WO2007101587A1 - New synergistic herbicidal compositions - Google Patents

New synergistic herbicidal compositions Download PDF

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Publication number
WO2007101587A1
WO2007101587A1 PCT/EP2007/001706 EP2007001706W WO2007101587A1 WO 2007101587 A1 WO2007101587 A1 WO 2007101587A1 EP 2007001706 W EP2007001706 W EP 2007001706W WO 2007101587 A1 WO2007101587 A1 WO 2007101587A1
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Prior art keywords
methyl
amino
chloro
spp
methoxy
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PCT/EP2007/001706
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French (fr)
Inventor
Giovanni Meazza
Franco Bettarini
Luca Fornara
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Isagro Ricerca SRL
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Isagro Ricerca SRL
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Priority to AU2007222703A priority Critical patent/AU2007222703A1/en
Priority to EP07722959A priority patent/EP1998616A1/en
Priority to BRPI0708418-8A priority patent/BRPI0708418A2/en
Priority to CA002643719A priority patent/CA2643719A1/en
Priority to US12/224,481 priority patent/US20090029857A1/en
Publication of WO2007101587A1 publication Critical patent/WO2007101587A1/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to new herbicidal compositions . More specifically, the present invention relates to new compositions comprising a particular derivative of 3- methoxy-2-butenoic acid in a synergistic mixture with one or more known herbicides, and the use thereof as herbicides for the control of weeds in agricultural crops.
  • European patent applications EP 796845 and EP 1020448 describe 3-arylheterocyclic products with a herbicidal activity and the use thereof for the control of weeds in agricultural crops.
  • An object of the present invention therefore relates to synergistic herbicidal compositions comprising a component [A] and a component [B] , wherein the component [A] is the compound having formula (I)
  • component [B] consists of at least one product selected from the following herbicides [1] acetochlor (2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6- methylphenyl) acetamide) ;
  • diflufenican N- (2, 4-difluorophenyl) -2- [3- (trifIu- oromethyl) phenoxy] -3-pyridinecarboxamide) ;
  • fluroxypyr [4 (4-amino-3, 5-dichloro-6-fluoro-2- pyridinyl) oxy] acetic acid
  • glufosinate ammonium ( ⁇ ) -2-amino-4- (hydroxymethyl- phosphinyl) butanoate)
  • glyphosate N- (phosphonomethyl) glycine
  • halosulfuron (3-chloro-5- [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-lH- pyrazole-4-carboxylic acid) and its methyl ester; [25] imazamox (2- [4 , 5-dihydro-4-methyl-4- ( 1-methylethyl) - 5-oxolH-imidazol-2-yl] -5- (methoxymethyl) -3- pyridinecarboxylic acid;
  • MSMA monosodium methyl arsonate
  • pinoxaden (8- (2, 6-diethyl-4-methylphenyl) -1, 2, 4 , 5- tetrahydro-7-oxo-7H-pyrazolo [1, 2-d] [1, 4 , 5] oxadiazepin-9- yl 2, 2-dimethylpropanoate) ;
  • prometryn N, N' -bis (1-methylethyl) -6- (methylthio) - 1, 3, 5-triazine-2, 4-diamine
  • An object of the present invention also relates to the use of synergistic herbicidal compositions comprising a component [A] and a component [B] , wherein component [A] is the compound having formula (I)
  • component [B] consists of at least one prod- uct selected from the following herbicides: [I] acetochlor (2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6- methylphenyl) acetamide) ;
  • diflufenican N- (2, 4-difluorophenyl) -2- [3- (trifIu- oromethyl) phenoxy] -3-pyridinecarboxamide) ;
  • dimethenamid [RS) -2-chloro-N- (2, 4-dimethyl-3- thienyl) -N- (2-methoxy-l-methylethyl) acetamide) ;
  • fluroxypyr [4 (4-amino-3, 5-dichloro-6-fluoro-2- pyridinyl) oxy] acetic acid
  • halosulfuron (3-chloro-5- [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-lH- pyrazole-4-carboxylic acid) and its methyl ester; [25] imazamox (2- [4 , 5-dihydro-4-methyl-4- (1-methylethyl) - 5-oxolH-imidazol-2-yl] -5- (methoxymethyl) -3- pyridinecarboxylic acid;
  • MSMA monosodium methyl arsonate
  • prometryn N, N' -bis (1-methylethyl) -6- (methylthio) - 1, 3, 5-triazine-2, 4-diamine; [45] propachlor (2-chloro-N- (methylethyl) -N-phenyl- acetamide) ;
  • terbuthylazine 6-chloro-N- ( 1, 1-dimethylethyl) -N ' - ethyl-1, 3, 5-triazine-2, 4-diamine
  • component [B] is preferably selected from bromoxynil, diflufenican, flufenacet, glyphosate, ioxynil, isoproturon, mesotrione, S-metolachlor .
  • Component [A], a compound having formula (I) can be prepared according to the method described in EP1020448 and as specified in detail in Example 1 described below.
  • the components [B] are known commercial products or products in the commercialization phase and are therefore indicated with their common ISO (International Standard Organization) name and with the chemical names according to Chemical Abstracts.
  • ISO International Standard Organization
  • the structural formulae of these products, as also the main applications as herbicides are specified, among others, in "The Pesticide Manual” 13 a edition (2003), Ed. C. D. S. Tomlin, published by the British Crop Protection Council, Farnham (UK) .
  • Compound [35] (orthosulfamuron) is described in international patent application WO 98/40361.
  • the use of the herbicidal compositions, object of the present invention is particularly advantageous with respect to the use of the single components [A] and [B] as, in addition to having a wider action range, reduced dosages of the products can be adopted for obtaining the same herbicidal effect;
  • the compositions according to the present invention are effective in the post-emergence and pre-emergence control of numerous monocotyledonous and dicotyledonous weeds.
  • said compositions have a reduced or zero phytotoxicity with respect to important agricultural crops thus making their use possible in the selective control of weeds.
  • the compositions can also be used as total herbicides, in relation to the quantity of active principles adopted.
  • weeds which can be effectively controlled using the compositions of the present invention are: Abutilon theophrasti, Adonis spp., Ambrosia spp., Alisma plantago, Amaranthus spp., Amni maius, Anagallis arvensis, Anthemis spp., Aphanes arvensis, Atriplex patula, Bidens pilosa, Capsella bursa-pastoris, Chenopo- dium album, Convolvulus sepium, Datura stramonium, Euphorbia spp., Fumaria officinalis, Galeopsis tetrahit, Galinsoga ciliata, Galium aparine, Geranium spp., Helian- thus spp., Ipomea spp., Kochia scoparia, Lamium spp., Ma- tricaria spp., Monochoria vaginalis, Myosotis arvensis, Papaver
  • Examples of agrarian crops which can be advantageously treated with the compositions of the invention are: wheat (Triticum sp. ) , barley (Hordeum vulgare) , maize (Zea mays), soybean (Glycine max) , rice (Oryza sa- tiva) , cotton (Gossypium hirsutum) , sugarcane (Saccharum officinarum) .
  • components [A] and [B] defined above can be mixed within a very wide ratio, in relation to various factors such as, for example: the component (s) [B] se- lected, the weeds to be attacked, the degree of infestation, the climatic conditions, the characteristics of the soil, the application method.
  • the ratio between the weight quantity of component [A] and the weight quantity of the component (s) [B], can vary from 1:0,1 to 1:10,000, preferably from 1:1 to 1:1,000.
  • the herbicidal compositions, object of the present invention can be applied in such quantities as to guarantee applicative dos- ages of compound (I) within the range of 0,5-200 g/ha, preferably 1-100 g/ha, and applicative dosages of the component (s) [B] within the range of 1-10,000 g/ha, preferably 10-5,000 g/ha.
  • a further object of the present invention relates to a method for the control of weeds in cultivated areas by applying the compositions described above.
  • herbicidal compositions object of the present invention, in the form of suitable formula- tions which can be already prepared or obtained at the moment of use.
  • This can be effected either by formulating component [A] together with component (s) [B] in the desired ratio, to give the final composition, or by preparing the composition at the moment of use by mixing the relative quantities of component [A] and component (s) [B] , formulated separately.
  • compositions can be used in the form of dry powders, wettable powders, emulsifying concentrates, micro- emulsions, pastes, granulates, solutions, suspensions, etc.: the choice of the type of composition will depend on the specific use.
  • compositions are prepared according to known methods, for example by diluting or dissolving the active substance with a solvent medium and/or solid diluent, op- tionally in the presence of surface-active agents.
  • Inert solid diluents or supports which can be used are: kaolin, alumina, silica, talc, bentonite, gypsum, quartz, dolomite, attapulgite, montmorillonites, diatoma- ceous earth, cellulose, starch, etc.
  • Inert liquid diluents which can be used are water, or organic solvents such as aromatic hydrocarbons (xylols, alkylbenzol mixtures, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), halogenated aromatic hydrocarbons (chlorobenzol, etc.), alcohols (methanol, pro- panol, butanol, octanol, etc.), esters (isobutyl acetate, etc.), ketones (acetone, cyclohexanone, acetophenone, isophorone, ethylamylketone, etc.), or vegetable or mineral oils and mixtures thereof, etc.
  • aromatic hydrocarbons xylols, alkylbenzol mixtures, etc.
