• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Herbicidal formulation comprising diclofop-methyl and clodinafop-propargyl. The present invention relates to a synergistic herbicidal formulation comprising diclofop-methyl and clodinafop-propargyl and to a method of controlling weeds in wheat, rye and triticale crops. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2573714A1
    申请号:ES201531667
    申请日:2015-11-18
    公开日:2016-06-09
    发明作者:José Fernando Trindade Dos Santos NEVES；Juan Antonio BAVIERA MORENO
    申请人:Sapec Agro S A；SAPEC AGRO SA；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Herbicidal formulation comprising diclofop-methyl and clodinafop-propargil Field of the invention
    The present invention relates to a herbicidal formulation, comprising diclofop-methyl and clodinafop-propargyl, and its use in crop protection.
    Background of the invention
    The compound (I), diclofop-methyl [IUPAC: (RS) -2- [4- (2,4-dichlorophenoxy) phenoxy] methyl propionate], is an ester of an aryloxyphenoxypropionic acid, with the following structural formula:
    image 1
    CH3
    (I)
    Diclofop-methyl is a systemic herbicide absorbed essentially by the leaves, and quickly transported to the growing areas of the leaves and stems. At the level of the biochemical mode of action, it interferes with the biosynthesis of fatty acids. It is indicated for the post-emergency control of infesting grasses in wheat, triticale, barley and sugar and fodder beet crops. It was first described by Hoechst in 1971 (document DE2136828).
    The compound (II), clodinafop-propargyl [IUPAC: (R) -2- [4- (5-chloro-3-fluoro-2-
    pyridyloxy) phenoxy] prop-2-inyl propionate], is also an ester of an aryloxyphenoxypropionic acid, with the following structural formula:
    image2
    CH3
    OR
    "-" '^ Ch
    O (II)
    Clodinafop-propargyl is a systemic herbicide, indicated for control in
    Possession of infesting grass in the cultivation of wheat, rye and triticale. It was first described by Ciba-Geigy in 1982 (document EP083556B1).
    It is known that the application of certain herbicides can cause explicit damage through 5 phytotoxicity phenomena in some crops; To solve this problem, substances known as antidotes can be associated with the herbicides, which can protect the crops, by activating their metabolism and thus increasing the degradation of the herbicidal molecule inside the plant and corresponding deactivation without, at the same time, influencing substantially in the herbicidal action on the infestants that are intended to be chemically controlled.
    One of these substances is the compound (IN), cloquintocet-mexyl [IUPAC: (5-chloroquinolin-8-yloxy) 1-methylhexyl acetate], whose structural formula is as follows:
    fifteen
    image3
    It was first described by Ciba-Geigy in 1983 (document EP094349B1).
    Patent EP0191736B1 refers to a method of treating crops 20 against the harmful effects of herbicides of the acid esters family 2- [4- (5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propionic as, for example, clodinafop-propargil, which includes the application to plants or to soil of antidotes with the general formula (IV)
    R
    3
    R
    4
    image4
    (IV)
    which includes cloquintocet-mexyl (the case in which R1, R2, R4, R5 and R6 are hydrogen, R3 is
    chlorine, A represents CH2 and Z corresponds to the group C (O) O-CH (CH3) - (CH2) 4-CH3). The patent also refers to compositions comprising a compound of the family of esters of 2- [4- (5-doro-3-fluoro-2-pyridyloxy) phenoxy] propionic acid and an antidote with the general formula (IV) .
    5
    EP1555876B1 discloses the use of compounds with the general formula (V)
    image5
    R4 '
    2
    (V)
    10 in particular mefenpyr-diethyl (in which (R1) n is 2,4-dichloro, R3 is methyl and R4 and R2 are both ethyl), to increase control over the infestants of one or more herbicides of the family of aryloxyphenoxypropionates. The patent presents a list of twenty-one compounds of the family referred to, but does not refer specifically to the combination of diclofop-methyl with clodinafop-propargyl.
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    EP1585392B1 refers to the use of herbicides, in particular aryloxyphenoxypropionates or cyclohexanedione oximes or their mixtures as herbicides, without suggesting the association of diclofop-methyl with clodinafop-propargyl.
