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, and also acid (5-chloro-8-quinolinoxy) acetic (S2-10), its hydrates and salts, for example, their lithium salts, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO-A-2002/34048; b) (5-chloro-8-quinolinoxy) malonic acid-type compounds (S2b), preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-diallyl acid ester) -chloro-8-quinolinoxy) malonic, (5-chloro-8-quinolinoxy) malonic acid methyl ethyl ester and relational compounds as described in EP-A-0 582 198. S3) Compounds of formula (S3) in which the index symbols have the following meanings: Rc1 is (C1 -C4) alkyl, (C1 -C4) haloalkyl, (C2 -C4) alkenyl, (C2 -C4) halo (C3 -C7) cycloalkyl, preferably dichloromethyl;

Rc2, Rc3 are the same or different and are hydrogen, (C1-C4) -alkyl, (C2-C4) -alkenyl, (C2-C4) -alkyl, (C1-C4) -haloalkyl, (C2-C4) -haloalkenyl, ( (C 1 -C 4) -alkylcarbamoyl- (C 1 -C 4) alkyl, (C 2 -C 4) alkenylcarbamoyl- (C 1 -C 4) alkyl, (C 1 -C 4) alkyl (C 1 -C 4) alkyl, dioxolanyl (C 1 -C 4) C4) -alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or Rc2 and Rc3 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine ring, piperidine, morpholine, hexahydropyrimidine or benzoxazine; preferably: dichloroacetamide-like active substances, which are often used as pre-emergence antidotes (soil-active antidotes), such as, for example "dichlormid" (N, N-diallyl-2,2-dichloroacetamide) (S3 -1), "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2- Stauffer (S3-3) dimethyl-1,3-oxazolidine), "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine), (S3-4), "PPG-1292" (N-allyl-N - [(1,3-dioxolan-2-yl) methyl] dichloroacetamide) from PPG Industries (S3-5), "DKA-24" (N-allyl-N- [ (allylamocarbonyl) methyl] dichloroacetamide) from Sagro-Chem (S3-6), "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro [4,5] decane) from Nitrokemia or Monsanto (S3-7), "TI-35" (1-dichloroacetylazepan) from TRI-Chemical RT (S3-8) "diclonon" (dicyclonon) or "BAS145138" or "LAB145138" (S3-9) (3- dichloroacetyl-2,5,5-trimethyl-1,3-diaza-bicyclo [4.3.0] nonane) from BASF, "furilazole" or "MON 13900" ((RS) -3-dichloroacetyl-5- (2-furyl) -2,2-dimethyloxazolidine) (S3-10) and also its (R) isomer (S3-11). S4) N-Acylsulfonamides of formula (S4) and their salts in which symbols and indices have the following meanings: XD is CH or N;

Rd1 is CO-NRd5Rd6 or NHCO-Rd7;

Rd2 is halogen, (C1 -C4) -haloalkyl, (C1 -C4 -haloalkoxy, nitro, (C1 -C4) alkyl, (C1 -C4) alkoxy, (C1 -C4 -alkylsulfonyl, (C1 -C4) -alkoxycarbonyl or (C1-C4) ) alkylcarbonyl;

R d 3 is hydrogen, (C 1 -C 4) alkyl, (C 2 -C 4) alkenyl or (C 2 -C 4) alkyl;

Rd4 is halogen, nitro, (C1 -C4) alkyl, (C1 -C4) haloalkyl, (C1 -C4) haloalkoxy, (C3 -C6) cycloalkyl, phenyl, (C1 -C4) alkoxy, cyano, (C1 -C4) alkylthio, (C1 -C4) alkylsulfinyl, (C1 -C4) alkylsulfonyl, (C1 -C4) alkoxycarbonyl or (C1 -C4) alkylcarbonyl;

Rd5 is hydrogen, (C1 -C6) -alkyl, (C3 -C6) -cycloalkyl, (C2-C6) -alkyl, (C2-C6) -alkyl, (C5-C6) -cycloalkenyl, phenyl or heterocyclyl of 3 to 5. 6-membered vD containing heteroatoms of the group consisting of nitrogen, oxygen and sulfur, the last seven mentioned radicals being replaced by vD substituents of the group consisting of halogen, (C1 -C6) alkoxy, (CrC6) - haloalkoxy, (C1 -C2) alkylsulfinyl, (C1 -C2) alkylsulfonyl, (C3 -C6) cycloalkyl, (C1 -C4) alkoxycarbonyl, (C1 -C4) alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (C1 -C4) alkyl (C1 -C4) haloalkyl; Rd6 is hydrogen, (C1-C6) -alkyl, (C2-C6) -alkenyl or (C2-C6) -alkynyl, the last three mentioned radicals being substituted by vD radicals from the group consisting of halogen, hydroxy, (C1 -C4) alkyl, (C1 -C4) alkoxy and (C1 -C4) alkylthio, or Rd5 and Rd6 together with the nitrogen atom they contain form a pyrrolidinyl or piperidinyl radical;

Rd 7 is hydrogen, (C 1 -C 4) alkylamino, di (C 1 -C 4) alkylamino, (C 1 -C 6) alkyl, (C 3 -C 6) cycloalkyl, with the last 2 mentioned radicals being substituted by vD substituents of the group consisting of halogen, (C1 -C4) alkoxy, halo- (C1 -C6) alkoxy and (C1 -C4) alkylthio and, in the case of cyclic radicals, also (C1 -C4) alkyl and (C1 -C4) haloalkyl; nD is 0, 1 or 2; mD is 1 or 2; vD is 0, 1, 2 or 3, of which N-acylsulfonamides type compounds of formula (S4a) are preferred. below, which are known, for example, from WO-A-97/45016 wherein Rd 7 is (C 1 -C 6) alkyl, (C 3 -C 6) cycloalkyl, with the last 2 mentioned radicals being substituted by vD substituents. of the group consisting of halogen, (C1 -C4) alkoxy, halo (C1 -C6) alkoxy and (C1 -C4) alkylthio and, in the case of cyclic radicals, also (C1 -C4) alkyl and (C1 -C4) alkyl ) -haloalkyl;

Rd4 is halogen, (C1 -C4) alkyl, (C1 -C4) alkoxy, CF3; mD 1 or 2; vD is 0, 1, 2 or 3; and also acylsulfamoylbenzamides, for example of formula (S4b) below, which are known, for example, from WO-A-99/16744, for example those in which Rd5 = cyclopropyl and (Rd4) = 2-OMe (" cyprosulfamide ", S4-1), Rd5 = cyclopropyl and (RD4) = 5-CI-2-OMe (S4-2), Rd5 = ethyl and (Rd4) = 2-OMe (S4-3), Rd5 = isopropyl and (Rd4) = 5-CI-2-OMe (S4-4) and Rd5 = isopropyl and (RD4) = 2-OMe (S4-5) and also N-acylsulfamoylphenyl urea type compounds of the formula (S4C), which are EP-A-365484, wherein Rd8 and Rd9 independently of each other are hydrogen, (C1-C8) -alkyl, (C3-C8) -cycloalkyl, (C3-C6) -alkenyl, ( C3 -C6) -alkyl, Rd4 is halogen, (C1 -C4) alkyl, (C1 -C4) alkoxy, CF3, mD is 1 or 2; for example 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoyl sulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea. 55) Active substances of the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), eg 3,4,5-triacetoxybenzoic acid ethyl ester, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5 -dihydroxybenzoic acid, 4-hydroxyisalicylic acid, 4-fluororsalicylic acid, 2-hydroxycinnamic acid, 1,2-dihydro-2-oxo-6-trifluoromethylpyridin-3-carboxamide, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001. 56) Active substances of the 1,2-dihydroquinoxalin-2-one class (S6), eg 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, 1 -methyl-3- (2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2-aminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxalin-2 -one-hydrochloride, 1- [2- (diethylamino) ethyl] -6,7-dimethyl-3-thiophen-2-yl-quinoxalin-2 (1 H) -one, 1- (2-methylsulfonylaminoethyl) -3- (2-thienyl) -1,2-dihydroxy-noxalin-2-one, as described in WO-A-2005/112630. 57) Compounds of formula (S7) as described in WO-A-1998/38856, wherein the symbols and indices have the following meanings: Re1, Re2 independently of each other are halogen, (C1 -C4) alkyl (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkylamino, di (C 1 -C 4) alkylamino, nitro;

Ae is COORe3 or COSRe4 Re3, Re4 independently of each other are hydrogen, (C1 -C4) alkyl, (C2 -C6) alkenyl, (C2 -C4) alkynyl, cyanoalkyl, (C1 -C4) haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl or alkylammonium, εε1 isOoul; nE2, nE3 independently of each other are 0, 1 or 2, preferably diphenylmethoxyacetic acid ethyl diphenylmethoxyacetic acid ester, diphenylmethoxyacetic acid methyl ester (CAS Reg. No .: 41858-19-9) (S7-1). S8) Compounds of formula (S8), as described in WO-A-98/27049, wherein XF is CH or N, nF is, if XF = N, an integer from 0 to 4 and for XF ser = CH, an integer from 0 to 5, Rf1 is halogen, (C1 -C4) alkyl, (C1 -C4) haloalkyl, (C1 -C4) alkoxy, (C1 -C4) haloalkoxy, nitro, (C 1 -C 4) alkylthio, (C 1 -C 4) alkylsulfonyl, (C 1 -C 4) alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy, R 2 is hydrogen or (C 1 -C 4) alkyl, R 3 is hydrogen, (C 1 -C 7) (C 2 -C 4) -alkyl, (C 2 -C 4) -alkenyl or aryl, each of the carbon-containing radicals mentioned above being unsubstituted or substituted by one or more, preferably by up to three, the same or different radicals, from the group consisting of halogen and alkoxy, or salts thereof, preferably compounds, wherein XF is CH, np is an integer from 0 to 2, Rf1 is halogen, ( (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkyl oxy, Rf2 is hydrogen or (C1 -C4) alkyl, Rf3 is hydrogen, (C1 -C4 alkyl, (C2 -C4) alkenyl, (C2 -C4) alkynyl or aryl, each of which carbon-containing radicals mentioned above are unsubstituted or substituted by one or more, preferably by up to three, the same or different radicals from the group consisting of halogen and alkoxy; or salts thereof, S9) Active substances of the class of 3- (5-tetrazolylcarbonyl) -2-quinolones (S9), for example 1,2-dihydro-4-hydroxy-1-ethyl-3- (5 -tetrazolylcarbonyl) -2-quinolone (CAS Reg. No .: 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg. No .: 95855-008), as described in WO-A-1999/000020. S10) Compounds of formula (S10a) or (S10b) as described in WO-A-2007/023719 and WO-A-2007/023764 wherein Rg1 is halogen, (C1 -C4) alkyl, methoxy, nitro, cyano , CF3, OCF3 YG, ZG independently of each other are O or S, nG is an integer from 0 to 4, Rg2 is (C1 -C6) -alkyl, (C2 -C6) -alkenyl, (C3-C6) -cycloalkyl aryl; benzyl, halobenzyl, Rg3 is hydrogen or (C1 -C6) alkyl. 511) Oxyimino compound-type active compounds (S11), which are known as seed disinfectants, such as, for example, "o-xabetrinyl" ((Z) -1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is known as a seed disinfectant antidote for metolachlor damage, "fluxophenim" (1- (4-chlorophenyl) -2,2,2-trifluor-1-ethanone 0- ( 1,3-dioxolan-2-ylmethyl) oxime) (S11-2), which is known as a seed disinfectant antidote, for millet against metolachlor damage, and "cytometrinyl" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) ace-tonitrile) (S11-3), which is known as a seed disinfectant antidote, for millet against metolachlor damage. 512) Active substances of the isothiochromanone class (S12), such as, for example, methyl - [(3-oxo-1H-2-benzothiopyran-4 (3H) -lidene) methoxy] acetate (CAS Reg. No .: 205121-04-6) (S12-1) and related compounds of WO-A-1998/13361. 513) One or more compounds of the group (S13): "naphthalic anhydride" (S13-1-naphthalenedicarboxylic anhydride) (S13-1), which is known as the corn seed disinfectant antidote against damage by the herbicide thiocarbamate, "fenclorim" ( 4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as an antidote for pretylachlor in rice, "flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate ) (S13-3), which is known as a seed disinfectant antidote for millet against damage by alachlor and metolachlor, "CL-304415" (CAS Reg. No .: 31541-57-8) (4-carboxy-3) acid Cianamid, 4-dihydro-2H-1-benzopyran-4-acetic) (S13-4), which is known as the corn antidote against imidazolinone damage, "MG-191" (CAS Reg. No .: 96420-72-3) Nitrokemia (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5), which is known as the corn antidote, "MG-838" (CAS Registry No .: 133993 -74-5) 2-Propenyl (1-oxa-4-azaspiro [4.5] decan-4-carbodithioate) (S13-6), " disulfotone "(0.0-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7)," β-diethyl) O-phenyl phosphorothioate (S13-8), "methenate" (4-methylcarbamate) (chlorophenyl) (S13-9). 514) Active substances which, in addition to having a beneficial effect against harmful plants, also have an antidote effect on cutlery, such as rice, such as, for example, "dimepiperate" or "MY-93" (S-1- Methyl-phenylethyl-piperidin-1-carbothioate), which is known as a rice antidote against damage by the herbicide molinate, "daimuron" or "SK 23" (1- (1-methyl-1-phenylethyl) -3-p-tolylurea ), which is known as a rice antidote against damage by the herbicide imazosulfurone, "cumiluron" = "JC-940" (3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenyl-ethyl) urea, JP-A-60087254), which is known as a rice antidote against damage by some herbicides, "methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone), which is known as a rice antidote to damage by some herbicides, Kumiai's "CSB" (1-bromo-4- (chloromethylsulfonyl) benzene), (CAS Reg. No. 54091-06-4), which is known as an antidote to damage by some herbicides in rice, 515 ) Active substances which are mainly used as herbicides but also have an antidote effect on crop plants, for example (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid (R S) -α-2- (4-Chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy-butyl) butyric acid (2,4-DB), (4-chloro-o- tolyloxy) acetic (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1- (ethoxycarbonyl) ethyl-3 2,6-Dichloro-2-methoxybenzoate (lactidichloroethyl).

Especially preferred as compounds which enhance compatibility with crop plants (component (b1)) are cloquintocetetyl, phenochlorazole, isoxadifenethyl, mefenpyridyl, phenlorim, cumiluron, S4-1 and S4-5, being particularly highlighted cloquinto-ket-mexilic and mefenpir-diethyl. Also highlighted is cytosulfamide (S4-1).