  • aliphatic hydrocarbons hexane, cyclohexane, etc.
  • halogenated aromatic hydrocarbons chlorobenzol, etc.
  • Surface-active agents which can be used are wetting and emulsifying agents of the non-ionic type (polyethoxy- lated alkylphenols, polyethoxylated fatty alcohols, etc.), of the anionic type (alkylbenzenesulfonates, al- kylsulfonates, etc.), of the cationic type (quaternary salts of alkylammonium, etc.). It is also possible to add dispersing agents (for example lignin and its salts, cellulose derivatives, alginates, etc.), stabilizers (for example antioxidants, ultraviolet-ray absorbers, etc.).
  • dispersing agents for example lignin and its salts, cellulose derivatives, alginates, etc.
  • stabilizers for example antioxidants, ultraviolet-ray absorbers, etc.
  • herbicides which can be added to the compositions, object of the invention, are: acifluorfen, aclonifen, AKH-7088, ametryn, amicarbazone, amitrole, anilofos, asulam, azafenidin, azimsulfuron, aziprotryne, BAY MKH 6561, benazolin, benfluralin, ben- furesate, bensulide, bentazone, benzfendizone, benzobicy- clon, benzofenap, benzthiazuron, bifenox, bilanafos, bro- macil, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chlometh- oxyfen,
  • the concentration of active substances [A] + [B] , in the above compositions can vary within a wide range, depending on the active principles selected, the applications for which they are destined, the environmental conditions and the type of formulation.
  • the overall composition of active substances can generally range from 1 to 90%, preferably from 5 to 75%.
  • the mixture is diluted with water (2 litres) and extracted with methylene chloride (3 x 0.5 litres).
  • the extract is washed to neutral- ity with water, anhydrified with sodium sulfate; the organic solvent is then removed by distillation under vacuum and the raw product is purified by chromatography on a silica gel column, eluting with hexane/ethyl acetate 65:35. 35 g of a dense oil are obtained, which solidifies after a few days giving a white product with a melting point of 66-69°C.
  • the herbicidal activity in post-emergence of the compositions of the invention was evaluated according to the following operating procedures.
  • the vegetable species of interest (weeds or crops) were planted in vases having an upper diameter of 10 cm, a height of 10 cm and containing sandy earth. Water was added to each vase in a suitable quantity for the germination of the seeds. The vases were then divided into four groups for each weed or crop.
  • the first group of vases was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [A] at a dosage D A .
  • the second group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [B] at a dosage D B .
  • the third group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and the composition C according to the present in- vention, containing components [A] and [B] at dosages, D A and D B , respectively.
  • the fourth group was treated with a hydroacetone solution only, containing acetone at 10% by volume and Tween 20 at 0.5%, and was used as a comparative reference (blank) .
  • the herbicidal activity was evaluated (expressed as a % of the damage observed on the vegetable species) for the composition C (Ec) and for the two components [A] and [B] tested sepa- rately (E A , E 5 ) .
  • Crops tested were: wheat, barley, maize, soybean, rice, cotton. b) Determination of the herbicidal activity and phyto- toxicity in pre-emergence .
  • the herbicidal activity in pre-emergence of the compounds of the invention was evaluated according to the following operating procedures.
  • the vegetable species of interest (weeds or crops) were planted in vases having an upper diameter of 10 cm, a height of 10 cm and containing sandy earth.
  • the first group of vases was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [A] at a dosage D A .
  • the second group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [B] at a dosage D B .
  • the third group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and the composition C according to the present invention, containing components [A] and [B] at dosages, D A e D B , respectively.
  • the fourth group was treated with a hydroacetone solution only, containing acetone at 10% by volume and Tween 20 at 0.5%, and was used as a comparative reference (blank) .
  • E A activity observed for [A] at a dosage D A ;
  • E B activity observed for [B] at a dosage D B .

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Synergistic compositions are described, having a high herbicidal activity and containing the compound having formula (I ) : in a mixture with one or more known herbicidal products.

Description

NEW SYNERGISTIC HERBICIDAL COMPOSITIONS
The present invention relates to new herbicidal compositions . More specifically, the present invention relates to new compositions comprising a particular derivative of 3- methoxy-2-butenoic acid in a synergistic mixture with one or more known herbicides, and the use thereof as herbicides for the control of weeds in agricultural crops. European patent applications EP 796845 and EP 1020448 describe 3-arylheterocyclic products with a herbicidal activity and the use thereof for the control of weeds in agricultural crops. These documents generically envisage the association of the compounds claimed with other herbicidal products, but no information is provided either as to what the herbicidal compounds suitable for the purpose are, or what are the possible enhancing effects of these compositions compared with the use of 3- arylheterocyclic compounds alone on the herbicidal activ- ity with respect to weeds. The Applicant has now surprisingly found that when the derivative of 3-methoxy-2-butenoic acid having general formula (I),
Figure imgf000003_0001
(D i.e. methyl (E) -4- [2-chloro-5- (4-chloro-5-difluoro- methoxy-l-methylpyrazol-3-yl) -4-fluorophenoxy] -3-methoxy- but-2-enoate, corresponding to Compound N. 2 of EP1020448, is used in association with at least one of the herbicidal products selected from those specified hereunder, it produces synergistic herbicidal mixtures, i.e. mixtures having a much more enhanced herbicidal activity with respect to weeds compared with what is expected based on the activities of products used separately. The phytotoxicity with respect to agricultural crops, on the contrary, remains unvaried, or even lower than the expected value, thus allowing considerable advantages to be obtained in the practical use of these mixtures . An object of the present invention therefore relates to synergistic herbicidal compositions comprising a component [A] and a component [B] , wherein the component [A] is the compound having formula (I)
Figure imgf000004_0001
(I) methyl (E) -4- [2-chloro-5- (4-chloro-5-difluoro-methoxy-1- methylpyrazol-3-yl) -4-fluorophenoxy] -3-methoxy-but-2- enoate, and component [B] consists of at least one product selected from the following herbicides [1] acetochlor (2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6- methylphenyl) acetamide) ;
[2] alachlor (2-chloro-N- (2, 6-diethylphenyl) -N- (methoxy- methyl) acetamide) ; [3] amidosulfuron (N- [ [ [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] amino] sulfonyl] -N-methylmethanesulfon- amide) ;
[4] atrazine ( 6-chloro-N-ethyl-N ' - (1-methylethyl) -1, 3, 5- triazine-2, 4-diamine) ; [5] beflubutamid (2- [4-fluoro-3- (trifluoromethyl) - phenoxy] -N- (phenylmethyl) butanamide) ; [6] bensulfuron-methyl (methyl [ [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] - benzoate) ;
[7] bispyribac-sodium (sodium 2, 6-bis [ (4 , 6-dimethoxy-2- pyrimidinyl) oxy] benzoate) ;
[8] bromoxynil (3, 5-dibromo-4-hydroxybenzonitrile) ;
[9] chlorimuron-ethyl (ethyl [ [ [ [ (4-chloro-6-methoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate;
[10] chlorotoluron (N ' - (3-chloro-4-methylphenyl) -N, N- dimethylurea) ;
[11] chlorsulfuron (2-chloro-N- [ [ (4-methoxy-6-methyl-l, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfonamide) ;
[12] clodinafop-propargyl (propynyl (R) -2- [4- [ (5-chloro- 3-fluoro-2-pyridinyl) oxy] phenoxy] propanoate) ; [13] clomazone (2- [ (2-chlorophenyl) methyl] -4 , 4-dimethyl- 3-isoxazolidinone;
[14] diflufenican (N- (2, 4-difluorophenyl) -2- [3- (trifIu- oromethyl) phenoxy] -3-pyridinecarboxamide) ;
[15] dimethenamid ( [RS) -2-chloro-N- (2, 4-dimethyl-3- thienyl) -N- (2-methoxy-l-methylethyl) acetamide) ;