    20 The publication "Influence of vegetable and mineral oils on the efficacy of some postemergence herbicides for grass weed control in wheat", Journal of Pesticide Science (Tokyo, Japan) (2006), 31 (3), pages 339-343, se It refers to tests in which the effect of the addition of vegetable or mineral oils on the efficacy of herbicides applied in post-emergence in wheat cultivation was studied, during which one of the products under test was a diclofop-methyl mixture with phenoxaprop-p-ethyl There is no reference or suggestion concerning the use of the mixture of diclofop-methyl with clodinafop-propargyl.
    Detailed description of the invention
    30 It is common practice in the area of crop protection to develop formulations
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    that contain several active substances, with quite different purposes such as the management of resistant biotype development phenomena, the broadening of the biological action spectrum, avoiding successive applications of phytopharmaceutical products, etc. In general, users prefer Kquidas formulations, due to the ease in the operations of measurement, dilution in water and pulverization.
    Surprisingly, it was verified that by applying a combined composition of diclofop-methyl and clodinafop-propargil in post-emergence in wheat cultivation in the control of infesting grasses, in which the dose applied per hectare was approximately 30% of the dose submitted to test of pure diclofop-methyl and of approximately 40% of the dose tested for pure clodanifop-propargyl, results of biological efficacy similar to those obtained with 100% of the dose tested of any one of the components were obtained , which indicates a synergistic behavior of the mixture in relation to the active substances that compose it.
    The infesting grasses referred to in the present invention are, for example, Avena sp, Lolium sp, Alopecurus sp, Phalaris sp and Poa sp.
    An objective of the present invention is to provide a new synergistic herbicidal formulation, which comprises, in addition to the usual adjuvants, the active substances diclofop-methyl and clodinafop-propargyl.
    In an embodiment of the invention, the composition further comprises an antidote.
    Examples of antidotes that can be used in the present invention are cloquintocetmexyl, mefenpyr-diethyl and pheclorazol-ethyl, preferably chloquintocet-mexyl and mefenpyr-diethyl, more preferably chloquintecet-mexyl.
    In one embodiment of the invention, the herbicidal formulation comprises diclofop-methyl, in a concentration range between 100 and 400 g / liter, clodinafop-propargyl, in a concentration range between 10 and 40 g / liter, and cloquintocet- mexyl, in a concentration range between 2.50 and 10 g / liter.
    Preferably, the formulation comprises diclofop-methyl, in a range of
    concentrations between 200 and 400 g / liter, clodinafop-propargil, in a range of
    concentrations between 20 and 40 g / liter, and cloquintocet-mexyl, in a range of
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    concentrations between 5 and 10 g / liter.
    More preferably, the formulation comprises 250 g / liter of diclofop-methyl, 25 g / liter of clodinafop-propargyl and 6.25 g / liter of cloquintocet-mexyl.
    The formulation according to the invention can be presented in the form of an emulsion concentrate or in the form of an oil-in-water emulsion.
    Emulsion concentrates are prepared by dissolving the active substances in organic solvents, such as mixtures of aromatic compounds C9 to C12, available under the trade name of Solvesso® 200 ND from Exxon Mobil and adding one or more non-ionic or anionic surfactants. Examples of non-ionic surfactants are polyethylene glycol esters of fatty acids, polyglycol ethers of fatty alcohols, or polyglycol ethers of alkylaryl compounds, with polyethylene glycol esters of fatty acids being preferred, particularly ethoxylated castor oil, available under the name commercial of Alkamuls® OR / 36 from Rhodia. Preferred anionic surfactants are alkylbenzenesulfonates, in particular the calcium salt of dodecylbenzenesulfonic acid, commercially available under the trade name Rhodacal® 70 / B from Rhodia.