Examples of the selective herbicide combinations according to the invention, which in each case comprise an active substance of formula (I) and, in each case, one of the antidotes defined above, are listed below: Active substance of formula (I) La-1 cloquintocet-mexican antidote la-1 fenclorazol-ethyl ester la-1 isoxadifen-ethyl la-1 mefenpyriethyl la-1 fenclorim la-1 cumiluron la-1 S4-1 la-1 S4-5 la-2 cloquintocet la-2 fenclorazol-ethyl ester la-2 isoxadifen-ethyl la-2 mefenpyriethyl la-2 phenlorim la-2 cumiluron la-2 S4-1 la-2 S4-5 la-3 cloquintocet-mexilic la-3 fenclorazol-ethyl ester la-3 isoxadifen-ethyl la-3 mefenpyriethyl la-3 phentlorim la-3 cumiluron la-3 S4-1 la-3 S4-5 Active substance of formula (I) la-4 cloquintocet-mexican antidote la-4 phenochlorazol-ethyl ester la-4 isoxadifen-ethyl la-4 mefenpyriethyl la-4 phenochlorim la-4 cumiluron la-4 S4-1 la-4 S4-5 la-5 cloquintocet-m la-5 fenclorazol-ethyl ester la-5 isoxadifen-ethyl la-5 mefenpyriethyl la-5 fenclorim la-5 cumiluron la-5 S4-1 la-5 S4-5 | -a-6 cloquintocet-mexil 6-fenclorazol-ethyl ester la-6 isoxadifen-ethyl la-6 mefenpyriethyl la-6 fenclorim la-6 cumiluron la-6 S4-1 la-6 S4-5 la-7 cloquintocet-mexico la-7 fenclorazol-ethyl ester | -a-7 isoxadifen-ethyl la-7 mefenpyriethyl la-7 phlorphlorine la-7 cumiluron la-7 S4-1 la-7 S4-5 | -a-8 cloquintocet-mexic Active substance of formula (I) Antidote la-8 fenclorazol-ethyl ester la-8 isoxadifen-ethyl la-8 mefenpyriethyl la-8 fenclorim la-8 cumiluron la-8 S4-1 la-8 S4-5 la-9 cloquintocet-mexylic la-9 fenclorazol- ethyl ester la-9 isoxadifen-ethyl la-9 mefenpyr-diethyl la-9 phlorochlorin la-9 cumiluron la-9 S4-1 la-9 S4-5 la-10 cloquintocet-mexico la-10 fenclorazol-ethyl ester la-10 isoxadifen-ethyl la-10 mefenpir-diethyl la-10 fenclorim la-10 cumilu ron la-10 S4-1 la-10 S4-5 la-11 cloquintocet-mexylic la-11 fenclorazol-ethyl ester la-11 isoxadifen-ethyl la-11 mefenpyriethyl la-11 fenclorim la-1 \ cumiluron la-11 S4-1 la-11 S4-5 la-12 cloquintocet-mexylic la-12 fenclorazol-ethyl ester Active substance of formula (I) la-12 isoxadifen-ethyl antidote la-12 mefenpyridyl la-12 fenclorim la-12 cumiluron la-12 S4-1 la-12 S4-5 la-13 cloquintocet-mexylic la-13 fenclorazol-ethyl ester la-13 isoxadifen-ethyl la-13 mefenpyridyl la-13 fenclorim la-13 cumiluron la-13 S4- 1 la-13 S4-5 la-14 cloquintocet-mexican la-14 fenclorazol-ethyl ester la-14 isoxadifen-ethyl la-14 mefenpyriethyl la-14 fenclorim la-14 cumiluron la-14 S4-1 la-14 S4 -5 la-15 cloquintocet-mexicano la-15 fenclorazol-ethyl ester la-15 isoxadifen-ethyl la-15 mefenpyriethyl la-15 fenclorim la-15 cumiluron la-15 S4-1 la-15 S4-5 la-16 cloquintocet-mexylic la-16 fenclorazol-ethyl é ter la-16 isoxadifen-ethyl Active substance of the formula (I) la-16 mefenpyridyl antidote la-16 phentlorim la-16 cumiluron la-16 S4-1 la-16 S4-5 la-17 cloquintocet-mexil la-17 fenclorazol-ethyl ester la-17 isoxadifen-ethyl la-17 mefenpyr-diethyl la-17 fenclorim la-17 cumiluron la-17 S4-1 la-17 S4-5 la-18 cloquintocet-mexic la-18 fenclorazol-ethyl ester la -18 isoxadifen-ethyl la-18 mefenpyr-diethyl la-18 phenochlorin la-18 cumiluron la-18 S4-1 la-18 S4-5 la-19 cloquintocet-mexico la-19 fenclorazol-ethyl ester la-19 isoxadifen-ethyl la-19 mefenpir-diethyl la-19 phenochlorin la-19 cumiluron la-19 S4-1 la-19 S4-5 la-20 cloquintocet-mexylic la-20 fenclorazol-ethyl ester la-20 isoxadifen-ethyl la-20 mefenpiron active ingredient of formula (I) Antidote la-20 phenochlorim la-20 cumiluron la-20 S4-1 la-20 S4-5 la-21 cloquintocet-mexilic la-21 fenclorazol-ethyl ester la-21 isoxadifen-ethyl 21 mef la-21 diethyl la-21 fenclorim la-21 cumiluron la-21 S4-1 la-21 S4-5 la-22 cloquintocet-mexylic la-22 fenclorazol-ethyl ester la-22 isoxadifen-ethyl la-22 mefenpir-diethyl la 22 fenclorim la-22 cumiluron la-22 S4-1 la-22 S4-5 la-23 cloquintocet-mexylic la-23 fenclorazol-ethyl ester la-23 isoxadifen-ethyl la-23 mefenpyridyl la-23 fenclorim la-23 cumiluron la-23 S4-1 la-23 S4-5 la-24 cloquintocet-mexylic la-24 fenclorazol-ethyl ester la-24 isoxadifen-ethyl la-24 mefenpir-diethyl la-24 fenclorim Active substance of formula (I) Antidote la-24 cumiluron la-24 S4-1 la-24 S4-5 la-25 cloquintocet-mexican la-25 fenclorazol-ethyl ester la-25 isoxadifen-ethyl la-25 mefenpyridyl la-25 fenclorim la-25 cumiluron la -25 S4-1 la-25 S4-5 la-26 cloquintocet-mexican la-26 fenclorazol-ethyl ester la-26 isoxadifen-ethyl la-26 mefenpyriethyl la-26 fenclorim la-26 cumiluron la-26 S4-1 la-26 S4-5 la-27 cloq uintocet-mexylic la-27 fenclorazol-ethyl ester la-27 isoxadifen-ethyl la-27 mefenpyriethyl la-27 fenclorim la-27 cumiluron la-27 S4-1 la-27 S4-5 la-28 cloquintocet-mexylic la- 28 fenclorazol-ethyl ester la-28 isoxadifen-ethyl la-28 mefenpir-diethyl la-28 fenclorim la-28 cumiluron Active substance of formula (I) Antidote la-28 S4-1 la-28 S4-5 la-29 cloquintocet- la-29 fenclorazol-ethyl ester la-29 isoxadifen-ethyl la-29 mefenpir-diethyl la-29 fenclorim la-29 cumiluron la-29 S4-1 la-29 S4-5 la-30 cloquintocet-mexico la-30 fenclorazole la-30 isoxadifen-ethyl ester la-30 mefenpyr-diethyl la-30 phlorochlorin la-30 cumiluron la-30 S4-1 la-30 S4-5 la-31 cloquintocet-mexico la-31 fenclorazol-ethyl ester la-30 31 isoxadifen-ethyl la-31 mefenpyr-diethyl la-31 phenochlorin la-31 cumiluron la-31 S4-1 la-31 S4-5 la-32 cloquintocet-mexic la-32 fenclorazol-ethyl ester la-32 isoxadifen-ethyl la -32 m efenpyr-diethyl la-32 fenclorim la-32 cumiluron la-32 S4-1 Active substance of formula (I) Antidote la-32 S4-5 la-33 cloquintocet-mexico la-33 fenclorazol-ethyl ester la-33 isoxadifen-ethyl la-33 mefenpir-diethyl la-33 phenochlorin la-33 cumiluron la-33 S4-1 la-33 S4-5 la-34 cloquintocet-mexylic la-34 fenclorazol-ethyl ester la-34 isoxadifen-ethyl la-34 mefenpiron diethyl la-34 fenclorim la-34 cumiluron la-34 S4-1 la-34 S4-5 la-35 cloquintocet-mexican la-35 fenclorazol-ethyl ester la-35 isoxadifen-ethyl la-35 mefenpyridyl la-35 fenclorim la-35 cumiluron la-35 S4-1 la-35 S4-5 la-36 cloquintocet-mexican la-36 fenclorazol-ethyl ester la-36 isoxadifen-ethyl la-36 mefenpyridyl la-36 fenclorim la-36 cumiluron la -36 S4-1 la-36 S4-5 Active substance of the formula (I) la-37 cloquintocet-mexican antidote la-37 fenclorazol-ethyl ester la-37 isoxadifen-ethyl la-37 mefenpyridyl la-37 37 cumiluron la-37 S4-1 la-37 S4-5 la-38 cloquintocet-mexican la-38 fenclorazol-ethyl ester la-38 isoxadifen-ethyl la-38 mefenpyriethyl la-38 fenclorim la-38 cumiluron la-38 S4 -1 la-38 S4-5 la-39 cloquintocet-mexican la-39 fenclorazol-ethyl ester la-39 isoxadifen-ethyl la-39 mefenpyriethyl la-39 fenclorim la-39 cumiluron la-39 S4-1 la-39 S4-5 la-40 cloquintocet-mexico la-40 fenclorazol-ethyl ester la-40 isoxadifen-ethyl la-40 mefenpyriethyl la-40 fenclorim la-40 cumiluron la-40 S4-1 la-40 S4-5 la- 41 cloquintocet-mexil Active substance of the formula (I) Antidote la-41 fenclorazol-ethyl ester la-41 isoxadifen-ethyl la-41 mefenpyridyl la-41 fenclorim la-41 cumiluron la-41 S4-1 la-41 S4- 5 la-42 cloquintocet-mexylic la-42 fenclorazol-ethyl ester la-42 isoxadifen-ethyl la-42 mefenpyriethyl la-42 fenclorim la-42 cumiluron la-42 S4-1 la-42 S4-5 la-43 cloquintocet la-43 fenclorazol-et il-la-43 isoxadifen-ethyl ester la-43 mefenpyr-diethyl la-43 phenochlorin la-43 cumiluron la-43 S4-1 la-43 S4-5 la-44 cloquintocet-mexico la-44 fenclorazol-ethyl ester la-44 isoxadifen-ethyl la-44 mefenpir-diethyl la-44 phenochlorin la-44 cumiluron la-44 S4-1 la-44 S4-5 la-45 cloquintocet-mexic la-45 fenclorazol-ethyl ester Active substance of formula (I) Antidote la-45 isoxadifen-ethyl la-45 mefenpir-diethyl la-45 phenochlorin la-45 cumiluron la-45 s4-1 la-45 s4-5 | -a-46 cloquintocet-mexico | -a-46 fenclorazol-ethyl ester la -46 isoxadifen-ethyl | -a-46 mefenpyr-diethyl la-46 phenlorim la-46 cumiluron la-46 S4-1 la-46 cloquintocet-mexico la-47 fenclorazol-ethyl ester | - a-47 isoxadifen-ethyl la-47 mefenpyr-diethyl la-47 phenolim la-47 cumiluron la-47 S4-1 la-47 S4-5 | -a-48 cloquintocet-mexico la-48 fenclorazol-ethyl ester | -a -48 isoxadifen-ethyl | -a-48 mefenpyriethyl la-48 fenclorim la- 48 cumiluron la-48 S4-1 la-48 S4-5 la-49 cloquintocet-mexylic la-49 fenclorazol-ethyl ester la-49 isoxadifen-ethyl Active substance of formula (I) la-49 mefenpyriethyl antidote la-49 fenclorim la-49 cumiluron la-49 S4-1 la-49 S4-5 la-50 cloquintocet-mexican la-50 fenclorazole ethyl ester la-50 isoxadifen-ethyl la-50 mefenpyriethyl la-50 fenclorim la-50 cumiluron la-50 S4-1 la-50 S4-5 la-51 cloquintocet-mexican la-51 fenclorazol-ethyl ester la-51 isoxadifen-ethyl la-51 mefenpyridyl la-51 fenclorim la-51 cumiluron la-51 S4- 1 la-51 S4-5 la-52 cloquintocet-mexican la-52 fenclorazol-ethyl ester la-52 isoxadifen-ethyl la-52 mefenpyriethyl la-52 fenclorim la-52 cumiluron la-52 S4-1 la-52 S4 -5 la-53 cloquintocet-mexic la-53 fenclorazol-ethyl ester la-53 isoxadifen-ethyl la-53 mefenpyriethyl Active substance of formula (I) Antidote la-53 fenclorim la-53 cumiluron la-53 S4-1 la -53 S4-5 la-5 4 cloquintocet-mexican la-54 fenclorazol-ethyl ester la-54 isoxadifen-ethyl la-54 mefenpyriethyl la-54 fenclorim la-54 cumiluron la-54 S4-1 la-54 S4-5 la-55 cloquintocet-mexylic la -55 fenclorazol-ethyl ester la-55 isoxadifen-ethyl la-55 mefenpyriethyl la-55 fenclorim la-55 cumiluron la-55 S4-1 la-55 S4-5 la-56 cloquintocet-mexico la-56 fenclorazol-ethyl la-56 isoxadifen-ethyl la-56 mefenpyr-diethyl la-56 phlorochlorin la-56 cumiluron la-56 S4-1 la-56 S4-5 la-57 cloquintocet-mexico la-57 fenclorazol-ethyl ester la-57 isoxadifen la-57 mefenpir-diethyl la-57 fenclorim Active substance of formula (I) Antidote la-57 cumiluron la-57 S4-1 la-57 cloquintocet-mexico la-58 fenclorazol-ethyl la-58 isoxadifen-ethyl la-58 mefenpyr-diethyl la-58 phenochlorin la-58 cumiluron la-58 S4-1 la-58 S4-5 la-59 cloquintocet-mexico la-59 fenclorazol-ethyl ester la-59 isoxadifen -ethyl a-59 mefenpir diethyl la-59 phenochlorin la-59 cumiluron la-59 S4-1 la-59 S4-5 la-60 cloquintocet-mexic la-60 fenclorazol-ethyl ester la-60 isoxadifen-ethyl la-60 mefenpiron diethyl la-60 fenclorim la-60 cumiluron la-60 S4-1 la-60 S4-5 la-61 cloquintocet-mexico la-61 fenclorazol-ethyl ester la-61 isoxadifen-ethyl la-61 mefenpir-diethyl la-61 fenclorim la-61 cumiluron Active substance of formula (I) Antidote la-61 S4-1 la-61 S4-5 la-62 cloquintocet-mexylic la-62 fenclorazol-ethyl ester la-62 isoxadifen-ethyl la-62 mefenpyr-diethyl la -62 fenclorim la-62 cumiluron la-62 S4-1 la-62 S4-5 la-63 cloquintocet-mexico la-63 fenclorazol-ethyl ester la-63 isoxadifen-ethyl la-63 mefenpyridyl la-63 63 cumiluron la-63 S4-1 la-63 S4-5 | -a-64 cloquintocet-mexylic la-64 fenclorazol-ethyl ester la-64 isoxadifen-ethyl la-64 mefenpyridyl la-64 fenclorim la-64 cumiluron la -64 S4-1 la-64 S4-5 | -a -65 cloquintocet-mexican la-65 fenclorazol-ethyl ester la-65 isoxadifen-ethyl la-65 mefenpyriethyl la-65 phentlorim la-65 cumiluron la-65 S4-1 Active substance of formula (I) Antidote la-65 S4 -5 la-66 cloquintocet-mexicano la-66 fenclorazol-ethyl ester la-66 isoxadifen-ethyl la-66 mefenpyriethyl la-66 fenclorim la-66 cumiluron la-66 S4-1 la-66 S4-5 la-67 la-67 fenclorazol-ethyl ester la-67 isoxadifen-ethyl la-67 mefenpyriethyl la-67 fenclorim la-67 cumiluron la-67 S4-1 la-67 S4-5 la-68 cloquintocet-mexicano la-67 68 fenclorazol-ethyl ester la-68 isoxadifen-ethyl la-68 mefenpyriethyl la-68 fenclorim la-68 cumiluron la-68 S4-1 la-68 S4-5 la-69 cloquintocet-mexico la-69 fenclorazol-ethyl ester la-69 isoxadifen-ethyl la-69 mefenpir-diethyl la-69 phentlorim la-69 cumiluron la-69 S4-1 la-69 S4-5 Active ingredient of formula (I) Cloquintocet-mexico | a-70 fenclora zol-ethyl ester la-70 isoxadifen-ethyl la-70 mefenpyr-diethyl la-70 phenolim la-70 cumiluron la-70 S4-1 la-70 S4-5 la-71 cloquintocet-mexico la-71 fenclorazol-ethyl ester la -71 isoxadifen-ethyl la-71 mefenpyriethyl la-71 phenochlorin la-71 cumiluron la-71 S4-1 la-71 S4-5 | -a-72 cloquintocet-mexico la-72 fenclorazol-ethyl ester | -a- 72 isoxadifen-ethyl la-72 mefenpyr-diethyl la-72 phenochlorin la-72 cumiluron la-72 S4-1 la-72 S4-5 | -a-73 cloquintocet-mexico la-73 fenclorazol-ethyl ester | -a-73 isoxadifen-ethyl la-73 mefenpyr-diethyl la-73 phenochlorin la-73 cumiluron la-73 S4-1 la-73 S4-5 la-74 cloquintocet-mexico Active substance of formula (I) Antidote la-74 fenclorazol-ethyl ester la-74 isoxadifen-ethyl la-74 mefenpyr-diethyl la-74 phenlorim la-74 cumiluron la-74 S4-1 la-74 S4-5 la-75 cloquintocet-mexico la-75 fenclorazole ethyl ester la-75 isoxadifen- la-75 mefenpir-diethyl la-75 fenclori m la-75 cumiluron la-75 S4-1 la-75 S4-5 lb-1 cloquintocet-mexico lb-1 fenclorazol-ethyl ester lb-1 isoxadifen-ethyl lb-1 mefenpir-diethyl lb-1 fenclorim lb-1 cumiluron lb-1 S4-1 lb-1 S4-5 lb-2 cloquintocet-mexilic lb-2 fenclorazol-ethyl ester lb-2 isoxadifen-ethyl lb-2 mefenpir-diethyl lb-2 fenclorim lb-2 cumiluron lb-2 S4- 1 lb-2 S4-5 lb-3 cloquintocet-mexican lb-3 fenclorazol-ethyl ester Active substance of formula (I) lb-3 isoxadifen-ethyl antidote | -b-3 mefenpyridyl lb-3 fenclorim lb-3 cumiluron lb-3 S4-1 lb-3 S4-5 lb-4 cloquintocet-mexilic lb-4 fenclorazol-ethyl ester lb-4 isoxadifen-ethyl lb-4 mefenpir-diethyl lb-4 fenclorim lb-4 cumiluron lb-4 S4- 1 lb-4 S4-5 lb-5 cloquintocet-mexican lb-5 fenclorazol-ethyl ester lb-5 isoxadifen-ethyl lb-5 mefenpyridyl lb-5 fenclorim lb-5 cumiluron lb-5 S4-1 lb-5 S4 -5 lb-6 cloquintocet-mexican lb-6 phenochlorazol-ethyl ester lb-6 isoxadifen-ethyl co lb-6 mefenpir diethyl lb-6 phenochlorin lb-6 cumiluron lb-6 S4-1 lb-6 S4-5 | -b-7 cloquintocet-mexilic lb-7 fenclorazol-ethyl ester lb-7 isoxadifen-ethyl Active substance of formula (I) lb-7 mefenpir diethyl antidote lb-7 phenochlorin lb-7 cumiluron lb-7 S4-1 lb-7 S4-5 lb-8 cloquintocet-mexico lb-8 fenclorazol-ethyl ester lb-8 isoxadifen-1 ethyl lb-8 mefenpir-diethyl lb-8 fenclorim lb-8 cumiluron lb-8 S4-1 lb-8 S4-5 lb-9 cloquintocet-mexico lb-9 fenclorazol-ethyl ester lb-9 isoxadifen-ethyl lb-9 mefenpir -liethyl lb-9 fenclorim lb-9 cumiluron lb-9 S4-1 lb-9 S4-5 lb-10 cloquintocet-mexico lb-10 fenclorazol-ethyl ester lb-10 isoxadifen-ethyl lb-10 mefenpyridyl lb-10 fenclorim lb-10 cumiluron lb-10 S4-1 lb-10 S4-5 lb-11 cloquintocet-mexico lb-11 fenclorazol-ethyl ester lb-11 isoxadifen-ethyl lb-11 mefenpir-diethyl Active substance of formula (I) Antidote lb-11 fenclorim lb-11 cumiluron lb-11 S4-1 lb-11 S4-5 lb-12 cloquintocet-mexico lb-12 fenclorazol-ethyl ester lb-12 isoxadifen-ethyl lb-12 mefenpir-diethyl lb-12 fenclorim lb-12 cumiluron lb-12 S4-1 lb- 12 S4-5 lb-13 cloquintocet-mexican lb-13 fenclorazol-ethyl ester lb-13 isoxadifen-ethyl lb-13 mefenpyriethyl lb-13 fenclorim lb-13 cumiluron lb-13 S4-1 lb-13 S4-5 lb -14 cloquintocet-mexican lb-14 phenochlorazole-ethyl ester lb-14 isoxadifen-ethyl lb-14 mefenpyriethyl lb-14 fenclorim lb-14 cumiluron lb-14 S4-1 lb-14 S4-5 lb-15 cloquintocet-mexican lb-15 fenclorazol-ethyl ester lb-15 isoxadifen-ethyl lb-15 mefenpyriethyl lb-15 fenclorim Active substance of formula (I) Antidote lb-15 cumiluron lb-15 S4-1 lb-15 S4-5 lb-16 cloquintocet-mexicano lb-16 fenclorazol-ethyl ester lb-16 isoxadifen-ethyl lb-16 mefenpir-diethyl lb-16 fenclorim lb-16 cumiluron lb-16 S4-1 lb-16 S4-5 lb-17 cloquintocet-mexicano lb- 17 fenclorazol-ethyl ester lb-17 i soxadifen-ethyl lb-17 mefenpir-diethyl lb-17 phenochlorin lb-17 cumiluron lb-17 S4-1 lb-17 S4-5 lb-18 cloquintocet-mexico lb-18 fenclorazol-ethyl ester lb-18 isoxadifen-ethyl lb- 18 mefenpir-diethyl lb-18 phenlorim lb-18 cumiluron lb-18 S4-1 lb-18 S4-5 lb-19 cloquintocet-mexico lb-19 fenclorazol-ethyl ester lb-19 isoxadifen-ethyl lb-19 mefenpir-diethyl lb -19 fenclorim lb-19 cumiluron Active substance of formula (I) Antidote lb-19 S4-1 lb-19 S4-5 | -b-20 cloquintocet-mexico | -b-20 fenclorazol-ethyl ester lb-20 isoxadifen-ethyl lb-20 mefenpir-diethyl lb-20 phenochlorin lb-20 cumiluron lb-20 S4-1 lb-20 S4-5 lb-21 cloquintocet-mexico lb-21 fenclorazol-ethyl ester lb-21 isoxadifen-ethyl lb-21 mefenpir- diethyl lb-21 fenclorim lb-21 cumiluron lb-21 S4-1 lb-21 S4-5 | -b-22 cloquintocet-mexico | -b-22 fenclorazol-ethyl ester lb-22 isoxadifen-ethyl | -b-22 mefenpir diethyl lb-22 fenclorim lb-22 cumiluron lb-2 2 S4-1 lb-22 S4-5 | -b-23 cloquintocet-mexican lb-23 fenclorazol-ethyl ester lb-23 isoxadifen-ethyl | -b-23 mefenpyriethyl lb-23 fenclorim lb-23 cumiluron lb-23 S4-1 Active substance of formula (I) lb-23 antidote S4-5 | -b-24 cloquintocet-mexican | -b-24 fenclorazol-ethyl ester lb-24 isoxadifen-ethyl lb-24 mefenpyridyl diethylbb-24 phenochlorim lb-24 cumiluron lb-24 S4-1 lb-24 S4-5 lb-25 cloquintocet-mexico | -b-25 fenclorazol-ethyl ester lb-25 isoxadifen-ethyl lb-25 mefenpyridyl lb-25 fenclorim lb-25 cumiluron lb-25 S4-1 lb-25 S4-5 | -b-26 cloquintocet-mexico lb-26 fenclorazol-ethyl ester lb-26 isoxadifen-ethyl | -b-26 mefenpir-diethyl lb-26 fenclorim lb-26 cumiluron lb-26 S4-1 lb-26 S4-5 lb-27 cloquintocet-mexican lb-27 fenclorazol-ethyl ester lb-27 isoxadifen-ethyl lb-27 mefenpir-diethyl lb-27 fenclorim lb-27 cumiluron lb-27 S4- 1 lb-27 S4-5 Active substance of formula (I) Antidote lb-28 cloquintocet-mex ileum lb-28 fenclorazol-ethyl ester lb-28 isoxadifen-ethyl lb-28 mefenpyriethyl lb-28 fenclorim lb-28 cumiluron lb-28 S4-1 lb-28 S4-5 lb-29 cloquintocet-mexico lb-29 fenclorazole lb-29 isoxadifen-ethyl ester lb-29 mefenpyr-diethyl lb-29 phentlorim lb-29 cumiluron lb-29 S4-1 lb-29 S4-5 lb-30 cloquintocet-mexican lb-30 fenclorazol-ethyl ester lb- 30 isoxadifen-ethyl lb-30 mefenpyr-diethyl lb-30 phenochlorin lb-30 cumiluron lb-30 S4-1 lb-30 S4-5 lb-31 cloquintocet-mexico lb-31 fenclorazol-ethyl ester lb-31 isoxadifen-ethyl lb -31 mefenpir-diethyl lb-31 fenclorim lb-31 cumiluron lb-31 S4-1 lb-31 S4-5 lb-32 cloquintocet-mexilic Active substance of formula (I) Antidote lb-32 fenclorazol-ethyl ester lb-32 isoxadifen leb-32 mefenpir-diethyl lb-32 phenochlorin lb-32 cumiluron lb-32 S4-1 lb-32 S4-5 lb-33 cloquintocet-mexico lb-33 fenclorazole ethyl ester lb-33 isoxadifen-ethyl lb-33 mefenpir-diet ileum lb-33 fenclorim lb-33 cumiluron lb-33 S4-1 lb-33 S4-5 lb-34 cloquintocet-mexico lb-34 fenclorazol-ethyl ester lb-34 isoxadifen-ethyl lb-34 mefenpyriethyl lb-34 fenclorim lb-34 cumiluron lb-34 S4-1 lb-34 S4-5 lb-35 cloquintocet-mexico lb-35 fenclorazol-ethyl ester lb-35 isoxadifen-ethyl lb-35 mefenpir-diethyl lb-35 fenclorim lb-35 cumiluron lb -35 S4-1 lb-35 S4-5 lb-36 cloquintocet-mexican lb-36 fenclorazol-ethyl ester Active substance of formula (I) lb-36 isoxadifen-ethyl antidote lb-36 mefenpir-diethyl lb-36 fenclorim lb- 36 cumiluron lb-36 S4-1 lb-36 S4-5 lb-37 cloquintocet-mexican lb-37 fenclorazol-ethyl ester lb-37 isoxadifen-ethyl lb-37 mefenpir-diethyl lb-37 fenclorim lb-37 cumiluron lb-37 S4-1 lb-37 S4-5 lb-38 cloquintocet-mexico lb-38 fenclorazol-ethyl ester lb-38 isoxadifen-ethyl lb-38 mefenpir-diethyl lb-38 fenclorim lb-38 cumiluron lb-38 S4-1 lb- 38 S4-5 lb-39 cloquintocet-m exile lb-39 fenclorazol-ethyl ester lb-39 isoxadifen-ethyl lb-39 mefenpir diethyl lb-39 fenclorim lb-39 cumiluron lb-39 S4-1 lb-39 S4-5 lb-40 cloquintocet-mexico lb-40 fenclorazole -butyl ester lb-40 isoxadifen-ethyl Active substance of the formula (I) lb-40 mefenpyridyl antidote lb-40 phentlorim lb-40 cumiluron lb-40 S4-1 lb-40 S4-5 lb-41 cloquintocet-mexican lb -41 fenclorazol-ethyl ester lb-41 isoxadifen-ethyl lb-41 mefenpyriethyl lb-41 fenclorim lb-41 cumiluron lb-41 S4-1 lb-41 S4-5 lb-42 cloquintocet-mexico lb-42 fenclorazol-ethyl lb-42 isoxadifen-ethyl lb-42 mefenpyr diethyl lb-42 phenochlorin lb-42 cumiluron lb-42 S4-1 lb-42 S4-5 lb-43 cloquintocet-mexico lb-43 fenclorazol-ethyl lb-43 isoxadifen leb-43 mefenpir-diethyl lb-43 phenochlorin lb-43 cumiluron lb-43 S4-1 lb-43 S4-5 lb-44 cloquintocet-mexico lb-44 fenclorazole-ethyl ester lb-44 isoxadifen-ethyl lb-44 mefenpir-di active substance of the formula (I) Antidote lb-44 phenochlorim lb-44 cumiluron lb-44 S4-1 lb-44 S4-5 lb-45 cloquintocet-mexico lb-45 fenclorazol-ethyl ester lb-45 isoxadifen-ethyl lb- 45 mefenpir diethyl lb-45 phenochlorim lb-45 cumiluron lb-45 S4-1 lb-45 S4-5 lb-46 cloquintocet-mexilic lb-46 fenclorazol-ethyl ester lb-46 isoxadifen-ethyl lb-46 mefenpir-diethyl lb -46 fenclorim lb-46 cumiluron lb-46 S4-1 lb-46 S4-5 lb-47 cloquintocet-mexico lb-47 fenclorazol-ethyl ester lb-47 isoxadifen-ethyl lb-47 mefenpir-diethyl lb-47 fenclorim lb- 47 cumiluron lb-47 S4-1 lb-47 S4-5 lb-48 cloquintocet-mexican lb-48 fenclorazol-ethyl ester lb-48 isoxadifen-ethyl lb-48 mefenpyridyl diethylbb-48 fenclorim Active substance of formula (I) Lb-48 cumiluron lb-48 antidote S4-1 lb-48 S4-5 lb-49 cloquintocet-mexico lb-49 phenochlorazole-ethyl ester lb-49 isoxadifen-ethyl lb-49 mefenpir-diethyl lb-49 fenclorim lb-49 cumiluron lb-49 S4-1 lb-49 S4-5 lb-50 cloquintocet-mexican lb-50 fenclorazol-ethyl ester lb-50 isoxadifen-ethyl lb-50 mefenpir-diethyl lb-50 fenclorim lb-50 cumiluron lb-50 S4- 1 lb-50 S4-5 lb-51 cloquintocet-mexican lb-51 fenclorazol-ethyl ester lb-51 isoxadifen-ethyl lb-51 mefenpyriethyl lb-51 fenclorim lb-51 cumiluron lb-51 S4-1 lb-51 S4 -5 lb-52 cloquintocet-mexican lb-52 fenclorazol-ethyl ester lb-52 isoxadifen-ethyl lb-52 mefenpyriethyl lb-52 fenclorim lb-52 cumiluron Active substance of formula (I) Antidote lb-52 S4-1 lb -52 S4-5 lb-53 cloquintocet-mexican lb-53 fenclorazol-ethyl ester lb-53 isoxadifen-ethyl lb-53 mefenpyriethyl lb-53 fenclorim lb-53 cumiluron lb-53 S4-1 lb-53 S4-5 lb-54 cloquintocet-mexico lb-54 fenclorazol-ethyl ester lb-54 isoxadifen-ethyl lb-54 mefenpyriethyl lb-54 fenclorim lb-54 cumiluron lb-54 S4-1 lb-54 S4-5 lb-55 cloquintocet- mexican lb-55 fenclorazol-ethyl ester lb-55 isoxadifen-ethyl lb-55 mefenpyriethyl lb-55 phenochlorin lb-55 cumiluron lb-55 S4-1 lb-55 S4-5 lb-56 cloquintocet-mexico lb-56 fenclorazol-ethyl ester lb-56 isoxadifen- ethyl lb-56 mefenpir-diethyl lb-56 phenochlorin lb-56 cumiluron lb-56 S4-1 Active substance of formula (I) lb-56 antidote S4-5 | -b-57 cloquintocet-mexican lb-57 fenclorazol-ethyl ester lb-57 isoxadifen-ethyl | -b-57 mefenpyr-diethyl lb-57 phenochlorin lb-57 cumiluron lb-57 S4-1 lb-57 S4-5 lb-58 cloquintocet-mexico | -b-58 fenclorazol-ethyl ester | -b-58 isoxadifen-ethyl lb-58 mefenpyriethyl lb-58 phenochlorin lb-58 cumiluron lb-58 S4-1 lb-58 S4-5 | -b-59 cloquintocet-mexican lb-59 fenclorazol-ethyl ester lb- 59 isoxadifen-ethyl lb-59 mefenpyriethyl lb-59 phenochlorin lb-59 cumiluron lb-59 S4-1 lb-59 S4-5 lb-60 cloquintocet-mexico lb-60 fenclorazol-ethyl ester | -b-60 isoxadifen- ethyl lb-60 mefenpir-diethyl lb-60 fenclorim lb-60 cumilur on lb-60 S4-1 lb-60 S4-5 Active substance of formula (I) Cloquintocet-mexilic lb-61 antidote lb-61 fenclorazol-ethyl ester lb-61 isoxadifen-ethyl lb-61 mefenpyr-diethyl lb-61 fenclorim lb-61 cumiluron lb-61 S4-1 lb-61 S4-5 lb-62 cloquintocet-mexico lb-62 fenclorazol-ethyl ester lb-62 isoxadifen-ethyl lb-62 mefenpir-diethyl lb-62 fenclorim lb-62 cumiluron lb -62 S4-1 lb-62 S4-5 lb-63 cloquintocet-mexico lb-63 fenclorazol-ethyl ester lb-63 isoxadifen-ethyl lb-63 mefenpyriethyl lb-63 fenclorim lb-63 cumiluron lb-63 S4-1 lb-63 S4-5 lb-64 cloquintocet-mexico lb-64 fenclorazol-ethyl ester lb-64 isoxadifen-ethyl lb-64 mefenpir-diethyl lb-64 fenclorim lb-64 cumiluron lb-64 S4-1 lb-64 S4- 5 lb-65 cloquintocet-mexilic Active substance of formula (I) Antidote lb-65 fenclorazol-ethyl ester lb-65 isoxadifen-ethyl lb-65 mefenpir-diethyl lb-65 fenclorim lb-65 cumiluron lb-65 S4-1 lb- 65 S4-5 lb-66 cloquint ocet-mexico lb-66 fenclorazol-ethyl ester lb-66 isoxadifen-ethyl lb-66 mefenpyriethyl lb-66 fenclorim lb-66 cumiluron lb-66 S4-1 lb-66 S4-5 lb-67 cloquintocet-mexil lb- 67 fenclorazol-ethyl ester lb-67 isoxadifen-ethyl lb-67 mefenpyriethyl lb-67 fenclorim lb-67 cumiluron lb-67 S4-1 lb-67 S4-5 lb-68 cloquintocet-mexico lb-68 fenclorazol-ethyl ester lb-68 isoxadifen-ethyl lb-68 mefenpyriethyl lb-68 phenochlorin lb-68 cumiluron lb-68 S4-1 lb-68 S4-5 lb-69 cloquintocet-mexico lb-69 fenclorazol-ethyl ester Active substance of the formula ( I) Isoxadifen-ethylbb-69 mefenpyr-diethyl antidote lb-69 phenlorim lb-69 cumluron lb-69 S4-1 lb-69 S4-5 lb-70 cloquintocet-mexican lb-70 fenclorazol-ethyl ester lb- 70 isoxadifen-ethyl lb-70 mefenpyr-diethyl lb-70 phenochlorin lb-70 cumiluron lb-70 S4-1 lb-70 S4-5 lb-71 cloquintocet-mexico lb-71 fenclorazol-ethyl ester lb-71 isoxadifen-ethyl lb -71 mefen pyr diethyl lb-71 phenochlorim lb-71 cumiluron lb-71 S4-1 lb-71 S4-5 lb-72 cloquintocet-mexico lb-72 fenclorazol-ethyl ester lb-72 isoxadifen-ethyl lb-72 mefenpir-diethyl lb- 72 fenclorim lb-72 cumiluron lb-72 S4-1 lb-72 S4-5 lb-73 cloquintocet-mexico lb-73 fenclorazol-ethyl ester lb-73 isoxadifen-ethyl Active substance of formula (I) Antidote lb-73 mefenpir- diethyl lb-73 phenlorim lb-73 cumiluron lb-73 S4-1.  