[16] diuron (N' - (3, 4-dichlorophenyl) -N, N-dimethylurea) ;
[17] ethoxysulfuron ( 1- (4 , 6-dimethoxypyrimidin-2-yl) -3-
(ethoxyphenoxysulfonyl) urea) ;
[18] fenoxaprop-P ( (R) -2- [4- [ ( 6-chloro-2-benzoxazolyl) - oxy] phenoxy] propanoic acid) and its ethyl ester; [19] flufenacet (N- (4-fluorophenyl) -N- (1-methylethyl) -2- [ [5- (trifluoromethyl) -1, 3, 4-thiadiazol-2-yl] oxy] - acetamide) ;
[20] fluometuron (N, N-dimethyl-N' - [3- (trifluoromethyl) - phenyl] urea;
[21] fluroxypyr ( [4 (4-amino-3, 5-dichloro-6-fluoro-2- pyridinyl) oxy] acetic acid);
[22] glufosinate (ammonium (±) -2-amino-4- (hydroxymethyl- phosphinyl) butanoate) ; [23] glyphosate (N- (phosphonomethyl) glycine) and its salts;
[24] halosulfuron (3-chloro-5- [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-lH- pyrazole-4-carboxylic acid) and its methyl ester; [25] imazamox (2- [4 , 5-dihydro-4-methyl-4- ( 1-methylethyl) - 5-oxolH-imidazol-2-yl] -5- (methoxymethyl) -3- pyridinecarboxylic acid;
[26] ioxynil (4-hydroxy-3, 5-diiodobenzonitrile) ; [27] isoproturon (N, N-dimethyl-N '- [4- (1-methylethyl) - phenyl] urea) ;
[28] isoxaflutole ( (5-cyclopropyl-4-isoxazolyl) - [2- (methylsulfonyl) -4- (trifluorometyl) phenyl] methanone) ; [29] linuron (N ' - (3, 4-dichlorophenyl) -N-methoxy-N-methyl- urea) ; [30] MCPA ( (4-chloro-2-methylphenoxy) acetic acid) and its thioethyl ester;
[31] MCPB (4- (4-chloro-2-methylphenoxy)butanoic acid);
[32] mesotrione (2- [4- (methylsulfonyl) -2-nitrobenzoyl] -
1, 3-cyclohexandione) ; [33] metolachlor (2-chloro-N- (2-ethyl-6-methylphenyl) -N-
(2-methoxy-l-methylethyl) acetamide) ;
[34] S-metolachlor (mixture of two enantiomers of metolachlor, containing 80-100% of 2-chloro-N- (2-ethyl-6- methylphenyl) -N- [ (IS) -2-methoxy-l-methylethyl] - acetamide) ;
[35] metribuzin (4-amino-6- ( 1 , 1-dimethylethyl) -3- (methyl- thio) -l,2,4-triazin-5 (4H) -one) ;
[36] metsulfuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] - sulfonyl] -benzoate) ;
[37] MSMA (monosodium methyl arsonate) ;
[38] orthosulfamuron (2- [ [ [ [ [ (4, 6-dimethoxy-2-pyrimidin- yl) amino] carbonyl] amino] sulfonyl] amino-N, N-dimethy1- benzamide) ; [39] pendimethalin (N- (1-ethylpropyl) -3, 4-dimethyl-2, 6- dinitrobenzenamine) ;
[40] penoxsulam (2- (2, 2-difluoroethoxy) -N- (5, 8-dimethoxy)
[1,2,4] triazolo [1, 5-c] pyrimidin-2-yl) -6- (trifluoromethyl) benzenesulfonamide) ; [41] pethoxamid (2-chloro-N- (2-ethoxyethyl) -N- (2-methyl- 1-phenyl-l-propenyl) acetamide) ;
[42] picolinafen (N- (4-fluorophenyl) -6- [3- (trifluoro- methyl) phenoxy] -2-pyridinecarboxamide) ;
[43] pinoxaden (8- (2, 6-diethyl-4-methylphenyl) -1, 2, 4 , 5- tetrahydro-7-oxo-7H-pyrazolo [1, 2-d] [1, 4 , 5] oxadiazepin-9- yl 2, 2-dimethylpropanoate) ;
[44] prometryn (N, N' -bis (1-methylethyl) -6- (methylthio) - 1, 3, 5-triazine-2, 4-diamine;
[45] propachlor (2-chloro-N- (methylethyl) -N-phenyl- acetamide) ;
[46] propanil (N- (3, 4-dichlorophenyl) propanamide) ;
[47] propoxycarbazone (methyl 2- [ [ [ (4 , 5-dihydro-4-methyl- 5-oxo-3-propoxy-lH-l, 2, 4-triazol-l-yl) carbonyl] amino] - sulfonyl] benzoate) ; [48] sulcotrione (2- [2-chloro-4- (methylsulfonyl) - benzoyl] -1, 3-cyclohexanedione) ;
[49] sulfosulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] -2- (ethylsulfonyl) imidazo [1, 2-a] pyridin-3- sulfonamide) ; [50] terbuthylazine ( 6-chloro-N- ( 1, 1-dimethylethyl) -N ' - ethyl-1, 3, 5-triazine-2, 4-diamine) ;
[51] thifensulfuron-methyl (methyl 3- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] - 2-thiophenecarboxylate) ; [52] triasulfuron (2- (2-chloroethoxy) -N- [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfonamide) ;
[53] tribenuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6-methyl- 1, 3, 5-triazin-2-yl) methylamino] carbonyl] amino] - sulfonyl] benzoate) ;
[54] trifloxysulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidin-2- yl) amino] carbonyl] -3- (2,2, 2-trifluoroethoxy) -2-pyridine- sulfonamide) ; [55] trifluralin (2, 6-dinitro-N, N-dipropyl-4- (trifluoro- methyl) benzeneamine) .
An object of the present invention also relates to the use of synergistic herbicidal compositions comprising a component [A] and a component [B] , wherein component [A] is the compound having formula (I)
2
Figure imgf000009_0001
( D methyl [E) -4- [2-chloro-5- (4-chloro-5-difluoro-methoxy-1- methylpyrazol-3-yl) -4-fluorophenoxy] -3-methoxy-but-2- enoate, and component [B] consists of at least one prod- uct selected from the following herbicides: [I] acetochlor (2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6- methylphenyl) acetamide) ;
[2] alachlor (2-chloro-N- (2, 6-diethylphenyl) -N- (methoxy- methyl) acetamide) ; [3] amidosulfuron (N- [ [ [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] amino] sulfonyl] -N-methylmethanesulfon- amide) ;
[4] atrazine ( 6-chloro-N-ethyl-N ' - (1-methylethyl) -1, 3, 5- triazine-2, 4-diamine) ; [5] beflubutamid (2- [4-fluoro-3- (trifluoromethyl) - phenoxy] -N- (phenylmethyl) butanamide) ;
[6] bensulfuron-methyl (methyl [ [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] - benzoate) ; [7] bispyribac-sodium (sodium 2, 6-bis [ (4 , 6-dimethoxy-2- pyrimidinyl) oxy] benzoate) ;
[8] bromoxynil (3, 5-dibromo-4-hydroxybenzonitrile) ; [9] chlorimuron-ethyl (ethyl [ [ [ [ (4-chloro-6-methoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate; [10] chlorotoluron (N ' - (3-chloro-4-methylphenyl) -N, N- dimethylurea) ;
[II] chlorsulfuron (2-chloro-N- [[ (4-methoxy-6-methyl-l, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfonamide) ;
[12] clodinafop-propargyl (propynyl [R) -2- [4- [ (5-chloro- 3-fluoro-2-pyridinyl) oxy] phenoxy] propanoate) ; [13] clomazone (2- [ (2-chlorophenyl) methyl] -4 , 4-dimethyl- 3-isoxazolidinone;
[14] diflufenican (N- (2, 4-difluorophenyl) -2- [3- (trifIu- oromethyl) phenoxy] -3-pyridinecarboxamide) ; [15] dimethenamid ( [RS) -2-chloro-N- (2, 4-dimethyl-3- thienyl) -N- (2-methoxy-l-methylethyl) acetamide) ;
[16] diuron (N' - (3, 4-dichlorophenyl) -N, N-dimethylurea) ;
[17] ethoxysulfuron ( 1- (4 , 6-dimethoxypyrimidin-2-yl) -3-
(ethoxyphenoxysulfonyl) urea) ; [18] fenoxaprop-P ( (R) -2- [4- [ ( 6-chloro-2-benzoxazolyl) - oxy] phenoxy] propanoic acid) and its ethyl ester;
[19] flufenacet (N- (4-fluorophenyl) -N- ( 1-methylethyl) -2-
[ [5- (trifluoromethyl) -1, 3, 4-thiadiazol-2-yl] oxy] - acetamide) ; [20] fluometuron (N, N-dimethyl-N' - [3- (trifluoromethyl) - phenyl] urea;
[21] fluroxypyr ( [4 (4-amino-3, 5-dichloro-6-fluoro-2- pyridinyl) oxy] acetic acid);
[22] glufosinate (ammonium (±) -2-amino-4- (hydroxymethyl- phosphinyl) butanoate) ;
[23] glyphosate (N- (phosphonomethyl) glycine) and its salts;
[24] halosulfuron (3-chloro-5- [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-lH- pyrazole-4-carboxylic acid) and its methyl ester; [25] imazamox (2- [4 , 5-dihydro-4-methyl-4- (1-methylethyl) - 5-oxolH-imidazol-2-yl] -5- (methoxymethyl) -3- pyridinecarboxylic acid;
[26] ioxynil (4-hydroxy-3, 5-diiodobenzonitrile) ; [27] isoproturon (N, N-dimethyl-N '- [4- (1-methylethyl) - phenyl] urea) ;
[28] isoxaflutole ( (5-cyclopropyl-4-isoxazolyl) - [2-
(methylsulfonyl) -4- (trifluorometyl) phenyl] methanone) ;
[29] linuron (N ' - (3, 4-dichlorophenyl) -N-methoxy-N-methyl- urea) ;
[30] MCPA ( (4-chloro-2-methylphenoxy) acetic acid) and its thioethyl ester;
[31] MCPB (4- (4-chloro-2-methylphenoxy) butanoic acid);
[32] mesotrione (2- [4- (methylsulfonyl) -2-nitrobenzoyl] - 1, 3-cyclohexandione) ;
[33] metolachlor (2-chloro-N- (2-ethyl-6-methylphenyl) -N-
(2-methoxy-l-methylethyl) acetamide) ;
[34] S-metolachlor (mixture of two enantiomers of metolachlor, containing 80-100% of 2-chloro-N- (2-ethyl-6- methylphenyl) -N- [ (IS) -2-methoxy-l-methylethyl] - acetamide) ;
[35] metribuzin ( 4-amino-β- ( 1, 1-dimethylethyl) -3- (methyl- thio) -1,2, 4-triazin-5 (4H) -one) ;
[36] metsulfuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] - sulfonyl] -benzoate) ;
[37] MSMA (monosodium methyl arsonate) ;
[38] orthosulfamuron (2- [ [ [ [ [ (4 , 6-dimethoxy-2-pyrimidin- yl) amino] carbonyl] amino] sulfonyl] amino-N, N-dimethyl- benzamide) ;
[39] pendimethalin (N- (1-ethylpropyl) -3, 4-dimethyl-2, 6- dinitrobenzenamine) ;
[40] penoxsulam (2- (2, 2-difluoroethoxy) -N- (5, 8-dimethoxy)
[l,2,4]triazolo[l,5-c] pyrimidin-2-yl) -6- (trifluoromethyl) benzenesulfonamide) ;
[41] pethoxamid (2-chloro-N- (2-ethoxyethyl) -N- (2-methyl- 1-phenyl-l-propenyl) acetamide) ;
