CA1170854A - Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beet - Google Patents
Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beetInfo
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- CA1170854A CA1170854A CA000381118A CA381118A CA1170854A CA 1170854 A CA1170854 A CA 1170854A CA 000381118 A CA000381118 A CA 000381118A CA 381118 A CA381118 A CA 381118A CA 1170854 A CA1170854 A CA 1170854A
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Case 5-12947/=
Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beet Abstract of the Disclosure The invention relates to a composition which contains, on the one hand, a 4-(3',5'-dichloropyridyl-2'-ox)-.alpha.-phenoxypropionic acid propargyl ester of the formula
Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beet Abstract of the Disclosure The invention relates to a composition which contains, on the one hand, a 4-(3',5'-dichloropyridyl-2'-ox)-.alpha.-phenoxypropionic acid propargyl ester of the formula
Description
85~1 Case 5-12947/=
Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beet ._ The present invention relates to a synergistic composition comprising a combination of herbicides and which is most suitable for selec~ively controlling weeds, especially in crops of sugar beet and fodder beet. The invention also relates to a method of controlling weeds which comprises the use of the novel composition, especially in crops of sugar beet and fodder beet.
The most frequently encountered and most important weeds in crops of sugar beet and fodder beet at the present time are species of the genera Amaranthus (foxtail), Chenopodium (goosefoot), Sinapis (mustard), Panicum (panic grass) and certain Avena species (wild oats).
Excellent postemergence selective herbicides against monocot weeds are 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl esters of the formula I
~Cl ca3 Cl~ --o~ O-CH-CO-Z-CH2-C-.. ...
wherein 7 is oxygen or sulfur.
~ 3 7~85 The two compounds of formula I, viz. 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (Ia) and 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxy-thiopropionic acid propargyl ester (Ib), processes for the production thereof and the use thereof as selective herbicides, are described in European patent publication 3114.
Dicot weeds are often successfully controlled postemergence with 4-amino-3-methyl-6-phenyl[4H]-1,2,4-triazin-5-one (Metamitron) of the formula IIa ~ ~ -C~ (IIa) or with methyl-3-m-tolylcarbamoyloxyphenylcarbamate (Phenmedipham) of the formula IIb -O~C~N~~t~ il-o-C-NH~ CH3 (IIb) Metamitron and its herbicidal activity were described e.g. at the 3rd Int. Meeting of Selective Weed Control in Beet Crops, Paris, 1975. Phenmedipham and its herbicidal properties are reported on e.g. in Abstr. 6th Int. Congr. Pl. Prot., Vienna, 1967, page 433.
Surprisingly, it has now been found that a combination of the two compounds of the formulae I and II, in a ratio varying within specific limits, exerts a synergistic action which is able to control the majority of all important weeds in crops of sugar beet and fodder beet without damaging these crops. The principal weeds in i ~ 7~85'1 these crops, such as species of the dicot Amaranthus, Chenopodium and Sinapis varieties, as well as the monocot Panicum and Avena varieties, are selectively destroyed in the emergent beet crops.
Accordingly, the invention provides a synergistic composition for selectively controlling weeds, which composition comprises, on the one hand, a 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester of the formula I
Cl CH3 (I) Cl~ o ~ O-CH-CO-Z-CH2-C -CH , wherein Z is oxygen or sulfur, and, on the other, 4-amino-3-methyl-6-phenyl~[4H]-1,2,4-triazin-5-one (IIa) or methyl-3-m-tolylcarbamoyloxyphenylcarbamate (IIb), together with carriers and/or other adjuvants, the amount of component (II) being approximately ecIual to, or in excess of, component (I~.
It is surprising that the combination of a compound of the formula I with a compound of the formula II not only brings about an expected aclditive enhancement of the activity spectrum against the customary weeds associated with sugar beet and fodder beet, but gives rise to a synergistic effect which potentiates the action of both components from two points of view.
On the one hand, the rates of application of the single compounds I and II are distinctly reduced while the same good action is retained. On the other hand, the combination also achieves a high degree of weed control where both single compounds .~ r~
~3--117~
have become totally ineffective at too low rates of application.
The consequence is a substantial broadening of the activity spectrum against weeds and an additional increase in the safety margin on application to crops of sugar beet, as is necessary and desirable in the event of unintentional overapplication.
The composition of this invention can also be used for selectively controlling weeds in crops of other dicot plants having similar sensitivity to herbicides and similar weed in~estation.
The herbicidal combination employed in the practice of this invention will preferably contain a compound of the formula (I~ and a compound of the formula (II) in a ratio of 1:1 to 1:4, most preferably 1:1 to 1:2.
~,_ -3a-~7~85' The herbicidal combination has an excellent action against weeds without having any noticeable effects in crops of sugar beet and fodder beet when used in the conventional rates of application o 0.2 to 4 kg/ha, preferably 0.5 to 3 kg/ha.
The present invention also relates to the use of the composition, i.e. to a method of selectively controlling grasses and weeds postemergence in beet crops.
In addition to the novel combination of active ingredients, the composition of this invention also contains suitable carriers and/or other adjuvants. These can be solid or liquid and correspond to the substances conventionally employed in the art of formulation, e.g. natural or regenerated mineral substances, solvents, dispersants a wetting agents, tackifiers, thickerners, binders or fertilisers. Suitable formulations are therefore e.g.
emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granula~es, and also encapsulations in e.g.
polymer substances. The methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances, just like the nature of the compositions.
The formulations, i.e. the compositions or preparations containing the herbicidal combination of the invention and, where appropriate, a solid or liquid adjuvant~ are prepared ~n known manner, eOg. by homogeneously mixing and/or grinding the active ingredients wi~h ex~enders, e.g. solven~s, solid carriers and, where appropriate, surface-active compounds (surfactants).
i97~5 Suitable solvents are: aromatic hydrocarbons, pre~erably ~he fractions containing 8 to 12 car~on atoms, e~g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, Pthylene glycol, ethylene glycol monomethyl or monoethyl ether, ketcnes such as cyclohexanone, strongly polar solvents such as N-m~thyl-2-pyrrolidone, dimethyl sulfoxide or dime~hyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are po~ous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand.
In addition, a great number of pregranulated materials of inorgar.ic or organlc nature can be used, e.g. especially dolimite or pulverised plant residues.
Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, disper~ing and wetting properties. The term llsurfactants" will also be understood as comprising mixtures of surfactants.
i~7~8 Suitable anionic surfactants can be both water-soluble soaps and water-soluble syn~he~ic surface-active compounds .
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C2z), e.g. the sodium or potassium salts of oLeic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however~ so-called synthetic surfactants are u~ed, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl-arylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C~-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligno-sulfonic acid, of dodecylsulfate or of a mixture of fa~ty alcohol sulfates obtained ~rom natural fatty acid~. These compounds also comprise the salts of sulfuric acid e~ters and sulfonic acids of adducts of fatty alcohols and ethylene oxide. The ~ulfonated benzimids~Qle derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulf-onates are the sodium, calcium or triethanolamlne salts of docecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g.
I ~ 7~8S'l salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
~ on-ionic surfactants are preferably polyglycol ether deriva~ives of aliphatic or cycloaliphatic alcohols, or saturated or unsat~rated fatty acids and alkylphenols, said derivati~es containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with poly-propylene glycol, ethylenediaminepolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether group~ and 10 to 100 propylene glycol ether groups. These compounds usually co~tain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanol~, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxypolyethoxyethanol. Patty acid esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one polyglycol ether or C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or 7~85.,i ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in the following publications: "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, 1979;
Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. Inc., New York~ 1964.
The concentration of active ingredient in commercial composi~ions is from 0.1 to 95% by weight, preferably from 1 to 80% by weight.
Preferred formulations are composed in particular of the following constituents (% = percentage by weight):
Solutions active ingredient: 5 to 95%, preferably 10 to 80%
solvent: 95 to 5%, preferably 90 to 0%
surfactant: 1 to 30%, preferably 2 to 20%
Emulsifiable concentrates .
active ingredient:10% to 50%, preferably 10 to 40%
solvent:5% to 30%, preferably 10 to 20%
liquid carrier:20% to 95%, preferably 40 to 80%
Dusts active ingredient:0,5 to 10%, preferably ? to 8%
solid carrier:99.5 to 90%, preferably 98 to 2%
1 3 ~8~.1 SusPension concentrates active ingredient: 5 to 75~, preferably 10 to 50%
water: 94 to 25%, preferably 90 to 30%
surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders active ingredient: 5 to 90%, preferably 10 to 80% and, most preferably, 20 to 60%
surfactant: 0.~ to 20%, preferably 1 ~o 15%
solid carrier: 5 to 90%, preferably 30 to 70%
Granula~es .
active ingredient: 0.5 to 30%, preferably 3 to 15%
solid carrier: 99.5 ~o 70%, preferably 97 ~o 85%.
Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formNlatîons. The formNlations can be diluted to a concentration as low as 0.001%.
The compositions of the invention can be mi~ed with other biocidal compounds or composi~ions. Accordingly, in addition to containing the compounds of the general formula I and of the formula II, the compositions of the invention can also contain e.g. insecticides, fungicides, bactericidesg fungistats, bacteriostats, or nematocides, in order to broaden the activity spectrum.
Herbicide~ always have a synergistic effect if the herbicidal action of the combination o I + II is greater than the sum o the action of the individual ac~ive i~gredients.
)37~85~
The expected plant growth E for a given combination of two herbicides can be calculated as follows ~c. COLBY, S.R., "Calcuïating synergistic and antagonistic responses of herbicide composition~'i, Weeds 15, pages 20-22 1967):
Y
. _ wherein X - the percentage growth (compared with untreated plants) after treatment with a herbicide I a~ a rate of application of p kg per hectare, Y ~ the percentage growth after treatment with a her~icide II at a rate of application of q kg per hectare, and E - the expected percentage growth (compared with the control plants) after treatment with the herbicidal mixture of I + II at a rate of application of p ~ q kg of active ingredient per hectare.
If the actually observed value i9 lower than the expected vaLue E" then there i8 gynergism.
The synergistic effect of the combination of compounds I and II is demonstrated in the first of the following Examples.
~7~85~1 Example 1:
The test plants are sown, in a greenhouse, in plastic containers filled with 30 litres of sterilised garden soil.
The p;ants are then sprayed postemergence in the 2- to 3-leaf stage with an aqueous dispersion of the combination of herbicides. The rate of application of the dispersion is 50 ml/m2. Evaluation is made after 15 days at 17-23C
and a relative humidity of 60-70%, and daily watering of the containers. The degree of damage to the plants is assessed linearly in accordance with the following rating:
1 - plants withered 5 - medium damage 9 - normal state.
The following results are obtained with different mixture ratios and total amounts of active ingredient:
) Table 1: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and Metamitron (compound IIa), and mixtures thereof, when applied post-emergence:
. ~
Metamitron (compound IIa) kg a.i./ha 1.0 0.5 0.25 0 ~ ., . u~ ~ _ u~ ~
compound Ia kg a.i./ha - o o o o o o o o ~ o . . __ . _ sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 9 fodder beet 'Corona' 9 9 9 9 9 9 9 9 9 9 Panicum crus-galli 9 1 1 9 1 1 9 1 1 Avena fatua 2 1 1 9 1 1 9 1 1 Amaranthus retroflexus 2 1 1 6 1 1 9 3 9 9 Chenopodium album 6 1 1 9 2 2 9 3 9 9 Sinapis arve~sis 9 4 3 _ 9 9 . .
l~7~85 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table l, then it is evident that the observed growth figures given for Amaranthus retr., Chenopodium alb. and Sinapis arvenis are lower than those calculated.
The synergistic effect of the combination of 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxy)-~-phenoxypropionic acid propargyl ester and Metamitron is thus demonstrated (cf. Table 2).
able 2: Values calculated by the method of Colby for demonstrating the synergism of 4-~3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and Metamitron (compound IIa).
, ... . . . .