    Oil-in-water emulsions are obtained according to the following procedure:
    a) prepare an oily phase containing the active substances and, if present, the antidote dissolved in a solvent, for example a mixture of aromatic compounds C9 to C12 (Solvesso® 200 ND of Exxon Mobil), and add one or more surfactants Especially preferred are polymeric non-ionic surfactants, commercially available under the name of Croda's Atlox® 4914 and Atlas® G5002L;
    b) preparing an aqueous phase containing a thickening agent, xanthan gum, an antifreeze agent, such as glycerol, an antifoaming agent, water and a bactericidal agent, such as 1,2-benzothiazolin-3-one, available under the name commercial Proxel® GXL, from Arch Biocides; Y,
    c) add with agitation, the oily phase to the aqueous phase in a vessel equipped with a high shear mixer.
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    Examples
    The following examples should be understood as illustrative, not intended in any way to limit the present invention.
    Example 1
    A formulation in the form of emulsion concentrate is made using the following composition:
    Diclofop-methyl (expressed as 100%) 250 g / liter
    Clodinafop-propargil (expressed as 100%) 25 g / liter
    Cloquintocet-mexyl (expressed as 100%) 6.25 g / liter
    Alkamuls® OR / 36 60 g / liter
    Rhodacal® 70 / B 60 g / liter
    10 g / liter antifoaming agent
    Solvesso® 200 ND up to 1 liter.
    Example 2
    A formulation in the form of an emulsion of oil in water is carried out using the following composition and procedure:
    Oily phase:
    Diclofop-methyl (expressed as 100%) 100 g / liter
    Clodinafop-propargil (expressed as 100%) 10 g / liter
    Cloquintocet-mexyl (as 100%) 2.5 g / liter
    Atlas® G-5002L 25 g / liter
    Atlox® 4914 25 g / liter
    Solvesso® 200 ND 350 g / liter
    Aqueous phase:
    Xanthan gum 2 g / liter
    1 g / liter antifoaming agent
    Glycerol 45 g / liter
    Proxel® GXL 1 g / liter
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    Water up to 1 liter (approximately 465 g / liter)
    The components of the oily and aqueous phases are mixed together with gentle agitation until two solutions are obtained; In a vessel equipped with a high shear mixer, the oily phase is added with stirring to the aqueous phase to obtain a homogeneous dispersion of oily phase drops in a continuous aqueous phase.
    Another objective of the present invention is to provide a control procedure for infesting grasses in wheat, rye and triticale crops, which comprises applying, in an emergency, the formulation according to the invention diluted in a sufficient amount of water (usually 200 to 600 liters per hectare in land application by tractor) to guarantee homogeneous application on the culture of 200 to 300 g of diclofop-methyl and 20 to 30 g of clodinafop-propargyl.
    Synergistic effect
    A greenhouse study was conducted to assess the existence of a synergistic effect of the binary formulation compared to its components. Avena fatua and Lolium multiflornm were used as examples of infestants.
    The formulation used was the formulation described in example 1.
    The study consisted of a previous trial, in which the efficacy data obtained were used to determine the values of ER50 (application dose, in g / ha, which results in an average efficacy value of 50%) and ER70 for the binary mixture, and a main test performed with the application doses obtained in the previous test.
    The formulations containing each of the active substances and the binary mixture in water were diluted and applied with a flow rate of 400 liters per hectare on the infestants. The tests were performed with 10 repetitions per group.
    After application, the infestants were placed in a greenhouse with controlled temperature, humidity and lighting, in a random manner and relocated at the end of 7 and 14 days, to minimize any environmental difference in the growth of the infestants. The efficacy was evaluated at the end of 7, 14 and 21 days.
    To quantify the synergistic effect resulting from the association of the active substances, the method described by Colby was used (Colby, SR, "Calculating synergistic and antagonistic response of herbicide compositions", Weeds 15, p. 20-22, 1967), according to which the expected efficiency (EE) for the mixture of active ingredients 5 determined using the Colby formula is compared:
    EE = x + y - (xy) / 100
    in which:
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    -EE is the expected efficiency, in%, using the mixture of active compounds A and B at concentrations a and b;
    -x is the efficiency, in%, using the active compound A in the concentration a;
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    -y is the efficiency, in%, using active compound B in concentration b; with the effectiveness observed experimentally.
    20 If the observed efficiency (E) exceeds that calculated (EE), there is a synergistic effect.
    Pretest:
    Table 1 presents the application doses corresponding to ER50 and ER70 for each of the 25 infestants.
