The invention is in the technical field of crop protection products which can be used against unwanted vegetation on noncrop land, for preparing seed or in plant crops and which comprise, as herbicidally active compounds, a combination of at least two herbicides, where one herbicide component is selected from the group consisting of certain bicyclically substituted azines.
Compounds from the structural class of Nsubstituted aminostriazines having bicyclic radicals on the amino group are known as herbicides (see, for example, WOA97/31904 or U.S. Pat. No. 6,069,114). The compounds are effective against a broad spectrum of harmful plants both when applied by the preemergence method and when applied by the postemergence method, a nonselective use for controlling unwanted vegetation or a selective use in plant crops, if appropriate in combination with safeners, being possible.
The efficacy of these herbicides against harmful plants is at a high level, but depends in general on the application rate, the formulation in question, the spectrum of harmful plants, the harmful plants to be controlled in each case, the climatic and soil conditions and the like. Another criterion is the duration of action, or the breakdown rate of the herbicide. If appropriate, changes in the sensitivity of harmful plants, which may occur upon prolonged use of the herbicides or within geographic limitations, must also be taken into consideration. The compensation of losses in action in the case of individual harmful plants by increasing the application rates of the herbicides is only possible to a certain degree, for example because such a procedure frequently reduces the selectivity of the herbicides or because the action is not improved, even when applying higher rates. In some cases, the selectivity in crops can be improved by adding safeners. In general, however, there remains a need for methods to achieve the herbicidal action with a lower application rate of active compounds. Not only does a lower application rate reduce the amount of an active compound required for application, but, as a rule, it also reduces the amount of formulation auxiliaries required. It both reduces the economic input and improves the ecological compatibility of the herbicide treatment.
One possibility of improving the application profile of a herbicide can consist in combining the active compound with one or more other active compounds which contribute the desired additional properties. However, the combined use of a plurality of active compounds frequently causes phenomena of physical and biological incompatibility, for example a lack of stability in a coformulation, decomposition of an active compound, or antagonism of the active compounds. What is desired are, in contrast, combinations of active compounds having an advantageous activity profile, high stability and, if possible, an unexpected synergistically improved action, which allows the application rate to be reduced in comparison with the individual application of the active compounds to be combined.
It is already known that the combination of other herbicides with herbicides from the broadly defined class of the aminostriazines which are Nsubstituted by arylalkyl radicals may result in synergistic effects (see WOA00/1 6627). Specific examples of combinations of other herbicides with aminostriazines having bicyclic radicals on the amino group are not described in this publication. Owing to the relatively strong differences between the aminostriazines having arylalkyl radicals on the amino group on the one hand and having bicyclic radicals on the other hand, where, in addition to the structural changes, differences can also be observed in changed activity characteristics, synergistic effects for the bicyclically substituted compounds, in particular individual stereoisomers thereof, are not to be expected in the same manner.
Surprisingly, it has now been found that active compounds of the herbicide type mentioned act in a particularly favorable manner against unwanted vegetation when they are used in combination with certain structurally different herbicides. They are preferably used on noncrop land, plantation crops and crops which are substantially tolerant to the application of the herbicides, if appropriate with added safeners.
Accordingly, the invention provides herbicide combinations comprising an effective amount of components (A) and (B) where
component (A) is one or more herbicides of the formula (I) or salts thereof
[Herbicides (A)]
component (B) is one or more herbicides (B) which are structurally different from the herbicides (A) present in each case, selected from the group of compounds consisting of
The herbicide combinations according to the invention may comprise further components, for example other active compounds against harmful organisms such as harmful plants, plantdamaging animals or plantdamaging fungi, in particular compounds from the group of the herbicides, fungicides, insecticides, acaricides, nematicides and miticides and related substances, or else crop protection agents of a different type (for example safeners, resistance inductors), plant growth regulators and/or formulation auxiliaries and/or additives customary in crop protection. Here, the components may be formulated (finished formulation) and applied together, or they can be formulated separately and applied together, for example by the tank mix method or in a sequential application.
The individual herbicides of the formula (I) present as component (A) are hereinbelow also referred to as compounds (A) or active compounds (A). Correspondingly, the individual herbicides present as component (B) are hereinbelow also referred to as compounds (B) or active compounds (B).
The synergistic effects are observed when the active compounds (A) and (B) are applied together; however, they may frequently also occur when the compounds are applied as a split application over time. Another possibility is the application of the herbicides or the herbicide combinations in a plurality of portions (sequential application), for example one or more preemergence applications may be followed by a postemergence application, or an early postemergence application may be followed by applications at medium or late postemergence. Preferred is the joint or nearly simultaneous application of the active compounds of the combination in question, if appropriate in a plurality of portions. However, it is also possible to apply the individual active compounds of a combination at different times, which may be advantageous in the individual case. It is also possible to integrate other crop protection agents, such as the active compounds mentioned (fungicides, insecticides, acaricides, etc.) and/or various auxiliaries, adjuvants and/or fertilizer applications with the application of this system.
Application by the preemergence or postemergence method is, depending on the context in which the terms are used, to be understood as meaning the application of the active compounds before or after the point in time when the harmful plants become visible above the ground, respectively, or the application of the active compounds against the harmful plants before the emergence of the crop plants and after the emergence of the crop plants, respectively.
By applying the herbicides (A) and (B) in combination, it is possible to achieve application properties superior to what might be expected for the combination based on the known properties of the individual herbicides. The synergistic effects permit, for example, a reduction in the application rates of the individual active compounds, a higher efficacy at the same application rate, the control of previously uncontrolled species of harmful plants (gaps), higher residual action, longer longterm action, a more rapid onset of action, an extension of the period of application and/or a reduction of the number of individual applications required and—as a result for the user—weed control systems which are more advantageous economically and ecologically.
In formula (I) for compounds of the herbicidally active components (A) and in all subsequent formulae, the following definitions apply:
The formula (I) also includes all stereoisomers of the compounds whose specific stereochemical configuration is not expressly expressed by the formula, and mixtures thereof. Such compounds of the formula (I) contain one or more asymmetrical carbon atoms or else double bonds which are not specifically shown in the general formulae (I). The formula (I) embraces all possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereoisomers, Z and E isomers, and these stereoisomers can be obtained by customary methods from mixtures of the stereoisomers or else by stereoselective reactions in combination with the use of stereochemically pure starting materials.
By forming an adduct of a suitable inorganic or organic acid, such as, for example, HCl, HBr, H_{2}SO_{4 }or HNO_{3}, or else oxalic acid or sulfonic acids, to a basic group, such as, for example, amino or alkylamino, the compounds of the formula (I) are capable of forming salts. Suitable substituents present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form inner salts with groups which for their part are protonatable, such as amino groups.
It is also possible to form salts by replacing the hydrogen of suitable substituents, such as, for example, sulfonic acids or carboxylic acids, by an agriculturally useful cation. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, especially sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts.
The term “(C_{1}C_{4})alkyl” is an abbreviated notation for openchain alkyl having one to 4 carbon atoms, i.e. it comprises the radicals methyl, ethyl, 1propyl, 2propyl, 1butyl, 2butyl, 2methylpropyl or tertbutyl. Correspondingly, general alkyl radicals having a wider stated range of carbon atoms, for example “(C_{1}C_{6})alkyl”, also comprise straightchain or branched alkyl radicals having a larger number of carbon atoms, i.e., for example, also the alkyl radicals having 5 and 6 carbon atoms.
Unless specifically indicated, the lower carbon skeletons, for example those having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, are preferred for the hydrocarbon radicals, such as alkyl, alkenyl and alkynyl radicals, including in composite radicals. Alkyl radicals, including the composite meanings, such as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl, n or ipropyl, n, i, t or 2butyl, pentyls, hexyls, such as nhexyl, ihexyl and 1,3dimethylbutyl, heptyls, such as nheptyl, 1methylhexyl and 1,4dimethylpentyl; alkenyl and alkynyl radicals denote the possible unsaturated radicals which correspond to the meaning of the alkyl radicals; alkenyl is, for example, vinyl, allyl, 1methyl2propenyl, 2methyl2propenyl, 2butenyl, pentenyl, 2methylpentenyl or hexenyl, preferably allyl, 1methylprop2en1yl, 2methylprop2en1yl, but2en1yl, but3en1yl, 1methylbut3en1yl or 1methylbut2en1yl. (C_{2}C_{6})Alkynyl is, for example, ethynyl, propargyl, 1methyl2propynyl, 2methyl2propynyl, 2butynyl, 2pentynyl or 2hexynyl, preferably propargyl, but2yn1yl, but3yn1yl or 1methylbut3yn1yl.
Cycloalkyl denotes a carbocyclic saturated ring system having preferably 38 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Cycloalkenyl denotes a carbocyclic nonaromatic partially unsaturated ring system having preferably 48 carbon atoms, for example 1cyclobutenyl, 2cyclobutenyl, 1cyclopentenyl, 2cyclopentenyl, 3cyclopentenyl, or 1cyclohexenyl, 2cyclohexenyl, 3cyclohexenyl, 1,3cyclohexadienyl or 1,4cyclohexadienyl.
Halogen denotes, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, alkenyl and alkynyl denote alkyl, alkenyl and alkynyl, respectively, which are partially or fully substituted by identical or different halogen atoms, preferably selected from the group consisting of fluorine, chlorine and bromine, in particular from the group consisting of fluorine and chlorine, for example monohaloalkyl, perhaloalkyl, CF_{3}, CHF_{2}, CH_{2}F, CF_{3}CF_{2}, CH_{2}FCHCl, CCl_{3}, CHCl_{2}, CH_{2}CH_{2}Cl; haloalkoxy is, for example, OCF_{3}, OCHF_{2}, OCH_{2}F, CF_{3}CF_{2}O, OCH_{2}CF_{3 }and OCH_{2}CH_{2}Cl; this applies correspondingly to haloalkenyl and other halogensubstituted radicals.
In the case of radicals having carbon atoms, preference is given to those having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Preference is generally given to substituents selected from the group consisting of halogen, for example fluorine and chlorine, (C_{1}C_{4})alkyl, preferably methyl or ethyl, (C_{1}C_{4})haloalkyl, preferably trifluoromethyl, (C_{1}C_{4})alkoxy, preferably methoxy or ethoxy, (C_{1}C_{4})haloalkoxy, nitro and cyano. Particular preference is given here to the substituents methyl, methoxy, fluorine and chlorine.
Acyl denotes a radical of an organic acid which, formally, is formed by removing a hydroxyl group from the acid function, it also being possible for the organic radical in the acid to be attached to the acid function via a heteroatom. Examples of acyl are the radical —CO—R of a carboxylic acid HO—CO—R and radicals of acids derived therefrom, such as thiocarboxylic acid, unsubstituted or Nsubstituted iminocarboxylic acids or the radical of carbonic acid monoesters, Nsubstituted carbamic acid, sulfonic acids, sulfinic acids, Nsubstituted sulfonamido acids, phosphonic acids, phosphinic acids.
Acyl denotes, for example, formyl, alkylcarbonyl, such as [(C_{1}C_{4})alkyl]carbonyl, phenylcarbonyl, alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, Nalkyl1iminoalkyl and other radicals of organic acids. Here, the radicals may in each case be substituted further in the alkyl or phenyl moiety, for example in the alkyl moiety by one or more radicals selected from the group consisting of halogen, alkoxy, phenyl and phenoxy; examples of substituents in the phenyl moiety are the substituents which have already been mentioned further above in a general manner for substituted phenyl.
Acyl preferably denotes an acyl radical in the narrower sense, i.e. a radical of an organic acid where the acid group is attached directly to the carbon atom of an organic radical, for example formyl, alkylcarbonyl, such as acetyl or [(C_{1}C_{4})alkyl]carbonyl, phenylcarbonyl, alkylsulfonyl, alkylsulfinyl and other radicals of organic acids.
If a general radical is designated (defined) as “hydrogen”, this means an attached hydrogen atom.
The “ylposition” of a radical (for example of an alkyl radical) denotes its point of attachment.
Hereinbelow, compounds of the formula (I) and salts thereof which can be used according to the invention are, in short, also referred to as “compounds (I) according to the invention”.
The compounds of the formula (I) are known in principle from WO 97/31904 or can be prepared by the processes described therein. Of particular interest are compounds of the formula (I) or salts thereof in which
R^{1 }is H or a group of the formula CZ^{1}Z^{2}Z^{3 }in which
R^{2 }is H, (C_{1}C_{4})alkyl, (C_{1}C_{4})haloalkyl, (C_{3}C_{4})alkenyl, (C_{3}C_{4})haloalkenyl, (C_{3}C_{4})alkynyl, (C_{3}C_{4})haloalkynyl or an acyl radical having 1 to 12 carbon atoms (preferably an acyl radical selected from the group consisting of formyl, phenylcarbonyl, phenoxycarbonyl, where phenyl in the two lastmentioned radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C_{1}C_{2})alkyl, (C_{1}C_{2})haloalkyl, (C_{1}C_{2})alkoxy, (C_{1}C_{2})haloalkoxy and nitro, or (C_{1}C_{6})alkylcarbonyl, (C_{1}C_{6})alkoxycarbonyl or (C_{1}C_{6})alkylsulfonyl),
R^{3 }is H, (C_{1}C_{4})alkyl or (C_{1}C_{4})haloalkyl,
R^{4 }is H, (C_{1}C_{3})alkyl or (C_{1}C_{3})alkoxy,
R^{5}, R^{6}, R^{7 }and R^{8 }are each independently of one another H, (C_{1}C_{3})alkyl, halogen, (C_{1}C_{3})alkoxy, and
A is a divalent group of the formula CH_{2 }or O or a direct bond, preferably CH_{2 }or a direct bond, in particular a direct bond.
Preference is given to optically active compounds of the formula (I) and salts thereof in which the stereochemical configuration at the carbon atom marked 1 in formula (I) is the (R)configuration with a stereochemical purity of 60 to 100% (R), preferably 70100% (R), in particular 80 to 100% (R), in each case based on the content of stereoisomers having (R) and (S)configuration in this position. The configuration is assumed to have been determined using the Cahn/Ingold/Prelog system, the priority of the substituents in position 1 being as follows:
1. priority is given to substituted NH; 2. priority is given to the bond to the phenyl ring; 3. priority is given to the other carbon ring atom, 4. priority is given to the hydrogen atom.
Preference is furthermore given to optically active compounds of the formula (I) and salts thereof in which R^{1 }is a group of the formula CZ^{1}Z^{2}Z^{3}, where CZ^{1}Z^{2}Z^{3 }is defined as above, in particular to those compounds in which the stereochemical configuration at the carbon atom of the group CZ^{1}Z^{2}Z^{3 }is the (R,S)configuration or the (R)configuration with a stereochemical purity of 60 to 100% (R), preferably 70100% (R), in particular 80 to 100% (R), in each case based on the content of stereoisomers having (R) and (S)configuration in this position.
Suitable combination partners (A) are, for example, certain compounds of the formula (I) from Table 1 below.
Notes for Table 1:
In Table 1, the compounds are designated by the chemical formula of the main component, this component being present in a chemical purity of at least 95% by weight of the compound. It is, of course, also possible to use the compounds in lower purities. In particular if minor components of the compounds consist predominantly or entirely of active stereoisomers of the respective compounds (A), similar efficacies are achieved during application. Accordingly, preferred herbicides (A) are also mixtures of two or more compounds (A) from Table 1. For reasons of easier preparability, in practice, preference is especially also given to herbicides (A) comprising, as main component, a compound (A) from Table 1 and, as minor components, stereoisomers of the compound (A), preferably those which are also mentioned in Table 1.
If, in the chemical formula in question in Table 1, the stereochemical orientation at a carbon atom is given and the stereochemical orientation is additionally assigned using the system of Cahn, Ingold and Prelog, the main component of the compound is a stereoisomer or a stereoisomer mixture which has the R or Sconfiguration at the carbon atom referred to; the compound (A) is thus optically active.
If the stereochemistry is not assigned by an R or Sconfiguration, the main component is a compound which, at the carbon atom in question, has the RSconfiguration (racemic).
If a plurality of stereocenters are present and the configuration is in each case assigned by R or S, these are optically active compounds having the stereochemistry mentioned at the centers referred to.
If, in the case of a plurality of centers, no R or Sconfiguration is assigned, the compounds are racemic mixtures, i.e. the nonchiral stereoisomers contained therein (enantiomers of a pair of enantiomers) are present in the mixture in identical proportions. Unless indicated in more detail, in Table 1, in the case of racemic compounds (A) having a plurality of stereocenters, the diastereoisomeric components are present in approximately identical proportions. However, for practical application, in the case of racemic compounds having a plurality of stereocenters, mixtures of diastereomers (in each case in racemic form) having different proportions of the diastereomeric components are possible.
In the bicyclic radical, the carbon atom which is attached to the amino group is carbon atom 1. In the side group (unless the radical is H) the carbon atom attached directly to the triazine ring is referred to as 1*.
TABLE 1  
Compounds of the formula (I) (herbicide (A)):  
Compound  
No.  Chemical formula or chemical name 
A1 