P~ a ~ /ha l.o 0.5 0.25 ~ -~ ..... _. .~ .. ____ compound Ia o. 5 0.25 0.5 0.25 0.25 ~ . . / _ . _ _ _ .,~ ~ .,~ a~ .,1 a) ,-~ aJ ., ~ J~ e J e ~ a) u ~ ~ a) u ~ ~ U a1 ~ ~ U ~ ~ C~ U
aJ ~ ~ ~ ~ ~ ~ a ~1 ~_I J- ~ ~4~ JJ ~ p~ ~ ~ p~
a) ~ ~ a) ~ X ~ a) ~ a~
. . _ ... ... . . __ .
sugar beet '~a~emono' 100 100 100 100 100 100 100 100 100 100 fodder beet 'Corona' 100 100 100 100 100 100 100 100 100 100 Panicum c.g. 1 1 1 1 1 1 1 1 Avena fatua 1 1 1 1 1 1 1 1 A~aranthus retr. 1 12 1 12 1 62 1 62 25 100 Chenopodium alb. 1 62 1 62 12 100 12 100 25 100 Sinapis arvensis37 100 25 100 100 100 100 100 100 100 _ . . .~
0~5' ) Table 3: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and Phenmedipham (compound IIb) and mixtures thereof, when applied post-emergence:
Phenmediph~ ~c~pound Ilb) kg a.i./ha `` l.0 0.5 0.25 o . ~ . ~ _ .
compound Ia kg a.i./ha -o o o o o o o o o o . . _ sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 9 fodder beet 'Corona' 9 ~ 9 9 9 9 9 9 9 9 Panicum crus-galli 2 1 1 3 1 1 8 1 1 1 Avena fatua 9 l l 9 l l 9 l l l Amara~thu~ retrofle~us 9 6 6 9 7 3 9 9 9 9 Che~opodium album 3 3 ~ 4 ~ 3 9 3 9 9 Sinapi8 arven~i~ 2 2 1 7 2 4 9 7 9 9 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 3, then it is evident that the observed growth figures given for Amaranthus retr., Chenopodium alb. and Sinapis arvensis are lower than those calculated.
The synergistic effect of the combination of 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester and Phenmedipham is thus demonstrated (cf. Table 4).
able 4: Values calculated by the method of Colby for demonstrating the synergism of 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia~ and Phenmedipham (compound IIb).
Ig~85'~
.. . _ .. . . _ . . , Cok~poaui~/hlb ¦ l.o 0.5 0.2;
compound Ia 1 0.5 0.25 0.5 0.25 0.25 k~ a.i./ha . . . .
.~ ~ .~ ~ ,~ ~ .5 ~ .
E~ ~ ~ ~ ~ u u ~ ~ a) ~ a~ u ~ s~ a~ U a ~ ~ ~ ~ ~ ~ ~ ~ 3 J ~ Q~ J ~ ~ ~ ~1 P~
a) ~ ~ ~ ~ ~ ~ * ~ ~ a~ cd X
;~
. . , . ..
sugar beet 'Kaweno' 100 100 100100 100 lOolOo 100 100 100 fodder beet 'Corona' 100100100 100 100100 100 100 100 100 Panicu~ c.g. 1 1 1 1 1 1 1 1 Avena fatua 1 1 1 1 1 1 1 1 ~maranthus retr. 62100 62 100 75 100 100 100 100 100 Chenopodium alb. 2S 25 12. 25 25 37 25 37 25 100 Sinapi~ ar~7ensis 12-~12 1 12 12 75 37. 75 t5 100 ) TabLe 5: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxythiopropionic acid propargyl ester (compound Ib) and Metamitron (compound IIa) and mixtures thereo~, when applied postemergence.
~etam~n (comp.~a~kg a.iiha _ 0.5 0.25 O
.... _~ u~ ~ . ~ ~ ~
compound Ib kg a.i./ha o o o o o o o o o o _ ._ _ ~
sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 g fodder beet 'Corona' 9 9 9 9 9 9 9 9 9 9 Panicum crus-galli 9 1 1 9 1 1 9 1 1 AYena fatua . 2 1 1 9 1 1 9 1 1 AmR~anthus retroflexus 2 1 1 6 1 2 9 2 9 9 Chenopotium album 6 1 1 9 1 2 9 2 9 9 ~ ~ 4 8 9 8 7 9 9 9 9 .
~ ~ 7~8 5 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 5, then it is evident that the observed growth figures given for Amaranthus retr., Chenopodium alb.
and Sinapis arvensis are lower than those calculated. The synergistic effect of the combination of 4-(3',5'-dichloro-pyridyl-2l-oxy)--phenoxythiopropionic acid propargyl ester and Metamitron is thus demonstrated (cf.
Table 6).
able 6: Values calculated by the method of Colby for demonstrating the synergism of 4-(3',5'-dichloropyridyl-2'-oxy)-~-pheno~ythiopropionic acid propargyl ester (compound Ib) and Metamitron (compound IIa).
.. _ .
compound IIa l.o 0.5 0.25 kg a.i./ha_ 0.5 0.25 o 5 0.2s 0.2 ~ ":1 D ~I D ~ D = D ~ ~
sugar beet 'Kawemono' 100 100 100 100 100 100 100 100 100 100 fodder beet 'Corona' 100 100 100 100 100 100 100 100 100 100 Panicum c.g. 1 1 1 1 1 1 1 1 Avena ~atua 1 1 1 1 1 1 1 1 Amaranthus retr.1 12 1 12 1 62 12 62 12 100 Chenopodium al~.1 62 1 62 1 100 12 109 12 100 Sinapis arvensis37 100 87 100 87 100 75 100 100 100 l~7~85 ) Table 7: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-a-phenoxythiopropionic acid propargyl ester (compound Ib) and Phenmedipham (compound IIb) and mixtures thereof, when applied postemergence.
Phenmedipham (comp. IIb) ¦
kg a~i./ha l.o 0.5 O.Z5 O
._ . ., . ._ , __ compound Ib kg a.i./ha -o -o o o o o o o o o , ... _ . _ ~ . _.
sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 9 fodder beet 'Corona' 9 9 9 9 9 9 9 9 9 9 P~nicum crus-galli 2 1 1 3 1 1 8 1 1 Ava~a fatua g 1 1 g l l 9 1 1 1 ra~thu~ retroflexus 9 7 8 9 7 9 9 9 9 Chenopotiu~ album 3 2 2 4 2 2 9 9 9 SiDapi arv~n-~is 2 2 2 7 3 4 9 9 9 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 7, then it is evidént that the observed growth figures given for Amaranthus retr., Chenopodium alb. and Sinapis arvensis are lower than those calculated.