[42] picolinafen (N- (4-fluorophenyl) -6- [3- (trifluoromethyl ) phenoxy] -2-pyridinecarboxamide ) ; [43] pinoxaden (8- (2, 6-diethyl-4-methylphenyl) -1, 2, 4 , 5- tetrahydro-7-oxo-7H-pyrazolo [1,2-d] [1,4,5] oxadiazepin-9- yl 2, 2-dimethylpropanoate) ;
[44] prometryn (N, N' -bis (1-methylethyl) -6- (methylthio) - 1, 3, 5-triazine-2, 4-diamine; [45] propachlor (2-chloro-N- (methylethyl) -N-phenyl- acetamide) ;
[46] propanil (N- ( 3, 4-dichlorophenyl) propanamide) ;
[47] propoxycarbazone (methyl 2- [ [ [ (4 , 5-dihydro-4-methyl- 5-oxo-3-propoxy-lH-l, 2, 4-triazol-l-yl) carbonyl] amino] - sulfonyl] benzoate) ; [48] sulcotrione (2- [2-chloro-4- (methylsulfonyl) - benzoyl] -1, 3-cyclohexanedione) ;
[49] sulfosulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] -2- (ethylsulfonyl) imidazo [ 1, 2-a] pyridin-3- sulfonamide) ;
[50] terbuthylazine ( 6-chloro-N- ( 1, 1-dimethylethyl) -N ' - ethyl-1, 3, 5-triazine-2, 4-diamine) ;
[51] thifensulfuron-methyl (methyl 3- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] - 2-thiophenecarboxylate) ;
[52] triasulfuron (2- (2-chloroethoxy) -N- [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfonamide) ;
[53] tribenuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6-methyl- 1, 3, 5-triazin-2-yl)methylamino] carbonyl] amino] - sulfonyl] benzoate) ;
[54] trifloxysulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidin-2- yl) amino] carbonyl] -3- (2,2, 2-trifluoroethoxy) -2-pyridine- sulfonamide) ; [55] trifluralin (2, 6-dinitro-N, N-dipropyl-4- (trifluoro- methyl) benzeneamine) ; for the control of weeds in agricultural crops.
In particular, component [B] is preferably selected from bromoxynil, diflufenican, flufenacet, glyphosate, ioxynil, isoproturon, mesotrione, S-metolachlor . Component [A], a compound having formula (I), can be prepared according to the method described in EP1020448 and as specified in detail in Example 1 described below.
The components [B] are known commercial products or products in the commercialization phase and are therefore indicated with their common ISO (International Standard Organization) name and with the chemical names according to Chemical Abstracts. The structural formulae of these products, as also the main applications as herbicides are specified, among others, in "The Pesticide Manual" 13a edition (2003), Ed. C. D. S. Tomlin, published by the British Crop Protection Council, Farnham (UK) . Compound [35] (orthosulfamuron) is described in international patent application WO 98/40361.
As already mentioned, the use of the herbicidal compositions, object of the present invention, is particularly advantageous with respect to the use of the single components [A] and [B] as, in addition to having a wider action range, reduced dosages of the products can be adopted for obtaining the same herbicidal effect; the compositions according to the present invention are effective in the post-emergence and pre-emergence control of numerous monocotyledonous and dicotyledonous weeds. At the same time, said compositions have a reduced or zero phytotoxicity with respect to important agricultural crops thus making their use possible in the selective control of weeds. When required, the compositions can also be used as total herbicides, in relation to the quantity of active principles adopted. Examples of weeds which can be effectively controlled using the compositions of the present invention are: Abutilon theophrasti, Adonis spp., Ambrosia spp., Alisma plantago, Amaranthus spp., Amni maius, Anagallis arvensis, Anthemis spp., Aphanes arvensis, Atriplex patula, Bidens pilosa, Capsella bursa-pastoris, Chenopo- dium album, Convolvulus sepium, Datura stramonium, Euphorbia spp., Fumaria officinalis, Galeopsis tetrahit, Galinsoga ciliata, Galium aparine, Geranium spp., Helian- thus spp., Ipomea spp., Kochia scoparia, Lamium spp., Ma- tricaria spp., Monochoria vaginalis, Myosotis arvensis, Papaver rhoeas, Phaseolus aureus, Polygonum spp., Portu- laca oleracea, Raphanus raphanistrum, Rumex crispus, Se- necio vulgaris, Sesbania exaltata, Sida spinosa, Sinapis arvensis, Solanum nigrum, Sonchus spp., Stellaria media, Thlaspi arvense, Veronica spp., Vicia spp., Viola spp., Xanthium spp., Aegilops tauschii, Alopecurus myosuroides, Apera spp., Avena fatua, Brachiaria spp., Bromus spp., Cenchrus echinatus, Commelina bengalensis, Cynodon dacti- lon, Cyperus spp., Digitaria spp., Echinocloa spp., Eleu- sine indica, Elymus repens, Eragrostis pilosa, Eriochloa villosa, Fimbristylis spp., Heleocaris avicularis, Heteranthera spp., Leptochloa spp., Lolium spp., Panicum spp., Phalaris spp., Poa spp., Scirpus spp., Setaria viridis, Sorghum spp. Examples of agrarian crops which can be advantageously treated with the compositions of the invention are: wheat (Triticum sp. ) , barley (Hordeum vulgare) , maize (Zea mays), soybean (Glycine max) , rice (Oryza sa- tiva) , cotton (Gossypium hirsutum) , sugarcane (Saccharum officinarum) .
In the herbicidal compositions, object of the present invention, components [A] and [B] defined above can be mixed within a very wide ratio, in relation to various factors such as, for example: the component (s) [B] se- lected, the weeds to be attacked, the degree of infestation, the climatic conditions, the characteristics of the soil, the application method.
In general, the ratio between the weight quantity of component [A] and the weight quantity of the component (s) [B], can vary from 1:0,1 to 1:10,000, preferably from 1:1 to 1:1,000.
For practical use in agriculture, the herbicidal compositions, object of the present invention, can be applied in such quantities as to guarantee applicative dos- ages of compound (I) within the range of 0,5-200 g/ha, preferably 1-100 g/ha, and applicative dosages of the component (s) [B] within the range of 1-10,000 g/ha, preferably 10-5,000 g/ha.
A further object of the present invention relates to a method for the control of weeds in cultivated areas by applying the compositions described above.
For practical use in agriculture, it is often advantageous to adopt the herbicidal compositions, object of the present invention, in the form of suitable formula- tions which can be already prepared or obtained at the moment of use. This can be effected either by formulating component [A] together with component (s) [B] in the desired ratio, to give the final composition, or by preparing the composition at the moment of use by mixing the relative quantities of component [A] and component (s) [B] , formulated separately.
Compositions can be used in the form of dry powders, wettable powders, emulsifying concentrates, micro- emulsions, pastes, granulates, solutions, suspensions, etc.: the choice of the type of composition will depend on the specific use.
The compositions are prepared according to known methods, for example by diluting or dissolving the active substance with a solvent medium and/or solid diluent, op- tionally in the presence of surface-active agents. Inert solid diluents or supports which can be used are: kaolin, alumina, silica, talc, bentonite, gypsum, quartz, dolomite, attapulgite, montmorillonites, diatoma- ceous earth, cellulose, starch, etc. Inert liquid diluents which can be used are water, or organic solvents such as aromatic hydrocarbons (xylols, alkylbenzol mixtures, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), halogenated aromatic hydrocarbons (chlorobenzol, etc.), alcohols (methanol, pro- panol, butanol, octanol, etc.), esters (isobutyl acetate, etc.), ketones (acetone, cyclohexanone, acetophenone, isophorone, ethylamylketone, etc.), or vegetable or mineral oils and mixtures thereof, etc.
Surface-active agents which can be used are wetting and emulsifying agents of the non-ionic type (polyethoxy- lated alkylphenols, polyethoxylated fatty alcohols, etc.), of the anionic type (alkylbenzenesulfonates, al- kylsulfonates, etc.), of the cationic type (quaternary salts of alkylammonium, etc.). It is also possible to add dispersing agents (for example lignin and its salts, cellulose derivatives, alginates, etc.), stabilizers (for example antioxidants, ultraviolet-ray absorbers, etc.).
In order to widen the action range of the above com- positions, it is possible to add other active ingredients such as, for example, other herbicides, antidotes, fungicides, insecticides, acaricides, fertilizers, etc.