lb-73 S4-5 lb-74 cloquintocet-mexican lb-74 fenclorazol-ethyl ester lb-74 isoxadifen-ethyl lb-74 mefenpir-diethyl lb-74 fenclorim lb-74 cumiluron lb-74 S4-1 lb-74 S4- 5 lb-75 cloquintocet-mexico lb-75 fenclorazol-ethyl ester lb-75 isoxadifen-ethyl lb-75 mefenpyriethyl lb-75 fenclorim lb-75 cumiluron lb-75 S4-1 lb-75 S4-5 lb-76 cloquintocet mexylic lb-76 fenclorazol-ethyl ester lb-76 isoxadifen-ethyl lb-76 mefenpyriethyl lb-76 fenclorim lb-76 cumiluron lb-76 S4-1 lb-76 S4-5 lb-77 cloquintocet-mexico lb-77 fenclorazol-ethyl ester lb-77 isoxadifen-ethyl lb-77 mefenpir-diethyl Active ingredient of formula (I) Antidote lb-77 fenclorim lb-77 cumiluron lb-77 S4-1 lb-77 S4-5 lb-78 cloquintocet-mexico lb-78 fenclorazol-ethyl ester lb-78 isoxadifen-ethyl lb-78 mefenpyriethyl lb-78 fenclorim lb-78 cumiluron lb-78 S4-1 lb-78 S4-5 lb-79 cloquintocet-mexico lb-79 fenclorazol- ethyl ester | -b-79 isoxad ifene-ethyl lb-79 mefenpir-diethyl lb-79 phenochlorin lb-79 cumiluron lb-79 S4-1 lb-79 S4-5 lc-1 cloquintocet-mexico lc-1 fenclorazol-ethyl ester lc-1 isoxadifen-ethyl lc- 1 mefenpir-diethyl lc-1 phenochlorim lc-1 cumiluron lc-1 S4-1 lc-1 S4-5 | -c-2 cloquintocet-mexico | -c-2 fenclorazol-ethyl ester lc-2 isoxadifen-ethyl lc-2 mefenpir diethyl lc-2 fenclorim Active substance of formula (I) Antidote lc-2 cumiluron 1-0-2 S4-1 lc-2 S4-5 lc-3 cloquintocet-mexico lc-3 fenclorazol-ethyl ester lc-3 isoxadifen lc-3 mefenpir-diethyl lc-3 phenochlorin lc-3 cumiluron lc-3 S4-1 lc-3 S4-5 lc-4 cloquintocet-mexico lc-4 fenclorazol-ethyl ester lc-4 isoxadifen-ethyl lc-4 mefenpir diethyl lc-4 phenlorim lc-4 cumiluron lc-4 S4-1 lc-4 S4-5 lc-5 cloquintocet-mexilic lc-5 fenclorazol-ethyl ester lc-5 isoxadifen-ethyl lc-5 5 fenclorim lc-5 cumiluron lc-5 S4-1 lc-5 S4-5 lc-6 cloquintocet-mex co lc-6 fenclorazol-ethyl ester lc-6 isoxadifen-ethyl lc-6 mefenpyriethyl lc-6 fenclorim lc-6 cumiluron Active substance of formula (I) Antidote lc-6 S4-1 lc-6 S4-5 lc- 7 cloquintocet-mexico lc-7 fenclorazol-ethyl ester lc-7 isoxadifen-ethyl lc-7 mefenpir-diethyl lc-7 fenclorim lc-7 cumiluron lc-7 S4-1 lc-7 S4-5 lc-8 cloquintocet-mexico lc -8 fenclorazol-ethyl ester lc-8 isoxadifen-ethyl lc-8 mefenpyriethyl lc-8 fenclorim lc-8 cumiluron lc-8 S4-1 lc-8 S4-5 lc-9 cloquintocet-mexico lc-9 fenclorazol-ethyl lc-9 isoxadifen-ethyl ester lc-9 mefenpyr diethyl lc-9 phenlorim lc-9 cumiluron lc-9 S4-1 lc-9 S4-5 lc-10 cloquintocet-mexico lc-10 fenclorazol-ethyl lc-10 isoxadifen lc-10 mefenpir-diethyl lc-10 phenochlorin lc-10 cumiluron lc-10 S4-1 Active substance of formula (I) lc-10 antigen S4-5 lc-11 cloquintocet-mexico lc-11 fenclorazol-ethyl ester lc -11 isoxadifen-ethyl lc-11 mefe npyr-diethyl lc-11 phenochlorin lc-11 cumiluron lc-11 S4-1 lc-11 S4-5 lc-12 cloquintocet-mexico lc-12 fenclorazol-ethyl ester lc-12 isoxadifen-ethyl lc-12 mefenpyridyl diethyl 12 fenclorim lc-12 cumiluron lc-12 S4-1 lc-12 S4-5 lc-13 cloquintocet-mexico lc-13 fenclorazol-ethyl ester lc-13 isoxadifen-ethyl lc-13 mefenpiri-diethyl lc-13 fenclorim lc-13 cumiluron lc-13 S4-1 lc-13 S4-5 lc-14 cloquintocet-mexico lc-14 fenclorazol-ethyl ester lc-14 isoxadifen-ethyl lc-14 mefenpyridyl lc-14 cumiluron lc-14 S4 -1 lc-14 S4-5 Active substance of formula (I) Cloquintocet-mexican lc-15 antidote lc-15 fenclorazol-ethyl ester lc-15 isoxadifen-ethyl lc-15 mefenpyr-diethyl lc-15 fenclorim lc-15 cumiluron lc -15 S4-1 lc-15 S4-5 lc-16 cloquintocet-mexico lc-16 fenclorazol-ethyl ester lc-16 isoxadifen-ethyl lc-16 mefenpyridyl lc-16 fenclorim lc-16 cumiluron lc-16 S4-1 lc-16 S4-5 lc-17 block intocet-mexico lc-17 fenclorazol-ethyl ester lc-17 isoxadifen-ethyl lc-17 mefenpir-diethyl lc-17 fenclorim lc-17 cumiluron lc-17 S4-1 lc-17 S4-5 lc-18 cloquintocet-mexico lc- 18 fenclorazol-ethyl ester lc-18 isoxadifen-ethyl lc-18 mefenpyriethyl lc-18 fenclorim lc-18 cumiluron lc-18 S4-1 lc-18 S4-5 lc-19 cloquintocet-mexico Active substance of formula (I) Lc-19 phenochlorazole ethyl ester lc-19 isoxadifen-ethyl ester lc-19 mefenpyriethyl lc-19 fenclorim lc-19 cumiluron lc-19 S4-1 lc-19 S4-5 lc-20 cloquintocet-mexico lc-20 fenclorazole lc-20 isoxadifen-ethyl ester lc-20 mefenpyr diethyl lc-20 phenlorim lc-20 cumiluron lc-20 S4-1 lc-20 S4-5 lc-21 cloquintocet-mexico lc-21 fenclorazol-ethyl ester lc- 21 isoxadifen-ethyl lc-21 mefenpyr-diethyl lc-21 phenochlorin lc-21 cumiluron lc-21 S4-1 lc-21 S4-5 lc-22 cloquintocet-mexico lc-22 fenclorazol-ethyl ester lc-22 isoxadifen-ethyl -22 me fenpyr-diethyl lc-22 fenclorim lc-22 cumiluron lc-22 S4-1 lc-22 S4-5 lc-23 cloquintocet-mexilic lc-23 fenclorazol-ethyl ester Active substance of formula (I) lc-23 isoxadifen-ethyl antidote lc-23 mefenpir-diethyl lc-23 phenolimc lc-23 cumiluron lc-23 S4-1 lc-23 S4-5 lc-24 cloquintocet-mexico lc-24 fenclorazol-ethyl ester lc-24 isoxadifen-ethyl lc-24 mefenpyr diethyl lc-24 phenlorim lc-24 cumiluron lc-24 S4-1 lc-24 S4-5 lc-25 cloquintocet-mexico lc-25 fenclorazol-ethyl ester lc-25 isoxadifen-ethyl lfen-diethyl lc-25 fenclorim lc-25 cumiluron lc-25 S4-1 lc-25 S4-5 lc-26 cloquintocet-mexico lc-26 fenclorazol-ethyl ester lc-26 isoxadifen-ethyl lc-26 mefenpir-diethyl lc-26 fenclorim lc-26 cumiluron lc -26 S4-1 lc-26 S4-5 lc-27 cloquintocet-mexico lc-27 fenclorazol-ethyl ester lc-27 isoxadifen-ethyl Active substance of formula (I) lc-27 mefenpyridyl antidote lc-27 fenclorim lc- 27 cumiluron lc-27 S4-1 lc-27 S4-5 lc-28 cloquintocet-mexico lc-28 fenclorazol-ethyl ester lc-28 isoxadifen-ethyl lc-28 mefenpyridyl lc-28 cumiluron lc-28 S4 -1 lc-28 S4-5 lc-29 cloquintocet-mexico lc-29 fenclorazol-ethyl ester lc-29 isoxadifen-ethyl lc-29 mefenpyriethyl lc-29 fenclorim lc-29 cumiluron lc-29 S4-1 lc-29 S4-5 lc-30 cloquintocet-mexico lc-30 fenclorazol-ethyl ester lc-30 isoxadifen-ethyl lc-30 mefenpyriethyl lc-30 fenclorim lc-30 cumiluron lc-30 S4-1 lc-30 S4-5 lc- 31 cloquintocet-mexico lc-31 fenclorazol-ethyl ester lc-31 isoxadifen-ethyl lc-31 mefenpyriethyl Active substance of the formula (I) Antidote lc-31 fenclorim lc-31 cumiluron lc-31 S4-1 lc-31 S4- 5 lc-32 cloquintocet-mexico lc-32 fenclorazol-ethyl ester lc-32 isoxadifen-ethyl lc-32 mefenpyriethyl lc-32 fenclorim lc-32 cumiluron lc-32 S4-1 lc-32 S4-5 lc-33 cloquintocet lc-33 fenclorazol-eti lc-33 isoxadifen-ethyl ester lc-33 mefenpyr diethyl lc-33 phenolim lc-33 cumiluron lc-33 S4-1 lc-33 s4-5 lc-34 cloquintocet-mexico lc-34 fenclorazol-ethyl ester lc-34 isoxadifen-ethyl lc-34 mefenpyr-diethyl lc-34 phenlorim lc-34 cumiluron lc-34 S4-1 lc-34 S4-5 lc-35 cloquintocet-mexico lc-35 fenclorazol-ethyl ester lc-35 isoxadifen-ethyl 35 mefenpir-diethyl lc-35 phenlorim Active substance of formula (I) Antidote lc-35 cumiluron lc-35 S4-1 lc-35 S4-5.  lc-36 cloquintocet-mexico lc-36 fenclorazol-ethyl ester lc-36 isoxadifen-ethyl lc-36 mefenpyriethyl lc-36 fenclorim lc-36 cumiluron lc-36 S4-1 lc-36 S4-5 lc-37 cloquintocet- mexico lc-37 fenclorazol-ethyl ester lc-37 isoxadifen-ethyl lc-37 mefenpyriethyl lc-37 fenclorim lc-37 cumiluron lc-37 S4-1 lc-37 S4-5 lc-38 cloquintocet-mexico lc-38 fenclorazol lc-38 isoxadifen-ethyl ester lc-38 mefenpyr diethyl lc-38 phrenlorim lc-38 cumiluron lc-38 S4-1 lc-38 S4-5 lc-39 cloquintocet-mexico lc-39 fenclorazol-ethyl ester lc-38 39 isoxadifen-ethyl lc-39 mefenpyriethyl lc-39 phentlorim lc-39 cumiluron Active substance of formula (I) antidote lc-39 S4-1 lc-39 s4-5 cloquintocet-mexico lc-40 fenclorazol-ethyl lc-40 isoxadifen-ethyl lc-40 mefenpyriethyl lc-40 phenolimc lc-40 cumiluron lc-40 S4-1 lc-40 s4-5 lc-41 cloquintocet-mexico lc-41 fenclorazol-ethyl lc-41 isoxadifen -ethyl lc-41 mefenpir-diethyl lc-41 phenochlorin lc-41 cumiluron lc-41 S4-1 lc-41 S4-5 lc-42 cloquintocet-mexico lc-42 fenclorazol-ethyl ester lc-42 isoxadifen-ethyl lc-42 mefenpir lc-42 fenclorim lc-42 cumiluron lc-42 S4-1 lc-42 S4-5 lc-43 'cloquintocet-mexico lc-43 fenclorazol-ethyl ester lc-43 isoxadifen-ethyl lc-43 mefenpyridyl lc- 43 fenclorim lc-43 cumiluron lc-43 S4-1 Active substance of formula (I) Antidote lc-43 S4-5 lc-44 cloquintocet-mexico lc-44 fenclorazol-ethyl ester lc-44 isoxadifen-ethyl lc-44 mefenpyr diethyl lc-44 phenlorim lc-44 cumiluron lc-44 S4-1 lc-44 S4-5 lc-45 cloquintocet-mexico lc-45 fenclorazol-ethyl ester lc-45 isoxadifen-ethyl lc-45 mefenpyridyl diethyl lc-45 fenclorim lc-45 cumiluron lc-45 S4-1 lc-45 s4-5 lc-46 cloquintocet-mexico lc-46 fenclorazol-ethyl ester lc-46 isoxadifen-ethyl lc-46 mefenpir-diethyl lc-46 fenclorim lc-46 cumiluron lc -46 S4-1 lc-46 S 4-5 lc-47 cloquintocet-mexico lc-47 fenclorazol-ethyl ester lc-47 isoxadifen-ethyl lc-47 mefenpyriethyl lc-47 fenclorim lc-47 cumiluron lc-47 S4-1 lc-47 S4-5 Active substance of formula (I) Cloquintocet-mexican antidote lc-48 lc-48 phenochlorazol-ethyl ester lc-48 isoxadiphen-ethyl lc-48 mefenpyriethyl lc-48 fenclorim lc-48 cumiluron lc-48 S4-1 lc-48 S4- 5 lc-49 cloquintocet-mexico lc-49 fenclorazol-ethyl ester lc-49 isoxadifen-ethyl lc-49 mefenpyriethyl lc-49 fenclorim lc-49 cumiluron lc-49 S4-1 lc-49 S4-5 lc-50 cloquintocet lc-50 methylphenazole-ethyl ester lc-50 isoxadifen-ethyl lc-50 mefenpyriethyl lc-50 fenclorim lc-50 cumiluron lc-50 S4-1 lc-50 S4-5 lc-51 cloquintocet-mexico lc-51 fenclorazol-ethyl ester lc-51 isoxadifen-ethyl lc-51 mefenpir diethyl lc-51 fenclorim lc-51 cumiluron lc-51 S4-1 lc-51 S4-5 lc-52 cloquintocet-mexico Active substance of formula (I) Antidote lc-52 f enchlorazol-ethyl ester lc-52 isoxadifen-ethyl lc-52 mefenpyridyl lc-52 phenlorim lc-52 cumiluron lc-52 S4-1 lc-52 S4-5 lc-53 cloquintocet-mexico lc-53 fenclorazol-ethyl ester lc -53 isoxadifen-ethyl lc-53 mefenpyriethyl lc-53 phenochlorim lc-53 cumiluron lc-53 S4-1 lc-53 S4-5 lc-54 cloquintocet-mexico lc-54 fenclorazol-ethyl ester lc-54 isoxadifen-ethyl lc-54 mefenpyr-diethyl lc-54 phenlorim lc-54 cumiluron lc-54 S4-1 lc-54 S4-5 lc-55 cloquintocet-mexico lc-55 fenclorazol-ethyl ester lc-55 isoxadifen-ethyl lc-55 mefenpir diethyl lc-55 fenclorim lc-55 cumiluron lc-55 S4-1 lc-55 S4-5 lc-56 cloquintocet-mexico lc-56 fenclorazol-ethyl ester Active substance of formula (I) lc-56 isoxadifen-ethyl antidote 56 mefenpyridyl lc-56 phenolimon lc-56 cumiluron lc-56 S4-1 lc-56 S4-5 lc-57 cloquintocet-mexico lc-57 fenclorazol-ethyl ester lc-57 isoxadifen-ethyl lc-57 mefenpyridyl -57 f enchlorim lc-57 cumiluron lc-57 S4-1 lc-57 S4-5 lc-58 cloquintocet-mexico lc-58 fenclorazol-ethyl ester lc-58 isoxadifen-ethyl lc-58 mefenpyridyl lc-58 fenclorim lc-58 cumiluron lc-58 S4-1 lc-58 S4-5 lc-59 cloquintocet-mexico lc-59 fenclorazol-ethyl ester lc-59 isoxadifen-ethyl lc-59 mefenpir-diethyl lc-59 fenclorim lc-59 cumiluron lc-59 S4- 1 lc-59 S4-5 lc-60 cloquintocet-mexico lc-60 fenclorazol-ethyl ester lc-60 isoxadifen-ethyl Active substance of the formula (I) lc-60 mefenpyriethyl antidote lc-60 fenclorim lc-60 cumiluron lc- 60 S4-1 lc-60 S4-5 lc-61 cloquintocet-mexico lc-61 fenclorazol-ethyl ester lc-61 isoxadifen-ethyl lc-61 mefenpyriethyl lc-61 fenclorim lc-61 cumiluron lc-61 S4-1 lc -61 S4-5 lc-62 cloquintocet-mexico lc-62 fenclorazol-ethyl ester lc-62 isoxadifen-ethyl lc-62 mefenpyriethyl lc-62 fenclorim lc-62 cumiluron lc-62 S4-1 lc-62 S4-5 lc-63 cloquintocet-mexico lc-63 fenclorazol-ethyl ester lc-63 isoxadifen-ethyl lc-63 mefenpyriethyl lc-63 fenclorim lc-63 cumiluron lc-63 S4-1 lc-63 S4-5 lc-64 cloquintocet-mexico lc-64 fenclorazol-ethyl ester lc -64 isoxadifen-ethyl lc-64 mefenpyriethyl Active substance of the formula (I) Antidote lc-64 phentlorim lc-64 cumiluron lc-64 S4-1 lc-64 S4-5 lc-65 cloquintocet-mexico lc-65 fenclorazol- ethyl ester lc-65 isoxadifen-ethyl lc-65 mefenpyriethyl lc-65 phenlorim lc-65 cumiluron lc-65 S4-1 lc-65 S4-5 lc-66 cloquintocet-mexico lc-66 fenclorazol-ethyl ester lc-66 isoxadifen-ethyl lc-66 mefenpyriethyl lc-66 phenochlorim lc-66 cumiluron lc-66 S4-1 lc-66 S4-5 lc-67 cloquintocet-mexico lc-67 fenclorazol-ethyl ester lc-67 isoxadifen-ethyl 67 mefenpir-diethyl lc-67 phenolimon lc-67 cumiluron lc-67 S4-1 lc-67 S4-5 lc-68 cloquintocet-mexico lc-68 fenclorazol-ethyl ester lc-68 isoxadifen-ethyl lc-68 -68 fenclorim Active substance of formula (I) Antidote lc-68 cumiluron lc-68 S4-1 lc-68 S4-5 lc-69 cloquintocet-mexilic lc-69 fenclorazole-ethyl ester lc-69 isoxadifen-ethyl mefenpyridyl lc-69 fenclorim lc-69 cumiluron lc-69 S4-1 lc-69 S4-5 lc-70 cloquintocet-mexico lc-70 fenclorazol-ethyl ester lc-70 isoxadifen-ethyl lc-70 mefenpir-diethyl lc-70 fenclorim lc -70 cumiluron lc-70 S4-1 lc-70 S4-5 lc-71 cloquintocet-mexico lc-71 fenclorazol-ethyl ester lc-71 isoxadifen-ethyl lc-71 mefenpir-diethyl fclorim lc-71 cumiluron lc- 71 S4-1 lc-71 S4-5 lc-72 cloquintocet-mexico lc-72 fenclorazol-ethyl ester lc-72 isoxadifen-ethyl lc-72 mefenpyriethyl lc-72 fenclorim lc-72 cumiluron Active substance of formula (I) Lc-72 S4-1 lc-72 antidote S4-5 lc-73 cloquintocet-mexico lc-73 fenclorazol-ethyl ester lc-73 isoxadifen-ethyl lc-73 mefenpyr diethyl lc-73 fenclorim lc-73 cumiluron lc-73 S4 -1 l- c-73 S4-5 lc-74 cloquintocet-mexico lc-74 fenclorazol-ethyl ester lc-74 isoxadifen-ethyl lc-74 mefenpyriethyl lc-74 fenclorim lc-74 cumiluron lc-74 S4-1 lc-74 S4- 5 lc-75 cloquintocet-mexico lc-75 fenclorazol-ethyl ester lc-75 isoxadifen-ethyl lc-75 mefenpyriethyl lc-75 fenclorim lc-75 cumiluron lc-75 S4-1 lc-75 S4-5 lc-76 cloquintocet mc-lc-76 fenclorazol-ethyl ester lc-76 isoxadifen-ethyl lc-76 mefenpir-diethyl lc-76 fenclorim lc-76 cumiluron lc-76 S4-1 Active substance of formula (I) Antidote lc-76 S4-5 lc -77 cloquintocet-mexico lc-77 fenclorazol-ethyl ester lc-77 isoxadifen-ethyl lc-77 mefenpyriethyl lc-77 fenclorim lc-77 cumiluron lc-77 S4-1 lc-77 S4-5 lc-78 cloquintocet-mexico lc-78 fenclorazol-ethyl ester lc-78 isoxadifen-ethyl lc-78 mefenpyriethyl lc-78 fenclorim lc-78 cumiluron lc-78 S4-1 lc-78 S4-5 lc-79 cloquintocet-mexico lc-79 fenclorazol ethyl ester lc-79 isoxadif eno-ethyl lc-79 mefenpyriethyl lc-79 phenochlorin lc-79 cumiluron lc-79 S4-1 lc-79 S4-5 lc-80 cloquintocet-mexico lc-80 fenclorazol-ethyl ester lc-80 isoxadifen-ethyl 80 mefenpir-diethyl lc-80 fenclorim lc-80 cumiluron lc-80 S4-1 lc-80 S4-5 Active substance of the formula (I) lc-81 cloquintocet-mexican antidote lc-81 fenclorazol-ethyl ester lc-81 isoxadifen-1 lc-81 mefenpir-diethyl lc-81 phenochlorin lc-81 cumiluron lc-81 S4-1 lc-81 S4-5 lc-82 cloquintocet-mexico lc-82 fenclorazol-ethyl ester lc-82 isoxadifen-ethyl lc-82 mefenpir lc-82 fenclorim lc-82 cumiluron lc-82 S4-1 lc-82 S4-5 lc-83 cloquintocet-mexico lc-83 fenclorazol-ethyl ester lc-83 isoxadifen-ethyl lc-83 mefenpyriethyl lc-83 fenclorim lc-83 cumiluron lc-83 S4-1 lc-83 S4-5 lc-84 cloquintocet-mexico lc-84 fenclorazol-ethyl ester lc-84 isoxadifen-ethyl lc-84 mefenpyriethyl lc-84 fenclorim lc-84 cumiluron lc-84 S4-1 lc-84 S4-5 lc-85 cloquintocet-mexilic Active substance of formula (I) Antidote lc-85 fenclorazole ethyl ester lc-85 isoxadifen-ethyl lc-85 mefenpyridyl lc-85 fenclorim lc-85 cumiluron lc-85 S4-1 lc-85 S4-5 lc-86 cloquintocet-mexico lc-86 fenclorazol-ethyl ester lc-86 isoxadifen-ethyl lc-86 mefenpyriethyl lc-86 fenclorim lc-86 cumiluron lc-86 S4-1 lc- 86 S4-5 lc-87 cloquintocet-mexico lc-87 fenclorazol-ethyl ester lc-87 isoxadifen-ethyl lc-87 mefenpyriethyl lc-87 fenclorim lc-87 cumiluron lc-87 S4-1 lc-87 S4-5 lc -88 cloquintocet-mexico lc-88 fenclorazol-ethyl ester lc-88 isoxadifen-ethyl lc-88 mefenpyriethyl lc-88 fenclorim lc-88 cumiluron lc-88 S4-1 lc-88 S4-5 lc-89 cloquintocet-mexico lc-89 fenclorazol-ethyl ester Active substance of formula (I) lc-89 isoxadifen-ethylic antidote lc-89 mefenpyriethyl lc-89 fenclorim lc-89 cumiluron lc-89 S4-1 lc-89 S4-5 ld-1 cloquintocet-mexico l -d-1 fenclorazol-ethyl ester ld-1 isoxadifen-ethyl ld-1 mefenpyriethyl ld-1 fenclorim ld-1 cumiluron ld-1 S4-1 ld-1 S4-5 ld-2 cloquintocet-mexico ld-2 fenclorazol ld-2 isoxadifen-ethyl ester ld-2 mefenpyr diethyl ld-2 phenlorim ld-2 cumiluron ld-2 S4-1 ld-2 S4-5 ld-3 cloquintocet-mexico ld-3 fenclorazol-ethyl ester ld- 3 isoxadifen-ethyl 1d-3 mefenpyriethyl 1d-3 phenochlorin ld-3 cumiluron ld-3 S4-1 ld-3 S4-5 ld-4 cloquintocet-mexilic ld-4 fenclorazol-ethyl ester ld-4 isoxadifen-ethyl active formula (I) Ld-4 mefenpyr-diethyl antidote ld-4 phenochlorin ld-4 cumiluron ld-4 S4-1 ld-4 S4-5 ld-5 cloquintocet-mexico ld-5 fenclorazol-ethyl ester ld-5 isoxadifen ld-5 mefenpir-diethyl ld-5 phenochlorin ld-5 cumiluron ld-5 S4-1 ld-5 S4-5 ld-6 cloquintocet-mexico ld-6 fenclorazol-ethyl ester ld-6 isoxadifen-ethyl ld-6 mefenpir-diethyl ld-6 fenclorim ld-6 cumiluron ld-6 S4-1 l -d-6 S4-5 ld-7 cloquintocet-mexico ld-7 fenclorazol-ethyl ester ld-7 isoxadifen-ethyl ld-7 mefenpyridyl ld-7 fenclorim ld-7 cumiluron ld-7 S4-1 ld-7 S4 -5 ld-8 cloquintocet-mexico ld-8 fenclorazol-ethyl ester ld-8 isoxadifen-ethyl ld-8 mefenpir diethyl Active substance of the formula (I) Antidote ld-8 fenclorim ld-8 cumiluron ld-8 S4-1 ld -8 S4-5 | -d-9 cloquintocet-mexican ld-9 fenclorazol-ethyl ester ld-9 isoxadifen-ethyl ld-9 mefenpyridyl ld-9 fenclorim ld-9 cumiluron ld-9 S4-1 ld-9 S4 -5 | -d-10 cloquintocet-mexican | -d-10 fenclorazol-ethyl ester ld-10 isoxadifen-ethyl ld-10 mefenpyriethyl ld-10 fenclorim ld-10 cumiluron ld-10 S4-1 ld-10 S4- 5 | -d-11 cloquintocet-mexico ld-11 fenclorazol-ethyl ester ld-11 isoxadifen-ethyl ld-11 mefenpyriethyl ld-11 fenclorim ld-11 cumiluron ld-11 S4-1 ld-11 S4-5 | - cloquintocet-mexico eM2 ld-12 fenclorazol-ethyl ester ld-12 isoxadifen-ethyl ld-12 mefen pyrdiethyl ld-12 fenclorim Active substance of formula (I) Antidote ld-12 cumiluron ld-12 S4-1 ld-12 S4-5 ld-13 cloquintocet-mexico ld-13 fenclorazol-ethyl ester ld-13 isoxadifen-ethyl ld-13 mefenpir-diethyl ld-13 phenochlorim ld-13 cumiluron ld-13 S4-1 ld-13 S4-5 ld-14 cloquintocet-mexico ld-14 fenclorazol-ethyl ester ld-14 isoxadifen-ethyl ld-14 mefenpir- diethyl ld-14 fenclorim ld-14 cumiluron ld-14 S4-1 ld-14 S4-5 ld-15 cloquintocet-mexico ld-15 fenclorazol-ethyl ester ld-15 isoxadifen-ethyl ld-15 mefenpyridyl ld-15 fenclorim ld-15 cumiluron ld-15 S4-1 ld-15 S4-5 lf-1 cloquintocet-mexico lf-1 fenclorazol-ethyl ester lf-1 isoxadifen-ethyl lf-1 mefenpir-diethyl lf-1 fenclorim lf-1 cumiluron Substance active ingredient of formula (I) Lf-1 S4-1 lf-1 S4-5 lf-2 cloquintocet-mexilic lf-2 fenclorazol-ethyl ester lf-2 isoxadifen-ethyl ester lf-2 mefenpir-diethyl ester lf-2 fenclorim lf- 2 cumiluron lf-2 S 4-1 lf-2 S4-5 lf-3 cloquintocet-mexico lf-3 fenclorazol-ethyl ester lf-3 isoxadifen-ethyl lf-3 mefenpyriethyl lf-3 fenclorim lf-3 cumiluron lf-3 S4-1 lf- 3 S4-5 lf-4 cloquintocet-mexican lf-4 phenochlorazol-ethyl ester lf-4 isoxadifen-ethyl lf-4 mefenpyriethyl lf-4 phenlorim lf-4 cumiluron lf-4 S4-1 lf-4 S4-5 lf -5 cloquintocet-mexican lf-5 fenclorazol-ethyl ester lf-5 isoxadifen-ethyl lf-5 mefenpir-diethyl lf-5 fenclorim lf-5 cumiluron lf-5 S4-1 Active substance of formula (I) Antidote lf-5 S4 -5 lf-6 cloquintocet-mexicano lf-6 fenclorazol-ethyl ester lf-6 isoxadifen-ethyl lf-6 mefenpyriethyl lf-6 fenclorim lf-6 cumiluron lf-6 S4-1 lf-6 S4-5 lf-7 cloquintocet-mexico lf-7 phenochlorazol-ethyl ester lf-7 isoxadifen-ethyl lf-7 mefenpyriethyl lf-7 fenclorim lf-7 cumiluron lf-7 S4-1 lf-7 S4-5 | -f-8 cloquintocet-mexico lf-8 fenclorazol-ethyl ester lf-8 isoxadifen-ethyl lf-8 mefenpir-diethyl lf-8 fenclorim lf-8 cumiluron lf-8 S4-1 lf-8 S4-5 lf-9 cloquintocet-mexico lf-9 fenclorazol-ethyl ester lf-9 isoxadifen-ethyl lf-9 mefenpyridyl lf-9 fenclorim lf -9 cumiluron lf-9 S4-1 lf-9 S4-5 Active substance of formula (I) Antidote | -f-10 cloquintocet-mexilic | -f-10 fenclorazol-ethyl ester lf-10 isoxadifen-ethyl lf-10 mefenpir lf-10 fenclorim lf-10 cumiluron lf-10 S4-1 lf-10 S4-5 lf-11 cloquintocet-mexico lf-11 fenclorazol-ethyl ester lf-11 isoxadifen-ethyl lf-11 mefenpyr-diethyl lf-11 fenclorim lf-11 cumiluron lf-11 S4-1 lf-11 S4-5 lf-12 cloquintocet-mexico lf-12 fenclorazol-ethyl ester lf-12 isoxadifen-ethyl lf-12 mefenpyr-diethyl lf-12 fenclorim lf-12 cumiluron lf-12 S4-1 lf-12 S4-5 lf-13 cloquintocet-mexilic lf-13 fenclorazol-ethyl ester lf-13 isoxadifen-ethyl lf-13 mefenpir-diethyl lf-13 fenclorim lf-13 cumiluron lf-13 S4- 1 lf-13 S4-5 | -f-14 cloquintocet-mexico Substance active formula (I) Antidote.  lf-14 fenclorazol-ethyl ester lf-14 isoxadifen-ethyl lf-14 mefenpyriethyl lf-14 fenclorim lf-14 cumiluron lf-14 S4-1 lf-14 S4-5 lf-15 cloquintocet-mexico lf-15 fenclorazol- ethyl ester lf-15 isoxadifen-ethyl lf-15 mefenpyr diethyl lf-15 phenlorim lf-15 cumiluron lf-15 S4-1 lf-15 S4-5 lf-16 cloquintocet-mexico lf-16 fenclorazol-ethyl ester lf-16 isoxadifen-ethyl lf-16 mefenpyr-diethyl lf-16 fenclorim lf-16 cumiluron lf-16 S4-1 lf-16 S4-5 lf-17 cloquintocet-mexico lf-17 fenclorazol-ethyl lf-17 isoxadifen-ethyl lf-17 mefenpir-diethyl lf-17 fenclorim lf-17 cumiluron lf-17 S4-1 lf-17 S4-5 lf-18 cloquintocet-mexilic lf-18 fenclorazol-ethyl Active substance of formula (I) lf-18 isoxadifen-ethyl antidote -18 mefenpyriethyl lf-18 phenochlorim lf-18 cumiluron lf-18 S4-1 lf-18 S4-5 lf-19 cloquintocet-mexico lf-19 fenclorazol-ethyl lf-19 isoxadifen-ethyl lf-19 mefenpyridyl lf -19 fe nchlorim lf-19 cumiluron lf-19 S4-1 lf-19 S4-5 lf-20 cloquintocet-mexico lf-20 fenclorazol-ethyl lf-20 isoxadifen-ethyl lf-20 mefenpyridyl lf-20 fenclorim lf-20 cumiluron lf -20 S4-1 lf-20 S4-5 lf-21 cloquintocet-mexico lf-21 fenclorazol-ethyl lf-21 isoxadifen-ethyl lf-21 mefenpyriethyl lf-21 fenclorim lf-21 cumiluron lf-21 S4-1 lf -21 S4-5 lf-22 cloquintocet-mexican lf-22 fenclorazol-ethyl lf-22 isoxadifen-ethyl Active substance of the formula (I) Lf-22 mefenpir-diethyl antidote lf-22 fenclorim lf-22 cumiluron lf-22 S4- 1 lf-22 S4-5 lf-23 cloquintocet-mexico lf-23 fenclorazol-ethyl lf-23 isoxadifen-ethyl lf-23 mefenpyriethyl lf-23 fenclorim lf-23 cumiluron lf-23 S4-1 lf-23 S4- 5 lf-24 cloquintocet-mexico lf-24 fenclorazol-ethyl lf-24 isoxadifen-ethyl lf-24 mefenpyriethyl lf-24 fenclorim lf-24 cumiluron lf-24 S4-1 lf-24 S4-5 lf-25 cloquintocet- mexican lf-25 fenclorazol-et lf-25 isoxadifen-ethyl lf-25 mefenpyriethyl lf-25 phentlorim lf-25 cumiluron lf-25 S4-1 lf-25 S4-5 Surprisingly, it has also been found that the combinations of active substances defined above of the compounds of formula (I) and antidotes of the above group (b '), have a particularly high herbicidal activity, compatibility with very good crop plants, and can be used on various crops, particularly cereals (mainly wheat), but also in soybeans, potatoes, corn and rice for selective weed control.