The synergistic effect of the combination of 4 (3',5'-dichloropyridyl-2'-oxy)-a-phenoxythiopropionic acid propargyl ester and Phenmedipham is thus demonstrated (cf. Table 8).
able 8: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2l-oxy)-a-phenoxythiopropionic acid propargyl ester (compound Ib) and Phenmedipham (compcund IIb).
~ ~ 7~5~i compkund Iib/ha ¦ 1.0 0.5 0.25 comp~und Ib/h ¦ 0 5 0.25 0.5 0.25 0.25 ~ a~ a~ aJ Q~
.,1 ~ .~ a~ .,~ ~ .,~ ~ .,~ v e ~ ~ ~ e ~ E ~ ~i ~
aJ ~ ~ u ~ ~ a~ u a~ 5 a~ a) ~ c~
J~ 1 a) ~ d ~ d a~ ~d X ~ ~ ~ ~C td a) ~ X
~ ~ ~ ~ ~ ~ '13 ~ ~ ~ ~ ~
.. - _ . . . _ .
sugar beet 'Kaweno' 100 loO loO lOo 100 lOo loo loo loo loo fodder beet 'Corona' 100 100 100 100 100 loO lOo loo lOo loo Pa~ic~m c.g. 1 1 1 1 1 1 1 1 Avena f atua l 1 1 1 1 1 1 1 kmaranthu~ retr.7,5lOo 87 lOo 75 100 100 100 lOo 100 Che~opodium alb.12 25 12 25 12 37 25 37 37 100 51~apl~ ar~ens~512 1~ 12 12 25 75 37 75 100 100 .
Formulation Examples Example 2 Formulation examples for syner~istic mixtures of com~ounds of the formulae I and II (throughout, percentages are by we~t) a) Wettable powders a) b) c) d) compound Ia or Ib 10% 20% 5% 30%
compound IIa or IIb 10% 40% 15% 30%
sodium lignosulfonate 5% 5% 5% 5%
sodium laurylsulfate 3% - 3%
sodium diisobutylnaphthalene-sulfonate - 6% - 6%
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% - 2%
highly dispersed silicic acid 5% 27% 5% 27%
kaolin 67% - 67%
- 18 ~
The active ingredient mixture is thoroughly mixed with the adjuvants and tha mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
b) Emulsifiable concentrates a) b) c) compound Ia or Ib 5% 5% 12%
compound IIa or IIb 5% 20% 13%
octylphenol polyethylene glycol ether ~4-5 moles of ethylene oxide) 3% 3% 3%
calcium dodecylbenzene-sulfonate 3% 3% 3%
castor oil polyglycol ether (36 moles of ethylene oxide) 4% 4% 4%
cyclohexanone 30% 30% 30%
~ylene mixture 50% 35% 35%
Emulsions of any required concentration can be obtained from these concentratesby dilution wi~h water.
c) Dusts a) b) c) d) compound Ia or Ib 2% 4% 2% 4%
compound IIa or IIb 3% 4% 4% 8%
talcum 95% - 94%
kaolin - 92% - 88%
Dusts which are ready for use are obtained by mixing the active ingredient mixture with the ~arriers, and grinding the mixture in a suitable mill.
1 J ~&5~i d) xtruder ~ranulates a) b) c) compound Ia or Ib 5% 3% 5%
compound IIa or IIb 5% 7% 15%
sodium lignosulfonate 2% 2% 2%
carboxymethylcellulose 1% 1% 1%
kaolin 87% 87% 77%
The active ingredient mixture is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
e) Coated granulates a) b) compound Ia or Ib 1.5% 3%
compound IIa or IIb 1.5% 5%
polyethylene glycol 200 3.0% 3%
kaolin 94.0% 89%
The finely ground active ingredient mixture îs uniformly applied, in a mixer, to the kaolin moistened with poly-ethylene glycol Non-dusty coated granulates are obtained in this manner.
f) Suspension concentrates a) b) compound Ia or Ib 20% 20%
compound IIa or IIb 20% 40%
ethylene glycol 10% 10%
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% 5%
" i 1 7~8~1 20 ~
sodium lignosulfonate10% 10.0%
carboxymethylcellulose1% 1.0%
37% aqueous formaldehyde solution 0.2 % 0.2%
silicone oil in the form of a 75% aqueous emulsion0.8% 0.8%
water 32.0% 12.0%
The finely ground active ingredient mixture is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beet ._ The present invention relates to a synergistic composition comprising a combination of herbicides and which is most suitable for selec~ively controlling weeds, especially in crops of sugar beet and fodder beet. The invention also relates to a method of controlling weeds which comprises the use of the novel composition, especially in crops of sugar beet and fodder beet.
The most frequently encountered and most important weeds in crops of sugar beet and fodder beet at the present time are species of the genera Amaranthus (foxtail), Chenopodium (goosefoot), Sinapis (mustard), Panicum (panic grass) and certain Avena species (wild oats).
Excellent postemergence selective herbicides against monocot weeds are 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl esters of the formula I
~Cl ca3 Cl~ --o~ O-CH-CO-Z-CH2-C-.. ...
wherein 7 is oxygen or sulfur.
~ 3 7~85 The two compounds of formula I, viz. 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (Ia) and 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxy-thiopropionic acid propargyl ester (Ib), processes for the production thereof and the use thereof as selective herbicides, are described in European patent publication 3114.
Dicot weeds are often successfully controlled postemergence with 4-amino-3-methyl-6-phenyl[4H]-1,2,4-triazin-5-one (Metamitron) of the formula IIa ~ ~ -C~ (IIa) or with methyl-3-m-tolylcarbamoyloxyphenylcarbamate (Phenmedipham) of the formula IIb -O~C~N~~t~ il-o-C-NH~ CH3 (IIb) Metamitron and its herbicidal activity were described e.g. at the 3rd Int. Meeting of Selective Weed Control in Beet Crops, Paris, 1975. Phenmedipham and its herbicidal properties are reported on e.g. in Abstr. 6th Int. Congr. Pl. Prot., Vienna, 1967, page 433.
Surprisingly, it has now been found that a combination of the two compounds of the formulae I and II, in a ratio varying within specific limits, exerts a synergistic action which is able to control the majority of all important weeds in crops of sugar beet and fodder beet without damaging these crops. The principal weeds in i ~ 7~85'1 these crops, such as species of the dicot Amaranthus, Chenopodium and Sinapis varieties, as well as the monocot Panicum and Avena varieties, are selectively destroyed in the emergent beet crops.