A2 

A3 

A4 

A5 

A6 

A7 

A8 

A9 

A10 

A11 

A12 

A13 

A14 

A15 

A16 

A17 

A18 

A19 

A20 

A21 

A22 

A23 

A24 

A25 

A26 

A27 

A28 

A29 

A30 

A31 

A32 

A33 

A34 

A35 

A36 

A37 

A38 

A39 

A40 

A41 

A42 

A43 

A44 

A45 

A46 

A47 

A48 

A49 

A50 

A51 

A52 

A53 

A54 

A55 

A56 

A57 

A58 

A59 

A60 

A61 

A62 

A63 

A64 

A65 

A66 

A67 

A68 

A69 

A70 

A71 

A72 

A73 

A74 

A75 

A76 

A77 

A78 

A79 

A80 

A81 

A82 

A83 

A84 

A85 

A86 

A87 

A88 

A89 

A90 

A91 

A92 

A93 

A94 

A95 

A96 

A97 

A98 

A99 

A100 

A101 

A102 

A103 

A104 

A105 

A106 

A107 

A108 

A109 

A110 

A111 

A112 

A113 

A114 

A115 

A116 

A117 

A118 

A119 

A120 

A121 

A122 

A123 

A124 

A125 

A126 

A127 

The application rates of the herbicides (A) are known in principle and are in the range from 0.5 to 2000 g of active compound per hectare, preferably from 1 to 800 g of active compound per hectare, in particular from 5 to 500 g of active compound per hectare. In the combinations according to the invention, in the context of the application rates mentioned, lower application rates of the active compound in question are required compared to the application on its own.
Suitable combination partners (B) [=component (B)] are, for example, the following compounds, differing from compounds (A), of subgroups (B1) to (B3), where the herbicides are in most cases referred to by the “common name” according to the literature reference “The Pesticide Manual” 13th Ed., British Crop Protection Council 2003, abbreviated as “PM”:
(B1) soilacting herbicides which are particularly suitable for preemergence application against monocotyledonous or dicotyledonous harmful plants, for example one or more compounds selected from the group consisting of
(B1.1) soilacting herbicides which are particularly suitable for preemergence application against monocotyledonous and dicotyledonous harmful plants, for example one or more compounds selected from the group consisting of
for example one or more compounds selected from the group consisting of
(B2) foliaracting herbicides which are particularly suitable for postemergence application against monocotyledonous or dicotyledonous harmful plants, for example one or more compounds selected from the group consisting of
(B2.1) foliaracting herbicides which are particularly suitable for postemergence application against monocotyledonous and dicotyledonous harmful plants,
for example one or more compounds selected from the group consisting of
(B2.2) foliaracting herbicides which are particularly suitable for the postemergence application against dicotyledonous harmful plants, for example one or more compounds selected from the group consisting of
(B2.3) foliaracting herbicides which are particularly suitable for postemergence application against monocotyledonous harmful plants,
for example the compound
(B3) soil and foliaracting herbicides which are suitable for pre or postemergence application against monocotyledonous or dicotyledonous harmful plants, for example one or more compounds selected from the group consisting of
(B3.1) soil and foliaracting herbicides which are particularly suitable for postemergence application against monocotyledonous or dicotyledonous harmful plants, for example one or more compounds selected from the group consisting of
(B3.2) soil and foliaracting herbicides which are particularly suitable for the postemergence application against dicotyledonous harmful plants,
for example one or more compounds selected from the group consisting of
From the combinations defined above, preference is given to those which comprise a herbicide from group (A) and a herbicide from group (B). Furthermore, the combinations according to the invention may be used together with other active compounds, such as the active compounds mentioned (herbicides, fungicides, insecticides, acaricides, etc.) and/or plant growth regulators or auxiliaries from the group of the formulation auxiliaries and additives customary in crop protection.
Accordingly, the invention also provides the herbicidal compositions which comprise the active compound combinations according to the invention together with formulation auxiliaries, if appropriate further additives and if appropriate further crop protection agents.
The invention also provides the use or the application method where the active compound combinations according to the invention are used as herbicides and plant growth regulators, preferably as herbicides and plant growth regulators comprising a synergistically effective amount of the respective active compound combination contained therein.
Below, specific herbicide combinations (Aa)+(Bb) are referred to by the term Ka.b, where a is the respective code from the number of the herbicide (A) from Table 1 [codes 1 to 127 of the compounds (A1) to (A127)] and b is the respective code of the herbicide component (B) according to Table 2 below [codes 1 to 103 of the compounds (B1.1.1) to (B3.2.3)]:
TABLE 2  
Codes for the herbicide component B (see subtables 2a to 2i)  
Table 2a  
Code  Component B 
1  (B1.1.1) 
2  (B1.1.2) 
3  (B1.1.3) 
4  (B1.1.4) 
5  (B1.1.5) 
Table 2b  
Code  Component B 
6  (B1.1.6) 
7  (B1.1.7) 
8  (B1.1.8) 
9  (B1.1.9) 
10  (B1.1.10) 
Table 2c  
Code  Component B 
11  (B1.1.11) 
12  (B1.1.12) 
13  (B1.2.1) 
14  (B1.2.2) 
Table 2d  
Code  Component B 
15  (B2.1.1) 
16  (B2.1.1.1) 
17  (B2.1.1.2) 
18  (B2.1.1.3) 
19  (B2.1.1.4) 
20  (B2.1.2) 
21  (B2.1.2.1) 
22  (B2.1.2.2) 
23  (B2.1.2.3) 
24  (B2.1.3) 
25  (B2.1.4) 
26  (B2.1.4.1) 
27  (B2.1.4.2) 
28  (B2.1.4.3) 
29  (B2.1.4.4) 
30  (B2.1.4.5) 
31  (B2.1.5) 
32  (B2.1.6) 
33  (B2.1.6.1) 
34  (B2.1.6.2) 
35  (B2.1.7) 
36  (B2.1.8) 
37  (B2.1.8.1) 
38  (B2.1.9) 
Table 2e  
Code  Component B 
39  (B2.1.10) 
40  (B2.1.10.1) 
41  (B2.1.11) 
42  (B2.1.12) 
43  (B2.1.12.1) 
44  (B2.1.12.2) 
45  (B2.1.13) 
46  (B2.1.13.1) 
47  (B2.1.14) 
48  (B2.1.14.1) 
49  (B2.2.1) 
50  (B2.2.2) 
51  (B2.2.3) 
52  (B2.2.3.1) 
53  (B2.2.3.2) 
54  (B2.2.3.3) 
55  (B2.2.4) 
56  (B2.2.4.1) 
57  (B2.2.4.2) 
58  (B2.2.5) 
59  (B2.2.5.1) 
60  (B2.2.5.2) 
61  (B2.2.5.3) 
62  (B2.2.6) 
Table 2f  
Code  Component B 
63  (B2.2.6.1) 
64  (B2.2.7) 
65  (B2.2.8) 
66  (B2.2.8.1) 
67  (B2.2.9) 
68  (B2.2.10) 
69  (B2.2.10.1) 
70  (B2.2.10.2) 
71  (B2.2.10.3) 
72  (B2.2.10.4) 
73  (B2.2.10.5) 
74  (B2.2.10.6) 
75  (B2.2.11) 
76  (B2.2.11.1) 
77  (B2.2.12) 
78  (B2.2.12.1) 
79  (B2.2.12.2) 
80  (B2.2.13) 
81  (B2.2.14) 
82  (B2.3.1) 
Table 2g  
Code  Component B 
83  (B3.1.1) 
84  (B3.1.2) 
85  (B3.1.3) 
86  (B3.1.4) 
87  (B3.1.5) 
88  (B3.1.6) 
89  (B3.1.7) 
90  (B3.1.8) 
91  (B3.1.9) 
Table 2h  
Code  Component B 
92  (B3.1.10) 
93  (B3.1.11) 
94  (B3.1.12) 
95  (B3.1.12.1) 
96  (B3.1.13) 
97  (B3.1.14) 
98  (B3.1.14.1) 
99  (B3.1.14.2) 
100  (B3.1.15) 
Table 2i  
Code  Component B 
101  (B3.2.1) 
102  (B3.2.2) 
103  (B3.2.3) 
Thus, in the short annotation, a combination of the herbicides (A5) and (B2.1.2.3) is referred to as K5.23.
Examples of preferred combinations are:
A herbicide from the group of the herbicides (A1) to (A127) and herbicides from the group (B1) or (B2) or (B3), for example a herbicide from the group of the herbicides (A1) to (A127) and herbicides from the group (B1.1), (B1.2), (B2.1), (B2.2), (B2.3), (B3.1) or (B3.2), specifically one of the combinations K1.1, K1.2, K1.3, K1.4, K1.5, K1.6, K1.7, K1.8, K1.9, K1.10, K1.11, K1.12, K1.13, K1.14, K1.15, K1.16, K1.17, K1.18, K1.19, K1.20, K1.21, K1.22, K1.23, K1.24, K1.25, K1.26, K1.27, K1.28, K1.29, K1.30, K1.31, K1.32, K1.33, K1.34, K1.35, K1.36, K1.37, K1.38, K1.39, K1.40, K1.41, K1.42, K1.43, K1.44, K1.45, K1.46, K1.47, K1.48, K1.49, K1.50, K1.51, K1.52, K1.53, K1.54, K1.55, K1.56, K1.57, K1.58, K1.59, K1.60, K1.61, K1.62, K1.63, K1.64, K1.65, K1.66, K1.67, K1.68, K1.69, K1.70, K1.71, K1.72, K1.73, K1.74, K1.75, K1.76, K1.77, K1.78, K1.79, K1.80, K1.81, K1.82, K1.83, K1.84, K1.85, K1.86, K1.87, K1.88, K1.89, K1.90, K1.91, K1.92, K1.93, K1.94, K1.95, K1.96, K1.97, K1.98, K1.99, K1.100, K1.101, K1.102, K1.103, K2.1, K2.2, K2.3, K2.4, K2.5, K2.6, K2.7, K2.8, K2.9, K2.10, K2.11, K2.12, K2.13, K2.14, K2.15,K2.16, K2.17, K2.18, K2.19, K2.20, K2.21, K2.22, K2.23, K2.24, K2.25, K2.26, K2.27, K2.28, K2.29, K2.30, K2.31, K2.32, K2.33, K2.34, K2.35, K2.36, K2.37, K2.38, K2.39, K2.40, K2.41, K2.42, K2.43, K2.44, K2.45, K2.46, K2.47, K2.48, K2.49, K2.50, K2.51, K2.52, K2.53, K2.54, K2.55, K2.56, K2.57, K2.58, K2.59, K2.60, K2.61, K2.62, K2.63, K2.64, K2.65, K2.66, K2.67, K2.68, K2.69, K2.70, K2.71, K2.72, K2.73, K2.74, K2.75, K2.76, K2.77, K2.78, K2.79, K2.80, K2.81, K2.82, K2.83, K2.84, K2.85, K2.86, K2.87, K2.88, K2.89, K2.90, K2.91, K2.92, K2.93, K2.94, K2.95, K2.96, K2.97, K2.98, K2.99, K2.100, K2.101, K2.102, K2.103, K3.1, K3.2, K3.3, K3.4, K3.5, K3.6, K3.7, K3.8, K3.9, K3.10, K3.11, K3.12, K3.13, K3.14, K3.15, K3.16, K3.17, K3.18, K3.19, K3.20, K3.21, K3.22, K3.23, K3.24, K3.25, K3.26, K3.27, K3.28, K3.29, K3.30, K3.31, K3.32, K3.33, K3.34, K3.35, K3.36, K3.37, K3.38, K3.39, K3.40, K3.41, K3.42, K3.43, K3.44, K3.45, K3.46, K3.47, K3.48, K3.49, K3.50, K3.51, K3.52, K3.53, K3.54, K3.55, K3.56, K3.57, K3.58, K3.59, K3.60, K3.61, K3.62, K3.63, K3.64, K3.65, K3.66, K3.67, K3.68, K3.69, K3.70, K3.71, K3.72, K3.73, K3.74, K3.75, K3.76, K3.77, K3.78, K3.79, K3.80, K3.81, K3.82, K3.83, K3.84, K3.85, K3.86, K3.87, K3.88, K3.89, K3.90, K3.91, K3.92, K3.93, K3.94, K3.95, K3.96, K3.97, K3.98, K3.99, K3.100, K3.101, K3.102, K3.103, K4.1, K4.2, K4.3, K4.4, K4.5, K4.6, K4.7, K4.8, K4.9, K4.10, K4.11, K4.12, K4.13, K4.14, K4.15, K4.16, K4.17, K4.18, K4.19, K4.20, K4.21, K4.22, K4.23, K4.24, K4.25, K4.26, K4.27, K4.28, K4.29, K4.30, K4.31, K4.32, K4.33, K4.34, K4.35, K4.36, K4.37, K4.38, K4.39, K4.40, K4.41, K4.42, K4.43, K4.44, K4.45, K4.46, K4.47, K4.48, K4.49, K4.50, K4.51, K4.52, K4.53, K4.54, K4.55, K4.56, K4.57, K4.58, K4.59, K4.60, K4.61, K4.62, K4.63, K4.64, K4.65, K4.66, K4.67, K4.68, K4.69, K4.70, K4.71, K4.72, K4.73, K4.74, K4.75, K4.76, K4.77, K4.78, K4.79, K4.80, K4.81, K4.82, K4.83, K4.84, K4.85, K4.86, K4.87, K4.88, K4.89, K4.90, K4.91, K4.92, K4.93, K4.94, K4.95, K4.96, K4.97, K4.98, K4.99, K4.100, K4.101, K4.102, K4.103, K5.1, K5.2, K5.3, K5.4, K5.5, K5.6, K5.7, K5.8, K5.9, K5.10, K5.11, K5.12, K5.13, K5.14, K5.15, K5.16, K5.17, K5.18, K5.19, K5.20, K5.21, K5.22, K5.23, K5.24, K5.25, K5.26, K5.27, K5.28, K5.29, K5.30, K5.31, K5.32, K5.33, K5.34, K5.35, K5.36, K5.37, K5.38, K5.39, K5.40, K5.41, K5.42, K5.43, K5.44, K5.45, K5.46, K5.47, K5.48, K5.49, K5.50, K5.51, K5.52, K5.53, K5.54, K5.55, K5.56, K5.57, K5.58, K5.59, K5.60, K5.61, K5.62, K5.63, K5.64, K5.65, K5.66, K5.67, K5.68, K5.69, K5.70, K5.71, K5.72, K5.73, K5.74, K5.75, K5.76, K5.77, K5.78, K5.79, K5.80, K5.81, K5.82, K5.83, K5.84, K5.85, K5.86, K5.87, K5.88, K5.89, K5.90, K5.91, K5.92, K5.93, K5.94, K5.95, K5.96, K5.97, K5.98, K5.99, K5.100, K5.101, K5.102, K5.103, K6.1, K6.2, K6.3, K6.4, K6.5, K6.6, K6.7, K6.8, K6.9, K6.10, K6.11, K6.12, K6.13, K6.14, K6.15, K6.16, K6.17, K6.18, K6.19, K6.20, K6.21, K6.22, K6.23, K6.24, K6.25, K6.26, K6.27, K6.28, K6.29, K6.30, K6.31, K6.32, K6.33, K6.34, K6.35, K6.36, K6.37, K6.38, K6.39, K6.40, K6.41, K6.42, K6.43, K6.44, K6.45, K6.46, K6.47, K6.48, K6.49, K6.50, K6.51, K6.52, K6.53, K6.54, K6.55, K6.56, K6.57, K6.58, K6.59, K6.60, K6.61, K6.62, K6.63, K6.64, K6.65, K6.66, K6.67, K6.68, K6.69, K6.70, K6.71, K6.72, K6.73, K6.74, K6.75, K6.76, K6.77, K6.78, K6.79, K6.80, K6.81, K6.82, K6.83, K6.84, K6.85, K6.86, K6.87, K6.88, K6.89, K6.90, K6.91, K6.92, K6.93, K6.94, K6.95, K6.96, K6.97, K6.98, K6.99, K6.100, K6.101, K6.102, K6.103, K7.1, K7.2, K7.3, K7.4, K7.5, K7.6, K7.7, K7.8, K