In such a case, it should be considered surprising that of a plurality of known antidotes which are capable of antagonizing the harmful effect of a herbicide on crop plants, therefore the above related compounds of group (b ') are suitable for almost completely suppressing the harmful effect of compounds of formula (I) on crop plants, without in this case substantially impairing herbicidal efficiency in relation to weeds.

In this case, the particularly advantageous effect of the particularly preferred combination components of group (b '), particularly as regards the protection of cereal plants such as, for example, wheat, barley and rye, should be highlighted. also corn and rice as crop plants.

The compounds according to the invention are generally defined by formula (I). Preferred substituents or scopes of the related radicals in the above and below formulas are explained below: X preferably represents C1 -C4 alkyl, C3 -C6 cycloalkyl or C1 -C4 alkoxy, Y preferably represents hydrogen, C1 -C4 alkoxy. C 4 -C 4 alkyl or C 1 -C 4 alkoxy, Z preferably represents hydrogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, A, B and the carbon atom to which they are attached preferably represents C 3 -C 8 -cycloalkyl or C5-C8-cycloalkenyl, in which optionally one or two ring members are substituted by oxygen and / or sulfur and which are optionally mono- or tetrasubstituted by C1-C8-alkyl, C1-C8-alkenyl, (VCU-alkylene, C1-C8-haloalkyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C8-alkoxy, C1-C6-haloalkoxy, hydroxy, hydroxy-C1-C4-alkyl or benzyloxy, or another C3 -C8 -cycloalkyl condensed ring, in which optionally one or two ring members are substituted by oxygen or sulfur, or which optionally is mono- or disubstituted by C1 -C8 alkyl, or A, B and the carbon atom to which they are attached preferably represents a carbonyl group, represents a C1 -C4 alkylene group or represents a group = N -OR9, G preferably represents hydrogen (a) or preferably represents one of the groups in which E represents a metal ion equivalent or an ammonium ion, L represents oxygen or sulfur, and M represents oxygen or sulfur, R 1 preferably represents C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 1 -C 6 alkoxyC 1 -C 6 alkyl, C 1 -C 6 alkylthioC 1 -C 6 alkyl, polyC 1 -C 8 alkoxy; C 1 -C 8 alkyl in each case optionally substituted by halogen or C 3 -C 8 cycloalkyl optionally substituted by halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy in which optionally one or more (preferably no more than two) non-directly adjacent ring members are replaced by oxygen and / or sulfur, represents phenyl, optionally substituted a by halogen, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 alkylsulfonyl represents phenyl C 1 -C 6 alkyl substituted by halogen, nitro, cyano, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 haloalkyl or C1 -C6 haloalkoxy preferably represents 5- or 6-membered hetaryl e.g. pyrazolyl, thiazolyl , pyridyl, pyrimidyl, furanyl or thienyl), optionally substituted by halogen- or C1-C8-alkyl, represents phenoxy-C1 -C6 -alkyl, optionally substituted by halogen or C1-C6-alkyl or represents hethoxy-C1-C6-alkyl 5- or 6-membered alkyl (e.g. pyridyl-C 1 -C 6 alkyl, pyrimidyl C 1 -C 6 alkyl or thiazolyloxy C 1 -C 6 alkyl), optionally substituted by halogen, amino or C 1 -C 6 alkyl, 2'R preferably C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 1 -C 8 alkoxy-C 2 -C 8 alkyl, polyC 1 -C 8 alkoxy-C 2 -C 8 alkyl, in each case optionally substituted by halogen, represents C 3 -C 8 -cycloalkyl optionally substituted by halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy preferably represents phenyl or benzyl, in each case optionally substituted by halogen, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 -C 1-6 alkoxy, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy, 3 R preferably represents C 1 -C 8 alkyl optionally substituted by halogen or represents phenyl or benzyl, in each case optionally substituted by halogen, C 1 -C 6 -alkoxy. C 6 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano or nitro, R 4 and R 5 independently of each other preferably represent C 1 -C 8 alkyl, C 1 -C 8 alkoxy C 1 -C 8 alkylamino, D 1- (C 1 -C 8 alkyl) amino, C 1 -C 8 alkylthio, C 2 -C 8 alkenylthio, C 3 -C 7 cycloalkylthio, in each case optionally substituted with halogen, or represent phenyl, phenoxy or phenythio in each case optionally substituted by halogen, nitro, cyano, C1 -C4 alkoxy, C1 -C4 haloalkoxy, C1 -C4 alkylthio, C1 -C4 haloalkylthio, C1 -C4 a C1-4 alkyl haloalkyl, R7 and R7 independently of each other preferably represent hydrogen, C1 -C8 alkyl, C3 -C8 cycloalkyl, C1 -C8 alkoxy, C3 -C8 alkenyl, C1-6 alkyl. C8-C1 -C8 alkoxyalkyl, in each case optionally substituted by halogen, represent phenyl, optionally substituted by C1 -C8 -haloalkyl, C1 -C8 -alkyl or C1 -C8, represent benzyl, optionally substituted by halogen-, C1-8 C8-alkyl, C1-C8-haloalkyl or C1-C8-alkoxy, or together represent a C3-C6-alkylene radical, optionally substituted by C1-C4-alkyl, where optionally a carbon atom is substituted by oxygen or sulfur, R 9 represents preferably hydrogen, represents C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, CH 2 C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, in each case mono- halosubstituted or represents phenylC 1 -C 2 alkyl or hetarylC 1 -C 2 alkyl, in each case optionally mono- to trisubstituted. o by alkyl, halogen, alkoxy, haloalkyl or haloalkoxy.

In the definitions of radicals cited as preferred, halogen represents fluorine, chlorine, bromine and iodine, particularly fluorine, chlorine and bromine. With the terms alkyl, alkylidene and alkenyl both linear and branched hydrocarbon radicals are indicated. X is particularly preferably methyl, ethyl, cyclopropyl, methoxy or ethoxy, Y is particularly preferably hydrogen, methyl or ethyl, Z is particularly preferably hydrogen, methyl, ethyl or cyclopropyl A, B and the carbon atom to which they are attached represent particularly preferably C3-C8-cycloalkyl or C5-C8-cycloalkenyl, in which one or two ring members are optionally substituted by oxygen and / or sulfur and which are optionally mono- or tetrasubstituted by C 1 -C 4 alkyl, C 1 -C 4 alkenyl, a group = CH 2, trifluoromethyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxyC 1 -C 2 alkyl or with one of the groups A, B and the carbon atom to which they are attached represent particularly preferably a carbonyl group, represent a C1 -C4 alkylene group or represent a group = N-OR9, G represents particularly hydrogen (a) or preferably represents one of groups in which E represents a metal ion equivalent or an ammonium ion, L represents oxygen or sulfur, and M represents oxygen or sulfur, R1 represents particularly preferably C1 -C8 alkyl, C2 -C8 alkenyl, C1 -C4 alkoxy -C 1 -C 2 alkyl, C 1 -C 4 alkylthio-C 1 -C 2 alkyl optionally in each case mono- to trisubstituted by fluorine or chlorine, or preferably represents C 3 -C 6 -cycloalkyl, optionally mono- to disubstituted. fluorine, chlorine, C1 -C2 alkyl or C1 -C2 alkoxy, in which optionally one or two non-directly adjacent ring members are substituted by oxygen, represents phenyl optionally mono- disubstituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 2 haloalkyl or C 1 -C 2 haloalkoxy, 2 R is particularly preferably C 1 -C 8 alkyl, C 2 -C 8 alkenyl or C 1 -C 4 alkoxy -C 2 -C 4 -alkyl, in each case optionally mono- to trisubstituted by fluorine, represents C 3 -C 6 -cyclo alkyl, optionally monosubstituted by C1 -C2 alkyl or C1 -C2 alkoxy or represents phenyl or benzyl, in each case optionally mono- substituted by fluorine, chlorine, bromine, cyano, nitro, C1 -C4 alkyl, C1 -C 3 -alkoxy, trifluoromethyl or trifluoromethoxy, 3 R is particularly preferably C 1 -C 6 alkyl, optionally mono- to trisubstituted by fluorine, or represents phenyl optionally monosubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C1 -C4 alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, R4 represents particularly preferably C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 alkylamino, di (C1 -C6 alkyl) amino, C1-4. C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio, in each case optionally mono- to trisubstituted by fluorine or chlorine, or represents phenyl, phenoxy or phenylthio, in each case optionally monosubstituted by fluorine , chloro, bromo, nitro, cyano, C1 -C3 alkoxy, C1 -C3 haloalkoxy, C1 -C3 alkylthio, C1 -C3 haloalkyl R 1, C 1 -C 3 alkyl or trifluoromethyl, R 5 is particularly preferably C 1 -C 6 alkoxy or C 1 -C 6 alkylthio, optionally monosubstituted by chlorine, R R is particularly preferably hydrogen, C 1 -C 6 alkyl C3 -C6 cycloalkyl, C1 -C6 alkoxy, C3 -C6 alkenyl, C1 -C6 alkoxy C1 -C4 alkyl represents phenyl optionally monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, C1 -C4 alkyl or C1 -C4 alkoxy represents benzyl, optionally monosubstituted by fluorine, chlorine, bromine, C1 -C4 alkyl, trifluoromethyl or C1 -C4 alkoxy, R7 particularly preferably represents C1 -C6 alkyl, C3 -C6 alkenyl or C1 -C 6 -C 1 -C 4 alkoxyalkyl, R 7 and R 5 together particularly preferably represent a C 4 -C 5 alkylene radical, optionally substituted by methyl or ethyl, in which optionally a group methylene is substituted by oxygen or sulfur, R9 represents particularly preferably hydrogen, resides C1 -C4 alkyl, C3 -C6 cycloalkyl, CH2 C3 -C6 cycloalkyl, C3 -C4 alkenyl, C3 -C4 alkynyl, in each case optionally mono- to trisubstituted by fluorine or chlorine, represents benzyl or pyridinylmethyl, in each case optionally mono- or disubstituted by C 1 -C 2 alkyl, C 1 -C 2 alkoxy, fluoro, chloro, bromo, trifluoromethyl or trifluoromethoxy.

In the definitions of radicals cited as particularly preferred, halogen represents fluorine, chlorine and bromine, particularly fluorine and chlorine. With the terms alkyl, alkylidene and alkenyl are indicated both linear and branched hydrocarbon radicals. X is especially preferably methyl, ethyl, cyclopropyl, methoxy or ethoxy (especially ethyl), Y is especially preferably hydrogen, methyl or ethyl (especially methyl), Z is especially preferably hydrogen, methyl, ethyl or cyclopropyl, A, B and the carbon atom to which they are attached, preferably represent C 3 -C 7 cycloalkyl or C 5 -C 7 cycloalkenyl, in which optionally one or two ring members are substituted by oxygen and / or sulfur and which is optionally mono-, di-, tri- or tetras-substituted by methyl, in each case monosubstituted by ethyl, a group = CH 2, methoxy or ethoxy, A, B and the carbon atom to which they are attached represents especially preferably a carbonyl group, represents a group = CH2, represents a group = CH2-CH3, represents a group = CH2-C2H5 or represents a group = N-OR9, G particularly preferably represents hydro (a) or represents one of the groups in which E represents a metal ion equivalent (Na + or K +), L represents oxygen or sulfur and M represents oxygen or sulfur, R1 represents especially preferably C1 -C6 alkyl, C 2 -C 6 -alkenyl, C 1 -C 2 -alkoxyC 1 -alkyl, C 1 -C 2 -alkylthio-C 1-6 alkyl represents C 3 -C 6 cyclopropyl, which is optionally monosubstituted by fluoro, chloro, methyl or methoxy or represents C 1 -C 4 alkyl , which is monosubstituted by chlorine, represents phenyl, optionally monosubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy, 2 R is especially preferably C1 -C6 alkyl, C2 -C6- alkenyl or C 1 -C 4 alkoxy-C 2 -C 3 alkyl, phenyl or benzyl, in each case optionally mono- to trisubstituted by fluorine, 3 R represents especially preferably C 1 -C 6 alkyl or represents phenyl, optionally monosubstituted by chlorine or C1-C4-alkyl, R9 represents Especially preferably hydrogen represents methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl or tert-butyl, in each case optionally substituted by fluorine, represents allyl, chloroalyl, propynyl, butinyl, chlorobenzyl, chloropyridylmethyl CH (CH 3) -C 4 CH, cyclopropyl, cyclobutyl, cyclopentyl, CH 2 -cyclopropyl, Ch 2 -cyclobutyl or CH 2 -cyclopentyl. X most preferably represents methyl, ethyl or methoxy, Y most preferably represents methyl or ethyl, Z most preferably represents hydrogen, methyl or ethyl, A, B and the carbon atom to which they are attached, most preferably represent C5 -C7 -cycloalkyl or C7-cycloalkenyl, in which optionally one or two ring members are substituted by oxygen and / or sulfur and which is optionally mono-, di-, tri- or tetras-substituted by methyl, in each case monosubstituted by ethyl, a group = CH 2, methoxy, ethoxy or benzyloxy, A, B and the carbon atom to which they are attached, represent mainly preferably a group. carbonyl, represent a group = CH2, or represent a group = N-OR9, G represents preferably hydrogen (a) or represents one of the groups in which E represents a metal ion equivalent (Na +), L represents oxygen and M represents oxygen R 1 represents mainly preferably C 1 -C 6 alkyl, or C 1 -C 2 alkoxyC 1 alkyl or C 1 -C 4 alkoxy Cralkyl or represents C 1 -C 4 alkyl, monosubstituted by chlorine, represents phenyl, monosubstituted by chlorine methyl or methoxy, R 2 is mainly preferably C 1 -C 8 alkyl, R 3 is preferably preferably methyl, phenyl or p-methylphenyl, R 9 is preferably preferably hydrogen, methyl, propyl, i-butyl, tert-butyl, CH2 CF3, propynyl (CH2-CeCH), CH (CH3) -CHS, cyclopropyl, cyclopentyl, CH2-cyclopropyl, CH2-cyclopentyl.

The definitions of radicals or explanations, listed above generally or in preferred scopes, may be combined in any way, therefore, also between the respective preferred scopes and scopes. They apply to end products as well as correspondingly to precursors and intermediate products.

In accordance with the invention, compounds of formula (I) are preferred, in which a combination of the meanings set forth above are present as preferred (preferably).

Particularly preferred according to the invention are compounds of formula (I), in which a combination of the meanings set forth above as particularly preferred is present.

Especially preferred according to the invention are compounds of formula (I), in which a combination of the meanings set forth above as especially preferred is present.

According to the invention, compounds of formula (I) are particularly preferred, in which a combination of the meanings set forth above are presently preferred.

In accordance with the invention, compounds of formula (I), in which a combination of the meanings set forth above as presently preferred, are presently preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediyl or alkenyl, also in connection with heteroatoms, such as, for example, in alkoxy, may as far as possible be linear or branched in each case.

Optionally substituted radicals, when not otherwise indicated, may be mono- or polysubstituted, and in polysubstitutions the substituents may be identical or different.