Examples of other herbicides which can be added to the compositions, object of the invention, are: acifluorfen, aclonifen, AKH-7088, ametryn, amicarbazone, amitrole, anilofos, asulam, azafenidin, azimsulfuron, aziprotryne, BAY MKH 6561, benazolin, benfluralin, ben- furesate, bensulide, bentazone, benzfendizone, benzobicy- clon, benzofenap, benzthiazuron, bifenox, bilanafos, bro- macil, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chlometh- oxyfen, chloramben, chlorbromuron, chlorbufam, chlor- flurenol, chloridazon, chlornitrofen, chloroxuron, chlor- propham, chlorthal, chlorthiamid, cinidon ethyl, cinmeth- ylin, cinosulfuron, clethodim, clomeprop, clopyralid, cloransulam-methyl, cumyluron (JC-940), cyanazine, cy- cloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D, 2,4-DB, daimuron, dalapon, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclo- fop, diclosulam, diethatyl, difenoxuron, difenzoquat, di- flufenzopyr, dimefuron, dimepiperate, dimethachlor, di- methametryn, dinitramine, dinoseb, dinoseb acetate, di- noterb, diphenamid, dipropetryn, diquat, dithiopyr, 1- diuron, eglinazine, endothal, EPTC, esprocarb, ethalflu- ralin, ethametsulfuron-methyl, ethidimuron, ethiozin (SMY 1500), ethofumesate, ethoxyfen-ethyl (HC-252), etobenza- nid (HW 52), fentrazamide, fenuron, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate (JV 485) , flucarbazone-sodium, fluchloralin, flufenpyr ethyl, flumetsulam, flumiclorac-pentyl, flumi- oxazin, flumipropin, fluoroglycofen, fluoronitrofen, flu- poxam, flupropanate, flupyrsulfuron, flurenol, fluridone, flurochloridone, flurtamone, fluthiacet-methyl, fome- safen, foramsulfuron, fosamine, furyloxyfen, haloxyfop, haloxyfop-P-methyl, hexazinone, imazamethabenz, iraazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indano- fan, iodosulfuron, isopropalin, isouron, isoxaben, isoxa- chlortole, isoxapyrifop, KPP-421, lactofen, lenacil, LS830556, mecoprop, mecoprop-P, mefenacet, mesosulfuron, metamitron, metazachlor, methabenzthiazuron, methazole, methoprotryne, methyldymron, metobenzuron, metobromuron, metosulam, metoxuron, molinate, monalide, monolinuron, naproanilide, napropamide, naptalam, NC-330, neburon, ni- cosulfuron, nipyraclofen, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclome- fone, oxyfluorfen, paraquat, pebulate, pentanochlor, pen- toxazone, phenmedipham, picloram, piperophos, preti- lachlor, primisulfuron, prodiamine, profluazol, proglin- azine, prometon, propaquizafop, propazine, propham, pro- pisochlor, propyzamide, prosulfocarb, prosulfuron, pyra- clonil, pyraflufen-ethyl, pyrazogyl (HSA-961), pyrazoly- nate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyribu- ticarb, pyridafol, pyridate, pyriftalid, pyriminobac- methyl, pyrithiobac-sodium, quinclorac, quinmerac, quiza- lofop, quizalofop-P, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulfentrazone, sulfometuron-methyl, 2,3,6-TBA, TCA-sodium, tebutam, tebuthiuron, tepraloxy- dim, terbacil, terbumeton, terbutryn, thenylchlor, thi- azafluron, thiazopyr, thidiazimin, thiobencarb, tiocarba- zil, tioclorim, tralkoxydim, triallate, triaziflam, triclopyr, trietazine, triflusulfuron-methyl, tritosulfu- ron, UBI-C4874, vernolate.
The concentration of active substances [A] + [B] , in the above compositions can vary within a wide range, depending on the active principles selected, the applications for which they are destined, the environmental conditions and the type of formulation. The overall composition of active substances can generally range from 1 to 90%, preferably from 5 to 75%.
The following examples are provided for a better illustration of the invention. EXAMPLE 1 Preparation of methyl (E) -A- [2-chloro-5- (4-chloro-5- difluoromethoxy-l-methylpyrazol-3-yl) -4-fluorophenoxy] -3- methoxybut-2-enoate (component [A] ) .
14 g (101 mmoles) of potassium carbonate are added to a solution of 32.71 g (100 mmoles) of 4-chloro-3- [4- chloro-2-fluoro-5-hydroxyphenyl] -5-difluoromethoxy-1- methylpyrazole in 300 ml of N, N-dimethyl-formamide (DMF). The mixture is kept under stirring at room temperature for 30 minutes.
A solution of 18 g (109 mmoles) of methyl (E)-A- chloro-3-methoxy-2-butenoate in 30 ml of DMF is dripped into the suspension; at the end of the addition, the reaction mixture is heated to 500C for 4 hours.
At the end of the reaction, the mixture is diluted with water (2 litres) and extracted with methylene chloride (3 x 0.5 litres). The extract is washed to neutral- ity with water, anhydrified with sodium sulfate; the organic solvent is then removed by distillation under vacuum and the raw product is purified by chromatography on a silica gel column, eluting with hexane/ethyl acetate 65:35. 35 g of a dense oil are obtained, which solidifies after a few days giving a white product with a melting point of 66-69°C.
1H-NMR (CDCl3): δ 3,68 (s, 3H); 3,71 (s, 3H); 3,82 (s, 3H); 5,20 (s, IH); 5,28 (s, 2H); 6,69 (t, IH); 7,16 (d, IH aromatic); 7,21 (d, IH aromatic).
19F-NMR (CDCl3): δ a -121,1 (m, IF); -81,4 (d, 2F). EXAMPLE 2 a) Determination of the herbicidal activity and phyto- toxicity in post-emergence.
The herbicidal activity in post-emergence of the compositions of the invention was evaluated according to the following operating procedures.
The vegetable species of interest (weeds or crops) were planted in vases having an upper diameter of 10 cm, a height of 10 cm and containing sandy earth. Water was added to each vase in a suitable quantity for the germination of the seeds. The vases were then divided into four groups for each weed or crop.
Fifteen days after planting (ten in the case of wheat), i.e. when the weed seedlings and crops, depending on the species, had reached a height of 10-15 cm, the first group of vases was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [A] at a dosage DA.
The second group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [B] at a dosage DB.
The third group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and the composition C according to the present in- vention, containing components [A] and [B] at dosages, DA and DB, respectively.
The fourth group was treated with a hydroacetone solution only, containing acetone at 10% by volume and Tween 20 at 0.5%, and was used as a comparative reference (blank) .
All the vases were kept under observation in a conditioned environment under the following environmental conditions : temperature: 240C; - relative humidity: 60%; photo-period: 16 ore; light intensity: 10,000 lux.
Every two days the vases were uniformly watered to ensure a sufficient humidity degree for a good growth of the plants.
Fifteen days after treatment, the herbicidal activity was evaluated (expressed as a % of the damage observed on the vegetable species) for the composition C (Ec) and for the two components [A] and [B] tested sepa- rately (EA, E5) .
Weeds tested were: Abutilon theophrasti, Amaranthus retroflexus, Amni maius, Capsella bursa pastoris, Cheno- podium album, Convolvulus sepium, Galium aparine, Geranium dissectum, Ipomea purpurea, Matricaria chamomilla, Papaver rhoeas, Polygonum persicaria, Portulaca oleracea, Sida spinosa, Stellaria media, Veronica persica, Viola arvensis, Xanthium italicum, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus galli, Panicum dicothomiflorum, Setaria viridis, Sorgum halepense.
Crops tested were: wheat, barley, maize, soybean, rice, cotton. b) Determination of the herbicidal activity and phyto- toxicity in pre-emergence . The herbicidal activity in pre-emergence of the compounds of the invention was evaluated according to the following operating procedures.
The vegetable species of interest (weeds or crops) were planted in vases having an upper diameter of 10 cm, a height of 10 cm and containing sandy earth.
Water was added to each vase in a suitable quantity for the germination of the seeds. The vases were then divided into four groups for each weed or crop.
One day after planting, the first group of vases was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [A] at a dosage DA.
The second group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and component [B] at a dosage DB. The third group was treated with a hydroacetone dispersion containing acetone at 10% by volume, Tween 20 at 0.5%, and the composition C according to the present invention, containing components [A] and [B] at dosages, DA e DB, respectively.
The fourth group was treated with a hydroacetone solution only, containing acetone at 10% by volume and Tween 20 at 0.5%, and was used as a comparative reference (blank) .
All the vases were kept under observation in a conditioned environment under the following environmental conditions : temperature: 240C; relative humidity: 60%; - photo-period: 16 ore; light intensity: 10,000 lux.
Every two days the vases were uniformly watered to ensure a sufficient humidity degree for a good growth of the plants. Four weeks after treatment, the herbicidal activity was evaluated (expressed as a % of the damage observed on the vegetable species) for the composition (E0) and for the two components [A] and [B] tested separately (EA, EB) • Weeds tested were: Abutilon theophrasti, Amaranthus retroflexus, Amni maius, Capsella bursa pastoris, Cheno- podium album, Convolvulus sepium, Galium aparine, Geranium dissectum, Ipomea purpurea, Matricaria chamomilla, Papaver rhoeas, Polygonum persicaria, Portulaca oleracea, Sida spinosa, Stellaria media, Veronica persica, Viola arvensis, Xanthium italicum, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus galli, Panicum dicothomiflorum, Setaria viridis, Sorgum halepense . Crops tested were: wheat, barley, maize, soybean, rice, cotton.