Accordingly, the invention provides a synergistic composition for selectively controlling weeds, which composition comprises, on the one hand, a 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester of the formula I
Cl CH3 (I) Cl~ o ~ O-CH-CO-Z-CH2-C -CH , wherein Z is oxygen or sulfur, and, on the other, 4-amino-3-methyl-6-phenyl~[4H]-1,2,4-triazin-5-one (IIa) or methyl-3-m-tolylcarbamoyloxyphenylcarbamate (IIb), together with carriers and/or other adjuvants, the amount of component (II) being approximately ecIual to, or in excess of, component (I~.
It is surprising that the combination of a compound of the formula I with a compound of the formula II not only brings about an expected aclditive enhancement of the activity spectrum against the customary weeds associated with sugar beet and fodder beet, but gives rise to a synergistic effect which potentiates the action of both components from two points of view.
On the one hand, the rates of application of the single compounds I and II are distinctly reduced while the same good action is retained. On the other hand, the combination also achieves a high degree of weed control where both single compounds .~ r~
~3--117~
have become totally ineffective at too low rates of application.
The consequence is a substantial broadening of the activity spectrum against weeds and an additional increase in the safety margin on application to crops of sugar beet, as is necessary and desirable in the event of unintentional overapplication.
The composition of this invention can also be used for selectively controlling weeds in crops of other dicot plants having similar sensitivity to herbicides and similar weed in~estation.
The herbicidal combination employed in the practice of this invention will preferably contain a compound of the formula (I~ and a compound of the formula (II) in a ratio of 1:1 to 1:4, most preferably 1:1 to 1:2.
~,_ -3a-~7~85' The herbicidal combination has an excellent action against weeds without having any noticeable effects in crops of sugar beet and fodder beet when used in the conventional rates of application o 0.2 to 4 kg/ha, preferably 0.5 to 3 kg/ha.
The present invention also relates to the use of the composition, i.e. to a method of selectively controlling grasses and weeds postemergence in beet crops.
In addition to the novel combination of active ingredients, the composition of this invention also contains suitable carriers and/or other adjuvants. These can be solid or liquid and correspond to the substances conventionally employed in the art of formulation, e.g. natural or regenerated mineral substances, solvents, dispersants a wetting agents, tackifiers, thickerners, binders or fertilisers. Suitable formulations are therefore e.g.
emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granula~es, and also encapsulations in e.g.
polymer substances. The methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances, just like the nature of the compositions.
The formulations, i.e. the compositions or preparations containing the herbicidal combination of the invention and, where appropriate, a solid or liquid adjuvant~ are prepared ~n known manner, eOg. by homogeneously mixing and/or grinding the active ingredients wi~h ex~enders, e.g. solven~s, solid carriers and, where appropriate, surface-active compounds (surfactants).
i97~5 Suitable solvents are: aromatic hydrocarbons, pre~erably ~he fractions containing 8 to 12 car~on atoms, e~g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, Pthylene glycol, ethylene glycol monomethyl or monoethyl ether, ketcnes such as cyclohexanone, strongly polar solvents such as N-m~thyl-2-pyrrolidone, dimethyl sulfoxide or dime~hyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are po~ous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand.
In addition, a great number of pregranulated materials of inorgar.ic or organlc nature can be used, e.g. especially dolimite or pulverised plant residues.
Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, disper~ing and wetting properties. The term llsurfactants" will also be understood as comprising mixtures of surfactants.
i~7~8 Suitable anionic surfactants can be both water-soluble soaps and water-soluble syn~he~ic surface-active compounds .
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C2z), e.g. the sodium or potassium salts of oLeic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however~ so-called synthetic surfactants are u~ed, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl-arylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C~-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligno-sulfonic acid, of dodecylsulfate or of a mixture of fa~ty alcohol sulfates obtained ~rom natural fatty acid~. These compounds also comprise the salts of sulfuric acid e~ters and sulfonic acids of adducts of fatty alcohols and ethylene oxide. The ~ulfonated benzimids~Qle derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulf-onates are the sodium, calcium or triethanolamlne salts of docecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g.
I ~ 7~8S'l salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
~ on-ionic surfactants are preferably polyglycol ether deriva~ives of aliphatic or cycloaliphatic alcohols, or saturated or unsat~rated fatty acids and alkylphenols, said derivati~es containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with poly-propylene glycol, ethylenediaminepolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether group~ and 10 to 100 propylene glycol ether groups. These compounds usually co~tain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanol~, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxypolyethoxyethanol. Patty acid esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one polyglycol ether or C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or 7~85.,i ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in the following publications: "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, 1979;
Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. Inc., New York~ 1964.
The concentration of active ingredient in commercial composi~ions is from 0.1 to 95% by weight, preferably from 1 to 80% by weight.
Preferred formulations are composed in particular of the following constituents (% = percentage by weight):
Solutions active ingredient: 5 to 95%, preferably 10 to 80%
solvent: 95 to 5%, preferably 90 to 0%
surfactant: 1 to 30%, preferably 2 to 20%
Emulsifiable concentrates .
active ingredient:10% to 50%, preferably 10 to 40%
solvent:5% to 30%, preferably 10 to 20%
liquid carrier:20% to 95%, preferably 40 to 80%
Dusts active ingredient:0,5 to 10%, preferably ? to 8%
solid carrier:99.5 to 90%, preferably 98 to 2%
1 3 ~8~.1 SusPension concentrates active ingredient: 5 to 75~, preferably 10 to 50%
water: 94 to 25%, preferably 90 to 30%
surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders active ingredient: 5 to 90%, preferably 10 to 80% and, most preferably, 20 to 60%
surfactant: 0.~ to 20%, preferably 1 ~o 15%
solid carrier: 5 to 90%, preferably 30 to 70%
Granula~es .
active ingredient: 0.5 to 30%, preferably 3 to 15%
solid carrier: 99.5 ~o 70%, preferably 97 ~o 85%.
Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formNlatîons. The formNlations can be diluted to a concentration as low as 0.001%.