Particularly prominently, G represents hydrogen. In addition to the compounds cited in the preparation examples, the following compounds of formula (1-la) are individually cited: Table 1: X = CH 3, Y = CH 3, Z = CH 3 Table 2: A and B as mentioned in Table 1 and X = C 2 H 5; Y = CH3; Z = CH 3 Table 3: A and B as mentioned in Table 1 and X = C 2 H 5; Y = CH3; Z = C 2 H 5 Table 4: A and B as mentioned in Table 1 and X = C 2 H 5; Y = C 2 H 5; Z = C 2 H 5 Table 5: A and B as mentioned in Table 1 and X = 4; Y = CH3; Z = CH 3 Table 6: A and B as mentioned in Table 1 and X = 4; Y = CH3; Z = C 2 H 5 Table 7: A and B as mentioned in Table 1 and X = OCH 3; Y = CH3; Z = CH 3 Table 8: A and B as mentioned in Table 1 and X = OC 2 H 5; Y = CH3; Z = CH3 Table 9: A and B as mentioned in Table 1 and X = OCH3; Y = CH3; Z = C 2 H 5 Table 10: A and B as mentioned in Table 1 and X = OC 2 H 5; Y = CH3; Z = C 2 H 5 Table 11: A and B as mentioned in Table 1 and X = C 2 H 5; Y = CH3; Z = H Table 12: A and B as mentioned in Table 1 and X = 1 Y = CH 3; Z = ^ Table 13: A and B as mentioned in Table 1 and X = C 2 H 5; Y = C2H5; Z = CH3 It has been described in the literature how the action of various active substances can be enhanced by the addition of ammonium salts. But in this case, they are detergent-acting salts (e.g. WO 95/017817) or salts which have relatively long alkyl and / or aryl substituents that have a permeabilizing action or that increase the solubility of the substances. (e.g., EP-A 0 453 086, EP-A 0 664 081, FR-A 2 600 494, US 4,844,734, US 5 462 912, US 5 538 937, US-A 03/0224939, US-A 05/0009880, US-A 05/0096386). Furthermore, the prior art describes action only for certain active substances and / or for specific applications of the corresponding compositions. In still other cases, they are salts of sulfonic acids, in which the acids themselves have a paralyzing effect on insects (US 2,842,476). A reinforcement of action, for example by ammonium sulfate is described, for example, for glyphosate, phosphinothricin and phenyl substituted cyclic ketoenols (US 6 645 914, EP-A2 0 036 106, WO 07/068427). A corresponding reinforcing action on insecticides has already been described in WO 07/068428.

Also the use of ammonium sulfate as a formulation adjuvant is described for certain active substances and applications (WO 92/16108), but therein serves to stabilize the formulation, not to reinforce the action.

Also surprisingly, it has now been found that the action of phenyl-substituted bicyclooctan-1,3-dione class insecticides and / or acaricides and / or herbicides of the formula (I) can be clearly increased by the addition of ammonium or phosphonium salts to the application solution or by incorporation of those salts into a formulation containing as a active substance phenyl-substituted bicyclo-octan-1,3-dione derivatives of the formula (I) of action herbicide and / or insecticide and / or petted. Also subject to the invention are agents containing phenyl substituted bicyclooctan-1,3-dione derivatives of herbicidal and / or insecticidal and / or acaricidal action and ammonium or phosphonium salts which enhance the namely formulated active substances as well as ready-to-use products (spray broths). Finally, it is a further object of the invention to use such agents to control harmful insects and / or mites and / or undesirable plant growth.

The active substances may be used in the compositions according to the invention over a wide concentration range. In this case, the concentration of active substances in the formulation normally amounts to 0.1 to 50% by weight.

Ammonium and phosphonium salts, which according to the invention reinforce the action of plant protection agents containing fatty acid biosynthesis inhibitors, are defined by the formula (ΙΙΓ) in which D represents nitrogen or phosphorus, D represents preferably nitrogen, R 26, R 27, R 28 and R 29 independently of one another represent optionally substituted hydrogen or C 1 -C 8 alkyl, or optionally substituted C 1 -C 8 alkylene, mono- or poly-unsaturated, wherein the substituents may be selected from halogen, nitro and cyano, R 26, R 27, R 28 and R 29 independently of one another preferably represent hydrogen or optionally substituted C 1 -C 4 alkyl, and substituents may be selected from halogen, nitro and cyano, R26, R27, R28 and R29 independently of each other, preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or te Rc-butyl, R26, R27, R28 and R29 are especially preferably hydrogen, n represents 1,2, 3 or 4, n preferably 1 or 2, R 30 represents an organic or inorganic anion, R 30 represents preferably hydrogen carbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrophosphate, dihydrophosphate, hydrosulfate, tartrate, sulfate, nitrate, thiosulfate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate or oxalate, R 30 is mainly preferably lactate, sulfate, nitrate, thiosulfate, thiocyanate, oxalate or formate. R30 represents especially preferably sulfate.

The ammonium and phosphonium salts of formula (ΙΙΓ) may be used over a broad concentration range to enhance the action of plant-protecting agents containing phenyl-substituted bicyclo-octan-1,3-dione derivatives. of formula (I). In general, ammonium salts or phosphonium salts are used in the ready-to-use plant protection composition at a concentration of 0.5 to 80 mmol / l, preferably 0.75 to 37.5 mmol / l, particularly preferably 1.5 to 25 mmol / l. In the case of a formulated product, the concentration of ammonium salt and / or phosphonium salt in the formulation is chosen such that it is within the general, preferred or particularly preferred scope cited, after the formulation has been diluted to desired active substance concentration. The concentration of salt in the formulation is typically from 1% to 50% by weight.

In a preferred embodiment of the invention, activity is enhanced by adding to the plant protection compositions not only an ammonium salt and / or a phosphonium salt, but additionally also a penetrating agent. It is considered entirely surprising that in such cases an even greater increase in activity is observed. Therefore, the present invention also provides the use of a combination of penetrating agent and ammonium salts and / or phosphonium salts to enhance the activity of plant protection agents, which comprise as active substance bicyclooctane-1 derivatives. Phenyl-substituted 3-dione, herbicides and / or acaricides and / or insecticides, penetrating agents and ammonium and / or phosphonium salts, including specifically not only formulated active substances, but also ready-to-use compositions (broths). pulverization). Finally, the invention further provides the use of such compositions for controlling harmful insects, and / or mites and / or undesirable plant growth.

In the present context, suitable penetration agents are all substances that are commonly used to enhance the penetration of agrochemical active compounds in plants. In this context, penetration agents are defined by the fact that they penetrate from the aqueous spray broth and / or spray coating on the plant cuticles, thereby increasing the mobility of the active substances in the cuticles. The method described in the literature (Baur et al, 1997, Pesticide Science 51, 131-152) can be used to determine this property.

Examples of suitable penetrating agents include alkanol alkoxylates. Penetrating agents according to the invention are alkanol alkoxylates of formula (IV) wherein R represents straight or branched alkyl of 4 to 20 carbon atoms, R ' represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl, AO represents an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or represents mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals, and v represents a number from 2 to 30. A preferred group of penetrating agents are alkanol alkoxylates of the formula R -0 - (-E0-) nR '(IV'-a) wherein R is as defined above, R' is as defined above, EO represents -CH 2 -CH 2 -O-, n represents a number from 2 to Another preferred group of penetrating agents are alkanol alkoxylates of the formula wherein R is as defined above, R is (R) - (- E0-) p - (- P0-) q R '(IV'-b) it's t al as defined above, EO represents -CH 2 -CH 2 -O-, PO represents p represents a number from 1 to 10, and q represents a number from 1 to 10. Another preferred group of penetrating agents are alkanol alkoxylates of formula R Wherein R is as defined above, R 'is as defined above, EO represents -CH 2 -CH 2 -O-, PO r is a number from 1 to 10, and s is a number from 1 to 10. Another preferred group of penetrating agents are alkanol alkoxylates of the formula R-0 - (- E0-) p - (- B0- ) qR '(IV'-d) wherein ReR' are as defined above, EO represents -CH2-CH2-0-, BO represents p is a number from 1 to 10 and q is a number from 1 to 10. Preferred group of penetrating agents are alkanol alkoxylates of the formula R-O - (- B0-) r - (- E0-) s -R '(IV'-e) wherein R are R1 are as defined above BO represents EO represents -CH 2 -CH 2 O-, r represents a number from 1 to 10 and s represents a number from 1 to 10. of penetrating agents are alkanol alkoxylates of the formula CH 3 - (CH 2) t -CH 2 O - (-CH 2 -CH 2 O-) u-R '(IV'-f) wherein R' is as defined above, t represents a number from 8 to 13, u represents a number from 6 to 17.

In the formulas indicated above, R preferably represents butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl. , decyl, n-dodecyl, isododecyl, lauryl, myristyl, isotridecyl, trime-tilnonyl, palmityl, stearyl or eicosyl.

As an example of an alkanol alkoxylate of formula (IV-c), mention may be made of 2-ethylhexyl alkoxylate of the formula wherein EO represents -CH 2 -CH 2 O-, PO represents numbers 8 and 6 represent mean values. .

As an example of an alkanol alkoxylate of formula (IV-c), the formula CH3- (CH2) 10-O - (- EO-) 6 - (-BO-) 2-CH3 (IV-d-1) may be cited. ) where EO represents -CH2-CH2-0-, BO represents the numbers 10, 6 and 2 represent mean values.

Particularly preferred alkanol alkoxylates of formula (IV-f) are compounds of this formula wherein t is 9 to 12 and 7 to 9 is particularly preferred. f-1) CH3- (CH2) t-CH2-0 - (- CH2-CH2-0-) uH (IV-f-1) where t represents the average value 10.5 and i represents the average value 8.4 .

A general definition of alkanol alkoxylates is given by the above formulas. These substances are mixtures of the indicated type with different chain lengths. For the indices, therefore, average values are calculated, which may also differ from integers.

Alkanol alkoxylates of the mentioned formulas are known and in part are commercially available or may be prepared by known methods (according to WO 98/35 553, WO 00/35 278 and EP-A0 681 865).

Penetrating agents are also of interest, for example, substances which stimulate the availability of the compounds of formula (I) in the spray coating. They belong, for example, to mineral or vegetable oils. As oils are of interest all mineral or vegetable oils - optionally modified which may normally be used in agrochemicals. For example, sunflower oil, rapeseed oil, olive oil, castor oil, beet oil, corn seed oil, cottonseed oil and soybean oil or the esters of the oils are cited. Rapeseed oil, sunflower oil and their methyl or ethyl esters are preferred. The concentration of penetrating agents in the agents according to the invention may be varied over a wide range. In a formulated plant protection agent, it is generally from 1 to 95%, preferably from 1 to 55% by weight, most preferably from 15 to 40% by weight. In ready-to-use agents (spray broths), concentrations are generally between 0.1 and 10 g / l, preferably between 0.5 and 5 g / l.

Plant protection agents according to the invention may also contain other components, for example surfactants or dispersing or emulsifying agents.

As nonionic surfactants or dispersion adjuvants are of interest all substances of this type which can normally be used in agrochemicals. Preferably, polyethylene oxide-polypropylene oxide block copolymers, linear alcohol polyethylene glycol ethers, ethylene oxide and / or propylene oxide fatty acid reaction products, polyvinyl alcohol, polyvinylpyrrolidone are cited. , mixed polymers of polyvinyl alcohol and polyvinylpyrrolidones, as well as copolymers of (meth) acrylic acid and esters of (meth) acrylic acid, as well as alkyl ethoxylates and alkylaryl ethoxylates, which may optionally be phosphated and optionally neutralized with bases. , for example, sorbitol ethoxylates as well as polyoxyalkylenamine derivatives are cited.

As anionic surfactants are of interest all substances of this type which can normally be used in agrochemicals. Alkaline and alkaline earth metal salts of alkylsulfonic acids or alkylarylsulfonic acids are preferred.

Another preferred group of anionic surfactants or dispersion aids are poorly oil-soluble salts of polystyrenesulfonic acids, salts of polyvinylsulfonic acids, salts of naphthalinsulfonic formaldehyde condensation products, salts of naphthalinsulfonic acid condensation products, phenolsulfonic acid and formaldehyde, as well as ligninsulfonic acid salts.

Additives, which may be contained in the formulations according to the invention, are of interest, emulsifiers, foam inhibiting agents, preservatives, antioxidants, dyes and inert fillers.

Preferred emulsifiers are nonylphenols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethoxylated arylalkylphenols, as well as ethoxylated and propoxylated arylalkylphenols, as well as sulfated or -ethoxy propylated arylalkylphenols being sulfated derivatives, Sorbitan compounds, such as polyethylene sorbitan oxide fatty acid esters and sorbitan fatty acid esters, are cited by way of example. With good compatibility with plants and favorable toxicity for warm-blooded animals and good compatibility with the environment, the active substances are suitable for protection of plants and plant organs, for increased crop productivity, improving crop material quality. and for the control of animal pests, particularly insects, mites, helminths, nematodes and molluscs, which are present in agriculture, gardening, breeding, forests, gardens and leisure facilities, the protection of stored products and the protection of materials as well as in the hygiene sector. They may preferably be used as plant protection agents. They are effective against normally sensitive and resistant species, as well as against all stages of development or individual stages of development. To the above mentioned pests belong: Of the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.

From the Arachnida class, for example, Acarus spp., Acena sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus vien nensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp. Dermanyssus gallinae, Eotetranychus spp., Epitrimerus piri, Eutetranychus pp., Eriophyes spp., Halotydeus destructor, Hemitarsonamus spp., Hyalomma spp., Ixodes spp. ., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonamus latus, Psoroptes spp., Rhipi-cephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steno-tarsonamus spp. ■ From the Bivalva class, for example, Dreissena spp.

From the order of the Chilopoda, for example, Geophilus spp., Scutige spp.

Of the order Coleoptera, for example Acalymma vittatum, A-canthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp. , Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites zealand. spp., Curculio spp., Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp., Epilachna spp., Faustinus spp., Gibbium psyllo, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, False hypera, Hypothenemus spp., Lachnosterna consanguinea, Lema spp., Leptinotarsa decemlineata, Leucoptera spp. , Megascelis spp., Melanotus spp., Meligethes ae-neus, Melolontha sp. Phyllotreta spp., Popillia japonica, Premno-trypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Symphyle-tes spp., Tanymecus spp. molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of Diptera, for example Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chironomus spp., Chrysomyia spp. spp., Contarinia spp., Cordylobia anthropo-phaga, Culex spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Erosocnemus spp., Fannia spp., Gas-trophilus spp. ., Flydrellia spp., Flylemyia spp., Hyppobosca spp., Hypoderma spp., Liromyomy spp., Lucilia spp., Musca spp., Nezara spp., Oscinella frit, Pegomyia spp., Phorbia spp. spp., Psila rosae, Rhagoletis spp., Stomoxis spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp.

From the Gastropoda class, for example, Arion spp., Biomphaliaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncome-lania spp., Pomacea spp., Succinea spp.

From the Helminth class, for example Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubicoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp. Dicrocoelium spp, Dictyocau-lus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp. spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistoso-men spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stroniloides spp., Taenia saginata, Taenia solium , Trichinella pseudopsiralis, Trichostron-gulus spp., Trichuris trichuria, Wuchereria bancrofti.

In addition, it is possible to control protozoans such as Eimeria.

From the order of the Heteroptera, for example, Anasa tristis, Antesti-opsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Collim spp., Creontiades dilutus, Dasynus piperis, Diche-lops furcatus. , Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eury-gaster spp., Heliopeltis spp., Hordes nobilellus, Leptocorisa spp., Leptoglos-sus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monalonara atra-tump, ., Oebalus spp., Pentomidae, Piesma quadrata, Pezezororus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singu-laris, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp.

Of the order Homoptera, for example Acyrthosipon spp., A-crogonia spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolo-bus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aoni-diella spp. Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycau-dus helichrysii , Ceratovacuna lanigera, Cercopidae, Cero-plastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomyti-lus halli, Coccus spp. Diapus spp. Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythronaura spp., Ferrisia spp., Geococcus coffeae, Hieroglyagus spod. Hyalopterus arundinis, Icerya spp. Idioc Erus spp., Idioscopus spp., Lao-delphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Ma-crosiphum spp., Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Me-topolophium dirhodum, Monallia monallia Monalliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilapan / ata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myp., Paratrioza spp. Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Plano-coccus spp., Protopulvinaria piriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp. Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina leurodes spp., Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.

From the order of the Hymenoptera, for example Athalia spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Isopoda, for example, Armadillidium vulgare, O-niscus asellus, Porcellio scaber.

From the order of the Isoptera, for example Acromyrmex spp., Atta spp., Cornitermes cumulans, Microtermes obesi, Odontotermes spp., Reticu-litermes spp.

From the order of the Lepidoptera, for example Acronicta major, Ado-xophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois tran-sitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Ca-coecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonalla, Carposina niponansis, Cheimatobia brumata, Chilo spp., Choristonaura spp. , Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Di-aphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, E-lasmopalpus lignosellus, Eldana saccharin, Ephella epiphinae , Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonalla, Gracillaria spp., Grapholitha spp., Helicoverpa spp., Heliothis spp. Hof-mannophila pseudospretella, Homoeosoma s , Homona spp., Hyponomeu-ta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antenata, Lobesia spp., Loxagrotis albicosta, Lyobia sp. spp., Ma-lacosoma neustria, Maruca testulalis, Mamestra brassicae, Mocis spp., My-thimna separata, Nymphula spp., Oiketicus spp., Oria spp., Ostrinia spp., Oulema oryzae, Panolis fiam mea, Pamara spp., Pectinophora spp., Períleucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllo-norycter spp., Pieris spp., Platynota stuttana, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Protopar spp. , Pseudaletia spp., Pseudoplusia includens, Pirausta nubilalis, Nude Rachiplusia, Schoenobius spp., Scirpophaga spp., Scotia segetum, Sesamia spp., Sparganothis spp., Stathmopoda spp., Stomopa spp. -nivorous, Thermesia gemmatalis, Tinea pellionalla, Tineola bisselliella, Tortrix spp., Trichoplusia spp., Tuta absolut, Virachola spp.

From the order of Orthoptera, for example, Acheta domesticus, Blatta orientis lis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leu-cophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.

From the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis.

From the order of the Symphyla, for example, Scutigerella spp ..

From the order of the Thysanoptera, for example, Anaphothrips obscu-rus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Franklini-ella spp.

From the order of the Thysanura, for example, Lepisma saccharina.

Plant parasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp. semipenetrans, Xi-phinema spp.

At certain concentrations or amounts of application, the compounds according to the invention may also optionally be used as herbicides, antidotes, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides. , antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (Mycoplasma-like-organism) and RLO (Rickettsia-like-organism). Optionally, they may also be used as intermediates or precursors for the synthesis of other active substances.

Active substances can be transformed into the usual formulations such as solutions, emulsions, spray powders, water and oil based suspensions, powders, dusting agents, pastes, soluble powders, soluble granules, sprinkling granules, suspension concentrates. -emulsion, active substance impregnated natural materials, active substance impregnated synthetic materials, fertilizers, as well as thin encapsulations in polymeric materials.

Such formulations are produced in a known manner, for example by mixing the active substances with diluents, thus liquid solvents and / or solid carriers, optionally under the use of surfactants, hence emulsifiers and / or dispersing and / or dispersing agents. foaming agents. Production of the formulations takes place at appropriate facilities or before or during application.

As adjuvants can be used substances which are suitable to impart to the agent itself and / or preparations derived therefrom (eg spray broths, seed disinfectants) special properties such as certain technical properties and / or also special biological properties. . Typical adjuvants of interest are diluents, solvents and carriers.

Suitable diluents are, for example, water, organic, polar and non-polar chemical liquids, for example of the aromatic and non-aromatic hydrocarbon class (such as paraffins, alkylbenzenes, alkylnaphthalines, chlorobenzenes), alcohols and polyols. (which, optionally, may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), esters (also fats and oils) and (poly) ethers, of simple and substituted amines, amides lactams (such as N-alkylpyrrolidone) and lactones from sulfones and sulfoxides (such as dimethyl sulfoxide).

If water is used as a diluent, for example, organic solvents may also be used as auxiliary solvents. As liquid solvents are substantially of interest: aromatic compounds such as xylene, toluene or alkylnaphthalines, chlorinated aromatic compounds and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclo hexane, or paraffins, for example, petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol, as well as ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water.

According to the invention, carrier means a natural or synthetic, organic or inorganic substance, which may be solid or liquid, with which the active substances are mixed or bonded, for better applicability, particularly for application to plants or plant parts. The solid or liquid vehicle is generally inert and should be usable in agriculture.

Solid carriers are of interest: for example, ammonium salts and natural mineral flours such as kaolin, clayey earth, talc, calcium carbonate, quartz, atapulguita, montmorillonite or diatomite, and synthetic mineral flours such as Highly dispersed silicic acid, aluminum oxide and silicates as solid granular carriers are of interest: natural, crushed and fractionated minerals such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules of inorganic and organic flour as well as granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are of interest: for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty acid ethers, for example alkylaryl polyglycol ether, alkyl sulfonates alkyl sulfates, aryl sulfonates as well as protein hydrolysates; as dispersing agents are of interest nonionic and / or ionic substances, for example from the POE and / or POP alcohol ethers, acid and / or POP esters, alkyl aryl and / or POP - POE ethers, POE- and / or POP-polyol fat and / or POP-polyol added products, POE- and / or POP-sorbitan- or sugar added products, alkyl or aryl sulphates, sulphonates and phosphates the corresponding addition products of PO-ether. In addition, suitable oligomers or polymers, for example from vinyl, acrylic acid, EO and / or PO monomers alone or in association with, for example, (poly) alcohols or (poly) amines. Lignin and its sulphonic acid derivatives, simple and modified celluloses, aromatic and / or aliphatic sulfonic acids, and their addition products with formaldehyde may also be used.

Adhesives such as carboxymethylcellulose, natural and synthetic polymers in powder form, grain or latex such as gum arabic, polyvinyl alcohol, polyvinyl acetate as well as natural phospholipids such as cephalin and yeast may be used in the formulations. lecithins, and synthetic phospholipids.

Dyes such as inorganic pigments may be used, for example iron oxide, titanium oxide, iron cyan blue, and organic dyes such as alizarin, azoic and phthalocyanic dyes and trace nutrients such as iron salts , manganese, boron, copper, cobalt, molybdenum and zinc.

Other additives may be perfumes, optionally modified vegetable or mineral oils, waxes and nutrients (also trace nutrients) such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

In addition, stabilizers may be contained, such as low temperature stabilizers, preservatives, oxidation protection agents, photoprotectors or other agents that enhance chemical and / or physical stability.

The formulations generally contain from 0.01 to 98% by weight of active substance, preferably from 0.5 to 90%. The active substance according to the invention may be in its commercially available formulations as well as in the prepared application forms of such formulations in admixture with other active substances such as insecticides, baits, sterilizers, bactericides, carcinogens, nematicides, fungicides, growth regulating substances, herbicides, antidotes, fertilizers or semiochemicals.

It is also possible to mix with other known active substances such as herbicides, fertilizers, growth regulators, antidotes, semiochemicals, or with agents for enhancing plant properties.

The active substances according to the invention, in use as insecticides, may also be present in their commercially available formulations, as well as in the prepared application forms of these formulations, in admixture with synergists. Synergists are compounds in which the effect of the active substances is increased, without the added synergist having to be actively effective itself.

The active substances according to the invention, in use as insecticides, may also be present in their commercially available formulations, as well as in the prepared application forms of these formulations, in admixture with inhibitors, which reduce the degradation of the active substance. after application around the plant, on the surface of plant parts or in plant tissues. The active substance content of the prepared application forms of commercially available formulations may vary widely. The concentration of active substance in the application forms may be from 0.00000001 to 95% by weight of active substance, preferably from 0.00001 to 1% by weight. The application takes place in a usual way, adapted to the application forms.

According to the invention, all plants and plant parts can be treated. By plants is meant, in this case, all plants and plant populations, such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants that can be obtained by conventional cultivation and optimization methods, or by biotechnology or genetic technology methods or a combination of these methods, including transgenic plants and even plant species protected or not protected by copyright. species protection. By plant parts are meant all aerial and underground plant parts and organs, such as bud, leaf, flower and root, such as, for example, leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds, as well as roots, tubers and rhizomes. Plant parts also include harvesting material as well as vegetative and generative multiplication material, for example cuttings, tubers, rhizomes, seedlings and seeds. Treatment according to the invention of the plants and parts of plants with the active substances takes place directly or by action on the surroundings, habitat or storage place according to the usual treatment methods, for example by dipping, spraying , evaporation, spraying, spraying, direct application, injection and, in the case of multiplication material, particularly seeds, by coating one or more layers.

As already mentioned above, according to the invention all plants and parts thereof can be treated. In a preferred embodiment, plant species and plant varieties of wild-type or obtained by conventional biological cultivation methods, such as cross-linking or protoplastic fusion, are treated as well as parts thereof. In a preferred embodiment, plants and plant varieties that have been obtained by genetic technology methods, optionally in combination with conventional methods (Genetic Modified Organisms) and parts thereof, are treated. The term "parts" or "parts of plants" or "parts of plants" has been explained above.

Particularly preferably according to the invention, plants of the commercially available varieties or those in use are treated in each case. By plant varieties are meant plants with new properties ("traits"), which have been cultivated either by conventional breeding, mutagenesis, or recombinant DNA techniques. They can be varieties, biotypes and genotypes.