For both the post-emergence and pre-emergence treatment, a synergistic effect was observed each time the experimental herbicidal activity of the composition, Ec, proved to be higher than that calculated applying the Colby formula ("Weeds", 15 (1967), pages 20-22):
Eteor = EA + EB - Ej x E8 /100 wherein: Eteor = activity calculated for the composition consisting of [A] at a dosage DA + [B] at a dosage DB;
EA = activity observed for [A] at a dosage DA; EB = activity observed for [B] at a dosage DB.
In Table are reported the compositions for which a remarkable synergistic effect (Ec/Eteor > 1,10) against some important weeds in post-emergence or pre-emergence treatments, was observed. Table
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001

Claims

1. Synergistic herbicidal compositions comprising a component [A] and a component [B] , wherein the component [A] is the compound having formula (I)
Figure imgf000032_0001
(I) methyl (E) -4- [2-chloro-5- (4-chloro-5-difluoro-methoxy-1- methylpyrazol-3-yl) -4-fluorophenoxy] -3-methoxy-but-2- enoate, and component [B] consists of at least one product selected from the following herbicides: [1] acetochlor (2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6- methylphenyl) acetamide) ;
[2] alachlor (2-chloro-N- (2, 6-diethylphenyl) -N- (methoxy- methyl) acetamide) ; [3] amidosulfuron (N- [ [ [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] amino] sulfonyl] -N-methylmethanesulfon- amide) ;
[4] atrazine ( 6-chloro-N-ethyl-N ' - ( 1-methylethyl) -1, 3, 5- triazine-2, 4-diamine) ; [5] beflubutamid (2- [4-fluoro-3- (trifluoromethyl) - phenoxy] -N- (phenylmethyl) butanamide) ; [6] bensulfuron-methyl (methyl [ [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] - benzoate) ;
[7] bispyribac-sodium (sodium 2, 6-bis [ (4 , 6-dimethoxy-2- pyrimidinyl) oxy] benzoate) ;
[8] bromoxynil ( 3, 5-dibromo-4-hydroxybenzonitrile) ;
[9] chlorimuron-ethyl (ethyl [ [ [ [ (4-chloro-6-methoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate;
[10] chlorotoluron (N ' - (3-chloro-4-methylphenyl) -N, N- dimethylurea) ;
[11] chlorsulfuron (2-chloro-N- [ [ (4-methoxy-6-methyl-l, 3,
5-triazin-2-yl) amino] carbonyl] benzenesulfonamide) ;
[12] clodinafop-propargyl (propynyl {R) -2- [4- [ (5-chloro-
3-fluoro-2-pyridinyl) oxy] phenoxy] propanoate) ; [13] clomazone (2- [ (2-chlorophenyl) methyl] -4 , 4-dimethyl-
3-isoxazolidinone;
[14] diflufenican (N- (2 , 4-difluorophenyl) -2- [3- (trifIu- oromethyl ) phenoxy] -3-pyridinecarboxamide) ;
[15] dimethenamid ( [RS) -2-chloro-N- (2 , 4-dimethyl-3- thienyl) -N- (2-methoxy-l-methylethyl) acetamide) ;
[16] diuron (N' - (3, 4-dichlorophenyl) -N, N-dimethylurea) ;
[17] ethoxysulfuron (1- (4 , 6-dimethoxypyrimidin-2-yl) -3-
(ethoxyphenoxysulfonyl) urea) ;
[18] fenoxaprop-P ( (R) -2- [4- [ ( 6-chloro-2-benzoxazolyl) - oxy] phenoxy] propanoic acid) and its ethyl ester; [19] flufenacet (N- (4-fluorophenyl) -N- (1-methylethyl) -2- [ [5- (trifluoromethyl) -1,3, 4-thiadiazol-2-yl] oxy] - acetamide) ;
[20] fluometuron (N, N-dimethyl-N' - [3- (trifluoromethyl) - phenyl] urea;
[21] fluroxypyr ( [4 (4-amino-3, 5-dichloro-6-fluoro-2- pyridinyl) oxy] acetic acid);
[22] glufosinate (ammonium (±) -2-amino-4- (hydroxymethyl- phosphinyl) butanoate) ; [23] glyphosate (N- (phosphonomethyl) glycine) and its salts;
[24] halosulfuron (3-chloro-5- [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-lH- pyrazole-4-carboxylic acid) and its methyl ester; [25] imazamox (2- [4 , 5-dihydro-4-methyl-4- ( 1-methylethyl) -
5-oxolH-imidazol-2-yl] -5- (methoxymethyl) -3- pyridinecarboxylic acid;
[26] ioxynil (4-hydroxy-3, 5-diiodobenzonitrile) ;
[27] isoproturon (N, N-dimethyl-N '- [4- (1-methylethyl) - phenyl] urea) ;
[28] isoxaflutole ( (5-cyclopropyl-4-isoxazolyl) - [2-
(methylsulfonyl) -4- (trifluorometyl) phenyl]methanone) ;
[29] linuron (N ' - (3, 4-dichlorophenyl) -N-methoxy-N-methyl- urea) ; [30] MCPA ( (4-chloro-2-methylphenoxy) acetic acid) and its thioethyl ester;
[31] MCPB (4- (4-chloro-2-methylphenoxy)butanoic acid);
[32] mesotrione (2- [4- (methylsulfonyl) -2-nitrobenzoyl] - 1, 3-cyclohexandione) ; [33] metolachlor (2-chloro-N- (2-ethyl-6-methylphenyl) -N-
(2-methoxy-l-methylethyl) acetamide) ;
[34] S-metolachlor (mixture of two enantiomers of metolachlor, containing 80-100% of 2-chloro-N- (2-ethyl-6- methylphenyl) -N- [ (IS) -2-methoxy-l-methylethyl] - acetamide) ;
[35] metribuzin (4-amino-β- ( 1, 1-dimethylethyl) -3- (methyl- thio) -1,2, 4-triazin-5 (4H) -one) ;
[36] metsulfuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] - sulfonyl] -benzoate) ;
[37] MSMA (monosodium methyl arsonate) ;
[38] orthosulfamuron (2- [ [ [ [ [ (4 , 6-dimethoxy-2-pyrimidin- yl) amino] carbonyl] amino] sulfonyl] amino-N, N-dimethyl- benzamide) ; [39] pendimethalin (N- (1-ethylpropyl) -3, 4-dimethyl-2, 6- dinitrobenzenamine) ;
[40] penoxsulam (2- (2, 2-difluoroethoxy) -N- (5, 8-dimethoxy)
[1,2, 4]triazolo[l, 5-c] pyrimidin-2-yl) -6- (trifluoromethyl) benzenesulfonamide) ; [41] pethoxamid (2-chloro-N- (2-ethoxyethyl) -N- (2-methyl- 1-phenyl-l-propenyl) acetamide) ;
[42] picolinafen (N- (4-fluorophenyl) -6- [3- (trifluoro- methyl) phenoxy] -2-pyridinecarboxamide) ;
[43] pinoxaden (8- (2, β-diethyl-4-methylphenyl) -1, 2 , 4 , 5- tetrahydro-7-oxo-7H-pyrazolo [1, 2-d] [1, 4 , 5] oxadiazepin-9- yl 2, 2-dimethylpropanoate) ;
[44] prometryn (N, N' -bis (1-methylethyl) -6- (methylthio) - 1, 3, 5-triazine-2 , 4-diamine;
[45] propachlor (2-chloro-N- (methylethyl) -N-phenyl- acetamide) ;
[46] propanil (N- (3, 4-dichlorophenyl) propanamide) ;
[47] propoxycarbazone (methyl 2- [ [ [ (4 , 5-dihydro-4-methyl- 5-oxo-3-propoxy-lH-l, 2, 4-triazol-l-yl) carbonyl] amino] - sulfonyl] benzoate) ; [48] sulcotrione (2- [2-chloro-4- (methylsulfonyl) - benzoyl] -1, 3-cyclohexanedione) ;
[49] sulfosulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] -2- (ethylsulfonyl) imidazo [1, 2-a] pyridin-3- sulfonamide) ; [50] terbuthylazine ( 6-chloro-N- ( 1, 1-dimethylethyl) -N ' - ethyl-1, 3, 5-triazine-2, 4-diamine) ;
[51] thifensulfuron-methyl (methyl 3- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] - 2-thiophenecarboxylate) ; [52] triasulfuron (2- (2-chloroethoxy) -N- [ [ ( 4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfon- amide) ;
[53] tribenuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6-methyl- 1, 3, 5-triazin-2-yl) methylamino] carbonyl] amino] - sulfonyl]benzoate) ;
[54] trifloxysulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidin-2- yl) amino] carbonyl] -3- (2,2, 2-trifluoroethoxy) -2-pyridine- sulfonamide) ; [55] trifluralin (2, 6-dinitro-N, N-dipropyl-4- (trifluoro- methyl ) benzeneamine ).