7.9, K7.10, K7.11, K7.12, K7.13, K7.14, K7.15, K7.16, K7.17, K7.18, K7.19, K7.20, K7.21, K7.22, K7.23, K7.24, K7.25, K7.26, K7.27, K7.28, K7.29, K7.30, K7.31, K7.32, K7.33, K7.34, K7.35, K7.36, K7.37, K7.38, K7.39, K7.40, K7.41, K7.42, K7.43, K7.44, K7.45, K7.46, K7.47, K7.48, K7.49, K7.50, K7.51, K7.52, K7.53, K7.54, K7.55, K7.56, K7.57, K7.58, K7.59, K7.60, K7.61, K7.62, K7.63, K7.64, K7.65, K7.66, K7.67, K7.68, K7.69, K7.70, K7.71, K7.72, K7.73, K7.74, K7.75, K7.76, K7.77, K7.78, K7.79, K7.80, K7.81, K7.82, K7.83, K7.84, K7.85, K7.86, K7.87, K7.88, K7.91, K7.92, K7.93, K7.94, K7.95, K7.96, K7.97, K7.98, K7.99, K7.100, K7.101, K7.102, K7.103, K8.1, K8.2, K8.3, K8.4, K8.5, K8.6, K8.7, K8.8, K8.9, K8.10, K8.11, K8.12, K8.13, K8.14, K8.15, K8.16, K8.17, K8.18, K8.19, K8.20, K8.21, K8.22, K8.23, K8.24, K8.25, K8.26, K8.27, K8.28, K8.29, K8.30, K8.31, K8.32, K8.33, K8.34, K8.35, K8.36, K8.37, K8.38, K8.39, K8.40, K8.41, K8.42, K8.43, K8.44, K8.45, K8.46, K8.47, K8.48, K8.49, K8.50, K8.51, K8.52, K8.53, K8.54, K8.55, K8.56, K8.57, K8.58, K8.59, K8.60, K8.61, K8.62, K8.63, K8.64, K8.65, K8.66, K8.67, K8.68, K8.69, K8.70, K8.71, K8.72, K8.73, K8.74, K8.75, K8.76, K8.77, K8.78, K8.79, K8.80, K8.81, K8.82, K8.83, K8.84, K8.85, K8.86, K8.87, K8.88, K8.89, K8.90, K8.91, K8.92, K8.93, K8.94, K8.95, K8.96, K8.97, K8.98, K8.99, K8.100, K8.101, K8.102, K8.103, K9.1, K9.2, K9.3, K9.4, K9.5, K9.6, K9.7, K9.8, K9.9, K9.10, K9.11,K9.12, K9.13, K9.14, K9.15, K9.16, K9.17, K9.18, K9.19, K9.20, K9.21, K9.22, K9.23, K9.24, K9.25, K9.26, K9.27, K9.28, K9.29, K9.30, K9.31, K9.32, K9.33, K9.34, K9.35, K9.36, K9.37, K9.38, K9.39, K9.40, K9.41, K9.42, K9.43, K9.44, K9.45, K9.46, K9.47, K9.48, K9.49, K9.50, K9.51, K9.52, K9.53, K9.54, K9.55, K9.56, K9.57, K9.58, K9.59, K9.60, K9.61, K9.62, K9.63, K9.64, K9.65, K9.66, K9.67, K9.68, K9.69, K9.70, K9.71, K9.72, K9.73, K9.74, K9.75, K9.76, K9.77, K9.78, K9.79, K9.80, K9.81, K9.82, K9.83, K9.84, K9.85, K9.86, K9.87, K9.88, K9.89, K9.90, K9.91, K9.92, K9.93, K9.94, K9.95, K9.96, K9.97, K9.98, K9.99, K9.100, K9.101, K9.102, K9.103, K10.1, K10.2, K10.3, K10.4, K10.5, K10.6, K10.7, K10.8, K10.9, K10.10, K10.11, K10.12, K10.13, K10.14, K10.15, K10.16, K10.17, K10.18, K10.19, K10.20, K10.21, K10.22, K10.23, K10.24, K10.25, K10.26, K10.27, K10.28, K10.29, K10.30, K10.31, K10.32, K10.33, K10.34, K10.35, K10.36, K10.37, K10.38, K10.39, K10.40, K10.41, K10.42, K10.43, K10.44, K10.45, K10.46, K10.47, K10.48, K10.49, K10.50, K10.51, K10.52, K10.53, K10.54, K10.55, K10.56, K10.57, K10.58, K10.59, K10.60, K10.61, K10.62, K10.63, K10.64, K10.65, K10.66, K10.67, K10.68, K10.69, K10.70, K10.71, K10.72, K10.73, K10.74, K10.75, K10.76, K10.77, K10.78, K10.79, K10.80, K10.81, K10.82, K10.83, K10.84, K10.85, K10.86, K10.87, K10.88, K10.89, K10.90, K10.91, K10.92, K10.93, K10.94, K10.95, K10.96, K10.97, K10.98, K10.99, K10.100, K10.101, K10.102, K10.103, K11.1, K11.2, K11.3, K11.4, K11.5, K11.6, K11.7, K11.8, K11.9, K11.10, K11.11, K11.12, K11.13, K11.14, K11.15, K11.16, K11.17, K11.18, K11.19, K11.20, K11.21, K11.22, K11.23, K11.24, K11.25, K11.26, K11.27, K11.28, K11.29, K11.30, K11.31, K11.32, K11.33, K11.34, K11.35, K11.36, K11.37, K11.38, K11.39, K11.40, K11.41, K11.42, K11.43, K11.44, K11.45, K11.46, K11.47, K11.48, K11.49, K11.50, K11.51, K11.52, K11.53, K11.54, K11.55, K11.56, K11.57, K11.58, K11.59, K11.60, K11.61, K11.62, K11.63, K11.64, K11.65, K11.66, K11.67, K11.68, K11.69, K11.70, K11.71, K11.72, K11.73, K11.74, K11.75, K11.76, K11.77, K11.78, K11.79, K11.80, K11.81, K11.82, K11.83, K11.84, K11.85, K11.86, K11.87, K11.88, K11.89, K11.90, K11.91, K11.92, K11.93, K11.94, K11.95, K11.96, K11.97, K11.98, K11.99, K11.100, K11.101, K11.102, K11.103, K12.1, K12.2, K12.3, K12.4, K12.5, K12.6, K12.7, K12.8, K12.9, K12.10, K12.11, K12.12, K12.13, K12.14, K12.15, K12.16, K12.17, K12.18, K12.19, K12.20, K12.21, K12.22, K12.23, K12.24, K12.25, K12.26, K12.27, K12.28, K12.29, K12.30, K12.31, K12.32, K12.33, K12.34, K12.35, K12.36, K12.37, K12.38, K12.39, K12.40, K12.41, K12.42, K12.43, K12.44, K12.45, K12.46, K12.47, K12.48, K12.49, K12.50, K12.51, K12.52, K12.53, K12.54, K12.55, K12.56, K12.57, K12.58, K12.59, K12.60, K12.61, K12.62, K12.63, K12.64, K12.65, K12.66, K12.67, K12.68, K12.69, K12.70, K12.71, K12.72, K12.73, K12.74, K12.75, K12.76, K12.77, K12.78, K12.79, K12.80, K12.81, K12.82, K12.83, K12.84, K12.85, K12.86, K12.87, K12.88, K12.89, K12.90, K12.91, K12.92, K12.93, K12.94, K12.95, K12.96, K12.97, K12.98, K12.99, K12.100, K12.101, K12.102, K12.103, K13.1, K13.2, K13.3, K13.4, K13.5, K13.6, K13.7, K13.8, K13.9, K13.10, K13.11, K13.12, K13.13, K13.14, K13.15, K13.16, K13.17, K13.18, K13.19, K13.20, K13.21, K13.22, K13.23, K13.24, K13.25, K13.26, K13.27, K13.28, K13.29, K13.30, K13.31, K13.32, K13.33, K13.34, K13.35, K13.36, K13.37, K13.38, K13.39, K13.40, K13.41, K13.42, K13.43, K13.44, K13.45, K13.46, K13.47, K13.48, K13.49, K13.50, K13.51, K13.52, K13.53, K13.54, K13.55, K13.56, K13.57, K13.58, K13.59, K13.60, K13.61, K13.62, K13.63, K13.64, K13.65, K13.66, K13.67, K13.68, K13.69, K13.70, K13.71, K13.72, K13.73, K13.74, K13.75, K13.76, K13.77, K13.78, K13.79, K13.80, K13.81, K13.82, K13.83, K13.84, K13.85, K13.86, K13.87, K13.88, K13.89, K13.90, K13.91, K13.92, K13.93, K13.94, K13.95, K13.96, K13.97, K13.98, K13.99, K13.100, K13.101, K13.102, K13.103, K14.1, K14.2, K14.3, K14.4, K14.5, K14.6, K14.7, K14.8, K14.9, K14.10, K14.11, K14.12, K14.13, K14.14, K14.15, K14.16, K14.17, K14.18, K14.19, K14.20, K14.21, K14.22, K14.23, K14.24, K14.25, K14.26, K14.27, K14.28, K14.29, K14.30, K14.31, K14.32, K14.33, K14.34, K14.35, K14.36, K14.37, K14.38, K14.39, K14.40, K14.41, K14.42, K14.43, K14.44, K14.45, K14.46, K14.47, K14.48, K14.49, K14.50, K14.51, K14.52, K14.53, K14.54, K14.55, K14.56, K14.57, K14.58, K14.59, K14.60, K14.61, K14.62, K14.63, K14.64, K14.65, K14.66, K14.67, K14.68, K14.69, K14.70, K14.71, K14.72, K14.73, K14.74, K14.75, K14.76, K14.77, K14.78, K14.79, K14.80, K14.81, K14.82, K14.83, K14.84, K14.85, K14.86, K14.87, K14.88, K14.89, K14.90, K14.91, K14.92, K14.93, K14.94, K14.95, K14.96, K14.97, K14.98, K14.99, K14.100, K14.101, K14.102, K14.103, K15.1, K15.2, K15.3, K15.4, K15.5, K15.6, K15.7, K15.8, K15.9, K15.10, K15.11, K15.12, K15.13, K15.14, K15.15, K15.16, K15.17, K15.18, K15.19, K15.20, K15.21, K15.22, K15.23, K15.24, K15.25, K15.26, K15.27, K15.28, K15.29, K15.30, K15.31, K15.32, K15.33, K15.34, K15.35, K15.36, K15.37, K15.38, K15.39, K15.40, K15.41, K15.42, K15.43, K15.44, K15.45, K15.46, K15.47, K15.48, K15.49, K15.50, K15.51, K15.52, K15.53, K15.54, K15.55, K15.56, K15.57, K15.58, K15.59, K15.60, K15.61, K15.62, K15.63, K15.64, K15.65, K15.66, K15.67, K15.68, K15.69, K15.70, K15.71, K15.72, K15.73, K15.74, K15.75, K15.76, K15.77, K15.78, K15.79, K15.80, K15.81, K15.82, K15.83, K15.84, K15.85, K15.86, K15.87, K15.88, K15.89, K15.90, K15.91, K15.92, K15.93, K15.94, K15.95, K15.96, K15.97, K15.98, K15.99, K15.100, K15.101, K15.102, K15.103, K16.1, K16.2, K16.3, K16.4, K16.5, K16.6, K16.7, K16.8, K16.9, K16.10, K16.11, K16.12, K16.13, K16.14, K16.15, K16.16, K16.17, K16.18, K16.19, K16.20, K16.21, K16.22, K16.23, K16.24, K16.25, K16.26, K16.27, K16.28, K16.29, K16.30, K16.31, K16.32, K16.33, K16.34, K16.35, K16.36, K16.37, K16.38, K16.39, K16.40, 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K99.1, K99.2, K99.3, K99.4, K99.5, K99.6, K99.7, K99.8, K99.9, K99.10, K99.11, K99.12, K99.13, K99.14, K99.15, K99.16, K99.17, K99.18, K99.19, K99.20, K99.21, K99.22, K99.23, K99.24, K99.25, K99.26, K99.27, K99.28, K99.29, K99.30, K99.31, K99.32, K99.33, K99.34, K99.35, K99.36, K99.37, K99.38, K99.39, K99.40, K99.41, K99.42, K99.43, K99.44, K99.45, K99.46, K99.47, K99.48, K99.49, K99.50, K99.51, K99.52; K99.53, K99.54, K99.55, K99.56, K99.57, K99.58, K99.59, K99.60, K99.61, K99.62, K99.63, K99.64, K99.65, K99.66, K99.67, K99.68, K99.69, K99.70, K99.71, K99.72, K99.73, K99.74, K99.75, K99.76, K99.77, K99.78, K99.79, K99.80, K99.81, K99.82, K99.83, K99.84, K99.85, K99.86, K99.87, K99.88, K99.89, K99.90, K99.91, K99.92, K99.93, K99.94, K99.95, K99.96, K99.97, K99.98, K99.99, K99.100, K99.101, K99.102, K99.103, K100.1, K100.2, K100.3, K100.4, K100.5, K100.6, K100.7, K100.8, K100.9, K100.10, K100.11, K100.12, K100.13, K100.14, K100.15, K100.16, K100.17, K100.18, K100.19, K100.20, K100.21, 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K118.57, K118.58, K118.59, K118.60, K118.61, K118.62, K118.63, K118.64, K 18.65, K118.66, K118.67, K118.68, K118.69, K118.70, K118.71, K118.72, K118.73, K118.74, K118.75, K118.76, K118.77, K118.78, K118.79, K118.80, K118.81, K118.82, K118.83, K118.84, K118.85, K118.86, K 118.87, K118.88, K 118.89, K118.90, K118.91, K118.92, K118.93, K118.94, K 118.95, K118.96, K118.97, K118.98, K118.99, K118.100, K 18.101, K18.102, K18.103, K119.1, K119.2, K119.3, K119.4, K119.5, K119.6, K119.7, K119.8, K119.9, K119.10, K119.11, K119.12, K119.13, K119.14, K119.15, K119.16, K119.17, K119.18, K119.19, K119.20, K119.21, K119.22, K119.23, K119.24, K119.25, K119.26, K119.27, K119.28, K119.29, K119.30, K119.31, K119.32, K119.33, K119.34, K119.35, K119.36, K119.37, K119.38, K119.39, K119.40, K119.41, K119.42, K119.43, K119.44, K119.45, K119.46, K119.47, K119.48, K119.49, K119.50, K119.51, K119.52, K119.53, K119.54, K119.55, K119.56, K119.57, K119.58, K119.59, K119.60, K119.61, K119.62, K119.63, K119.64, 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K120.73, K120.74, K120.75, K120.76, K120.77, K120.78, K120.79, K120.80, K120.81, K120.82, K120.83, K120.84, K120.85, K120.86, K120.87, K120.88, K120.89, K120.90, K120.91, K120.92, K120.93, K120.94, K120.95, K120.96, K120.97, K120.98, K120.99, K120.100, K120.101, K120.102, K120.103, K121.1, K121.2, K121.3, K121.4, K121.5, K121.6, K121.7, K121.8, K121.9, K121.10, K121.11, K121.12, K121.13, K121.14, K121.15, K121.16, K121.17, K121.18, K121.19, K121.20, K121.21, K121.22, K121.23, K121.24, K121.25, K121.26, K121.27, K121.28, K121.29, K121.30, K121.31, K121.32, K121.33, K121.34, K121.35, K121.36, K121.37, K121.38, K121.39, K121.40, K121.41, K121.42, K121.43, K121.44, K121.45, K121.46, K121.47, K121.48, K121.49, K121.50, K121.51, K121.52, K121.53, K121.54, K121.55, K121.56, K121.57, K121.58, K121.59, K121.60, K121.61, K121.62, K121.63, K121.64, K121.65, K121.66, K121.67, K121.68, K121.69, K121.70, K121.71, K121.72, K121.73, K121.74, K121.75, K121.76, K121.77, K121.78, K121.79, K121.80, K121.81, K121.82, K121.83, K121.84, K121.85, K121.86, K121.87, K121.88, K121.89, K121.90, K121.91, K121.92, K121.93, K121.94, K121.95, K121.96, K121.97, K121.98, K121.99, K121.100, K121.101, K121.102, K121.103, K122.1, K122.2, K122.3, K122.4, K122.5, K122.6, K122.7, K122.8, K122.9, K122.10, K122.11, K122.12, K122.13, K122.14, K122.15, K122.16, K122.17, K122.18, K122.19, K122.20, K122.21, K122.22, K122.23, K122.24, K122.25, K122.26, K122.27, K122.28, K122.29, K122.30, K122.31, K122.32, K122.33, K122.34, K122.35, K122.36, K122.37, K122.38, K122.39, K122.40, K122.41, K122.42, K122.43, K122.44, K122.45, K122.46, K122.47, K122.48, K122.49, K122.50, K122.51, K122.52, K122.53, K122.54, K122.55, K122.56, K122.57, K122.58, K122.59, K122.60, K122.61, K122.62, K122.63, K122.64, K122.65, K122.66, K122.67, K122.68, K122.69, K122.70, K122.71, K122.72, K122.73, K122.74, K122.75, K122.76, K122.77, K122.78, K122.79, K122.80, K122.81, K122.82, K122.83, K122.84, K122.85, K122.86, K122.87, K122.88, K122.89, K122.90, K122.91, K122.92, K122.93, K122.94, K122.95, K122.96, K122.97, K122.98, K122.99, K122.100, K122.101, K122.102, K122.103, K123.1, K123.2, K123.3, K123.4, K123.5, K123.6, K123.7, K123.8, K123.9, K123.10, K123.11, K123.12, K123.13, K123.14, K123.15, K123.16, K123.17, K123.18, K123.19