Depending on the plant species or plant varieties, their location and growing conditions (soils, climate, growing season, nutrition), the treatment according to the invention may also have superadditive ("synergistic") effects. Thus, for example, smaller application amounts and / or broadening of the spectrum of action and / or intensification of the effect of materials and agents usable according to the invention, better plant growth, higher tolerance against high temperatures are possible. or low, higher tolerance against drought or soil water or salt content, more intense flowering, easier harvesting, accelerated ripening, higher crop yields, higher quality and / or higher food value of crop products, higher suitability for the storage and / or processability of harvest products, which outweigh the effects to be expected. Preferred transgenic (or genetically engineered) plants or varieties of plants to be treated according to the invention belong to all plants which by modification by genetic technology have obtained genetic material, which gives the plants particularly advantageous properties ("characteristics"). . Examples of these properties are better plant growth, higher tolerance to high or low temperatures, higher tolerance to drought or soil water or salt content, more intense flowering, easier harvesting, acceleration of maturation, higher crop yields. high, higher quality and / or higher nutritional value of crop products, higher storage aptitude and / or higher processability of crop products. Other particularly prominent examples of these characteristics are a higher defense of plants against animal and microbial pests such as insects, mites, phytopathogenic fungi, bacteria and / or viruses, as well as a higher tolerance of plants to certain herbicidal active substances. . Examples of transgenic plants include important crop plants such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed, as well as fruit plants (with apples, pears, citrus fruits and grapes). , particularly corn, soybeans, potatoes, cotton and rapeseed. As properties ("characteristics"), the highest defense of plants against insects by plant-formed toxins, particularly those which are produced in plants by the genetic material of Bacillus Thuringiensis (for example by the CrylA (a), CrylA genes, is particularly prominent). (b) CrylA ©, Crylla, CrylllA CRylllB2, Cry9c, Cry2Ab, Cry3Bb and CrylF as well as combinations thereof) (hereinafter, "Bt plants"). As properties ("characteristics"), the highest tolerance of plants to Systemic Acquired Resistance (SAR), systemin, phytoalexins, elicitors, as well as resistance genes and protein and toxins, are also particularly highlighted. corresponding. As properties ("characteristics"), in particular, the highest tolerance of plants for certain herbicidal active substances, for example imidazolinones, sulfonylureas, glyphosates or phosphinothricin (for example, "PAT" gene) is particularly emphasized. Genes which confer, in each case, the desired properties ("traits") may also appear in combinations with each other in transgenic plants. Examples of "Bt plants" include maize varieties, cotton varieties, soybean varieties, and potato varieties, which are marketed under the trade names GARD® INCOME (eg, corn, cotton, soy), Knock- Out® (eg corn), StarLink® (eg corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants include maize varieties, cotton varieties and soybean varieties, which are marketed under the trade names Roundup Ready® (glyphosate tolerance, eg corn, cotton and soybean), Liberty. Link® (tolerance to phosphinothricin, eg rapeseed), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulfonylureas, eg maize). As herbicide-resistant plants (conventionally cultivated for herbicide tolerance), we can also cite varieties marketed under the name of Clearfield® (eg maize). Of course, the above also applies to plant varieties to be developed in the future or to come to market in the future, with these genetic properties ("characteristics") or with genetic properties to be developed in the future.

The disclosed plants may be particularly advantageously treated according to the invention, the compounds according to formula (I) or the active substance mixtures according to the invention. Preferred scopes given above for active substances or mixtures also apply to the treatment of these plants. Particular emphasis should be given to the treatment of plants with the compounds or mixtures especially set forth herein.

The compounds of formula (I) (active substances) according to the invention exhibit excellent herbicidal action against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Also difficult to control perennial harmful plants that sprout from rozimas, roots of other permanent organs, are well covered by the active substances. The amount of active substance applied may vary over a wide range. It depends substantially on the type of effect desired. In general the application amounts are between 1 g and 10 kg of active substance per hectare of soil area, preferably between 5 g and 5 kg per ha. The advantageous effect of compatibility with crop plants of combinations of active substances is particularly pronounced in certain concentration ratios. But the weight ratios of the active substances in the active substance combinations can be varied within relatively large limits. In general, the 1 part by weight of active substance of formula (I) will fit from 0.001 to 1000 parts by weight, preferably from 0.01 to 100 parts by weight, most preferably from 0.05 to 20 parts by weight. one of the compounds that enhance compatibility with culture plans (antidotes), cited under (b1) above.

The active substance combinations according to the invention are generally applied in the form of ready formulations. But, the active substances contained in the active substance combinations can also be brought into application in individual formulations, mixed in application, i.e., as tank mixtures.

For certain application purposes, particularly in the post-emergence process, it may also be advantageous to incorporate in the formulations as other additives plant-compatible mineral or vegetable oils (e.g. the commercial preparation "Rako Binol") or ammonium salts. -nio, such as, for example, ammonium sulfate or ammonium thiocyanate.

The new combinations of active substances may be used as such, in the form of their formulations or in their ready-made application forms by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granulates. Application is in the usual manner, for example by watering, atomizing, spraying, dusting or spraying.

The application amounts of the active substance combinations may be varied within a given limit; they depend, among others, on weather conditions and soil factors. In general, the application amounts are from 0.001 to 5 kg per ha, preferably from 0.005 to 2 kg per ha, particularly preferably from 0.01 to 0.5 kg per ha.

The antidotes to be used according to the invention may be used, in each case, according to their properties, for preliminary treatment of the seed material of the crop plant (seed disinfection) or introduced into the seed furrows prior to sowing. or they may be applied separately from the herbicide or together with the herbicide before or after plant emergence.

Examples of the plants include important crop plants such as cereals (wheat, barley, rice), corn, soybeans, potatoes, cotton, rapeseed, sugar beet, as well as fruit (with apples , pears, citrus fruits and grapes), particularly cereals, corn, soybeans, potatoes, cotton and rapeseed.

According to the invention, all plants and plant parts can be treated. By plants is meant, in this case, all plants and plant populations, such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants that can be obtained by conventional cultivation and optimization methods, or by biotechnology or genetic technology methods or a combination of these methods, including transgenic plants and even plant species protected or not protected by copyright. species protection. By plant parts are meant all aerial and underground plant parts and organs, such as bud, leaf, flower and root, such as, for example, leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds, as well as roots, tubers and rhizomes. Plant parts also include harvesting material as well as vegetative and generative multiplication material such as cuttings, tubers, rhizomes, seedlings and seeds. Treatment according to the invention of the plants and parts of plants with the active substances takes place directly or by action on the surroundings, habitat or storage place according to the usual treatment methods, for example by dipping, spraying , evaporation, spraying, spraying, direct application, injection and, in the case of multiplication material, particularly seeds, by coating one or more layers.

Therefore, it is also an object of the present invention a process for controlling undesirable plants or for regulating plant growth, preferably in crop plants, in which one or more compounds according to the invention are applied to the plants. (eg noxious plants such as mono- or dicotyledonous weeds or undesirable crop plants), seeds (eg vegetative grains, seeds or multiplication organs such as tubers or bud sprouts) or over area over which plants grow (eg growing area). In this case, the compounds according to the invention may be applied, for example, to the process before seeding (optionally also by incorporation into the soil), preemergence or postemergence. By way of example, some representatives of the mono- and dicotile-dean weed flora may be cited individually, which may be controlled by the compounds according to the invention, without limitation to certain species.

Monocotyledonous weeds of the species: Aegilops, A-gropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenc-hrus, Commeliana, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinoc-hloa, Eleocharis, Eleusine, Eragrus Festuca, Fimbristyllis, Hete-ranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Dicotyledonous harmful plants of the species: Abutilon, Amaran-thus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsel-la, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datu-ra, Desmodium, Emex, Erysinum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Men-tha Mercurialis, Mullugo, Myosotis, Papaver Pharbitis, Plantago, Polygo-num, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapsis, Soianum, Sonchus, Sphenociea, Stellari-a, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

The mentioned plants may be particularly advantageously treated according to the invention with the compounds of general formula I or with the active substance mixtures according to the invention. Preferred scopes, indicated above in the active substances or mixtures, also apply to the treatment of these plants. Of particular note is the treatment of plants with the compounds or mixtures especially cited herein.

When the compounds according to the invention are applied to the soil surface, after treatment a growth arrest occurs and the noxious planes remain in the growth stage until the time of application or completely die after a certain time, so that, In this way, weed competition, which is harmful to crop plants, is permanently and very early eliminated.

Although the compounds according to the invention have excellent herbicidal action against single- and dicotyledonous weeds, the species Arachis, Beta, Brassica, Cucumis, Cucurbita, Helian-thus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum , Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Soianum, Vicia, or mo-nocotyledonous cultures of the Allium species, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, are damaged. only insignificantly or undamaged at all, depending on the structure of the respective compound according to the invention and its amount of application. For these reasons, the present compounds are very well suited for selective control of undesirable plant growth in plant crops, such as economically useful plant crops or ornamental plants.

In addition, the compounds according to the invention (depending on their respective structure and amount of application distributed) have exceptional growth regulating properties in crop plants. They intervene in a regulatory way in plant endogenous metabolism and thus can be used to selectively influence plant components and to facilitate harvesting, for example by activating desiccation and truncating growth. Moreover, they are also suitable for general control and inhibition of undesirable vegetative growth, without in this case killing the plants. Inhibition of vegetative growth is very important in many single- and dicotyledonous crops as, for example, the formation of a storehouse can be reduced or completely prevented.

As already mentioned above, all plants and parts thereof may be treated according to the invention. In a preferred embodiment, plant species and plant varieties of wild-type or obtained by conventional biological cultivation methods, such as cross-breeding or protoplastic fusion, are treated. In another preferred embodiment, transgenic plants and plant varieties are treated, which were obtained by methods of genetic technology, optionally in combination with conventional methods (Genetically Modified Organisms) and parts thereof. The terms "parts" or "parts of plants" or "parts of plants" have been explained above.

Particularly preferably, according to the invention, varieties of commercially traded plants or those in use are treated in each case. By plant varieties are meant plants with new properties ("traits"), which have been cultivated either by conventional breeding, mutagenesis, or recombinant DNA techniques. They can be varieties, biotypes and genotypes.

Depending on the plant species or plant varieties, their location and growing conditions (soils, climate, growing season, nutrition), the treatment according to the invention may also have superadditive ("synergistic") effects. Thus, for example, smaller application amounts and / or broadening of the spectrum of action and / or intensification of the effect of materials and agents usable according to the invention, better plant growth, higher tolerance against high temperatures are possible. or low, higher tolerance against drought or soil water or salt content, more intense flowering, easier harvesting, accelerated ripening, higher crop yields, higher quality and / or higher food value of crop products, higher suitability for the storage and / or processability of harvest products, which outweigh the effects to be expected.

Due to their herbicidal and plant growth regulating properties, active substances can also be used to control harmful plants in genetically engineered plant crops known or yet to be developed. Transgenic plants are generally distinguished by particularly advantageous properties, for example, resistance to certain pesticides, in particular certain herbicides, resistance to plant diseases or to disease-causing organisms in plants, such as as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate, for example, to the harvesting material as regards quantity, quality, storage suitability, composition and special components. Thus, transgenic plants with higher starch content or modified starch quality or those with another fat composition of the crop material are known. Other special properties may reside in a tolerance or resistance to abiotic stressors, for example heat, cold, drought, salt and ultraviolet radiation. Application of the compounds of formula (I) according to the invention to economically important transgenic crops of useful and ornamental plants, for example cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize is preferred. or also sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable varieties.

Preferably, the compounds of formula (I) may be used as herbicides in economically useful crop plants which are resistant or have been made resistant by genetic engineering to the phytotoxic effects of herbicides. Conventional methods for producing new plants, which have modified properties compared to previously existing plants, consist, for example, of classical cultivation processes and mutant generation. Alternatively, new plants with modified properties may be generated with the aid of genetic engineering processes (see, for example, EP-A-0221044, EP-A-0131624). Genetic modifications of crop plants have been described in various cases for the purpose of modifying the synthesized starch in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806), transgenic crop plants which are resistant to certain glyphosinate type herbicides (comparing, for example, EP-A-0242236, EP-A-242246) or glyphosate type (WO 92/00377) or sulfonylurea type (EP-A-0257993, US-A-5013659), - transgenic crop plants, for example cotton, which is capable of producing Bacillus thuringiensis toxins (Bt toxins), which render plants resistant to certain pests (EP-A-0142924, EP-A -0193259), - GMO plants with modified fatty acid composition (WO 91/13972), - GM plants with new secondary components or metabolites, eg new phytoalexins, which cause greater disease resistance (EPA 309862, EPA0464461), - genetically modified plants modified, with reduced photorespiration as they have higher yields and higher stress tolerance (EPA 0305398), - transgenic crop plants producing pharmaceutically or diagnostically important proteins ("molecular pharming"), - crop plants transgenic crops, which are distinguished by higher yield or better quality, - transgenic crop plants, which are distinguished by a combination, for example of the new properties mentioned above ("gene stacking").

Numerous molecular-biological techniques with which new transgenic plants with modified properties can be produced are in principle known; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. or Christou, "Trends in Plant Science" 1 (1996) 423-431.

To perform such recombinant manipulations, nucleic acid molecules may be introduced into plasmids, which allow for sequence mutagenesis or moidification by recombination of DNA sequences. With the aid of standard methods, for example, base exchanges may be performed, partial sequences may be removed or natural or synthetic sequences may be added. For ligation of the DNA fragments to each other, adapters or linkers may be inserted, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klona", VCH Weinheim 2nd ed., 1996. Plant cell production with reduced activity of a gene product can be obtained, for example, by expressing at least one antisense RNA, a sense RNA. for obtaining a cossupression effect or the expression of at least one correspondingly constructed ribozyme that specifically divides transcripts from the gene product cited above.

For this purpose, DNA molecules comprising the entire coding sequence of a gene product may be used, including any flanking sequences that may be present, as well as DNA molecules comprising only parts of the coding sequence. , and these parts must be long enough to cause an antisense effect on the cells. It is also possible to use DNA sequences, which have a high degree of homology to the coding sequences of a gene product, but are not entirely identical.

In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. But to obtain localization in a particular compartment, the coding region can, for example, be linked with DNA sequences, which guarantee localization in a particular compartment. Such sequences are known in the art (see, for example, Braun et al., EM-BO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846. Sonnewald et al., Plant J. 1 (1991), 95-106). Expression of nucleic acid molecules can also occur in plant cell organelles.

Transgenic plant cells can be regenerated to whole plants according to known techniques. Transgenic plants may in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants.

Thus, transgenic plants are obtainable which have properties modified by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

Preferably, the compounds (I) according to the invention may be used in transgenic crops, which are resistant to growth regulators such as, for example, dicamba, or herbicides, which inhibit essential plant enzymes, for example. acetolactate synthases (ALS), EPSP synthases, glutamine synthases, or hydroxyphenylpyruvate dioxigenases (HPPD), or resistant to sulfonylurea group herbicides, glyphosates, glufosinates or benzoylisoxazoles and similar active substances.

In the application of the active substances according to the invention to transgenic crops, in addition to the effects to be observed in other crops in relation to noxious plants, effects often occur which are specific for application to their transgenic crop, for example a spectrum. controlled or modified weeds, which can be controlled, modified application quantities, which can be used for application, preferably good suitability for combination with herbicides, for which transgence is resistant, as well as influence on growth and yield of transgenic crop plants.

Therefore, it is also an object of the invention to use the compounds of formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds according to the invention may be applied in the form of spray powders, emulsifiable concentrates, sprayable solutions, dusting or granulating agents in the usual preparations. Therefore, herbicidal agents and plant growth regulating agents containing the compounds according to the invention are also subject to the invention.

The compounds according to the invention may be formulated in various ways depending on the specified biological and / or physicochemical parameters. Formulation possibilities are of interest, for example: spray powders (WP), water soluble powders (SP), water soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil in water emulsions and water in oil, sprayable solutions, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusting agents (DP), disinfecting agents, spray granules and soil application, granulates (GR) in the form of microgranulates, spray granules, application and adsorption, water dispersible granules (WG), water soluble granules (SG), ULV formulations, microcapsules and waxes.

In principle, such types of individual formulations are known and are described, for example, in Winnacker-Küchler, "Chemische Tehnologie" [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg Pesticide Formulations, Marcei Dekker, NY, 1973; K. Martens, Spray Drying Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

Necessary formulation adjuvants such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Athylenoxidaddukte" [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

Based on these formulations, combinations with other pesticidal substances may also be produced, such as, for example, insecticides, acaricides, herbicides, fungicides, as well as with antidotes, fertilizers and / or growth regulators, e.g. a ready formulation or as a tank mix. Spray powders are powder which can be uniformly dispersed in water which, in addition to the active substance, contains, in addition to an inert diluent or substance, ionic and / or nonionic surfactants (crosslinkers, dispersing agents), for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycersulfates, alkanesulfonates, alkylbenzenesulfonates, 2,2'-dinaftylmethan-6,6'-disulfonate sodium disulfonate sodium or also sodium oleylmethyltaurate. For the production of spray powders, the herbicidal active substances are finely ground in standard apparatus such as pestle mills, blower mills and air blast mills and simultaneously or subsequently mixed with the formulation adjuvants.

Emulsifiable concentrates are produced by dissolving the active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or also higher boiling aromatic compounds or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants. ionic and / or nonionic type (emulsifiers). As emulsifiers, for example, alkylarylsulfonate calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, polyglycol ethers of fatty alcohol, condensation products may be used. propylene oxide-ethylene oxide, alkylpolyethers, sorbitan esters such as, for example, sorbitan fatty acid esters or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

Sprinkling agents are obtained by grinding the active substance with finely distributed solids, for example talc, natural clay such as kaolin, bentonite and pyrophyllite or diatomite.

Suspension concentrates may be water or oil based. They may be produced, for example, by wet grinding, by commercially available blood cell mills and optionally by the addition of surfactants, as already mentioned, for example, in the other formulation types.

Emulsions, for example oil-in-water (EW) emulsions, may be produced, for example, by agitators, colloid mills and / or static mixers, using organic, aqueous, and optionally surfactants such as are already cited in the other formulation types.

Granulates may be produced by diluting the active substance over adsorptive granulated inert material or by applying active substance concentrates by adhesives, eg polyvinyl alcohol, sodium polyacrylate or also mineral oils, onto the surface of vehicles. such as sand, kaolinites or granular inert material. Suitable active substances may also be granulated in the usual manner for the production of fertilizer grains - optionally in fertilizer media.

Water dispersible granules are generally produced according to usual methods such as spray drying, fluidized layer granulation, vessel granulation, mixing with high speed mixers and extrusion without producing fixed inert material.

For the production of vessel granules, fluidized layers, extrusion and spraying, see, for example, processes in Spray-Drying Handbook 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hil, New York 1973, p. 8-57.

For further details on formulating plant protection compositions, see, for example, GC Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

Agrochemical formulations generally contain from 0.1 to 99% by weight, particularly from 0.1 to 95% by weight, of compounds according to the invention.

In spray powders, the concentration of active substance is, for example, about 10 to 90 wt%, the remainder to 100 wt% consists of usual formulation components. In emulsifiable concentrates, the concentration of active substance may be about 1 to 90, preferably 5 to 80% by weight. Powdered formulations contain 1 to 30% by weight of active substance, preferably at least 5 to 20% by weight of active substance, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight. active substance weight. In water dispersible granules, the active substance content depends in part on whether the active compound is present in liquid or solid form and which granulation aids, fillers, etc. they're used. In water dispersible granules, the active substance content is, for example, from 1 to 95% by weight, preferably from 10 to 80% by weight.

In addition, the active substance formulations cited optionally contain adhesives, crosslinkers, dispersing agents, emulsifiers, penetrating agents, preservatives, frost and solvent protection agents, fillers, vehicles, antifoams, evaporation inhibitors and agents that influence pH value and viscosity. The term "active substances" or "compounds" always also includes the active substance combinations cited herein. The compounds of general structure (I) may be produced according to the invention according to processes A to H.

If according to process (A), for example 2,2-dimethyl-8 - [(2,6-diethyl-4-methyl) phenylacetyl] -1,3-dioxa- [4.4.0] - methyl ester bicyclononane-7-carboxylate, then the course of the process according to the invention can be represented by the following reaction scheme: Using, for example, according to process (B) 5 '- (2,6-diethyl 4-Methylphenyl-e-hydroxy-4-dimethyl-4α-Sa-α-tetrahydro-1β-spirot-1β-dioxolan-4,2'-pentalen] -4'-one and pivoloyl chloride as basic materials The course of the process according to the invention may be represented by the reaction scheme below: Using, for example, according to process (B) 5- (2,6-diethyl-4-methylphenyl) -6,6-hydroxy -2,2-dimethyl-1,3 ', 3a, 6a'-tetrahydro-4,4 H-spiro [1,3-dioxolan-4,2'-pentalen] -4'-one and acetic anhydride As basic materials, the course of the process according to the invention can be represented by the reaction scheme below: Using, for example, according to process (C) 5- (2,6-diethyl-4-methylphenyl) -6 '-hydró xi-2,2-dimethyl-1 ', 3,3a', 6a'-tetrahydro-4, H-spiro [1,3-dioxolan-4,2'-pentalen] -4'-one and chloroformate of ethyl as basic materials, the course of the process according to the invention may be represented by the reaction scheme below: Using, for example, according to process (D) 5 '- (2,6-diethyl-4-methylphenyl ) -6'-hydroxy-2,2-dimethyl-1,3,3,3a ', 6a'-tetrahydro-4, H-spiro [1,3-dioxolan-4,2'-pentalen] -4 '-one and methyl chloromonothioformate as basic materials, the course of the process according to the invention can be represented by the reaction scheme below: Using, for example, according to process (E) 5' - (2,6- diethyl-4-methylphenyl) -6'-hydroxy-2,2-dimethyl-1 ', 3', 3a ', 6a'-tetrahydro-4'H-spiro [1,3-dioxolan-4,2' -pentalen] -4'-one and methanesulfonyl chloride as basic materials, the reaction course can be represented by the reaction scheme below: Using, for example, according to process (F) 5- (2,6-diethyl -4-methylphenyl) -6,6-hydroxy-2,2-dimethyl-1 ', 3,3,3a, 6a'-tetrahydrofuran o-4, H-spiro [1,3-dioxolan-4,2'-pentalen] -4'-one 2,2,2-trifluoroethyl meta-notiophosphonyl chloride anhydride as basic materials, the course of the reaction may be represented by the reaction scheme below: Using, for example, according to process (G) 5 '- (2,6-diethyl-4-methylphenyl) -6,3-hydroxy-2,2-dimethyl-1,3 ', 3a', 6a, -tetrahydro-4'll-spiro [1,3-dioxolan-4,2'-pentalen] -4'-one and NaOH as components, the course of the process according to the invention can be represented by the reaction scheme below: Using, for example, according to process (H), variant a, 5, - (2,6-diethyl-4-methylphenyl) -6'-hydroxy-2,2- dimethyl-1,3,3,a, 6a, -tetrahydro-4'H-spiro [1,3-dioxolan-4,2'-pentalen] -4'-one and ethylisocyanate as basic materials, the course of the reaction can be represented by the reaction scheme below: Using, for example, according to process (H), variant β, 5, - (2,6-diethyl-4-methylphenyl) -6'-hydroxy-2, 2-dimethyl-1 ', 3,3a', 6a'-tetrahydro-4, H-spiro [1,3-dioxolan-4,2'-pentalen] -4 '-one and dimethylcarbamoyl chloride as basic materials, the reaction course can be represented by the reaction scheme below: The compounds required as basic material in process (A) according to the invention of formula (II) wherein 8 A , B, X, Y, Z and R have the meanings indicated above are new.

They can be prepared by known methods in principle.

5-Aryl-4-ketocarboxylic esters of formula (II) are obtained, for example, when 5-aryl-4-ketocarboxylic acids of formula (XIII) wherein X, Y, Z, A and B have the meanings indicated above. they are esterified (comparing, for example, Organikum, 15th Edition, Berlin, 1977, page 499) or alkylated (see Preparation Example).

Aryl ketocarboxylic acids of formula (XIII) wherein A, B, X, Y and Z have the meanings indicated above are new; but, they may be prepared by known methods in principle (WO 07/080066, WO 96/01 798, WO 97/14667, WO 98/39281, WO 01/74770).

Arylketocarboxylic acids of formula (XIII) are obtained, for example, when 2-phenyl-3-oxoadipic esters of formula (XIV) wherein A, B, X, Y and Z have the meanings indicated above and 88 'R and R represents alkyl (in particular C1 -C6 alkyl) and, when the compound of formula (XVI) is used, R represents hydrogen they are decarboxylated, optionally in the presence of a diluent, and optionally in the presence of a base or acid (comparing, for example, Organikum, 15th Edition, Berlin, 1977, pages 519-521). The compound of formula (XIV) in which 8 'A, B, X, Y, Z, R, R have the meanings given above and, 8 when the compound of formula (XVI) is used R represents hydrogen are new. .

The compounds of formula (XIV) are obtained, for example, when dicarboxylic semesterchlorides of formula (XV) wherein 8 A, B and R have the meanings indicated above and Hal represents chlorine or bromine or carboxylic anhydrides of formula (XVI) wherein A and B have the meanings indicated above are acetylated with a phenyl phenyl acetic ester of formula (XVII) wherein 8 X, Y, Z and R have the meanings indicated above in the presence of a diluent and in the presence of a base (comparing, for MS Chambers, EJ Thomas, DJ Williams, J. Chem. Soc. Chem. Commun. (1987), 1228, also comparing Preparation Examples).

Another proven method for preparing the compounds required as basic materials in process (A) of formula (II), wherein 8 A, B, X, Y, Z and R have the meanings indicated above is also, for example, the same. coupling of benzylzinc compounds of general formula (XVIII) wherein X, Y and Z have the meanings indicated above and Hal represents a halogen atom, preferably chlorine or bromine, optionally in the presence of a catalyst, with a chloride of dicarboxylic semester of the general formula (XV) or a carboxylic anhydride of the general formula (XVI).

Both the production and reaction of organic zinc compounds with carboxylic chlorides or carboxylic anhydrides are in principle known and can be carried out based on procedures described in the literature. Further details in this regard are described, for example, in Chem. Commun. 2008, 5824, WO 2007/113294, Tetrahedron Letters 30, 5069-5072 (1989) or Chem. Rev. 1993, 93, 2117-2188.

Acid halides of formula (III), carboxylic anhydrides of formula (IV), chloroformic acid esters or chloroformic acid thioesters of formula (V), chloromonothioformic acid esters or clo-rodithoform esters of formula (VI), chlorides sulfonyl compounds of formula (VII), phosphorus compounds of formula (VIII) and metal hydroxides, metal alkoxides or amines of formula (IX) and (X) and isocyanates of formula (XI) and carboxamide chlorides (XII) in addition , required as basic materials for carrying out processes (B), (C), (D), (E), (F), (G) and (H) according to the invention, are compounds generally known from organic chemistry. or inorganic.