     Application dose [l of product / ha]
     Infesting  ER Formulation according to example 1
     Avena fatua  ER50 0.5
     m X) -if 0  0.8
     Lolium  ER50 0.4
     multiflorum  m X) -si 0 0.6
    Table 1 - Application dose for each infestant
    Main Test:
    The main trial was carried out taking into account the application doses obtained during the previous test and provided the following efficacy results:
     Treatment    Time (days) Average efficiency (%) Expected efficiency according to Colby (%) A (%)
     Control    twenty-one - - -
     Diclofop-methyl  ER50 21 11 - -
     m X) -if 0  21 20 - -
     Clodinafop- Propargyl  ER50 21 19 - -
     m X) -if 0  21 66 - -
     Diclofop-methyl + clodinafop-propargyl  ER50 21 57 27.9 29.1
     m X) -if 0  21 81 72.8 8.2
     Table 2 - Resul  tados for the infesting Avena fatua
     Treatment    Time (days) Average efficiency (%) Expected efficiency according to Colby (%) A (%)
     Control    twenty-one - - -
     Diclofop-methyl  ER50 21 14 - -
     m X) -if 0  21 30 - -
     Clodinafop- Propargyl  ER50 21 34 - -
     m X) -if 0  21 48 - -
     Diclofop-methyl + clodinafop-propargyl  ER50 21 66 43.2 22.8
     m X) -if 0  21 69 63.6 5.4
    Table 3 - Results for the Lolium multiflornm infestant
    From the results presented above it can be concluded that the association of diclofop-methyl and clodinafop-propargil has a synergistic effect with respect to what would be expected taking into account the efficacy of each of the active substances applied in isolation.
    Efficiency and selectivity
    The efficacy and selectivity of a mixture comprising diclofop-methyl and 5 clodinafop-propargyl in the control of infesting grasses after application in
    Posemergence in wheat cultivation.
    The tests were carried out in France, and were carried out according to the Good Experimentation Practices defined by Regulation 1107/2009 of the European Union.
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    Randomized block trials were performed, with 4 repetitions, there being an untreated area next to each treated area.
    Tables 4 to 6 present the results of efficacy for the various grass 15 infestants of wheat cultivation, indicating, for each infestant, the average values of
    efficiency percentage.
     Cultivation: wheat  grams of% effective 55% effective 126
     Infestant: Poa annua  active substance / ha days after days after
     Number of trials: 1    application application
     Diclofop-methyl  756 95.0% 96.3%
     Clodinafop-Propargil +  60 + 92.5% 96.0%
     cloquintocet-mexyl  fifteen
     Diclofop-methyl +  250 + 87.5% 94.3%
     clodinafop-propargil +  25+
     cloquintocet-mexyl  6.25
    Table 4. Efficacy results on Poa annua
     Cultivation: Wheat Infestant: Lolium multiflorum Number of trials: 2  grams of active substance / ha% efficacy 46 days after application% efficiency 126 days after application
     Diclofop-methyl  756 63.1% 70.3%
     Clodinafop-Propargil +  60 + 70.0% 64.7%
     cloquintocet-mexyl  fifteen
     Diclofop-methyl +  250 + 66.9% 67.3%
     clodinafop-propargil +  25+
     cloquintocet-mexyl  6.25
     Table 5.  Efficacy results on Lolium multiflorum
     Cultivation: wheat  grams of% effective 53% effective 115
     Infestant: Alopecurus  active substance / ha days after days after
     myosuroides    application application
     Number of trials: 3
     Diclofop-methyl  756 62.8% 68.8%
     Clodinafop-Propargil +  60 + 64.4% 67.2%
     cloquintocet-mexyl  fifteen
     Diclofop-methyl +  250 + 64.7% 69.6%
     clodinafop-propargil +  25+
     cloquintocet-mexyl  6.25
    Table 6. Efficacy results on Alopecurus myosuroides
    5 None of the trials released signs of phytotoxicity with respect to wheat cultivation. The results in Tables 4 to 6 show that, due to the synergistic effect resulting from the combination of the active substances, it is possible to use lower doses of the active substances (33% of the diclofop-methyl test dose and 42 % of the dose tested by clodinafop-propargil) and obtain efficacy results in the control of wheat-infestants similar to those obtained when 100% of the dose tested of any one is used of the active substances.