, K123.20, K123.21, K123.22, K123.23, K123.24, K123.25, K123.26, K123.27, K123.28, K123.29, K123.30, K123.31, K123.32, K123.33, K123.34, K123.35, K123.36, K123.37, K123.38, K123.39, K123.40, K123.41, K123.42, K123.43, K123.44, K123.45, K123.46, K123.47, K123.48, K123.49, K123.50, K123.51, K123.52, K123.53, K123.54, K123.55, K123.56, K123.57, K123.58, K123.59, K123.60, K123.61, K123.62, K123.63, K123.64, K123.65, K123.66, K123.67, K123.68, K123.69, K123.70, K123.71, K123.72, K123.73, K123.74, K123.75, K123.76, K123.77, K123.78, K123.79, K123.80, K123.81, K123.82, K123.83, K123.84, K123.85, K123.86, K123.87, K123.88, K123.89, K123.90, K123.91, K123.92, K123.93, K123.94, K123.95, K123.96, K123.97, K123.98, K123.99, K123.100, K123.101, K123.102, K123.103, K124.1, K124.2, K124.3, K124.4, K124.5, K124.6, K124.7, K124.8, K124.9, K124.10, K124.11, K124.12, K124.13, K124.14, K124.15, K124.16, K124.17, K124.18, K124.19, K124.20, K124.21, K124.22, K124.23, K124.24, K124.25, K124.26, K124.27, K124.28, K124.29, K124.30, K124.31, K124.32, K124.33, K124.34, K124.35, K124.36, K124.37, K124.38, K124.39, K124.40, K124.41, K124.42, K124.43, K124.44, K124.45, K124.46, K124.47, K124.48, K124.49, K124.50, K124.51, K124.52, K124.53, K124.54, K124.55, K124.56, K124.57, K124.58, K124.59, K124.60, K124.61, K124.62, K124.63, K124.64, K124.65, K124.66, K124.67, K124.68, K124.69, K124.70, K124.71, K124.72, K124.73, K124.74, K124.75, K124.76, K124.77, K124.78, K124.79, K124.80, K124.81, K124.82, K124.83, K124.84, K124.85, K124.86, K124.87, K124.88, K124.89, K124.90, K124.91, K124.92, K124.93, K124.94, K124.95, K124.96, K124.97, K124.98, K124.99, K124.100, K124.101, K124.102, K124.103, K125.1, K125.2, K125.3, K125.4, K125.5, K125.6, K125.7, K125.8, K125.9, K125.10, K125.11, K125.12 K125.13, K125.14, K125.15, K125.16, K125.17, K125.18, K125.19, K125.20, K125.21, K125.22, K125.23, K125.24, K125.25, K125.26, K125.27, K125.28, K125.29, K125.30, K125.31, K125.32, K125.33, K125.34, K125.35, K125.36, K125.37, K125.38, K125.39, K125.40, K125.41, K125.42, K125.43, K125.44, K125.45, K125.46, K125.47, K125.48, K125.49, K125.50, K125.51, K125.52, K125.53, K125.54, K125.55, K125.56, K125.57, K125.58, K125.59, K125.60, K125.61, K125.62, K125.63, K125.64, K125.65, K125.66, K125.67, K125.68, K125.69, K125.70, K125.71, K125.72, K125.73, K125.74, K125.75, K125.76, K125.77, K125.78, K125.79, K125.80, K125.81, K125.82, K125.83, K125.84, K125.85, K125.86, K125.87, K125.88, K125.89, K125.90, K125.91, K125.92, K125.93, K125.94, K125.95, K125.96, K125.97, K125.98, K125.99, K125.100, K125.101, K125.102, K125.103, K126.1, K126.2, K126.3, K126.4, K126.5, K126.6, K126.7, K126.8, K126.9, K126.10, K126.11, K126.12, K126.13, K126.14, K126.15, K126.16, K126.17, K126.18, K126.19, K126.20, K126.21, K126.22, K126.23, K126.24, K126.25, K126.26, K126.27, K126.28, K126.29, K126.30, K126.31, K126.32, K126.33, K126.34, K126.35, K126.36, K126.37, K126.38, K126.39, K126.40, K126.41, K126.42, K126.43, K126.44, K126.45, K126.46, K126.47, K126.48, K126.49, K126.50, K126.51, K126.52, K126.53, K126.54, K126.55, K126.56, K126.57, K126.58, K126.59, K126.60, K126.61, K126.62, K126.63, K126.64, K126.65, K126.66, K126.67, K126.68, K126.69, K126.70, K126.71, K126.72, K126.73, K126.74, K126.75, K126.76, K126.77, K126.78, K126.79, K126.80, K126.81, K126.82, K126.83, K126.84, K126.85, K126.86, K126.87, K126.88, K126.89, K126.90, K126.91, K126.92, K126.93, K126.94, K126.95, K126.96, K126.97, K126.98, K126.99, K126.100, K126.101, K126.102, K126.103, K127.1, K127.2, K127.3, K127.4, K127.5, K127.6, K127.7, K127.8, K127.9, K127.10, K127.11, K127.12, K127.13, K127.14, K127.15, K127.16, K127.17, K127.18, K127.19, K127.20, K127.21, K127.22, K127.23, K127.24, K127.25, K127.26, K127.27, K127.28, K127.29, K127.30, K127.31, K127.32, K127.33, K127.34, K127.35, K127.36, K127.37, K127.38, K127.39, K127.40, K127.41, K127.42, K127.43, K127.44, K127.45, K127.46, K127.47, K127.48, K127.49, K127.50, K127.51, K127.52, K127.53, K127.54, K127.55, K127.56, K127.57, K127.58, K127.59, K127.60, K127.61, K127.62, K127.63, K127.64, K127.65, K127.66, K127.67, K127.68, K127.69, K127.70, K127.71, K127.72, K127.73, K127.74, K127.75, K127.76, K127.77, K127.78, K127.79, K127.80, K127.81, K127.82, K127.83, K127.84, K127.85, K127.86, K127.87, K127.88, K127.89, K127.90, K127.91, K127.92, K127.93, K127.94, K127.95, K127.96, K127.97, K127.98, K127.99, K127.100, K127.101, K127.102 and K127.103.
The application rates of the herbicides (B) are known in principle and are generally in the range from 1 g to 8000 g of AS/ha (g of AS/ha=g of active substance per hectare), preferably in the range from 5 g to 5000 g of AS/ha.
In the mixtures according to the invention, in the context of the application rates mentioned, lower application rates of the active compound in question are required compared to the individual application. The weight ratios (A):(B) are, depending on the effective application rates, generally in the range from 1:8000 to 800:1, preferably 1:100 to 100:1, and particularly in the range from 1:50 to 50:1.
Preference is given to herbicide combinations of one or more compounds (A) with one or more compounds of group (B1) or (B2) or (B3).
Preference is furthermore given to combinations of compounds (A) with one or more compounds (B) according to the scheme:
(A)+(B1)+(B2), (A)+(B1)+(B3), (A)+(B2)+(B3) or (A)+(B1)+(B2)+(B3).
The combinations according to the invention can furthermore be used together with other active compounds, for example from the group of the herbicides, safeners, fungicides, insecticides and plant growth regulators, or from the group of the formulation auxiliaries and additives customary in crop protection.
Additives are, for example, fertilizers and colorants. Of particular importance here are combinations to which one or more further active compounds of a different structure or safeners [active compounds (C)] are added, such as, for example, according to the scheme
(A)+(B1)+(C), (A)+(B2)+(C), (A)+(B3)+(C), (A)+(B1)+(B2)+(C), (A)+(B1)+(B3)+(C), (A)+(B2)+(B3)+(C) or (A)+(B1)+(B2)+(B3)+(C).
For combinations of the lastmentioned type with three or more active compounds, the preferred conditions illustrated below in particular for twocompound combinations according to the invention primarily also apply if they comprise the twocompound combinations according to the invention, and with respect to the twocompound combination in question.
In some cases, even combinations of different active compounds from the group (A) are synergistic, so that, based on these twocompound combinations, particularly favorable threecompound combinations with additional synergistic effects are possible.
Preference is given to combinations of active compounds (A) and (B) suitable for nonselective application.
Particular preference is given to combinations of active compounds (A) with active compounds (B) selected from the group consisting of:
simazine (B1.1.4), pendimethalin (B1.1.7), oxadiargyl (B1.1.8), isoxaben (B1.2.1), foramsulfuron (B2.1.5), iodosulfuron (B2.1.6), iodosulfuronmethyl sodium salt (B2.1.6.2), amicarbazone (B2.1.7), propoxycarbazone (B2.1.8), propoxycarbazone sodium salt (B2.1.8.1), metribuzine (B2.1.9), glufosinate (B2.1.1), glufosinateammonium (B2.1.1.1), glyphosate (B2.1.2), glyphosateisopropylammonium (B2.1.2.1), sulfosate (B2.1.3), metsulfuron (B2.1.10), metsulfuronmethyl (B2.1.10.1), imazapyr (B2.1.12), imazapyr acid (B2.1.12.1), imazapyrisopropylammonium (B2.1.12.2), paraquat (B2.1.13), paraquat dichloride (B2.1.13.1), triclopyr (B2.2.3), triclopyr acid (B2.2.3.1), triclopyrtriethylammonium salt (B2.2.3.2), triclopyrbutotyl ester (B2.2.3.3), amidosulfuron (B2.2.7), amitrole (B2.2.14), diuron (B3.2), oxyfluorfen (B3.1.1), oxadiazon (B3.1.8), diflufenican (B3.1.9), bromacil (B3.3) and norflurazon (B3.4).
Particular preference is given here to the combinations of active compounds (A) with active compounds (B) from the group consisting of:
oxadiargyl (B1.1.8), glufosinate (B2.1.1), glufosinateammonium (B2.1.1.1), glyphosate (B2.1.2), glyphosateisopropylammonium (B2.1.2.1), sulfosate (B2.1.3), foramsulfuron (B2.1.5), iodosulfuron (B2.1.6), iodosulfuronmethyl sodium salt (B2.1.6.2), amicarbazone (B2.1.7), propoxycarbazone (B2.1.8), propoxycarbazone sodium salt (B2.1.8.1), metribuzine (B2.1.9), amidosulfuron (B2.2.7), oxyfluorfen (B3.1.1), oxadiazon (B3.1.8), diflufenican (B3.1.9) and diuron (B3.2), in particular glufosinate (B2.1.1), glufosinateammonium (B2.1.1.1), glyphosate (B2.1.2), glyphosateisopropylammonium (B2.1.2.1), sulfosate (B2.1.3) and oxyfluorfen (B3.1.1).
The herbicide combinations according to the invention can also be combined with further herbicides and plant growth regulators, for example to complete the activity spectrum.
Examples of such further combination partners are herbicidally active compounds or plant growth regulators having a structure different from that of the herbicides (B) contained in the combinations, as described, for example, in the manual “The Pesticide Manual”, 13th Edition 2003, The British Crop Protection Council, or in the ePesticide Manual Version 3 (2003), or else as trade names and “common names” in the “Compendium of Pesticide Common Names” (searchable on the Internet), and in each case in the literature cited therein.
Below, examples of herbicides and plant growth regulators are given using their standardized active compound names according to the “International Organization for Standardization” (ISO) or by their chemical names or by a code number: acetochlor; acifluorfen(sodium); aclonifen; AKH 7088, i.e. [[[1[5[2chloro4(trifluoromethyl)phenoxy]2nitrophenyl]2methoxyethylidene]amino]oxy]acetic acid and its methyl ester; alachlor; alloxydim(sodium); ametryn; amicarbazone, amidochlor, amidosulfuron; aminopyralid, amitrol (aminotriazine); AMS, i.e. ammonium sulfamate; anilofos; asulam; atrazine; azafenidin; azimsulfuron (DPXA8947); aziprotryn; barban; BAS 516 H, i.e. 5fluoro2phenyl4H3,1benzoxazin4one; beflubutamid; benazolin(ethyl); benfluralin; benfuresate; bensulfuron(methyl); bensulide; bentazone(sodium); benzfendizone, benzobicyclone; benzofenap; benzofluor; benzoylprop(ethyl); benzthiazuron; bialaphos (bilanafos); bifenox; bispyribac(sodium); bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butafenacil; butamifos; butenachlor; buthidazole; butralin; butroxydim; butylate; cafenstrole (CH900); carbetamide; carfentrazone(ethyl); caloxydim, CDAA, i.e. 2chloroN,Ndi2propenylacetamide; CDEC, i.e. 2chloroallyl diethyldithiocarbamate; chlomethoxyfen; chloramben; chlorazifopbutyl; chlorbromuron; chlorbufam; chlorfenac; chlorfenprop, chlorflurenolmethyl; chloridazon; chlorimuron(ethyl); chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthaldimethyl; chlorthiamid; chlortoluron, cinidon(methyl or ethyl), cinmethylin; cinosulfuron; clethodim; clefoxydim, clodinafop and its ester derivatives (for example clodinafoppropargyl); clomazone; clomeprop; cloprop, cloproxydim; clopyralid; clopyrasulfuron(methyl); cloransulam(methyl); cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (for example butyl ester, DEH112); cyperquat; cyprazine; cyprazole; daimuron; 2,4D; 2,4DB; dalapon; dazomet, desmedipham; desmetryn; diallate; dicamba; dichlobenil; dichlorprop(P); diclofop and its esters such as diclofopmethyl; diclosulam, diethatyl(ethyl); difenoxuron; difenzoquat; diflufenican; diflufenzopyr; dimefuron; dimepiperate; dimethachlor; dimethametryn; dimethenamid (SAN582H); dimethenamid(P); dimethazone, dimethipin; dimexyflam, dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazineethyl; EL 77, i.e. 5cyano1(1,1dimethylethyl)Nmethyl1Hpyrazole4carboxamide; endothal; epoprodan, EPTC; esprocarb; ethalfluralin; ethametsulfuronmethyl; ethidimuron; ethiozin; ethofumesate; ethoxyfen