The compositions of the invention can be mi~ed with other biocidal compounds or composi~ions. Accordingly, in addition to containing the compounds of the general formula I and of the formula II, the compositions of the invention can also contain e.g. insecticides, fungicides, bactericidesg fungistats, bacteriostats, or nematocides, in order to broaden the activity spectrum.
Herbicide~ always have a synergistic effect if the herbicidal action of the combination o I + II is greater than the sum o the action of the individual ac~ive i~gredients.
)37~85~
The expected plant growth E for a given combination of two herbicides can be calculated as follows ~c. COLBY, S.R., "Calcuïating synergistic and antagonistic responses of herbicide composition~'i, Weeds 15, pages 20-22 1967):
Y
. _ wherein X - the percentage growth (compared with untreated plants) after treatment with a herbicide I a~ a rate of application of p kg per hectare, Y ~ the percentage growth after treatment with a her~icide II at a rate of application of q kg per hectare, and E - the expected percentage growth (compared with the control plants) after treatment with the herbicidal mixture of I + II at a rate of application of p ~ q kg of active ingredient per hectare.
If the actually observed value i9 lower than the expected vaLue E" then there i8 gynergism.
The synergistic effect of the combination of compounds I and II is demonstrated in the first of the following Examples.
~7~85~1 Example 1:
The test plants are sown, in a greenhouse, in plastic containers filled with 30 litres of sterilised garden soil.
The p;ants are then sprayed postemergence in the 2- to 3-leaf stage with an aqueous dispersion of the combination of herbicides. The rate of application of the dispersion is 50 ml/m2. Evaluation is made after 15 days at 17-23C
and a relative humidity of 60-70%, and daily watering of the containers. The degree of damage to the plants is assessed linearly in accordance with the following rating:
1 - plants withered 5 - medium damage 9 - normal state.
The following results are obtained with different mixture ratios and total amounts of active ingredient:
) Table 1: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and Metamitron (compound IIa), and mixtures thereof, when applied post-emergence:
. ~
Metamitron (compound IIa) kg a.i./ha 1.0 0.5 0.25 0 ~ ., . u~ ~ _ u~ ~
compound Ia kg a.i./ha - o o o o o o o o ~ o . . __ . _ sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 9 fodder beet 'Corona' 9 9 9 9 9 9 9 9 9 9 Panicum crus-galli 9 1 1 9 1 1 9 1 1 Avena fatua 2 1 1 9 1 1 9 1 1 Amaranthus retroflexus 2 1 1 6 1 1 9 3 9 9 Chenopodium album 6 1 1 9 2 2 9 3 9 9 Sinapis arve~sis 9 4 3 _ 9 9 . .
l~7~85 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table l, then it is evident that the observed growth figures given for Amaranthus retr., Chenopodium alb. and Sinapis arvenis are lower than those calculated.
The synergistic effect of the combination of 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxy)-~-phenoxypropionic acid propargyl ester and Metamitron is thus demonstrated (cf. Table 2).
able 2: Values calculated by the method of Colby for demonstrating the synergism of 4-~3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and Metamitron (compound IIa).
, ... . . . .
P~ a ~ /ha l.o 0.5 0.25 ~ -~ ..... _. .~ .. ____ compound Ia o. 5 0.25 0.5 0.25 0.25 ~ . . / _ . _ _ _ .,~ ~ .,~ a~ .,1 a) ,-~ aJ ., ~ J~ e J e ~ a) u ~ ~ a) u ~ ~ U a1 ~ ~ U ~ ~ C~ U
aJ ~ ~ ~ ~ ~ ~ a ~1 ~_I J- ~ ~4~ JJ ~ p~ ~ ~ p~
a) ~ ~ a) ~ X ~ a) ~ a~
. . _ ... ... . . __ .
sugar beet '~a~emono' 100 100 100 100 100 100 100 100 100 100 fodder beet 'Corona' 100 100 100 100 100 100 100 100 100 100 Panicum c.g. 1 1 1 1 1 1 1 1 Avena fatua 1 1 1 1 1 1 1 1 A~aranthus retr. 1 12 1 12 1 62 1 62 25 100 Chenopodium alb. 1 62 1 62 12 100 12 100 25 100 Sinapis arvensis37 100 25 100 100 100 100 100 100 100 _ . . .~
0~5' ) Table 3: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and Phenmedipham (compound IIb) and mixtures thereof, when applied post-emergence:
Phenmediph~ ~c~pound Ilb) kg a.i./ha `` l.0 0.5 0.25 o . ~ . ~ _ .
compound Ia kg a.i./ha -o o o o o o o o o o . . _ sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 9 fodder beet 'Corona' 9 ~ 9 9 9 9 9 9 9 9 Panicum crus-galli 2 1 1 3 1 1 8 1 1 1 Avena fatua 9 l l 9 l l 9 l l l Amara~thu~ retrofle~us 9 6 6 9 7 3 9 9 9 9 Che~opodium album 3 3 ~ 4 ~ 3 9 3 9 9 Sinapi8 arven~i~ 2 2 1 7 2 4 9 7 9 9 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 3, then it is evident that the observed growth figures given for Amaranthus retr., Chenopodium alb. and Sinapis arvensis are lower than those calculated.
The synergistic effect of the combination of 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester and Phenmedipham is thus demonstrated (cf. Table 4).
able 4: Values calculated by the method of Colby for demonstrating the synergism of 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia~ and Phenmedipham (compound IIb).
Ig~85'~
.. . _ .. . . _ . . , Cok~poaui~/hlb ¦ l.o 0.5 0.2;
compound Ia 1 0.5 0.25 0.5 0.25 0.25 k~ a.i./ha . . . .
.~ ~ .~ ~ ,~ ~ .5 ~ .
E~ ~ ~ ~ ~ u u ~ ~ a) ~ a~ u ~ s~ a~ U a ~ ~ ~ ~ ~ ~ ~ ~ 3 J ~ Q~ J ~ ~ ~ ~1 P~
a) ~ ~ ~ ~ ~ ~ * ~ ~ a~ cd X
;~
. . , . ..
sugar beet 'Kaweno' 100 100 100100 100 lOolOo 100 100 100 fodder beet 'Corona' 100100100 100 100100 100 100 100 100 Panicu~ c.g. 1 1 1 1 1 1 1 1 Avena fatua 1 1 1 1 1 1 1 1 ~maranthus retr. 62100 62 100 75 100 100 100 100 100 Chenopodium alb. 2S 25 12. 25 25 37 25 37 25 100 Sinapi~ ar~7ensis 12-~12 1 12 12 75 37. 75 t5 100 ) TabLe 5: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxythiopropionic acid propargyl ester (compound Ib) and Metamitron (compound IIa) and mixtures thereo~, when applied postemergence.