The compounds of the formulas (XV), (XVI) and (XVII) are compounds known in part from organic chemistry or known from the initial cited patent applications and / or may be prepared simply by methods known in principle or in principle. may be prepared according to the methods indicated in the initially cited patent applications.

For the production of benzylzinc compounds of formula (XVIII), benzyl compounds of formula (XIX) wherein X, Y and Z have the meaning given above and Hal represents a halogen atom, preferably chlorine or bromine, are used. as basic material. Some benzyl compounds of formula (XIX) are known, or may be prepared by known processes (see, for example, Chem. Ber. 118, 1968 (1985), Monatshefte Chemie 135, 251 (2004), Acta Chem. Scand. 1963, 17 and Preparation Examples). Process (A) is characterized in that the compounds of formula (II), in which A, B, X, Y, Z and R have the meaning given above, are subjected to intramolecular condensation in the presence of a base.

In process (A) according to the invention, all inert organic solvents with respect to the reaction components may be used as diluents. Preferably hydrocarbons such as toluene and xylene are still usable, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglyldimethyl ether, in addition polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl pyrrolidone. , doubly equimolar amounts. But it is also possible to use either component in a larger excess (up to 3 rnols). Process (B-α) is characterized in that compounds of formula (1a) are reacted in each case with carboxylic halides of formula (III), optionally in the presence of a diluent and optionally in the presence of a binder. of acid.

In process (Ba) according to the invention all inert organic solvents with respect to acid halides may be used as diluents. Preferably hydrocarbons such as benzine, benzene, toluene, xylene and tetraline are furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, in addition ketones such as as acetone and methyl isopropyl ketone, further ethers such as diethyl ether, tetrahydrofuran and dioxane, furthermore esters of carboxylic acid such as ethyl acetate, and also strongly polar solvents such as dimethyl sulfoxide and sulfole. If hydrolysis stability of the acid halide permits, the reaction may also be carried out in the presence of water.

As acid binders, in the reaction according to process (B-α) according to the invention all usual acid acceptors are of interest. Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and β, β-dimethyl aniline, preferably alkaline earth oxides, are preferably used. such as magnesium oxide and calcium oxide, furthermore alkaline and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, as well as alkaline hydroxides such as sodium hydroxide and potassium hydroxide.

Reaction temperatures may be varied within a wide range in the process (B-α) according to the invention. In general, work at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

In carrying out the process (B-α) according to the invention, the basic materials of formula (1-a) and the carboxylic halide of formula (III) are generally used in each case in approximately equivalent amounts. However, it is also possible to use carboxylic halide in a larger excess (up to 5 mmol). The finishing is according to usual methods. Process (Β-β) is characterized in that compounds of formula (1-a) are reacted with carboxylic anhydrides of formula (IV), optionally in the presence of a diluent and optionally in the presence of an acid binder.

As diluents may be used in the process (Β-β) according to the invention, preferably diluents, which are also preferably of interest in the use of acid halides. Moreover, an excessively used carboxylic anhydride can simultaneously serve as a diluent.

As optionally added acid binders are of interest in process (β-β), preferably acid binders, which are also preferably of interest in the use of acid halides.

Reaction temperatures may be varied within a broad process limit (Β-β) according to the invention. In general, work with temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

In carrying out process (Β-β) according to the invention, the basic materials of formula (1-a) and the carboxylic anhydride of formula (IV) are generally used in each case in approximately equivalent amounts. However, it is also possible to use carboxylic anhydride in a larger excess (up to 5 mo). The finishing is according to usual methods.

In general, the diluent and excess carboxylic acid anhydride as well as the carboxylic acid formed are removed by distillation or washing with an organic solvent or water. In general, the diluent and excess carboxylic anhydride as well as the formed carboxylic acid are removed by distillation or washing with an organic solvent or water. Process (C) is characterized in that compounds of formula (la) are reacted in each case with chloroformic acid esters or chloroformic acid thiolesters of formula (V), optionally in the presence of a diluent and optionally in the presence of an acid binder.

In the process (C) according to the invention, all the usual acid acceptors may be used as acid binders of interest in the reaction according to the process (C) according to the invention. Preferably tertiary amines such as triethylamine, DABCO, DBU, DBA, Hünig base and Ν, Ν-dimethyl aniline are furthermore useful, alkaline earth metal oxides such as magnesium oxide and calcium oxide in addition. alkaline and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, as well as alkaline hydroxides such as sodium hydroxide and potassium hydroxide.

As diluents can be used in process (C) according to the invention all inert solvents with respect to chloroformic acid esters or chloroformic acid thiolesters. Preferably hydrocarbons such as benzine, benzene, toluene, xylene and tetramine are furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, in addition ketones, such as acetone and methyl isopropyl ketone, still ethers, such as diethyl ether, tetrahydrofuran and dioxane, in addition, carboxylic esters such as ethyl acetate, and also strongly polar solvents such as dimethyl sulfoxide and sulfolane.

Reaction temperatures may be varied within a wide range in carrying out process (C) according to the invention. When working in the presence of an acid diluent and binder, then the reaction temperatures are generally from -20 ° C to + 100 ° C, preferably from 0 ° C to 50 ° C. Process (C) according to the invention is generally carried out under normal pressure.

In carrying out process (C) according to the invention, the basic materials of formula (1-a) and the corresponding chloroform ester or chloroform thiolester of formula (V) are generally used in each case in approximately equivalent amounts. However, it is also possible to use either component in a larger excess (up to 2 rnols). The finishing is according to usual methods. In general, the procedure is such that precipitated salts are removed and the remaining reaction mixture is concentrated by removal of the diluent. Process (D) according to the invention is characterized in that compounds of formula (1a) are reacted in each case with compounds of formula (VI) in the presence of a diluent and optionally in the presence of a acid binder.

In the production process (D), approximately 1 mol of chloromonothioform ester or chlorodithioform ester of formula (VI) is reacted per mole of the basic compound of formula (1a) at 0 to 120 ° C, preferably at 20 to 60 ° C. Ç.

As optionally added diluents are of interest all polar, inert organic solvents such as ethers, amides, sulphenes, sulfoxides, but also halogenated alkanes.

Preferably, dimethylsufoxide, tetrahydrofuran, dimethylformamide or methylene chloride are used.

If in a preferred embodiment the enolate salt of compounds (1a) is prepared by the addition of strong deprotonizing agents, such as, for example, sodium hydride or potassium tert-butylate, the additional addition of sodium binder may be dispensed with. acid.

If acid binders are used, then usual inorganic or organic bases are of interest, such as sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine. The reaction may be carried out under normal pressure or under elevated pressure, preferably working at normal pressure. The finishing is according to usual methods. Process (E) according to the invention is characterized in that compounds of formula (Ia) are reacted in each case with sulfonic chlorides of formula (VIII), optionally in the presence of a diluent and optionally in the presence of a diluent. presence of an acid binder.

In the production process (E), approximately 1 mol of sulfonic chloride of formula (VII) is reacted per mol of the basic compound of formula (Ia) at -20 to 150 ° C, preferably at 20 to 70 ° C. .

As optionally added diluents, all inert polar organic solvents such as ethers, amides, nitros, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride are of interest.

Preferably, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, dimethylformamide, methylene chloride are used.

If in a preferred embodiment the enolate salt of compound (1a) is prepared by the addition of strong deprotonizing agents (such as, for example, sodium hydride or potassium tert-butylate), the additional addition of acid binders.

If acid binders are used, then usual inorganic or organic bases are of interest, such as sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine. The reaction may be carried out under normal pressure or under elevated pressure, preferably working at normal pressure. The finishing is according to usual methods. Process (F) according to the invention is characterized in that compounds of formula (1a) are reacted in each case with phosphorus compounds of formula (VIII), optionally in the presence of a diluent and optionally in the presence of an acid binder.

In the production process (F), to obtain compounds of formula (le), react by 1 mol of compounds (la) or (1-a ') 1 to 2, preferably 1 to 1.3 mol of compound phosphorus of formula (IX) at temperatures from -40 to 150 ° C, preferably from -10 to 110 ° C.

As optionally added diluents are of interest all polar, inert organic solvents such as ethers, amides, nitros, sulfides, sulfones, sulfoxides etc.

Preferably, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, methylene chloride are used.

Optionally added acid binders of interest are usual inorganic or organic bases such as hydroxides, carbonates or amines. Examples are sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine. The reaction may be carried out at normal pressure or under elevated pressure, preferably at normal pressure. Finishing takes place according to usual methods of organic chemistry. Purification of the formed end products preferably takes place by crystallization, chromatographic purification or so-called "distillation", that is, removal of volatile components in vacuo. Process (G) is characterized in that compounds of formula (1a) are reacted in each case with metal hydroxides or metal alkoxides of formula (IX) or amines of formula (X), optionally in the presence of a diluent. .

As diluents can be used in process (G) according to the invention, preferably ethers, such as tetrahydrofuran, dioxane, diethyl ether, or alcohols such as methanol, ethanol, isopropanol, but also water. Process (G) according to the invention is generally carried out under normal pressure.

Reaction temperatures are generally from -20 ° C to 100 ° C, preferably from 0 ° C to 50 ° C. Process (H) according to the invention is characterized in that compounds of formula (1a) are reacted in each case (Ha) with compounds of formula (XI), optionally in the presence of a diluent and optionally in the presence of a catalyst, or (Η-β) with compounds of formula (XII), optionally in the presence of a diluent and optionally in the presence of an acid binder.

In the production process (H-α), approximately 1 mol of the isocyanate of formula (XII) is reacted per mol of the basic compound of the formulas (la) or (1-a ') at 0 to 100 ° C, preferably 20 to 50 ° C.

As optionally added diluents are of interest all inert organic solvents such as ethers, amides, nitriles, sulfoins or sulfoxides.

Optionally, catalysts may be added to accelerate the reaction. As catalysts, organic tin compounds such as, for example, dibutyltin dilaurate may be advantageously used. It preferably works at normal pressure.

In the production process (Η-β), approximately 1 mol of carbamidic chloride of formula (XII) is reacted per mol of the basic compound of formula (la) at -20 to 150 ° C, preferably 0 to 70 ° C. .

As optionally added diluents, all inert polar organic solvents such as ethers, esters, amides, sulfones, sulfoxides or halogenated hydrocarbons are of interest.

Preferably, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene chloride are used.

If in a preferred embodiment the enolate salt of the compounds is prepared by the addition of strong deprotonizing agents (such as, for example, sodium hydride or potassium tert-butylate), the additional addition of acid binders may be dispensed with. .

If acid binders are used then usual inorganic or organic bases are of interest, such as sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine. The reaction may be carried out at normal pressure or under elevated pressure, preferably at normal pressure. The finishing is according to usual methods. The preparation and use of the active substances according to the invention are illustrated in the following examples. PREPARATION EXAMPLES Examples la-1 and la-2 In 50 ml of anhydrous α, β-dimethylformamide, 4.62 g (11.5 mmol) methyl 8 - [(2,6-diethyl-4-methylphenyl) acetyl] -2,2 -dimethyl-1,3-dioxaspiro [4.4] nonane-7-carboxylate (according to example (II-5)) and 2.57 g of potassium tert-butoxide are heated to 50 ° C for 2 h. After cooling, the mixture is poured into ice water, acidified to pH 3 using concentrated hydrochloric acid and extracted three times with ethyl acetate. The organic phase is dried (magnesium sulfate), and the solvent is then distilled off and the residue is chromatographed on silica gel (ethyl acetate / hexane = 50:50). Fraction A: anti-isomer (1-a-1); yield 1.70 g (40%); colorless crystals with m.p.

104-105 ° C

Fraction B: syn isomer (1-a-2); yield 1.40 g (34%); colorless crystals with m.p. 88-89 ° C

Example la-3 In 40 ml of toluene, 0.79 g (2.64 mmol) of 2- (2,6-diethyl-4-methylphenyl) -3-hydroxy-3a, 4,6,6a-tetrahydropentene-1 , 5-dione (according to example (la-4)), 0.58 g (6.6 mmol) of 2-methylidenpropane-1,3-diol and 20 mg of p-toluene sulfonic acid are heated in a water for 3 h, and the mixture is then concentrated on a rotary evaporator and taken up in ethyl acetate. The mixture is extracted with bicarbonate solution and water, dried (magnesium sulfate), the solvent is distilled off and the residue is chromatographed on silica gel (ethyl acetate / hexane v: v = 35: 65) to obtain the compound of formula (la-3) as colorless crystals.

Yield: 0.52 g (53%) 1H-NMR (400 MHz, CDCl3): δ = 1.07 and 1.09 (in each case, t, in each case, 3H), 3.12 and 3.38 (in each case, mc, in each case, 1 H), 4.10-4.37 (m, 4 H), 4.39 (mc, 2 H) ppm Example la-4 2 ml of a solution of 2.5 % osmium tethoxide in t-butanol is added to 2.50 g (8.43 mmol) of 2- (2,6-diethyl-4-methylphenyl) -3-hydroxy-5-methyliden-4,5,6 , 6α-tetrahydropentalen-1 (3aH) -one (according to example la-5) and 9.02 g (42.16 mmol) of sodium meta-periodate in 50 ml of a water / tert-butanol mixture (v. / v = 50: 50), and the mixture is stirred at room temperature, then 50 ml of ethyl acetate is added for 10 minutes, and the mixture is stirred at room temperature for a further 2 h. The reaction mixture is then added to ice, taken up in ethyl acetate and extracted with water. After drying (magnesium sulfate) and distilling off the solvent, the residue is chromatographed on silica gel using ethyl acetate / hexane (v / v = 30: 70). 1.86 g (74.1%) of the compound of formula (1-4) is obtained as a viscous oil. 1H-NMR (400 MHz, CDCl3): δ = 2.31 (s, 3H), 2.52 and 2.74 (in each case, mc, broad, in each case, 2H), 3.41 and 3, 68 (in each case mc, broad in each case 1 H) ppm Example la-5 In 80 ml of N, N-dimethylformamide, 7.85 g (23.9 mmol) of methyl 2 - [(2, 6-Diethyl-4-methylphenyl) acetyl] -4-methylidencyclopentanecarboxylate (according to Example (11-1)) and 5.36 g (47.8 mmol) of potassium tert-butoxide are heated to 50 ° C by 2 h. After cooling, the mixture is added to ice water, acidified to pH 2 using concentrated hydrochloric acid and extracted with ethyl acetate. The organic phase is washed twice with water, dried (magnesium sulfate) and concentrated using a rotary evaporator. After chromatographic purification on silica gel (mobile phase ethyl acetate / hexane v: v = 40:60) 4.30 g (61%) of the compound of formula (la-5) are obtained as colorless crystals, with the point: mp 127-128 ° C. 1H-NMR (400 MHz, CDCl3): δ = 0.94 and 1.08 (in each case, t, in each case, 3H), 2.28 (s, 3H), 2.51 (mc, 4H), 4 0.89 (s, 2 H) ppm Example 1a-18 0.164 g (1.62 mmol) of triethylamine is added to 0.161 g (0.54 mmol) of 2- (2,6-diethyl-4-methylphenyl) -3 -hydroxy-3a, 4,6,6a-tetrahydropen-talen-1,5-dione (example la-4) and 0.090 g (1.08 mmol) of N-methylhydroxylamine hydrochloride in 10 ml of acetonitrile, and The mixture is stirred at room temperature for 6 h. The mixture is then added to ice, taken up in ethyl acetate, and the organic phase is separated and washed with water. After drying (magnesium sulfate), distilling off the solvent and chromatography on silica gel using ethyl acetate / hexane (v / v = 25: 75), finally 0.154 g (87%) of the compound is obtained. of formula (la-18) as a viscous, yellowish oil. 1H-NMR (400 MHz, CDCl3): δ = 2.62 (mc, 1H), 3.20 and 3.48 (in each case, mc, in each case, 1 H), 3.82 (s, 3 H) ppm Os The following compounds of formula (Ia) are obtained analogously to Examples (Ia-1) to (Ia-5) and (Ia-18) and according to the general indications for the preparation: Example Ib-1 At room temperature 0.100 g (0.27 mmol) of compound la-1 according to the invention (anti-isomer), 23.3 mg (0.297 mmol) of acetyl chloride and 82 mg (0.297 mmol) triethylamine are stirred in 5 ml of dichloromethane. romethane for 2 h. The reaction mixture is poured onto ice, taken up in dichloromethane, washed with water, dried (magnesium sulfate) and concentrated using a rotary evaporator. Chromatography on silica gel (mobile phase ethyl acetate / hexane v: v = 30:70) gives the compound (1-b-1) according to the invention as a colorless oil. Yield 76.6 mg (68%). 1H-NMR (400 MHz, CDCl3): δ 1.39 (s, 6 H), 2.10 (s, 3 H), 2.21 (s, 3 H), 3.85 (dd, 2 H) ppm The following compounds of formula (1b) are obtained analogously to examples (1b-1) according to the general indications for preparation: Example 1c-1 At room temperature, 82 mg (0.81 mmol) of triethylamine is added to 0.100 g (0.27 mmol) of the compound (la-1) according to the invention and 28 mg (0.30 mmol) of methyl chloroformate in 5 ml of dichloromethane, and the mixture is stirred for a further 1 h. . The reaction mixture is poured into ice water, taken up in dichloromethane, washed with water, dried (magnesium sulfate), and the solvent is distilled off.

After chromatographic purification on silica gel (ethyl acetate / hexane v / v = 20: 80) 104 mg (90%) of the desired compound of formula (1c-1) are obtained as colorless crystals with mp 111-112 ° C.

Example 1.c-17 0.98 ml of a 2.5% solution of osmium tethoxide in n-butanol are added to 1.50 g (4.05 mmol) of 2- (2,6-diethyl-4-methylphenyl) -5- methyliden-3-oxo-3,3a, 4,5,6,6a-hexahydropyren-1-yl ethyl carbonate (example 1c-5) and 4.33 g (20.24 mmol) of sodium meta-periodate in 150 ml of a water / tert-butanol mixture (v / v = 50: 50), and the mixture is stirred at room temperature for 10 minutes. 50 ml of ethyl acetate are then added, and the mixture is stirred at room temperature for a further 2 h. The reaction mixture is poured over ice, taken up in ethyl acetate and extracted with water. After drying (magnesium sulfate) and distilling off the solvent, the residue is chromatographed on silica gel using ethyl acetate / hexane (v / v = 30: 70) and 1.00 g (66%) of the desired compound is obtained. of formula (lc-17) as a viscous oil. 1H-NMR (400 MHz, CDCl3): δ = 1.26 (t, 3 H), 3.51 and 4.31 (in each case, mc, in each case, 1 H), 4.20 (mc, 2 H) ppm The following compounds of formula (1b) are obtained analogously to examples (1c-1) and (1c-17) and according to the general indications for the preparation: Example 1d-1 At room temperature, 57 mg (0.29 mmol) of p-toluenesulfonyl chloride and 0.1 ml of triethylamine are added to 100 mg (0.27 mmol) of compound (la-1) in 5 ml of dichloromethane. After 1 h stirring, the mixture is diluted with water and the organic phase is separated and washed twice with 1 N hydrochloric acid. After drying with magnesium sulfate and distilling off solvent, 120 mg (87%) are obtained. of the desired substance as colorless oil. 1H-NMR (400 MHz, CDCl3): δ = 0.98 and 1.03 (in each case, t, in each case, 3H), 2.30 and 2.39 (in each case, s, in each case, 1H), 3.15 and 3.90 ( in each case, mc, in each case, 1H), 3.98-4.35 (m, 4H), 5.65 (s, 2H) PPM.

The following compounds of formula (1d) are obtained analogously to example (1d-1) and according to the general indications for the preparation: Example 1f-1 0.040 g (0.242 mmol) of sodium methoxide is added to 0.094 g (0.242 mmol) of compound (1a-17) in 3 ml of absolute methanol, and the mixture is stirred at room temperature for a further 30 min.

After distilling off the solvent, 0.096 g (96%) of the compound of formula (1-1) according to the invention are obtained as colorless crystals having a melting point> 300 ° C. 1H-NMR (400 MHz, d6-DMSO): δ = 0.92 and 0.95 (in each case, t, in each case, 3 H), 2.22 (s, 3 H), 6.68 (mc, 2 H) ppm The following compounds of formula (1f) are obtained analogously to example (1f-1) and according to the general indications for the preparation: Preparation of 2 - [(2,6-diethyl-4-methylphenyl) base materials Acetyl] -4-methylidencyclohexanecarboxylic acid Example (XIII-1) (XVI-1) (XVII-1) (XIV-1) (XIII-1) A-30 ° C, 14.48 g (65.7 mmol) of Methyl 2-ethyl-4,6-dimethylphenyl acetate (XVI1-1) is slowly added dropwise to a solution of lithium diisopropylamine in 250 ml THF prepared from 16.3 g (164 mmol) diisopropiamine and the equimolar amount of a solution of n-butyllithium in hexane, and the mixture is stirred at room temperature for 45 min. At -20 ° C, 10.00 g (65.7 mmol) of 4-methylcyclopentane-1,2-dicarboxylic anhydride (XVI-1), dissolved in 20 ml of THF, are then added, and the mixture is stirred at room temperature for about 2 hours. from 12 h. To finish, 100 ml of saturated ammonium chloride solution is added, a layer of ethyl acetate is added on top and the mixture is washed with water, dried (magnesium sulfate) and concentrated using a rotary evaporator. 22.3 g of compound (XIV-1) is obtained as a reddish oil, which can be reacted without further purification. 1H-NMR (400 MHz, CDCl3): δ = 1.11 and 1.12, in each case, t, in each case, 3Η), 2.25-2.50 (m, 4 Η), 2.35 (s 3.69 (mc, 2H), 2.72-2.90 (m, 4H), 3.66 (s, 3H), 4.85 (s, 2H) ppm 10 g of Potassium in 100 ml of water is added to 22.3 g of intermediate (XIV-1), and the mixture is heated to reflux for 24 h. Then the mixture is allowed to cool to room temperature, acidified to pH 2 with 2N hydrochloric acid and stirred at room temperature for 1h and the precipitated solid is sucked off. Thus 10.3 g (45%) of 2 - [(2,6-diethyl-4-methylphenyl) acetyl] -4-methylidencyclohexanecarboxylic acid (XIII-1) is obtained as a yellowish solid which can be used without further purification for the next reaction step. 1H-NMR (400 MHz, CDCl3): δ = 1.12 (t, 6H), 2.45 (q, 4H), 3.90 (s, 2H), 4.91 (mc, 2H), 6, 89 (s, 2H) ppm Similarly, the following intermediates of the general formula (XIII)) were prepared: Similarly, the following intermediates of the general formula (XIIV)) were prepared: 2,6-diethyl-4-methylphenyl) acetyl] - 4-methylidencyclopentanecarboxylate Example (11-1) 5.45g (17.33 mmol) of 2 - [(2,6-diethyl-4-methylphenyl) acetyl] -4-methylidencyclohexanecarboxylic acid (XIII-1), together with 2, 38 g potassium carbonate and 2.62 g (20.8 mmol) of dimethyl sulfate, refluxed in 50 ml of acetone for 5 h, and then cooled, the reaction mixture is taken up in ethyl acetate, extracted with water and dried ( magnesium sulfate), and the solvent is distilled off. Silica gel chromatography is used in ethyl acetate / hexane (v / v = 30: 70) 3.93 g (69%) of methyl 2 - [(2,6-diethyl-4-methylphenyl) acetyl] is obtained. -4-methylidencyclohexanecarboxylate in formula (11-1). 1H-NMR (400 MHz, CDCl3): δ = 3.58 (s, 3H), 3.89 (s, 2H), 4.88 (s, 2H), 6.89 (s, 2H) ppm Ethyl 2 - [(2-ethyl-4,6-dimethylphenyl) acetyl] -4-oxocyclopentancarboxylate Example (II-2) 5.62 g (25.7 mmol) 2-ethyl-4,6-dimethylbenzyl chloride in 30 ml of THF are slowly added dropwise to a suspension of 3.85 g (28.3 mmol) of dry zinc chloride, 1.56 g (64.2 mmol) of magnesium shavings and 1.36 g (42, 4 mmol) of lithium chloride, such that the internal temperature does not exceed 35 ° C. After the addition is complete, the mixture is stirred at temperature for more than 2 h. At room temperature, the formed solution is added dropwise to a mixture of 5.62 g (25.7 mmol) of ethyl 2- (chlorocarbonyl) -4-oxocyclopentancarboxylate and 85 mg of bis (triphenylphosphino) palladium chloride (11) in 40 mL. THF, and the mixture is then stirred at room temperature for a further 3h. The mixture is added to water, extracted twice in each case in 50 ml of methyl tert-butyl ether and dried (magnesium sulfate), and the solvent is distilled off. After chromatography on silica gel using ethyl acetate / hexane (v / v = 30: 70), 4.89 g (57%) of the intermediate is obtained as colorless crystals with M.p. of 75 ° C. 1H-NMR (400 MHz, CDCl3): δ = 1.14 and 1.27 (in each case, t, in each case, 3H), 3.42-3.58 (m, 2H), 3.90 ( s, 2H), 4.19 (q, 2H) ppm Ethyl 2 - [(2,4,6-trimethylphenyl) acetyl] -4-oxocyclopentanecarboxylate Example (II-3) For a period of 2 h, 4.08 g (17.4 mmol) 2,4,6-trimethylbenzyl chloride in 40 ml THF are added dropwise to 1.70 g (26.1 mmol) zinc powder, activated with hydrochloric acid and dried over under reduced pressure, and 0.50 g of trimethylsilyl chloride in 30 ml, and the mixture is stirred at room temperature for a further 2 h.