and its esters (for example ethyl ester, HC252), ethoxysulfuron, etobenzanid (HW 52); F5231, i.e. N[2chloro4fluoro5[4(3fluoropropyl)4,5dihydro5oxo1Htetrazol1yl]phenyl]ethanesulfonamide; fenoprop; fenoxan, fenoxaprop and fenoxapropP and their esters, for example fenoxapropPethyl and fenoxapropethyl; fenoxydim; fentrazamide; fenuron; flamprop(methyl or isopropyl or isopropylL); flazasulfuron; florasulam; fluazifop and fluazifopP and their esters, for example fluazifopbutyl and fluazifopPbutyl; fluazolate, flucarbazone(sodium); flucetosulfuron, fluchloralin; flufenacet (FOE 5043), flufenpyr, flumetsulam; flumeturon; flumiclorac(pentyl); flumioxazin (S482); flumipropyn; fluometuron; fluorochloridone, fluorodifen; fluoroglycofen(ethyl); flupoxam (KNW739); flupropacil (UBIC4243); fluproanate, flupyrsulfuron(methyl, or sodium); flurenol(butyl); fluridone; flurochloridone; fluroxypyr(meptyl); flurprimidol, flurtamone; fluthiacet(methyl); fluthiamide (also known as flufenacet); fomesafen; foramsulfuron; fosamine; furilazole (MON 13900), furyloxyfen; glufosinate (ammonium); glyphosate(isopropylammonium); halosafen; halosulfuron(methyl) and its esters (for example the methyl ester, NC319); haloxyfop and its esters; haloxyfopP (=Rhaloxyfop) and its esters; HC252 (diphenyl ether), hexazinone; imazamethabenz(methyl); imazamethapyr; imazamox; imazapic, imazapyr; imazaquin and salts such as the ammonium salts; imazethamethapyr; imazethapyr, imazosulfuron; indanofan; iodosulfuron(methyl)(sodium), ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxachlortole; isoxaflutole; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPAthioethyl, MCPB; mecoprop(P); mefenacet; mefluidid; mepisulfuron (LGC42153), mesosulfuron(methyl); mesotrione; metam, metamifop, metamitron; metazachlor; methabenzthiazuron; methazole; methoxyphenone; methyldymron; metobenzuron, metobromuron; (S)metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuronmethyl; MK616; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6chloroN(3chloro2propenyl)5methylNphenyl3pyridazinamine; MT 5950, i.e. N[3chloro4(1methylethyl)phenyl]2methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4(2,4dichlorobenzoyl)1methyl5benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP020630); oxadiazone; oxasulfuron; oxaziclomefone; oxyfluorfen; paraquat; pebulate; pelargonic acid; pendimethalin; penoxulam; pentanochlor, pentoxazone; perfluidone; pethoxamid, phenisopham; phenmedipham; picloram; picolinafen; pinoxaden (NOA407855=flucetsulfuron), piperophos; piributicarb; pirifenopbutyl; pretilachlor; primisulfuron(methyl); procarbazone(sodium); procyazine; prodiamine; profluazole, profluralin; proglinazine(ethyl); prometon; prometryn; propachlor; propanil; propaquizafop; propazine; propham; propisochlor; propoxycarbazone(sodium), propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA152005); prynachlor; pyraclonil, pyraflufen(ethyl); pyrazolinate; pyrazon; pyrazosulfuron(ethyl); pyrazoxyfen; pyribenzoxim; pyributicarb; pyridafol; pyridate; pyriftalid, pyrimidobac(methyl); pyrithiobac(sodium) (KIH2031); pyroxofop and its esters (for example propargyl ester); quinclorac; quinmerac; quinoclamine, quinofop and its ester derivatives, quizalofop and quizalofopP and their ester derivatives, for example quizalofopethyl; quizalofopPtefuryl and ethyl; renriduron; rimsulfuron (DPXE 9636); S 275, i.e. 2[4chloro2fluoro5(2propynyloxy)phenyl]4,5,6,7tetrahydro2Hindazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2[[7[2chloro4(trifluoromethyl)phenoxy]2naphthalenyl]oxy]propanoic acid and its methyl ester; sulcotrione; sulfentrazone (FMC97285, F6285); sulfazuron; sulfometuron(methyl); sulfosate (ICIA0224); sulfosulfuron; TCA; tebutam (GCP5544); tebuthiuron; tepraloxydim; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. N,Ndiethyl3[(2ethyl6methylphenyl)sulfonyl]1H1,2,4triazole1carboxamide; thenylchlor (NSK850); thiafluamide; thiazafluron; thiazopyr (Mon13200); thidiazimin (SN24085); thidiazuron, thifensulfuron(methyl); thiobencarb; tiocarbazil; topramezone (BAS670H), tralkoxydim; triallate; triasulfuron; triaziflam; triazofenamide; tribenuron(methyl); 2,3,6trichlorobenzoic acid (2,3,6TBA), triclopyr; tridiphane; trietazine; trifloxysulfuron(sodium), trifluralin; triflusulfuron and esters (e.g. methyl ester, DPX66037); trimeturon; tritosulfuron; tsitodef; vernolate; WL 110547, i.e. 5phenoxy1[3(trifluoromethyl)phenyl]1Htetrazole; HOK201, HOK202, UBH509; D489; LS 82556; KPP300; NC324; NC330; KH218; DPXN8189; SC0774; TH547, DOWCO535; DK8910; V53482; PP600; MBH001; KIH9201; ET751; KIH6127; KIH2023 and KIH5996.
If the respective name (common name) includes more than one form of the active compound, the name preferably defines the commercially available form.
Each of the further active compounds mentioned (=active compounds (C*), (C1*), (C2*) etc.) can then preferably be combined with one of the twocompound combinations K1.1 to K127.103, according to the scheme (A)+(B)+(C*) or else according to scheme (A)+(B)+(C1*)+(C2*) etc. This also includes those multiple combinations in which the compounds (C*), (C1*) or (C2*) are selected from the group of the compounds (B), but are not identical to the compound (B) present in respective twocompound combinations.
Multiple combinations of active compounds (A) with a plurality of active compounds (B) are, for example
(A)+(B3.2)+(B2.1.4), preferably (A)+diuron (B3.2)+MSMA (B2.1.4.1), in particular in amounts of 1800 g of AS/ha (A) and 5002000 g of AS/ha (B3.2) and 10003000 g of AS/ha (B2.1.4.1);
(A)+(B3.2)+(B2.1.13), preferably (A)+diuron (B3.2)+paraquat dichloride (B2.1.13.1), in particular in amounts of 1800 g of AS/ha (A) and 100500 g of AS/ha (B3.2) and 1001000 g of AS/ha (B2.1.13.1);
(A)+(B3.2)+(B2.2.14), preferably (A)+diuron (B3.2)+amitrole (B2.2.14) in amounts of 1800 g of AS/ha (A) and 100500 g of AS/ha (B3.2) and 100500 g of AS/ha (B2.2.14);
(A)+(B3.2)+(B2.1.1), preferably (A)+diuron (B3.2)+glufosinateammonium (B2.1.1.1), in particular in amounts of 1800 g of AS/ha (A) and 5002000 g of AS/ha (B3.2) and 1001000 g of AS/ha (B2.1.1.1);
(A)+(B3.2)+(B2.1.2), preferably (A)+diuron (B3.2)+glyphosateisopropylammonium (B2.1.2.1), in particular in amounts of 1800 g of AS/ha (A) and 5002000 g of AS/ha (B3.2) and 5001500 g of AS/ha (B2.1.2.1);
(A)+(B3.2)+(B2.1.2)+petroleum, preferably (A)+diuron (B3.2)+glyphosateisopropylammonium (B2.1.2.1)+mineral oil, in particular in amounts of 1800 g of AS/ha (A) and 5002000 g of AS/ha (B3.2) and 5001500 g of AS/ha (B2.1.2.1) and 100500 g/ha mineral oil;
(A)+(B3.1.9)+(B2.1.2), preferably (A)+diflufenican (B3.1.9)+glyphosateisopropylammonium (B2.1.2.1), in particular in amounts of 1800 g of AS/ha (A) and 50500 g of AS/ha (B3.1.9) and 5001500 g of AS/ha (B2.1.2.1);
(A)+(B1.1.4)+(B3.1.10), preferably (A)+simazine (B1.1.4)+ametryn (B3.1.10) in amounts of 1800 g of AS/ha (A) and 10002500 g of AS/ha (B1.1.4) and 10002500 g of AS/ha (B3.1.10);
(A)+(B1.2.1)+(B1.1.10), preferably (A)+isoxaben (B1.2.1)+oryzalin (B1.1.10) in amounts of 1800 g of AS/ha (A) and 10250 g of AS/ha (B1.2.1) and 10003500 g of AS/ha (B1.1.10);
(A)+(B3.1.1)+(B1.1.10), preferably (A)+oxyfluorfen (B3.1.1)+oryzalin (B1.1.10), in particular in amounts of 1800 g of AS/ha (A) and 5002000 g of AS/ha (B3.1.1) and 10005000 g of AS/ha (B1.1.0).
The stated amounts are application rates (g of AS/ha=gram of active compound per hectare) and thus also define the ratios in a coformulation, a premix, a tank mix or a sequential application of the combined active compounds.
The combinations can be applied both by the preemergence method and by the postemergence method. This applies both to pre and postemergence with respect to the harmful plants and, in the selective control of harmful plants, to the pre or postemergence of the crop plants. Mixed forms are also possible, for example after the emergence of the crop plants the control of the harmful plants at their pre or postemergence stage.
Other suitable combination partners include crop plantprotecting active compounds (called “safeners” or “antidotes”) which are able to prevent or reduce phytotoxic effects of the herbicides in crop plants.
Suitable safeners for the abovementioned herbicidally active compounds (A) or combinations of herbicides (A) and (B) or generally for the combinations according to the invention are, for example, the following groups of compounds:
a) compounds of the type of the dichlorophenylpyrazoline3carboxylic acid, preferably compounds such as ethyl 1(2,4dichlorophenyl)5(ethoxycarbonyl)5methyl2pyrazoline3carboxylate (S11) (“mefenpyrdiethyl”, PM, pp. 622623), and related compounds, as described in WO 91/07874,
b) derivatives of dichlorophenylpyrazolecarboxylic acid, preferably compounds such as ethyl 1(2,4dichlorophenyl)5methylpyrazole3carboxylate (S12), ethyl 1(2,4dichlorophenyl)5isopropylpyrazole3carboxylate (S 13), ethyl 1(2,4dichlorophenyl)5(1,1dimethylethyl)pyrazole3carboxylate (S14), ethyl 1(2,4dichlorophenyl)5phenylpyrazole3carboxylate (S15) and related compounds, as described in EPA333 131 and EPA269 806.
c) compounds of the type of the triazolecarboxylic acids, preferably compounds such as fenchlorazole (ethyl ester), i.e. ethyl 1(2,4dichlorophenyl)5trichloromethyl(1H)1,2,4triazole3carboxylate (S 16), and related compounds (EPA174 562 and EPA346 620);
d) compounds of the type of the 5benzyl or 5phenyl2isoxazoline3carboxylic acid, or of the 5,5diphenyl2isoxazoline3carboxylic acid, preferably compounds such as ethyl 5(2,4dichlorobenzyl)2isoxazoline3carboxylate (S17) or ethyl 5phenyl2isoxazoline3carboxylate (S18) and related compounds, as described in WO 91/08202, or of ethyl 5,5diphenyl2isoxazolinecarboxylate (S19) (“isoxadifenethyl”, PM, p. 588) or npropyl 5,5diphenyl2isoxazolinecarboxylate (S110) or ethyl 5(4fluorophenyl)5phenyl2isoxazoline3carboxylate (S111), as described in the German patent application (WOA95/07897).
e) compounds of the type of the 8quinolineoxyacetic acid (S2), preferably 1methylhex1yl (5chloro8quinolineoxy) acetate (common name “cloquintocetmexyl” (S21) (see PM, pp. 196197)
and related compounds, as described in EPA86 750, EPA94 349 and EPA191 736 or EPA0 492 366.
f) compounds of the type of the (5chloro8quinolineoxy)malonic acid, preferably compounds such as diethyl (5chloro8quinolineoxy)malonate, diallyl (5chloro8quinolineoxy)malonate, methyl ethyl (5chloro8quinolineoxy)malonate and related compounds, as described in EPA0 582 198.
g) active compounds of the type of the phenoxyacetic or propionic acid derivatives or the aromatic carboxylic acids, such as, for example, 2,4dichlorophenoxyacetic acid (ester) (2,4D), 4chloro2methylphenoxypropionic ester (mecoprop), MCPA or 3,6dichloro2methoxybenzoic acid (ester) (dicamba).
h) active compounds of the type of the pyrimidines, such as, for example, “fenclorim” (PM, p. 406) (=4,6dichloro2phenylpyrimidine),
i) active compounds of the type of the dichloroacetamides, such as, for example,
“dichlormid” (PM, p. 284) (=N,Ndiallyl2,2dichloroacetamide),
“R29148” (=3dichloroacetyl2,2,5trimethyl1,3oxazolidine from Stauffer),
“benoxacor” (PM, pp. 7273) (=4dichloroacetyl3,4dihydro3methyl2H1,4benzoxazine)
“PPG1292” (=NallylN[(1,3dioxolan2yl)methyl]dichloroacetamide from PPG Industries),
“DK24” (=NallylN[(allylaminocarbonyl)methyl]dichloroacetamide from SagroChem),
“AD67” or “MON 4660” (=3dichloroacetyl1oxa3azaspiro[4,5]decane from Nitrokemia or Monsanto),
“diclonon” or “BAS145138” or “LAB145138” (=3dichloroacetyl2,5,5trimethyl1,3diazabicyclo[4.3.0]nonane from BASF) and
“furilazole” or “MON 13900” (see PM, 507) (=(RS)3dichloroacetyl5(2furyl)2,2dimethyloxazolidine)