2. The synergistic herbicidal compositions according to claim 1, characterized in that component [B] is selected from bromoxynil, diflufenican, flufenacet, glyphosate, ioxynil, isoproturon, mesotrione, S-metolachlor .
3. The synergistic herbicidal compositions according to claim 1, characterized in that the weight quantity of component [A] is such as to ensure applicative dosages of the compound (I) ranging from 0,5 to 200 g/ha.
4. The synergistic herbicidal compositions according to claim 3, characterized in that the applicative dosages of the compound (I) range from 1 to 100 g/ha.
5. The synergistic herbicidal compositions according to claim 1, characterized in that the applicative dosages of the component (s) [B] range from 1 to 10,000 g/ha.
6. The synergistic herbicidal compositions according to claim 5, characterized in that the applicative dosages of the component (s) [B] range from 10 to 5,000 g/ha.
7. The synergistic herbicidal compositions according to claim 1, characterized in that weight ratio between the quantity of component [A] and the quantity of compo- nent(s) [B] ranges from 1:0.1 to 1:10,000.
8. The synergistic herbicidal compositions according to claim 7, characterized in that the weight ratio ranges from 1:1 to 1:1,000.
9. The synergistic herbicidal compositions according to claim 1, characterized in that they consist of formulations in the form of dry powders, wettable powders, emulsifying concentrates, micro-emulsions, pastes, granulates, solutions, suspensions.
10. The synergistic herbicidal compositions according to claim 9, characterized in that they consist of formulations already prepared containing component [A] and component (s) [B], in the desired ratio, or obtained at the moment of use by mixing the relative quantities of compo- nent [A] and component (s) [B], formulated separately.
11. The synergistic herbicidal compositions according to claim 1, characterized in that they also contain further active substances such as, for example, other herbicides, antidotes, fungicides, insecticides, acaricides, fertil- izers, etc.
12. The synergistic herbicidal compositions according to claim 11, characterized in that the further herbicides are selected from: acifluorfen, aclonifen, AKH-7088, ametryn, amicarbazone, amitrole, anilofos, asulam, azafenidin, azimsulfuron, aziprotryne, BAY MKH 6561, benazolin, benfluralin, ben- furesate, bensulide, bentazone, benzfendizone, benzobicy- clon, benzofenap, benzthiazuron, bifenox, bilanafos, bro- macil, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chlometh- oxyfen, chloramben, chlorbromuron, chlorbufam, chlor- flurenol, chloridazon, chlornitrofen, chloroxuron, chlor- propham, chlorthal, chlorthiamid, cinidon ethyl, cinmeth- ylin, cinosulfuron, clethodim, clomeprop, clopyralid, cloransulam-methyl, cumyluron (JC-940), cyanazine, cy- cloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D, 2,4-DB, daimuron, dalapon, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclo- fop, diclosulam, diethatyl, difenoxuron, difenzoquat, di- flufenzopyr, dimefuron, dimepiperate, dimethachlor, di- methametryn, dinitramine, dinoseb, dinoseb acetate, di- noterb, diphenamid, dipropetryn, diquat, dithiopyr, 1- diuron, eglinazine, endothal, EPTC, esprocarb, ethalflu- ralin, ethametsulfuron-methyl, ethidimuron, ethiozin (SMY 1500), ethofumesate, ethoxyfen-ethyl (HC-252), etobenza- nid (HW 52), fentrazaraide, fenuron, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate (JV 485) , flucarbazone-sodium, fluchloralin, flufenpyr ethyl, flumetsulam, flumiclorac-pentyl, flumi- oxazin, flumipropin, fluoroglycofen, fluoronitrofen, flu- poxam, flupropanate, flupyrsulfuron, flurenol, fluridone, flurochloridone, flurtamone, fluthiacet-methyl, fome- safen, foramsulfuron, fosamine, furyloxyfen, haloxyfop, haloxyfop-P-methyl, hexazinone, imazamethabenz, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indano- fan, iodosulfuron, isopropalin, isouron, isoxaben, isoxa- chlortole, isoxapyrifop, KPP-421, lactofen, lenacil, LS830556, mecoprop, mecoprop-P, mefenacet, mesosulfuron, metamitron, metazachlor, methabenzthiazuron, methazole, methoprotryne, methyldymron, metobenzuron, metobromuron, metosulam, metoxuron, molinate, monalide, monolinuron, naproanilide, napropamide, naptalam, NC-330, neburon, ni- cosulfuron, nipyraclofen, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclome- fone, oxyfluorfen, paraquat, pebulate, pentanochlor, pen- toxazone, phenmedipham, picloram, piperophos, preti- lachlor, primisulfuron, prodiamine, profluazol, proglin- azine, prometon, propaquizafop, propazine, propham, pro- pisochlor, propyzamide, prosulfocarb, prosulfuron, pyra- clonil, pyraflufen-ethyl, pyrazogyl (HSA-961), pyrazoly- nate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyribu- ticarb, pyridafol, pyridate, pyriftalid, pyriminobac- methyl, pyrithiobac-sodium, quinclorac, quinmerac, quiza- lofop, quizalofop-P, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulfentrazone, sulfometuron-methyl, 2,3,6-TBA, TCA-sodium, tebutam, tebuthiuron, tepraloxy- dim, terbacil, terbumeton, terbutryn, thenylchlor, thi- azafluron, thiazopyr, thidiazimin, thiobencarb, tiocarba- zil, tioclorim, tralkoxydim, triallate, triaziflam, triclopyr, trietazine, triflusulfuron-methyl, tritosulfu- ron, UBI-C4874, vernolate.
13. The synergistic herbicidal compositions according to claim 11, characterized in that the concentration of ac- tive substances, also comprising [A] + [B] , ranges from 1 to 90%.
14. The synergic herbicidal compositions according to claim 13, characterized in that the concentration ranges from 5 to 75%.
15. Use of synergistic herbicidal compositions comprising a component [A] and a component [B] , wherein the component [A] is the compound having formula (I)
Figure imgf000042_0001
methyl (E) -4- [2-chloro-5- (4-chloro-5-difluoro-methoxy-1- methylpyrazol-3-yl) -4-fluorophenoxy] -3-methoxy-but-2- enoate, and component [B] consists of at least one prod- uct selected from the following herbicides:
[1] acetochlor (2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6- methylphenyl) acetamide) ;
[2] alachlor (2-chloro-N- (2, 6-diethylphenyl) -N- (methoxy- methyl) acetamide) ; [3] amidosulfuron (N- [ [ [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] amino] sulfonyl] -N-methylmethanesulfon- amide) ;
[4] atrazine ( 6-chloro-N-ethyl-N ' - (1-methylethyl) -1, 3, 5- triazine-2, 4-diamine) ; [5] beflubutamid (2- [4-fluoro-3- (trifluoromethyl) - phenoxy] -N- (phenylmethyl) butanamide) ;
[6] bensulfuron-methyl (methyl [ [ [ [ [ (4, 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] - benzoate) ; [7] bispyribac-sodium (sodium 2, β-bis [ (4 , 6-dimethoxy-2- pyrimidinyl) oxy] benzoate) ;
[8] bromoxynil (3, 5-dibromo-4-hydroxybenzonitrile) ;
[9] chlorimuron-ethyl (ethyl [ [ [ [ (4-chloro-6-methoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate; [10] chlorotoluron (N ' - (3-chloro-4-methylphenyl) -N, N- dimethylurea) ;
[11] chlorsulfuron (2-chloro-N- [ [ (4-methoxy-β-methyl-l, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfonamide) ;
[12] clodinafop-propargyl (propynyl (R) -2- [4- [ (5-chloro- 3-fluoro-2-pyridinyl) oxy] phenoxy] propanoate) ;
[13] clomazone (2- [ (2-chlorophenyl) methyl] -4 , 4-dimethyl- 3-isoxazolidinone;
[14] diflufenican (N- (2, 4-difluorophenyl) -2- [3- (trifIu- oromethyl ) phenoxy] -3-pyridinecarboxamide ) ; [15] dimethenamid ( (RS) -2-chloro-N- (2, 4-dimethyl-3- thienyl) -N- (2-methoxy-l-methylethyl) acetamide) ;
[16] diuron (N' - (3, 4-dichlorophenyl) -N, N-dimethylurea) ;
[17] ethoxysulfuron ( 1- (4, 6-dimethoxypyrimidin-2-yl) -3-
(ethoxyphenoxysulfonyl) urea) ; [18] fenoxaprop-P ( (R) -2- [4- [ ( 6-chloro-2-benzoxazolyl) - oxy] phenoxy] propanoic acid) and its ethyl ester;