Under reduced pressure, 1.56 g (17.4 mmol) of copper (1) cyanide and 1.65 g (38.8 mmol) of lithium chloride are heated to 150 ° C for 8 h and after cooling, ventilated with argon and incorporated in 25 ml THF. To the mixture is added at -25 ° C within 20 min the solution prepared above 2,4,6-triemylbenzylzene chloride and stirred for a further 20 min at that temperature. The mixture is cooled to -40 ° C, and a solution of 3.77 g (17.3 mmol) of ethyl 2- (chlorocarbonyl) -4-oxocyclopentancarboxylate in 20 ml of THF is added over a period of 30 min, and The mixture is allowed to warm to room temperature and stirred for a further 3 h.

To finish, 100 ml of water are added, the mixture is extracted with ethyl acetate and the extract is dried (magnesium sulfate) and the mixture is extracted with ethyl acetate and the extract is dried (magnesium sulfate) and then concentrated using a rotary evaporator. After chromatography on silica gel (ethyl acetate / hexane v / v = 30: 70), 1.98 g (27%) of the desired product is obtained. 1H-NMR (400 MHz, CDCl3): δ = 2.18 (s, 6H), 2.23 (s, 3H), 3.48 (mc, 2H), 3.82 and 3.88 (in each case , d, in each case, 1H), 4.18 (q, 2H) ppm Methyl 2 - [(2,6-diethyl-4-methylphenyl) acetyl] -4-hydroxy-4- (hydroxymethyl) cyclopentyl tancarboxylate Example (II-4) 2.39 g (7.27 mmol) of methyl 2 - [(2,6-diethyl-4-methylphenyl) acetyl] -4-methylidencyclohexanecarboxylate according to example (II-2) are 1.37 ml of osmium tethoxide solution (2.5% n-butanol solution) and 1.02 g (8.7 mmol) of N-methylmorpholine N-oxide in 25 ml of acetone / water (v / v = 5: 1), and the mixture is stirred at room temperature for 14 h. 0.745 g (3.64 mmol) of sodium dithionite is then added, and the mixture is stirred at room temperature for 10 min and the solvent is then removed under reduced pressure. The residue is taken up in ethyl acetate, and the mixture is extracted with water, dried (magnesium sulfate) and then concentrated using a rotary evaporator. In this way 2.45 g (92%) of a viscous yellowish oil are obtained which can be further reacted without further purification. 1H-NMR (400 MHz, CDCl3): δ = 1.70-2.25 (m, 4 H), 3.34 (mc, 1 H), 3.89 (dd, 2 H) ppm Methyl 8 - [(2 6-diethyl-4-methylphenyl) acetyl] -2,2-dimethyl-1,3-dioxaspiro [4.4] nonane-7-carboxylate (Example II-5) 1.16 g (3.19 mmol) of methyl 2 - [(2,6-diethyl-4-methylphenyl) acetyl] -4-hydroxy-4- (hydroxymethyl) cyclopentancarboxylate, 10 ml 2,2-dimethoxypropane and 30 mg p-toluenesulfonic acid are heated to reflux for 1 h . After cooling, the mixture is added to ice water and extracted with ethyl acetate, the extract is washed successively with sodium bicarbonate solution and water and dried (magnesium sulfate) and the solvent is distilled off under reduced pressure. Chromatography on silica gel (mobile phase ethyl acetate / hexane v / v = 35: 65) gives 0.92 g (71%) of a colorless oil. According to 1 H-NMR, a mixture of en-do / exo isomers of the compound of formula (II-5) is present. 1H-NMR (400 MHz, CDCl3): δ = 1.33-1.37 (Total singlet divided, 6 H), 2.26 (s, 3 H), 3.22 (mc, 1 H), 3.80-3.90 (m, 4 H), 6.89 (s, 2 H) ppm Ethyl 8 - [(2-ethyl-4,6-dimethylphenyl) acetyl] -1,4-dioxaspiro [4.4] nonane-7-carboxylate (Example 11-16) 1.20 g (3.63 mmol) of ethyl 2 - [(2-ethyl-4,6-dimethylphenyl) acetyl] -4-oxocyclopentancarboxylate according to example (II -2), 338 mg (5.4 mmol) of etandiol, 578 mg (5.4 mmol) trimethyl orthoformate and 20 mg p-toluenesulfonic acid in 30 mL toluene are stirred at room temperature for 24 h. The solvent is then distilled off and the residue is chromatographed on silica gel (mobile phase ethyl acetate / hexane v / v = 15: 85). Thus 819 mg (60%) of the desired compound is obtained as colorless crystals with m.p. from 72-73 ° C.

Similarly, the following intermediates of the general formula (II) were prepared: 2,6-Diethyl-4-methylbenzyl chloride Example (XIX-1) Under ice-cooling, 48.0 g (3 equivalents) of N, N-dimethylformamide , dissolved in 50 ml of THF, are added dropwise to a solution of 2,6-diethyl-4-methylphenylmagnesium bromide prepared from 6.00 g of magnesium shavings and 50 g of 1-bromo-2,6- diethyl-4-methylbenzene in 220 ml of THF, and the mixture is stirred at room temperature for a further 3 h. The mixture is poured into saturated ammonium chloride solution and extracted with ethyl acetate, and the extract is dried (magnesium sulfate) to give, after distilling off the solvent, 38.70 g (99%) of 2.6- diethyl-4-methylbenzaldehyde as a colorless oil, 1H-NMR (400 MHz, CD-Cl3): δ = 1.22 (t, 6H), 2.32 (s, 3H), 2.93 (q, 4H) 6.91 (s, 2H), 10.52 (s, 1H) The following compounds were prepared analogously: 2-ethyl-4,6-dimethylbenzaldehyde: 1H-NMR (400 MHz, CDCl3): 1.22 (t , 3H), 2.32 (s, 3H), 2.57 (s, 3H), 2.95 (q, 2H), 6.92 (mc, 2H), 10.55 (s, 1H) ppm 2 -methoxy-4,6-dimethylbenzaldehyde 2-methoxy-6-ethyl-4-methylbenzaldehyde 2-cyclopropyl-6-ethyl-4-methylbenzaldehyde 2.6-cyclopropyl-4-methylbenzaldehyde A solution of 35.5 g (201.4 mmol) of 2,6-diethyl-4-methylbenzaldehyde dissolved in 80 ml diethyl ether is added dropwise to a suspension of 2.10 g (55.4 mmol) lithium aluminum hydride in 200 ml diethyl ether. The mixture is then heated for a further 1 h. After cooling, the mixture is hydrolyzed with water and 10% sulfuric acid, separated and the aqueous phase further extracted twice with diethyl ether. After drying (magnesium sulfate), solvent distillation and chromatography of the crude product obtained on silica gel (ethyl acetate / hexane = 30:70) 33.10 g (92%) of 2,6-diethyl alcohol are obtained. -4-methylbenzyl as colorless crystals with mp from 71-72 ° C. 1H-NMR (400 MHz, CDCl3): δ = 1.22 (t, 6H), 2.30 (s, 3H), 2.74 (q, 4H), 4.71 (s, 2H), 6, 90 (s, 2H).

Direct preparation of 1-bromo-2,6-diethyl-4-methylbenzene 2,6-diethyl-4-methylbenzyl alcohol For a period of 30 min, formaldehyde gas (generated from 5.56 g paraformaldehyde) is introduced, with stirring, in a solution of 2,6-diethyl-4-methylphenylmagnesium bromide, prepared from 12.40 g (54.6 mmol) of 1-bromo-2,6-diethyl-4-methylbenzene and 1.47 g (60.65 mmol) of magnesium shavings in 50 ml of THF, and the mixture is then stirred at room temperature for a further 2 h. After distilling off the solvent and chromatography on silica gel (see above), 6.88 g (71%) of 2,6-diethyl-4-methylbenzyl alcohol are obtained.

The following compounds are prepared analogously: 2-ethyl-4,6-dimethylbenzyl alcohol: m.p. 40-41 ° C 2-methoxy-4,6-dimethylbenzyl alcohol: m.p. 63-65 ° C 2-cyclopropyl-6-ethyl-4-methylbenzyl alcohol 2,6-cyclopropyl-4-methylbenzyl alcohol 11.20 g (94.16 mmol) of thionyl chloride is slowly added dropwise to 15.26 g ( 85.6 mmol) of 2,6-diethyl-4-methylbenzyl alcohol in 200 ml of dichloromethane, and the mixture is then heated under reflux for 2 h. After cooling, the organic phase is separated, dried (magnesium sulfate), concentrated using a rotary evaporator and chromatographed on silica gel (ethyl acetate / hexane = 15:85). Thus 16.18 g (96%) of 2,6-diethyl-4-methylbenzyl chloride are obtained as a colorless oil. 1H-NMR (400 MHz, CDCl3): δ = 1.26 (t, 6H), 2.30 (s, 3H), 2.76 (q, 4H), 4.70 (s, 2H), 6.88 (s, 2H). 2,6-Diethyl-4-methylbenzyl bromide Example (XIX-2) 14.7 g (82.5 mmol) of 2,6-diethyl-4-methylbenzyl alcohol in 150 ml of hydrobromic acid is stirred at 100 ° C for 4 h. After melting, the mixture is extracted with dichloromethane and the extract is washed with water, dried (magnesium sulfate) and concentrated using a rotary evaporator. After distillation (110 ° C bath temperature, 30 Pa (0.3 mbar) 17.82 g (89%) of 2,6-diethyl-4-methylbenzyl bromide is obtained as a colorless oil. MHz, CDCl3): δ = 1.28 (t, 6H), 2.30 (s, 3H), 2.73 (q, 4H), 4.61 (s, 2H), 6.90 (s, 2H ).

The following precursors and intermediates of formula (XIX) were similarly obtained: 1. Pre-emergence herbicidal action Seeds of cultivated plants or mono- or dicotyledonous weeds were sown in wood fiber pots in a sandy clay soil and covered with earth. Test compounds, formed as wettable powders (WP), are then applied as an aqueous suspension, with a water application amount of 600 l / ha in conversion, with 0.2% crosslinker added in dosages. different over the surface of the roofing earth.

After treatment, the pots are placed in the greenhouse and kept under good growing conditions for the test plants. Assessment of emergency damage to test plants takes place after a test time of 3 weeks compared to untreated controls (herbicidal effect in percent: 100% effect = plants died, 0% effect = such like the control plants).

In addition to the above compounds, the following compounds, applied by the preemergence method at 320 g / ha ai, have a> 80% effect against Alopecurus myosuroides, Echinocloa crus-galli, Loli-a multiflorum and Setaria viridis: la -3, la-6, la-7, la-8, la-9, la-10, la-11, la-12, la-13, la-14, lb-4, lb-5, lb-6 , lb-7, lb-8, lc-3, lc-4, lc-5, lc-7, lc-9, lc-10, lc-11, lc-12, lc-14 Post-emergence herbicidal action Seeds of single- or dicotyledonous crop or weeds were sown in wood fiber pots on a sandy clay soil and covered with soil and grown in the greenhouse under good growing conditions. Greenhouse under good growing conditions. Two to three weeks after sowing, the test plants are treated at the leaf stage. Test compounds formulated as spray powders (WP) are sprayed at various dosages with a converted water application amount of 600 l / ha, with the addition of 0.2% crosslinkers on the green parts. of plants. After about 3 weeks of residence time of the test plants in the greenhouse under optimal growing conditions, the effect of the pre-prepared is visually evaluated, compared to untreated controls compared to untreated controls compared to untreated controls. treated (herbicidal effect in percent: 100% effect = plants died, 0% effect = such as control plants).

In addition to the above compounds, the following 80 g / ha post-emergence compounds had an effect of> 80% against Alopecurus myosuroides, Echinocloa crus-galli, Loli-um multiflorum and Setaría viridis: la-2, la-3, la-6, la-7, la-8, la-10, la-11, la-12, la-13, la-14, lb-2, lb-6, lb- 7, lc-3, lc-7, lc-8, lc-9, lc-10, lc-11, ic-12, lc-14, lc-15, lf-1 Use additionally If additionally to be tested if antidotes may improve the compatibility with plants of test substances in crop plants, the following possibilities are used for antidote application: - seeds of crop plants are disinfected before seeding with the antidote substance (indication of the amount percent antidote to seed weight) - crop plants are sprayed prior to application of the test substances with the antidote with a given amount of application per hectare are (usually 1 day before application of test substances) - the antidote is applied together with the test substance as a tank mix (indication of the amount of antidote in g / ha or as herbicide ratio).

Testing in cereals in the greenhouse Mefenpir 1 day before herbicide application 28 days after application Amount of application Summer wheat g ai / ha observed (%) la-2 50 60 25 50 12.5 40 la-2 50 + 50 5 Testing in greenhouse cereal containers Mefenpir 1 day before herbicide application + mefenpyr 25 + 50 5 12.5 + 50 0 10 days after application Amount of application Summer wheat g ai / ha observed (%) la-10 50 60 25 50 12.5 30 la-10 50 + 50 5 + mefenpyr 25 + 50 3 12.5 + 50 2 10 days after application Amount of application Summer wheat g ai / ha observed (%) lc-7 50 60 25 50 12.5 40 lc- 7 50 + 50 5 + mefenpyr 25 + 50 5 12.5 + 50 3 10 days after application Amount of application Summer wheat Testing on containers with cereals in the greenhouse Mefenpir 1 day before herbicide application g ai / ha observed (%) la -11 50 70 25 50 12.5 30 la-11 50 + 50 10 + mefenpyr 25 + 50 10 12.5 + 50 8 10 days after application Quantity application Summer wheat g ai / ha observed (%) la-14 50 60 25 60 12.5 50 la-14 50 + 50 10 + mefenpyr 25 + 50 10 12.5 + 50 5 10 days after application Amount of application Summer wheat g ai / ha observed (%) la-13 50 60. 25 50 Testing in cereals in the greenhouse Mefenpir 1 day before herbicide application 12.5 40 la-13 50 + 50 5 + mefenpyr 25 + 50 2 12.5 + 50 2 28 days after application Amount of summer wheat g ai / ha observed (%) lc-9 100 50 50 40 25 30 lc-9 100 + 50 10 + mefenpyr 50 + 50 5 25 + 50 0 Pre-emergence 80 g / ha Example Example No. 3 Method of compatibility with crop plants in field trials, in small lots Sowing usual in practice using single grain seeder Batch size: 11.15 m2 / two repetitions The treatment was carried out using a batch sprayer. The antidote was applied together with the test substance as a tank mix with 300 l / ha of water (indication of the amount of herbicide and antidote in g a.i./ha). The postemergence application was in the five leaf stage of maize. Compatibility with the crop plant was visually assessed 14 and 27 days after treatment (percentage compared to untreated plants), 100% damage = plants died, 0% damage = such as control plants).

Corn field test (Magixx Duo is cycloxidime tolerant) Postemergence method Example No. 4 Myzus test (spray treatment, MYZUPE) Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether To produce an appropriate active substance preparation, 1 part by weight of the active substance is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.

Pieces of cabbage leaves (Brassica pekinensis), which are infested with peach green aphid (Myzus persicae), are sprayed with an active substance preparation of the desired concentration.

After 6 days, the effect in% is determined. In this case, 100% means that all aphids have been exterminated; 0% means no aphids have been exterminated.

In this test, for example, the following compounds of the preparation examples had an effect of> 80% at an application amount of 500 g / ha: Ex: la-10, lc-10, lc-14 Plant-damaging insects Example 5 Heliothis virescens Test - Transgenic Plant Treatment Solvent: 7 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycolic ether To produce an appropriate active substance preparation, 1 part by weight of active substance is mixed with the indicated amount of solvent and the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Roundup Ready soybean sprouts (Glycine max) (trademark of Monsanto Comp., USA) are treated by soaking in the active ingredient preparation at the desired concentration and loaded with the Heliothis virescens tobacco caterpillar while the leaves are still moist. .

After the desired time, the extermination of the insects is determined. Example No. 6 Limit Concentration / Soil Insect Test - Treatment of Transgenic Plants Test Insect: Diabrotica balteata - Larvae in Solvent Solvent: 7 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycolic ether For production of a For the appropriate active ingredient preparation, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration. The active substance preparation is poured into the soil. In this case, the concentration of the active substance in the preparation is practically unimportant, only the amount by weight of active substance per unit volume of soil, which is indicated in ppm (mg / l), is decisive. The soil is filled into 0.25 I pots and left to stand at 20 ° C.

Immediately after preparation, 5 pre-germinated YIELD GUARD corn grains (trademark of Monsanto Comp., USA) are placed in each pot. After 2 days, the corresponding test insects are placed on the treated soil. After a further 7 days, the efficiency of the active substance is determined by counting the emerged maize plants (1 plant = 20% efficiency).

Example N ° 7 Increased plant penetration by ammonium or phosphonium salts and synergistic increase of plant penetration by ammonium / phosphonium salts in combination with penetration agents In this test the penetration of active substances by enzymatically isolated cuticles of apple leaves.

Leaves were used, which were cut in a fully developed state of Golden Delicious apple trees. The isolation of the cuticles took place in such a way that - first, discs of dyed-marked underside leaves were filled by vacuum infiltration with an adjusted 0.2 to 2% pectinase solution. in acidity at a pH between 3 and 4, - then sodium azide was added, and - the thus treated leaf discs were allowed to stand until the original leaf structure was dissolved and the non-cellular cuticle detached. .

Then only the cuticles on the upper sides of the leaves, free of hair and starlings, continued to be used. They were washed repeatedly, alternately, with water and a pH 7 buffer solution. The clean cuticles obtained were finally mounted on Teflon plates and smoothed and dried with a weak air blast.

In the next step, the cuticle membranes thus obtained were inserted into thin steel diffusion cells (= transport chambers) for membrane transport tests. To this end, the cuticles were placed with tweezers in the center over the greased edges of the diffusion cells and closed with a greased ring. The arrangement was selected such that the morphological external side of the cuticles was facing outwards, therefore into the air, while the original inside was facing inwards of the diffusion cell.

The diffusion cells were filled with a 30% ethylene glycol / water solution. To determine the penetration, 10 μΙ of the spray mixture of the composition mentioned below was applied in each case to the external side of the cuticles. The spray solution is prepared with medium hard local tap water.

After spray spray application, the water was allowed to evaporate and the chambers were inverted and placed in thermostatic vats in which the temperature and atmospheric humidity could be adjusted using a moderate air dye on the coated cuticles. spray (20 ° C, 60% rh). At regular intervals, an auto-display (autosampler) took aliquots and the active substance content was determined with HPLC.

The test results are shown in the table below. The numbers given are average values of eight to ten measurements. a.i. (0.2 g / l) AS = ammonium sulfate (0.7 g / l) Edenor Me SU 500 EW (2 g / l) CLAIMS

Claims (22)

1. Compounds, characterized in that they have the formula (I) wherein X represents methyl, ethyl or methoxy, Y represents methyl or ethyl, Z represents hydrogen, methyl or ethyl, A, B and the carbon atom to which are C5 -C7 -cycloalkyl or C7-dcloalkenyl, in which optionally one or two ring members are substituted by oxygen and / or sulfur and which is optionally mono-, di-, tri- or tetrasubstituted. by methyl, in each case monosubstituted by ethyl, a group = CH2, methoxy, ethoxy or benzyloxy, A, B and the carbon atom to which they are attached represent a group = CH2, represent a group = CH2-CH3, represent a group = CH2-C2H5 or represent a group = N-OR9, G represents hydrogen (a) or represents one of the groups in which E represents a metal ion equivalent, L represents oxygen or sulfur and M represents oxygen, R1 represents CrCe-alkyl or C1 -C2 alkoxy C1 -C4 alkyl, C1 -C2 alkoxy C1 -C4 alkyl or represents C1 -C10 alkyl which is monosubstituted by chlorine represents phenyl, which is optionally monosubstituted by chlorine, methyl or meoxy, R2 represents C1 -C6 alkyl, R3 represents methyl, phenylphenyl p-methylferila, R9 represents hydrogen, methyl, i-propyl t-butyl, tert-butyl, CH 2 CF 3, propynyl (CH 2 -C = CH), CH (CH 3) -C 2 CH, cyclopropyl, cyclopentyl, CH 2 -cidopropyl, CH 2 -cidopentyl. Process for preparing compounds of formula (I) as defined in claim 1, characterized in that it is for obtaining (A) Compounds of formula (1a) wherein A, B, X, Y and Z are as as defined in claim 1, ketocarboxylic acid esters of formula (II) wherein A, B, X, Y and Z are as defined in claim 1, and R represents alkyl, are cycled intramolecularly, if appropriate, in the presence of a diluent and in the presence of a base; (B) Compounds of formula (1b) wherein A, B, R 1, X, Y and Z are as defined in claim 1. Compounds of formula (la) as defined in claim 1, wherein A, B, X, Y and Z are as defined in claim 1, are in each case reacted (a) with acid halides of the formula (III) wherein R 1 is as defined in claim 1, and Hal represents halogen or (β) with carboxylic anhydrides of the formula (IV) wherein R1 above is as defined in claim 1, if appropriate, in the presence of a diluent and, if appropriate, in the presence of a binder. acid; (C) Compounds of formula (1-c) [. wherein A, B, R2, Μ, X, Y and 2 are as defined in claim 1, and L represents oxygen, compounds of formula (la) as defined in claim 1, wherein A, B, X, Y and Z are as defined in claim 1, are reacted in each case with chloroform acid esters of the formula (V) wherein R and M are as defined in claim 1, if appropriate; in the presence of a diluent and, if appropriate, in the presence of an acid ligand; (E) Compounds of formula (1d) wherein A, B, R, X, Y and Z are as defined in claim 1, compounds of formula (1a) as defined in claim 1, wherein A, B, X, Y and Z are as defined in claim 1, are reacted, in each case, with sulfonyl chlorides of the formula {VII} R3-SO2-C; (VII) wherein R above is as defined in claim 1, if appropriate, in the presence of a diluent and, if appropriate, in the presence of an acid binder, (G) Compounds of formula (If) E A, B, E, X, Y and Z are as defined in claim 1, compounds of formula (1a) as defined in claim 1, wherein A, B, X, Y and Z are as defined in claim 1 are reacted in each case by with metal or amine compounds of formulas (IX) and (X), respectively, Me (OR1 °) t (IX) wherein Me represents a mono- or divalent metal, t represents number 1 or 2, and 10 11 12 R R 1, R 2 independently of each other, represent hydrogen or alkyl, if appropriate, in the presence of a diluent. Compositions for controlling unwanted pests and / or vegetation, characterized in that they comprise at least one compound of formula (I) as defined in claim 1. Method for controlling animal pests and / or unwanted vegetation, characterized in that compounds of formula (I) as defined in claim 1 are allowed to act on pests, unwanted vegetation and / or their habitat. Use of compounds of formula (I) as defined in claim 1, characterized in that it is for controlling animal pests and / or unwanted vegetation. Process for preparing compositions for controlling unwanted pests and / or vegetation, characterized in that compounds of formula (I) as defined in claim 1 are mixed with diluents and / or surface active agents. Use of compounds of formula (I) as defined in claim 1, characterized in that it is for preparing compositions for controlling pests and / or unwanted vegetation. Compositions, characterized in that they comprise an effective amount of a combination of active substance, which comprises as components: (a ') at least one compound of formula (I) as defined in claim 1 in which A, B, G, X, Y and Z are as defined in claim 1, and (b ') at least one compound which enhances crop plant compatibility selected from the following group of compounds: S1, S2, S3, S4 , S5, S6, S7, S8, S9, S10, S11, S12, S13, S14. Compositions according to claim 8, characterized in that the compound which enhances the compatibility of cultivated plants is mexican cloquintocet. Compositions according to claim 8, characterized in that the compound which enhances the compatibility of cultivated plants is diethyl mefenpir. Compositions according to claim 8, characterized in that the compound which enhances the compatibility of cultivated plants is cyprosulfamide. Method for controlling unwanted vegetation, characterized in that a composition as defined in claim 8 is allowed to act on or around the plants. Use of a composition as defined in claim 8, characterized in that it is for controlling unwanted vegetation. A method for controlling unwanted vegetation, characterized in that a compound of formula (I) as defined in claim 1 and the compound which enhances crop compatibility as defined in claim 8 are allowed to act separately in accordance with the invention. near temporal succession, over or around the plants. Compounds, characterized in that they have the formula (II) wherein A, B, X, Y, Z and Rs are as defined in claim 1. Compounds, characterized in that they have the formula (XIII) wherein A, B, X, Y, and Z are as defined in claim 1. Compounds, characterized in that they have the formula (XIV) wherein A, B, X, Y, Z, Rb and R® are as defined in claim 1. 18. Compounds, characterized by the fact that they have the formula (XIX) in which X, Y, Z and Hal have the meanings indicated in the table: Compositions, characterized in that they comprise (a) at least one compound of formula (I) as defined in claim 1, or a composition as defined in claim 8, and (b) at least one salt of formula ( D) wherein D represents nitrogen or phosphorus, R, R, R and R independently of one another represent hydrogen or in each case optionally substituted C1 -C6 alkylene or optionally substituted mono- or polyunsaturated C1 -C6 alkylene, the substituents being selectable from halogen, nitro and damage, n represents 1,2, 3 or 4, R represents an inorganic or organic anion. Composition according to Claim 19, characterized in that it comprises at least one penetrating agent. A method for increasing the activity of pesticides and / or herbicides comprising an active compound of formula (I) as defined in claim 1 or a composition as defined in claim 8 characterized in that the ready-to-use composition comprises: Use (spray solution) is prepared using a salt of formula (III ') as defined in claim 19. Method according to claim 21, characterized in that the spray solution is prepared using a penetrating agent.