j) active compounds of the type of the dichloroacetone derivatives, such as, for example,
“MG 191” (CASReg. No. 96420723) (=2dichloromethyl2methyl1,3dioxolane from Nitrokemia),
k) active compounds of the type of the oxyimino compounds, which are known as seed dressings, such as, for example,
“oxabetrinil” (PM, pp. 724725) (=(Z)1,3dioxolan2ylmethoxyimino(phenyl)acetonitrile),
“fluxofenim” (PM, p.490) (=1(4chlorophenyl)2,2,2trifluoro1ethanone O(1,3dioxolan2ylmethyl)oxime, and
“cyometrinil” or “CGA43089” (PM, p. 1056) (=(Z)cyanomethoxyimino(phenyl)acetonitrile),
l) active compounds of the type of the thiazolecarboxylic acid esters, which are known as seed dressings, such as, for example,
“flurazole” (PM, pp. 473474) (=benzyl 2chloro4trifluoromethyl1,3thiazole5carboxylate), which is known as seed dressing safener for millet against damage caused by alachlor and metolachlor,
m) active compounds of the type of the naphthalenedicarboxylic acid derivatives, which are known as seed dressings, such as, for example,
“naphthalic anhydride” (PM, p. 1083) (=1,8naphthalenedicarboxylic anhydride),
n) active compounds of the type of the chromanacetic acid derivatives, such as, for example,
“CL 304415” (CASReg. No. 31541578) (=2(4carboxychroman4yl)acetic acid from American Cyanamid),
o) active compounds which have partial herbicidal action against harmful plants, such as, for example,
“dimepiperate” or “MY93” (PM, pp. 315317) (=S1methyl1phenylethyl piperidine1thiocarboxylate),
“daimuron” or “SK 23” (PM, p. 259) (=1(1methyl1phenylethyl)3ptolylurea),
“cumyluron”=“JC940” (=3(2chlorophenylmethyl)1(1methyl1phenylethyl)urea, see JPA60087254),
“methoxyphenone” or “NK 049” (=3,3′dimethyl4methoxybenzophenone),
“CSB” (=1bromo4(chloromethylsulfonyl)benzene) (CASReg. No. 54091064 from Kumiai),
p) Nacylsulfonamides of the formula (S3) and salts thereof,
q) acylsulfamoylbenzamides of the formula (S4) or salts thereof,
From among the safeners mentioned, (S11), (S19), (S21) and (S3), in particular (S11) and (S19), are of particular interest.
Some of the safeners have already been mentioned above as herbicides and, accordingly, in addition to the herbicidal action on harmful plants, also have a protective action on the crop plants.
Each of the safeners of groups a) to q) mentioned can be combined as further active compound (C) preferably with one of the twocompound combinations K1.1 to K127.103 mentioned which comprises a compound (B) having a structure different from the compound (C) in question, according to the scheme (A)+(B)+(C).
The herbicide combinations according to the invention may comprise further components, for example other active compounds against harmful organisms such as harmful plants, plantdamaging animals or plantdamaging fungi, in particular active compounds from the group of the herbicides, fungicides, insecticides, acaricides, nematicides and miticides, and related substances.
Fungicidally active compounds which can be used in combination with the herbicide combinations according to the invention are preferably commercially available active compounds, for example (analogously to the herbicides, the compounds are generally referred to by their common names):
2phenylphenol; 8hydroxyquinoline sulfate; acibenzolarSmethyl; actinovate; aldimorph; amidoflumet; ampropylfos; ampropylfospotassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarbisopropyl; benzamacril; benzamacrilisobutyl; binapacryl; biphenyl; bitertanol; blasticidinS; boscalid; bromuconazole; bupirimate; buthiobate; butylamine; calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone; chinomethionat; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; cis1(4chlorophenyl)2(1H1,2,4triazol1yl)cycloheptanol; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; diniconazoleM; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetylAl; fosetylsodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazol; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoximmethyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxylM; metconazole; methasulfocarb; methfuroxam; methyl 1(2,3dihydro2,2dimethyl1Hinden1yl)1Himidazole5carboxylate; methyl 2[[[cyclopropyl[(4methoxyphenyl)imino]methyl]thio]methyl]α(methoxymethylene)benzeneacetate; methyl 2[2[3(4chlorophenyl)1methylallylideneaminooxymethyl]phenyl]3methoxyacrylate; metiram; metominostrobin; metrafenone; metsulfovax; mildiomycin; monopotassium carbonate; myclobutanil; myclozolin; nabam, N(3ethyl3,5,5trimethylcyclohexyl)3formylamino2hydroxybenzamide; N(6methoxy3pyridinyl)cyclopropanecarboxamide; Nbutyl8(1,1dimethylethyl)1oxaspiro[4.5]decan3amine; natamycin; nitrothalisopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; penconazole; pencycuron; penthiopyrad; phosdiphen; phthalide; picobenzamid; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosinesodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine; quinconazole; quinoxyfen; quintozene; silthiofam; simeconazole; sodium tetrathiocarbonate; spiroxamine; sulfur; tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanatemethyl; thiram; tiadinil; tioxymid; toiclofosmethyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)N[2[4[[3(4chlorophenyl)2propynyl]oxy]3methoxyphenyl]ethyl]3methyl2[(methylsulfonyl)amino]butanamide; 1(1naphthalenyl)1Hpyrrole2,5dione; 2,3,5,6tetrachloro4(methylsulfonyl)pyridine; 2,4dihydro5methoxy2methyl4[[[[1[3(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]3H1,2,3triazol3one; 2amino4methylNphenyl5thiazolecarboxamide; 2chloroN(2,3dihydro1,1,3trimethyl1Hinden4yl)3pyridinecarboxamide; 3,4,5trichloro2,6pyridinedicarbonitrile; 3[(3bromo6fluoro2methyl1Hindol1yl)sulfonyl]N,Ndimethyl1H1,2,4triazole1sulfonamide; copper salts and copper preparations, such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulfate; cufraneb; copper(I) oxide; mancopper; oxinecopper.
Preferred fungicides are selected from the group consisting of benalaxyl, bitertanol, bromuconazole, captafol, carbendazim, carpropamid, cyazofamid, cyproconazole, diethofencarb, edifenphos, fenpropimorph, fentine, fluquinconazole, fosetyl, fluoroimide, folpet, iminoctadine, iprodionem, iprovalicarb, kasugamycin, maneb, nabam, pencycuron, prochloraz, propamocarb, propineb, pyrimethanil, spiroxamine, quintozene, tebuconazole, tolylfluanid, triadimefon, triadimenol, trifloxystrobin, zineb. Insecticidal, acaricidal, nematicidal, miticidal and related active compounds are, for example (analogously to the herbicides and fungicides, the compounds are, if possible, referred to by their common names):
alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metamsodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, acephate, azamethiphos, azinphos (methyl, ethyl), bromophosethyl, bromfenvinfos (methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (methyl/ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demetonSmethyl, demetonSmethylsulphon, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl Osalicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemetonmethyl, parathion (methyl/ethyl), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (methyl/ethyl), profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion, acrinathrin, allethrin (dcistrans, dtrans), betacyfluthrin, bifenthrin, bioallethrin, bioallethrinScyclopentylisomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, ciscypermethrin, cisresmethrin, cispermethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha, beta, theta, zeta), cyphenothrin, deltamethrin, empenthrin (1Risomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gammacyhalothrin, imiprothrin, kadethrin, lambdacyhalothrin, metofluthrin, permethrin (cis, trans), phenothrin (1Rtrans isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, taufluvalinate, tefluthrin, terallethrin, tetramethrin (1Risomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum), DDT, indoxacarb, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, nicotine, bensultap, cartap, camphechlor, chlordane, endosulfan, gammaHCH, HCH, heptachlor, lindane, methoxychlor spinosad, acetoprole, ethiprole, fipronil, vaniliprole, avermectin, emamectin, emamectinbenzoate, ivermectin, milbemycin, diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene, chromafenozide, halofenozide, methoxyfenozide, tebufenozide, bistrifluron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron, buprofezin, cyromazine, diafenthiuron, azocyclotin, cyhexatin, fenbutatinoxide, chlorfenapyr, binapacyrl, dinobuton, dinocap, DNOC, fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, hydramethylnon, dicofol, rotenone, acequinocyl, fluacrypyrim, Bacillus thuringiensis strains, spirodiclofen, spiromesifen, 3(2,5dimethylphenyl)8methoxy2oxo1azaspiro[4.5]dec3en4yl ethyl carbonate (alias: carbonic acid, 3(2,5dimethylphenyl)8methoxy2oxo1azaspiro[4.5]dec3en4yl ethyl ester, CASReg.No.: 382608108) and carbonic acid, cis3(2,5dimethylphenyl)8methoxy2oxo1azaspiro[4.5]dec3en4yl ethyl ester (CASReg.No.: 203313251), flonicamid, amitraz, propargite, N2[1,1dimethyl2(methylsulfonyl)ethyl]3iodoN1[2methyl4[1,2,2,2tetrafluoro1(trifluoromethyl)ethyl]phenyl]1,2benzenedicarboxami de (CASReg.No.: 272451657), thiocyclam hydrogen oxalate, thiosultapsodium, azadirachtin, Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec., Paecilomyces spec., thuringiensin, Verticillium spec., aluminum phosphide, methyl bromide, sulfuryl fluoride, cryolite, flonicamid, pymetrozine, clofentezine, etoxazole, hexythiazox, amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, chinomethionat, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone, japonilure, metoxadiazone, petroleum, piperonyl butoxide, potassium oleate, pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene, verbutin.
Insecticides which may preferably be used together with the herbicides are, for example, the following:
acetamiprid, acrinathrin, aldicarb, amitraz, acinphosmethyl, cyfluthrin, carbaryl, cypermethrin, deltamethrin, endosulfan, ethoprophos, fenamiphos, fenthion, fipronil, imidacloprid, methamidophos, methiocarb, niclosamide, oxydemetonmethyl, prothiophos, silafluofen, thiacloprid, thiodicarb, tralomethrin, triazophos, trichlorfon, triflumuron, terbufos, fonofos, phorate, chlorpyriphos, carbofuran, tefluthrin.
The active compound combinations according to the invention are suitable for controlling a broad spectrum of weeds on noncrop land, on paths, rail tracks, industrial terrain (“industrial weed control”) or in plantation crops, such as moderate, subtropical and tropical climates or geographies. Examples of plantation crops are oil palms, nuts (for example almonds, hazelnuts, walnuts, macadamia), coconut, berries, oil palms, rubber tree, citrus (for example orange, lemon, mandarin), bananas, pineapples, cotton, sugarcane, tea, coffee, cacao and the like. They are also suitable for use in the cultivation of fruits (for example pome fruit, such as apple, pear, cherry, mango, kiwi) and viticulture. The compositions can also be used for preparing the soil for sowing (“burndown” “notill” or “zerotill” method) or for treatment after harvest (“chemical fallow”). Potential applications of the active compound combinations extend to weed control in tree crops, for example young Christmas tree crops or eucalyptus plantations, in each case prior to planting or after transplanting (also by overtop treatment).
The compositions can also be used in selective crops of economically important crops, such as cereals (wheat, barley, rye), corn, rice, sugarbeet, sugarcane, oil seed rape, cotton and soybean. When using the active compounds (A) and (B) in crop plants such as cereals and corn, it may, depending on the crop plant, be expedient to apply a safener above certain application rates to prevent or reduce damage to the crop plant.