[19] flufenacet (N- (4-fluorophenyl) -N- (1-methylethyl) -2-
[ [5- (trifluoromethyl) -1, 3, 4-thiadiazol-2-yl] oxy] - acetamide) ; [20] fluometuron (N, N-dimethyl-N' - [3- (trifluoromethyl) - phenyl] urea;
[21] fluroxypyr ( [4 (4-amino-3, 5-dichloro-6-fluoro-2- pyridinyl) oxy] acetic acid);
[22] glufosinate (ammonium (±) -2-amino-4- (hydroxymethyl- phosphinyl) butanoate) ;
[23] glyphosate (N- (phosphonomethyl) glycine) and its salts;
[24] halosulfuron (3-chloro-5- [ [ [ [ (4 , 6-dimethoxy-2- pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-lH- pyrazole-4-carboxylic acid) and its methyl ester;
[25] imazamox (2- [4 , 5-dihydro-4-methyl-4- (1-methylethyl) -
5-oxolH-imidazol-2-yl] -5- (methoxymethyl) -3- pyridinecarboxylic acid;
[26] ioxynil (4-hydroxy-3, 5-diiodobenzonitrile) ; [27] isoproturon (N, N-dimethyl-N '- [4- ( 1-methylethyl) - phenyl] urea) ;
[28] isoxaflutole ( (5-cyclopropyl-4-isoxazolyl) - [2-
(methylsulfonyl) -4- (trifluorometyl) phenyl] methanone) ;
[29] linuron (N ' - (3, 4-dichlorophenyl) -N-methoxy-N-methyl- urea) ;
[30] MCPA ( (4-chloro-2-methylphenoxy) acetic acid) and its thioethyl ester;
[31] MCPB (4- (4-chloro-2-methylphenoxy) butanoic acid) ;
[32] mesotrione (2- [4- (methylsulfonyl) -2-nitrobenzoyl] - 1, 3-cyclohexandione) ; [33] metolachlor (2-chloro-N- (2-ethyl-6-methylphenyl) -N-
(2-methoxy-l-methylethyl) acetamide) ;
[34] S-metolachlor (mixture of two enantiomers of metolachlor, containing 80-100% of 2-chloro-N- (2-ethyl-6- methylphenyl) -N- [ (IS) -2-methoxy-l-methylethyl] - acetamide) ;
[35] metribuzin (4-amino-6- (1, 1-dimethylethyl) -3- (methyl- thio) -1, 2, 4-triazin-5 (4H) -one) ;
[36] metsulfuron-methyl (methyl 2- [ [ [ [ (4-methoxy-β- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] - sulfonyl] -benzoate) ;
[37] MSMA (monosodium methyl arsonate) ;
[38] orthosulfamuron (2- [ [ [ [ [ (4 , 6-dimethoxy-2-pyrimidin- yl) amino] carbonyl] amino] sulfonyl] amino-N, N-dimethyl- benzamide) ;
[39] pendimethalin (N- (1-ethylpropyl) -3, 4-dimethyl-2, 6- dinitrobenzenamine) ;
[40] penoxsulam (2- (2, 2-difluoroethoxy) -N- (5, 8-dimethoxy)
[l,2,4]triazolo[l, 5-c] pyrimidin-2-yl) -6- (trifluoromethyl) benzenesulfonamide) ;
[41] pethoxamid (2-chloro-N- (2-ethoxyethyl) -N- (2-methyl- 1-phenyl-l-propenyl) acetamide) ;
[42] picolinafen (N- (4-fluorophenyl) -6- [3- (trifluoromethyl ) phenoxy] -2-pyridinecarboxamide ) ; [43] pinoxaden (8- (2, 6-diethyl-4-methylphenyl) -1, 2 , 4 , 5- tetrahydro-7-oxo-7H-pyrazolo [1, 2-d] [1,4,5] oxadiazepin-9- yl 2, 2-dimethylpropanoate) ;
[44] prometryn (N, N' -bis (1-methylethyl) -6- (methylthio) - 1, 3, 5-triazine-2, 4-diamine; [45] propachlor (2-chloro-N- (methylethyl) -N-phenyl- acetamide) ;
[46] propanil (N- (3, 4-dichlorophenyl) propanamide) ;
[47] propoxycarbazone (methyl 2- [ [ [ (4 , 5-dihydro-4-methyl- 5-oxo-3-propoxy-lH-l, 2, 4-triazol-l-yl) carbonyl] amino] - sulfonyl] benzoate) ;
[48] sulcotrione (2- [2-chloro-4- (methylsulfonyl) - benzoyl] -1, 3-cyclohexanedione) ;
[49] sulfosulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidinyl) - amino] carbonyl] -2- (ethylsulfonyl) imidazo [ 1, 2-a] pyridin-3- sulfonamide) ;
[50] terbuthylazine ( 6-chloro-N- (1, 1-dimethylethyl) -N ' - ethyl-1, 3, 5-triazine-2 , 4-diamine) ;
[51] thifensulfuron-methyl (methyl 3- [ [ [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] - 2-thiophenecarboxylate) ;
[52] triasulfuron (2- (2-chloroethoxy) -N- [ [ (4-methoxy-6- methyl-1, 3, 5-triazin-2-yl) amino] carbonyl] benzenesulfon- amide) ;
[53] tribenuron-methyl (methyl 2- [ [ [ [ (4-methoxy-6-methyl- l,3,5-triazin-2-yl) methylamino] carbonyl] amino] - sulfonyl]benzoate) ;
[54] trifloxysulfuron (N- [ [ (4 , 6-dimethoxy-2-pyrimidin-2- yl) amino] carbonyl] -3- (2,2, 2-trifluoroethoxy) -2-pyridine- sulfonamide) ; [55] trifluralin (2 , 6-dinitro-N, N-dipropyl-4- (trifluoro- methyl ) benzeneamine ) for the control of weeds in agricultural crops.
16. Use of the synergistic herbicidal compositions according to any of the claims from 2 to 14, for the con- trol of weeds in agricultural crops.
17. Use according to claim 15 or 16 for the control, in both post-emergence and in pre-emergence, of monocotyle- donous and dicotyledonous weeds and/or for the treatment of agricultural crops.
18. Use according to claim 15 or 16 for the control of Abutilon theophrasti, Adonis spp. , Ambrosia spp., Alisma plantago, Amaranthus spp., Amni maius, Anagallis arven- sis, Anthemis spp. , Aphanes arvensis, Atriplex patula, Bidens pilosa, Capsella bursa-pastoris, Chenopodium al- bum, Convolvulus sepium, Datura stramonium, Euphorbia spp., Fumaria officinalis, Galeopsis tetrahit, Galinsoga ciliata, Galium aparine, Geranium spp., Helianthus spp., Ipomea spp., Kochia scoparia, Lamium spp., Matricaria spp., Monochoria vaginalis, Myosotis arvensis, Papaver rhoeas, Phaseolus aureus, Polygonum spp., Portulaca ol- eracea, Raphanus raphanistrum, Rumex crispus, Senecio vulgaris, Sesbania exaltata, Sida spinosa, Sinapis arven- sis, Solanum nigrum, Sonchus spp., Stellaria media, Thlaspi arvense, Veronica spp., Vicia spp., Viola spp., Xanthium spp., Aegilops tauschii, Alopecurus myosuroides, Apera spp., Avena fatua, Brachiaria spp., Bromus spp., Cenchrus echinatus, Commelina bengalensis, Cynodon dacti- lon, Cyperus spp., Digitaria spp., Echinocloa spp., Eleu- sine indica, Elymus repens, Eragrostis pilosa, Eriochloa villosa, Fimbristylis spp. , Heleocaris avicularis, Heteranthera spp., Leptochloa spp., Lolium spp., Panicum spp., Phalaris spp., Poa spp., Scirpus spp., Setaria viridis, Sorghum spp..
19. Use according to claim 15 or 16 for the treatment of wheat (Triticum sp.), barely (Hordeum vulgare) , maize
(Zea mays), soybean (Glycine max), rice (Oryza sativa) , cotton (Gossypium hirsutum) , sugarcane (Saccharum offici- narum) .
20. A method for the control of weeds in cultivated ar- eas by means of the application of synergistic herbicidal compositions according to any of the claims from 1 to 14.
PCT/EP2007/001706 2006-03-06 2007-02-26 New synergistic herbicidal compositions Ceased WO2007101587A1 (en)

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AU2007222703A AU2007222703A1 (en) 2006-03-06 2007-02-26 New synergistic herbicidal compositions
EP07722959A EP1998616A1 (en) 2006-03-06 2007-02-26 New synergistic herbicidal compositions
BRPI0708418-8A BRPI0708418A2 (en) 2006-03-06 2007-02-26 synergistic herbicidal compositions, use of memas, and method for weed control in cultivated areas
CA002643719A CA2643719A1 (en) 2006-03-06 2007-02-26 New synergistic herbicidal compositions
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EP1961304A1 (en) * 2007-02-23 2008-08-27 Isagro Ricerca S.r.l. High efficiency formulation with a reduced environmental impact
CN101971841A (en) * 2010-05-24 2011-02-16 北京颖新泰康国际贸易有限公司 Herbicide composition and application thereof
US10085451B2 (en) 2010-08-30 2018-10-02 Dow Agrosciences Llc Synergistic herbicidal composition containing penoxsulam and bentazon
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CN104137841A (en) * 2014-08-04 2014-11-12 安徽美兰农业发展股份有限公司 Fluroxypyr-mepthyl, 2,4-D isooctyl ester and florasulam compound suspending agent
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KR20180011129A (en) * 2015-06-05 2018-01-31 이 아이 듀폰 디 네모아 앤드 캄파니 2- (phenyloxy or phenylthio) pyrimidine derivatives as herbicides
KR102651771B1 (en) 2015-06-05 2024-03-28 에프엠씨 코포레이션 2-(phenyloxy or phenylthio)pyrimidine derivatives as herbicides
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WO2018119338A1 (en) 2016-12-22 2018-06-28 Fmc Corporation Mixtures of beflubutamid or optically enriched forms thereof with a second herbicide
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