    权利要求:
    Claims (10)
    [1]
    5
    [2]
    2.
    [3]
    3.
    10
    [4]
    Four.
    fifteen
    [5]
    5.
    20 6.
    [7]
    7.
    25
    [8]
    8.
    30
    [9]
    9.
    [10]
    10.
    Herbicidal synergistic composition, characterized in that it comprises diclofop-methyl and clodinafop-propargyl.
    Composition according to claim 1, characterized in that it additionally comprises an antidote.
    Composition according to claim 2, characterized in that the antidote is cloquintecet-mexyl.
    Composition according to claim 1, characterized in that it comprises diclofopmethyl, in a concentration range between 100 and 400 g / liter and clodinafop-propargyl, in a concentration range between 10 and 40 g / liter.
    Composition according to claim 4, characterized in that it comprises
    additionally cloquintocet-mexyl, in a concentration range between 2.5 and 10 g / liter.
    Composition according to claim 4, characterized in that it comprises diclofopmethyl, in a concentration range between 200 and 400 g / liter and clodinafop-propargyl, in a concentration range between 20 and 40 g / liter.
    Composition according to claim 6, characterized in that it comprises
    additionally cloquintocet-mexyl, in a concentration range between 5 and 10 g / liter.
    Composition according to claim 6, characterized in that it comprises 250 g / liter of diclofop-methyl and 25 g / liter of clodinafop-propargyl.
    Composition according to claim 8, characterized in that it comprises
    additionally 6.25 g / liter of cloquintocet-mexyl.
    Procedure for the control of infesting grasses in wheat, rye and triticale crops, characterized in that it comprises a step of applying, in post-emergency, the formulation according to claims 1 to 9.
    [11]
    11. Method according to claim 10, characterized in that 200 to 300 g / ha of diclofop-methyl and 20 to 30 g / ha of clodinafop-propargyl are applied.
    5
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    同族专利:
    公开号 | 公开日
    PT108094B|2017-02-13|
    ES2573714B2|2016-11-02|
    ITUB20156258A1|2017-06-03|
    FR3029392A1|2016-06-10|
    GR20150100498A|2016-07-29|
    PT108094A|2016-06-09|
    FR3029392B1|2018-01-12|
    GR1008950B|2017-02-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    ES2360662T3|1996-08-12|2011-06-08|Bayer Cropscience Ag|SYNERGIC COMBINATIONS OF ACTIVE SUBSTANCES FOR THE REPRESSION OF HARMFUL PLANTS IN CULTURES OF USEFUL PLANTS.|
    ES2324472T3|2003-01-06|2009-08-07|Yissum Research Development Company Of The Hebrew University Of Jerusalem|HERBICIDES THAT INHIBIT THE ACTION OF ACETIL-COA CARBOXYLASE IN VEGETABLES FOR USE AS PESTICIDES.|
    US20140031228A1|2012-07-24|2014-01-30|Dow Agrosciences Llc|HERBICIDAL COMPOSITIONS COMPRISING 4-AMINO-3-CHLORO-5-FLUORO-6- PYRIDINE-2-CARBOXYLIC ACID OR A DERIVATIVE THEREOF AND ACETYL-CoA CARBOXYLASE INHIBITORS|
    DE19520839A1|1995-06-08|1996-12-12|Hoechst Schering Agrevo Gmbh|Herbicidal agents containing 4-iodo-2- [3- ureidosulfonyl] benzoic acid esters|
    WO2003034351A2|2001-10-17|2003-04-24|Gary Malcolm Keyser|Security apparatus|
    CN100563108C|2003-03-06|2009-11-25|富士通微电子株式会社|The digital PLL circuit|
    JP2005054627A|2003-08-01|2005-03-03|Denso Corp|Throttle body|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    PT108094|2014-12-09|
    PT108094A|PT108094B|2014-12-09|2014-12-09|HERBICIDE FORMULATION COMPREENDING DICLOFOPE-METHYL AND CLODINAFOPE-PROPARGILO|
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