The multiple combinations according to the invention (=herbicidal compositions) are synergistically effective with respect to herbicide action and selectivity and have a favorable action with a view to the weed spectrum. They have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous or dicotyledonous harmful plants. The active compounds even act efficiently on perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs and which are difficult to control. In this context, it does not matter whether the substances are applied before sowing, preemergence or postemergence. Application by the early postsowing preemergence method or by the postemergence method of plantation crops against harmful plants which have not yet emerged or which have already emerged is preferred. The application may also be integrated into weed management systems with repeat split applications (sequence applications, sequentials).
Specifically, examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the active compound combinations according to the invention, without the enumeration being a restriction to certain species.
From among the monocotyledonous weed species, for example, the compositions control Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Festuca, Fimbristylis, Ischaemum, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagittaria, Scirpus, Setaria, Sphenoclea and Cyperus species from the annual group and, from the perennial weeds, Agropyron, Cynodon, Imperata and Sorghum, and also perennial Cyperus species.
In the case of dicotyledonous weed species, the activity spectrum extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida from the annual and Convolvulus, Cirsium, Rumex and Artemisia from the perennial weeds.
A herbicidal action is also observed against dicotyledonous harmful plants, such as Ambrosia, Anthemis, Carduus, Centaurea, Chenopodium, Datura, Emex, Galeopsis, Galinsoga, Kochia, Lepidium, Lindernia, Papaver, Portlaca, Polygonum, Ranunculus, Rorippa, Rotala, Seneceio, Sesbania, Solanum, Sonchus, Taraxacum, Trifolium, Urtica and Xanthium.
If the active compound combinations according to the invention are applied to the soil surface before germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have reached the cotyledonous stage but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
If the active compounds are applied postemergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated at a very early point in time and in a sustained manner.
The herbicidal compositions according to the invention are distinguished by a rapidly commencing and longlasting herbicidal action. As a rule, the rain fastness of the active compounds in the combinations according to the invention is advantageous. A particular advantage is that the dosages of compounds (A) and (B), which are used in the combinations and are effective, can be adjusted to such a low quantity that their soil action is optimally low. Not only does this allow them to be employed in sensitive crops in the first place, but ground water contaminations are virtually avoided. The combination according to the invention of active compounds allows the application rate of the active compounds required to be reduced considerably.
When herbicides of type (A)+(B) are used jointly superadditive (=synergistic) effects are observed. This means that the activity of the combinations exceeds the expected total of the activities of the individual herbicides employed. The synergistic effects allow the application rate to be reduced, a broader spectrum of broadleaf weeds and grass weeds to be controlled, a more rapid onset of the herbicidal action, a longer duration of action, a better control of the harmful plants using only one, or few, application(s), and the possible application period to be extended. In some cases, by using the compositions, the amount of harmful ingredients, such as nitrogen or oleic acid, and their introduction into the soil are reduced, too. The identified properties and advantages are of benefit for weed control practice to keep agricultural crops free from undesired competing plants and thus to safeguard and/or increase the quality and quantity of the yields. These novel combinations markedly exceed the technical state of the art with a view to the properties described.
While the combinations according to the invention have an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants are damaged only to a minor extent, if at all.
Some of the compositions according to the invention additionally have outstanding growthregulatory properties in crop plants. They engage in a plant's metabolism in a regulatory fashion and can thus be employed for targeted influencing of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, allowing lodging to be reduced or prevented completely.
On account of their herbicidal and plant growthregulatory properties, the compositions can also be employed for controlling harmful plants in crops of known genetically modified plants or genetically modified plants yet to be developed. As a rule, the transgenic plants are distinguished by particularly advantageous properties, in addition to resistances to the compositions according to the invention, for example by resistances to plant diseases or plant pathogens, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with respect to quantity, quality, storability, composition and specific constituents. Thus, transgenic plants with an increased starch content or in which the quality of the starch is altered, or those having a different fatty acid composition of the harvested material, are known.
Traditional ways of generating novel plants which have modified characteristics in comparison with existing plants consist, for example, in traditional breeding methods and the generation of mutants. Alternatively, novel plants with modified characteristics can be generated using recombinant procedures (see, for example, EPA0221044, EPA0131624). For example, a number of cases have been described of
A large number of molecularbiological techniques with which novel transgenic plants with modified properties can be generated are known in principle; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene und Klone” [Genes and Clones], VCH Weinheim 2nd Edition 1996 or Christou, “Trends in Plant Science” 1 (1996) 423431).
To carry out such recombinant manipulations, nucleic acid molecules which permit a mutagenesis or a sequence modification by recombination of DNA sequences can be introduced into plasmids. For example, it is possible with the aid of the abovementioned standard methods to carry out base exchanges, to remove subsequences or to add natural or synthetic sequences. Adapters or linkers may be added in order to link the DNA fragments to each other.
For example, plant cells with a reduced activity of a gene product can successfully be generated by expressing at least one suitable antisense RNA, a sense RNA to achieve a cosuppression effect or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.
To this end, it is possible to use firstly DNA molecules which encompass all of the coding sequence of a gene product including any flanking sequences which may be present and secondly DNA molecules which only encompass parts of the coding sequence, it being necessary for these parts to be of sufficient length to cause an antisense effect in the cells. Also possible is the use of DNA sequences which have a high degree of homology with the coding sequences of a gene product which are not entirely identical thereto.
When expressing nucleic acid molecules in plants, the protein synthesized may be localized in any compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible for example to link the coding region with DNA sequences which guarantee localization in a certain compartment. Sequences of this type are known to the person skilled in the art, (see, for example, Braun et al., EMBO J. 11 (1992), 32193227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846850; Sonnewald et al., Plant J.1 (1991), 95106).
The transgenic plant cells can be regenerated by known techniques to give intact plants. In principle, the transgenic plants can be plants of any desired plant species, i.e. both monocotyledonous and dicotyledonous plants. Transgenic plants are thus obtainable which have modified properties as a result of overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences, or expression of heterologous (=foreign) genes or gene sequences.
Accordingly, the invention also provides a method for controlling unwanted vegetation, preferably on noncrop land or in plantation crops, wherein one or more herbicides of type (A) and one or more herbicides of type (B) are applied to the harmful plants, to parts of plants or plant seeds thereof, or to the area under cultivation.
The invention also provides the use of the novel combinations of compounds (A)+(B) for controlling harmful plants, preferably on noncrop land and in plantation crops.
The active compound combinations according to the invention can also be present as mixed formulations of the two components, if appropriate with further active compounds, additives and/or customary formulation auxiliaries, which are then applied in a customary manner diluted with water, or are produced as tank mixes by joint dilution of the separately formulated or partially separately formulated components with water.
The compounds (A) and (B) or their combinations can be formulated in various ways, depending on the prevailing biological and/or chemicophysical parameters. Examples of suitable formulations which are possible are: wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW), such as oilinwater and waterinoil emulsions, sprayable solutions or emulsions, oil or waterbased dispersions, oil dispersions (OD), suspoemulsions, suspension concentrates (SC), dusts (DP), seeddressing products, granules for spreading and soil application or waterdispersible granules (WG), ULV formulations, microcapsules and waxes.
The individual formulation types are known in principle and are described, for example, in WinnackerKüchler, “Chemische Technologie” [Chemical Engineering], Volume 7, C. HanserVerlag Munich, 4th Ed. 1986, van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries required, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H. v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1950; 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; Schonfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Surfaceactive ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; WinnackerKüchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.
Based on these formulations, it is also possible to prepare combinations with other pesticidally active compounds such as other herbicides, fungicides or insecticides, and with safeners, fertilizers and/or growth regulators, for example in the form of a readymix or a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which, in addition to the active compound, also contain ionic and/or nonionic surfactants (wetters, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′dinaphthylmethane6,6′disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurate, in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or else higherboiling aromatics or hydrocarbons with addition of one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which can be used are: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitan esters.