~etam~n (comp.~a~kg a.iiha _ 0.5 0.25 O
.... _~ u~ ~ . ~ ~ ~
compound Ib kg a.i./ha o o o o o o o o o o _ ._ _ ~
sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 g fodder beet 'Corona' 9 9 9 9 9 9 9 9 9 9 Panicum crus-galli 9 1 1 9 1 1 9 1 1 AYena fatua . 2 1 1 9 1 1 9 1 1 AmR~anthus retroflexus 2 1 1 6 1 2 9 2 9 9 Chenopotium album 6 1 1 9 1 2 9 2 9 9 ~ ~ 4 8 9 8 7 9 9 9 9 .
~ ~ 7~8 5 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 5, then it is evident that the observed growth figures given for Amaranthus retr., Chenopodium alb.
and Sinapis arvensis are lower than those calculated. The synergistic effect of the combination of 4-(3',5'-dichloro-pyridyl-2l-oxy)--phenoxythiopropionic acid propargyl ester and Metamitron is thus demonstrated (cf.
Table 6).
able 6: Values calculated by the method of Colby for demonstrating the synergism of 4-(3',5'-dichloropyridyl-2'-oxy)-~-pheno~ythiopropionic acid propargyl ester (compound Ib) and Metamitron (compound IIa).
.. _ .
compound IIa l.o 0.5 0.25 kg a.i./ha_ 0.5 0.25 o 5 0.2s 0.2 ~ ":1 D ~I D ~ D = D ~ ~
sugar beet 'Kawemono' 100 100 100 100 100 100 100 100 100 100 fodder beet 'Corona' 100 100 100 100 100 100 100 100 100 100 Panicum c.g. 1 1 1 1 1 1 1 1 Avena ~atua 1 1 1 1 1 1 1 1 Amaranthus retr.1 12 1 12 1 62 12 62 12 100 Chenopodium al~.1 62 1 62 1 100 12 109 12 100 Sinapis arvensis37 100 87 100 87 100 75 100 100 100 l~7~85 ) Table 7: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2'-oxy)-a-phenoxythiopropionic acid propargyl ester (compound Ib) and Phenmedipham (compound IIb) and mixtures thereof, when applied postemergence.
Phenmedipham (comp. IIb) ¦
kg a~i./ha l.o 0.5 O.Z5 O
._ . ., . ._ , __ compound Ib kg a.i./ha -o -o o o o o o o o o , ... _ . _ ~ . _.
sugar beet 'Kawemono' 9 9 9 9 9 9 9 9 9 9 fodder beet 'Corona' 9 9 9 9 9 9 9 9 9 9 P~nicum crus-galli 2 1 1 3 1 1 8 1 1 Ava~a fatua g 1 1 g l l 9 1 1 1 ra~thu~ retroflexus 9 7 8 9 7 9 9 9 9 Chenopotiu~ album 3 2 2 4 2 2 9 9 9 SiDapi arv~n-~is 2 2 2 7 3 4 9 9 9 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 7, then it is evidént that the observed growth figures given for Amaranthus retr., Chenopodium alb. and Sinapis arvensis are lower than those calculated.
The synergistic effect of the combination of 4 (3',5'-dichloropyridyl-2'-oxy)-a-phenoxythiopropionic acid propargyl ester and Phenmedipham is thus demonstrated (cf. Table 8).
able 8: Tolerance and activity of 4-(3',5'-dichloro-pyridyl-2l-oxy)-a-phenoxythiopropionic acid propargyl ester (compound Ib) and Phenmedipham (compcund IIb).
~ ~ 7~5~i compkund Iib/ha ¦ 1.0 0.5 0.25 comp~und Ib/h ¦ 0 5 0.25 0.5 0.25 0.25 ~ a~ a~ aJ Q~
.,1 ~ .~ a~ .,~ ~ .,~ ~ .,~ v e ~ ~ ~ e ~ E ~ ~i ~
aJ ~ ~ u ~ ~ a~ u a~ 5 a~ a) ~ c~
J~ 1 a) ~ d ~ d a~ ~d X ~ ~ ~ ~C td a) ~ X
~ ~ ~ ~ ~ ~ '13 ~ ~ ~ ~ ~
.. - _ . . . _ .
sugar beet 'Kaweno' 100 loO loO lOo 100 lOo loo loo loo loo fodder beet 'Corona' 100 100 100 100 100 loO lOo loo lOo loo Pa~ic~m c.g. 1 1 1 1 1 1 1 1 Avena f atua l 1 1 1 1 1 1 1 kmaranthu~ retr.7,5lOo 87 lOo 75 100 100 100 lOo 100 Che~opodium alb.12 25 12 25 12 37 25 37 37 100 51~apl~ ar~ens~512 1~ 12 12 25 75 37 75 100 100 .
Formulation Examples Example 2 Formulation examples for syner~istic mixtures of com~ounds of the formulae I and II (throughout, percentages are by we~t) a) Wettable powders a) b) c) d) compound Ia or Ib 10% 20% 5% 30%
compound IIa or IIb 10% 40% 15% 30%
sodium lignosulfonate 5% 5% 5% 5%
sodium laurylsulfate 3% - 3%
sodium diisobutylnaphthalene-sulfonate - 6% - 6%
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% - 2%
highly dispersed silicic acid 5% 27% 5% 27%
kaolin 67% - 67%
- 18 ~
The active ingredient mixture is thoroughly mixed with the adjuvants and tha mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
b) Emulsifiable concentrates a) b) c) compound Ia or Ib 5% 5% 12%
compound IIa or IIb 5% 20% 13%
octylphenol polyethylene glycol ether ~4-5 moles of ethylene oxide) 3% 3% 3%
calcium dodecylbenzene-sulfonate 3% 3% 3%
castor oil polyglycol ether (36 moles of ethylene oxide) 4% 4% 4%
cyclohexanone 30% 30% 30%
~ylene mixture 50% 35% 35%
Emulsions of any required concentration can be obtained from these concentratesby dilution wi~h water.
c) Dusts a) b) c) d) compound Ia or Ib 2% 4% 2% 4%
compound IIa or IIb 3% 4% 4% 8%
talcum 95% - 94%
kaolin - 92% - 88%
Dusts which are ready for use are obtained by mixing the active ingredient mixture with the ~arriers, and grinding the mixture in a suitable mill.