Dusts are obtained by grinding the active compound with finely divided solid materials, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Granules can be prepared either by spraying the active compound onto adsorptive, granulated inert material or by applying active compound concentrates to the surface of carriers such as sand, kaolinites or granulated inert material with the aid of stickers, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active compounds can also be granulated in the fashion which is conventional for the production of fertilizer granules, if desired as a mixture with fertilizers. Waterdispersible granules are generally prepared by customary methods such as spray drying, fluidizedbed granulation, disk granulation, mixing with highspeed stirrers and extrusion without solid inert material.
As a rule, the agrochemical preparations comprise 0.1 to 99% by weight, in particular 2 to 95% by weight, of active compounds of types A and/or B, the following concentrations being customary depending on the type of formulation. In wettable powders, the active compound concentration is, for example, approximately 10 to 95% by weight, the remainder to 100% by weight being composed of customary formulation constituents. In the case of emulsifiable concentrates, the active compound concentration can amount to, for example, 5 to 80% by weight. Formulations in the form of dusts comprise in most cases 5 to 20% by weight of active compound, and sprayable solutions comprise approximately 0.2 to 25% by weight of active compound.
In the case of waterdispersible granules, the active compound content depends partly on whether the active compound is in liquid or solid form and on the granulation auxiliaries and fillers which are being used. In the case of the waterdispersible granules, the active compound content is generally between 10 and 90% by weight.
In addition, the active compound formulations mentioned comprise, if appropriate, the auxiliaries which are conventional in each case, such as stickers, wetters, dispersants, emulsifiers, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors, and pH and viscosity regulators.
For use, the formulations, which are present in commercially available form, are optionally diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and waterdispersible granules. Preparations in the form of dusts, soil granules, granules for broadcasting and sprayable solutions are usually not diluted further with other inert substances prior to use.
The active compounds can be applied to the plants, parts of the plants, seeds of the plants or the area under cultivation (soil of a field), preferably to the green plants and parts of the plants and, if appropriate, additionally to the soil of the field.
One possible use is the joint application of the active compounds in the form of tank mixes, the concentrated formulations of the individual active compounds, in optical formulations, jointly being mixed with water in the tank and the resulting spray mixture being applied.
A joint herbicidal formulation of the combination according to the invention of the active compounds (A) and (B) has the advantage of being easier to apply since the quantities of the components are already presented in the correct ratio to each other. Moreover, the adjuvants in the formulation can be matched optimally to each other, whereas a tank mix of different formulations may result in undesirable combinations of adjuvants.
a) A dust is obtained by mixing 10 parts by weight of an active compound/active compound mixture and 90 parts by weight of talc as inert material and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of an active compound/active compound mixture, 64 parts by weight of kaolincontaining quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetter and dispersant, and grinding the mixture in a pinneddisk mill.
c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of an active compound/active compound mixture with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example approx. 255 to 277° C.), and grinding the mixture in a ball mill to a fineness of below 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of an active compound/active compound mixture, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.
e) Waterdispersible granules are obtained by mixing
f) Waterdispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill,
Seeds or rhizome pieces of monocotyledonous and dicotyledonous harmful plants are placed in sandy loam in pots and covered with soil. The compositions, formulated as concentrated aqueous solutions, wettable powders or emulsion concentrates, are then applied to the surface of the covering soil as an aqueous solution, suspension or emulsion at an application rate of 300 to 800 1 of water/ha (converted) in a variety of dosages. After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the weeds. Visual scoring of plant or emergence damage is carried out after the test plants have emerged after an experimental period of 3 to 4 weeks in comparison with untreated controls. As demonstrated by the test results, the compositions according to the invention have an outstanding preemergence herbicidal action against a broad spectrum of weed grasses and broadleaf weeds.
Scoring and assessing of the synergistic herbicidal effects:
The herbicidal efficacy of the active compounds or active compound mixtures was scored visually by comparing the treated pots (soil) with untreated controls. The damage and development of all aboveground plant parts was recorded. Scoring was done on a percentage scale (100% action=all plants dead or not emerged; 50% action=50% of the plants and green plant parts dead or not emerged; 0% action=no discernible action=like control plot). The score figures of in any case 4 repetitions (pots) were averaged.
When applying the combinations according to the invention, herbicidal effects are frequently observed on a harmful plant species which exceed the formal total of the effects of the herbicides present when these are applied by themselves. Alternatively, it is observed in some cases that a lower application rate is required for the herbicide combination in order to achieve the same effect on a harmful plant species in comparison with the individual products. Such increases in action or efficacy, or reduced application rates, strongly suggest a synergistic effect. When the data observed already exceed the formal total of the data in the experiments with individual applications, they likewise exceed the expected value according to Colby, which is calculated using the formula below and is likewise regarded as an indication of synergism (cf. S. R. Colby; in Weeds 15 (1967) pp. 20 to 22):
E=A+B−(A−B/100)
In this formula:
The data observed in the experiments show, at suitably low dosages, an action of the combinations which exceeds the expected values according to Colby.
Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds are placed in sandy loam in pots, covered with soil and grown in the greenhouse under good growth conditions (temperature, atmospheric humidity, water supply). Three weeks after sowing, the test plants are treated in the threeleaf stage with the compositions according to the invention. The compositions according to the invention, formulated as wettable powders or emulsion concentrates, are sprayed onto the green plant parts in various dosages using an application rate of 300 to 800 l of water/ha (converted). After the test plants have remained in the greenhouse under optimum growth conditions for about 3 to 4 weeks, the effect of the preparations is scored visually in comparison with untreated controls (scoring as in Example 1). The compositions according to the invention also have good herbicidal postemergence action against a broad spectrum of economically important weed grasses and broadleaf weeds.
Here, effects of the combinations according to the invention are frequently observed which exceed the formal total of the effects of the herbicides when these are applied by themselves. The observed values for the tests show, at suitably low dosages, an effect of the combinations which exceeds the expected values according to Colby (cf. scoring in Example 1).
Corresponding to the greenhouse experiments of sections 1 and 2, the tests were carried out in the open on plots. Scoring was carried out analogously to the tests in sections 1 and 2.
Crop plants were grown in the open on plots under natural outdoor conditions, and seeds or rhizome pieces of typical harmful plants were laid out or the natural weed growth was utilized. Treatment with the compositions according to the invention was carried out after the harmful plants had emerged and the crop plants were, generally, at the 2 to 4leaf stage; in some cases (as stated), application of individual active compounds or active compound combinations was carried out preemergence or as a sequential treatment partly preemergence and/or postemergence.
In the case of plantation crops, it was generally only the soil between the individual crop plants that was treated with the active compounds.
After the application, for example 2, 4, 6 and 8 weeks after application, the effect of the preparations was scored visually by comparison with untreated controls (cf. scoring in Example 1). In the outdoor trial as well, the compositions according to the invention have synergistic herbicidal activity against a broad spectrum of economically important weed grasses and broadleaf weeds. The comparison showed that the combinations according to the invention in most cases have a higher, in some cases a considerably higher, herbicidal activity than the total of the activities of the individual herbicides, thus indicating synergism. Moreover, the effects in essential phases of the scoring period were above the expected values according to Colby (cf. scoring in Example 1), also indicating synergism. In contrast, the crop plants were, as a consequence of the treatments with the herbicidal compositions, damaged only to a small degree, if at all.
The following abbreviations are used in the description and the tables below: g of AS/ha=grams of active substance (=100% active compound) per hectare; the total of the activities of the individual applications is given as E^{A}; the expected values according to Colby are in each case given as E^{C};
Certain combinations were tested for their herbicidal activity in accordance to the general example in section 3 in combination with section 2 (postemergence method). The results are summarized in Table 2.
TABLE 2  
Herbicidal action  
Active  Application rate  [%] against  
compound(s)  [g of AS/ha]  Poa trivialis  Festuca rubra 
(A11)  200  0  0 
(B2.1.1.1)  600  88  87 
(A11) + (B2.1.1.1)  200 + 600  94  95 
(E^{A }= 88,  (E^{A }= 87,  
E^{C }= 88)  E^{C }= 87)  
Abbreviations in Table 2:  
Conditions: Outdoor trial, Application at stage 21 (Beginning of stocking) of the harmful plants, evaluation 35 days after treatment  
(A11) = Compound (A11) from Table 1 (compound (A)) = 2amino4[(1R)6methylindan1ylamino]6[(1R)1fluoroethyl]1,3,5triazine  
(B2.1.1.1) = Glufosinateammonium 
Certain combinations were tested for their herbicidal activity in accordance to the general example in section 3 in combination with section 2 (postemergence method). The results are summarized in Table 3.
TABLE 3  
Active  Application rate  Herbicidal action [%] against 
compound(s)  [g of AS/ha]  Lolium multiflorum 
(A11)  200  20 
300  50  
(B2.1.2.1)  1080  18 
(A11) + (B2.1.2.1)  200 + 1080  88 
(E^{A }= 38, E^{C }= 35)  
Abbreviations in Table 3:  
Conditions: Outdoor trial,  
Application at the 25leaf stage (postemergence) of the harmful plants, evaluation 55 days after treatment  
(A11) '2 Compound (A11) from Table 1 (compound (A)) = 2amino4[(1R)6methylindan1ylamino]6[(1R)1fluorethyl]1,3,5triazine  
(B2.1.2.1) = Glyphosateisopropylammonium 