1 J ~&5~i d) xtruder ~ranulates a) b) c) compound Ia or Ib 5% 3% 5%
compound IIa or IIb 5% 7% 15%
sodium lignosulfonate 2% 2% 2%
carboxymethylcellulose 1% 1% 1%
kaolin 87% 87% 77%
The active ingredient mixture is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
e) Coated granulates a) b) compound Ia or Ib 1.5% 3%
compound IIa or IIb 1.5% 5%
polyethylene glycol 200 3.0% 3%
kaolin 94.0% 89%
The finely ground active ingredient mixture îs uniformly applied, in a mixer, to the kaolin moistened with poly-ethylene glycol Non-dusty coated granulates are obtained in this manner.
f) Suspension concentrates a) b) compound Ia or Ib 20% 20%
compound IIa or IIb 20% 40%
ethylene glycol 10% 10%
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% 5%
" i 1 7~8~1 20 ~
sodium lignosulfonate10% 10.0%
carboxymethylcellulose1% 1.0%
37% aqueous formaldehyde solution 0.2 % 0.2%
silicone oil in the form of a 75% aqueous emulsion0.8% 0.8%
water 32.0% 12.0%
The finely ground active ingredient mixture is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A synergistic composition for selectively controlling weeds, which composition comprises, on the one hand, a 4-(3',5'-dichloropyridyl-2'-oxy)-.alpha.-phenoxypropionic acid propargyl ester of the formula I
(I) wherein Z is oxygen or sulfur, and, on the other, 4-amino-3-methyl-6-phenyl-[4H]-1,2,4-triazin-5-one (IIa) or methyl-3-m-tolylcarbamoyloxyphenylcarbamate (IIb), together with carriers and/or other adjuvants, the amount of component (II) being approximately equal to, or in excess of, component (I).
(I) wherein Z is oxygen or sulfur, and, on the other, 4-amino-3-methyl-6-phenyl-[4H]-1,2,4-triazin-5-one (IIa) or methyl-3-m-tolylcarbamoyloxyphenylcarbamate (IIb), together with carriers and/or other adjuvants, the amount of component (II) being approximately equal to, or in excess of, component (I).
2. A composition according to claim 1, in which the ratio of component (I) to component (II) is 1:1 to 1:4.
3. A composition according to claim 1, in which the ratio of component (I) to component (II) is 1:1 to 1:2.
4. A method of selectively controlling weeds in sugar beet and fodder beet, which method comprises treating weed-infested crops of sugar beet and fodder beet postemergence with a herbicidally effective amount of a composition according to claim 1.
5. A method according to claim 4, wherein the weeds to be controlled are dicots of the genera Chenopodium, Amaranthus and Sinapis, and monocot grasses of the genera Panicum and Avena.
6. A method according to claim 4 or 5, which comprises treating the crops of sugar beet and fodder beet at rates of application corresponding to 0.2 to 4 kg of total active ingredient per hectare.
7. A method according to claim 4 or 5, which comprises treating the crops of sugar beet and fodder beet at rates of application corresponding to 0.5 to 3 kg of total active ingredient per hectare.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH5193/80-1 | 1980-07-07 | ||
| CH519380 | 1980-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1170854A true CA1170854A (en) | 1984-07-17 |
Family
ID=4289485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381118A Expired CA1170854A (en) | 1980-07-07 | 1981-07-03 | Synergistic composition and method of selectively controlling weeds, especially in crops of sugar beet and fodder beet |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0043800A1 (en) |
| JP (1) | JPS5746902A (en) |
| BG (1) | BG35323A3 (en) |
| CA (1) | CA1170854A (en) |
| CS (1) | CS226431B2 (en) |
| DD (1) | DD201637A5 (en) |
| DK (1) | DK299281A (en) |
| GR (1) | GR74371B (en) |
| RO (1) | RO82548A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316387B1 (en) | 1996-08-12 | 2001-11-13 | Hoechst Schering Agrevo Gmbh | Synergistic active compound combinations for controlling harmful plants in crops of useful plants |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3205103A1 (en) * | 1982-02-12 | 1983-08-18 | Bayer Ag, 5090 Leverkusen | HERBICIDAL CONTAINING METAMITRON IN COMBINATION WITH PARTICULAR PHENOXYPROPIONIC ACID ESTERS |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2026865A (en) * | 1978-03-01 | 1980-02-13 | Ici Ltd | Herbicides |
-
1981
- 1981-07-01 EP EP19810810268 patent/EP0043800A1/en not_active Withdrawn
- 1981-07-02 RO RO81104755A patent/RO82548A/en unknown
- 1981-07-03 DD DD23143881A patent/DD201637A5/en unknown
- 1981-07-03 CS CS515681A patent/CS226431B2/en unknown
- 1981-07-03 CA CA000381118A patent/CA1170854A/en not_active Expired
- 1981-07-06 BG BG052772A patent/BG35323A3/en unknown
- 1981-07-06 DK DK299281A patent/DK299281A/en not_active Application Discontinuation
- 1981-07-06 GR GR65429A patent/GR74371B/el unknown
- 1981-07-07 JP JP10619081A patent/JPS5746902A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316387B1 (en) | 1996-08-12 | 2001-11-13 | Hoechst Schering Agrevo Gmbh | Synergistic active compound combinations for controlling harmful plants in crops of useful plants |
Also Published As
| Publication number | Publication date |
|---|---|
| GR74371B (en) | 1984-06-28 |
| DK299281A (en) | 1982-01-08 |
| RO82548B (en) | 1983-08-30 |
| CS226431B2 (en) | 1984-03-19 |
| BG35323A3 (en) | 1984-03-15 |
| EP0043800A1 (en) | 1982-01-13 |
| RO82548A (en) | 1983-09-26 |
| DD201637A5 (en) | 1983-08-03 |
| JPS5746902A (en) | 1982-03-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |