CA1168884A - Synergistic composition and method of selectively controlling weeds, especially in cereals - Google Patents
Synergistic composition and method of selectively controlling weeds, especially in cerealsInfo
- Publication number
- CA1168884A CA1168884A CA000381247A CA381247A CA1168884A CA 1168884 A CA1168884 A CA 1168884A CA 000381247 A CA000381247 A CA 000381247A CA 381247 A CA381247 A CA 381247A CA 1168884 A CA1168884 A CA 1168884A
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- Prior art keywords
- dimethylurea
- oxy
- composition according
- cereals
- chloro
- Prior art date
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Classifications
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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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)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicines Containing Plant Substances (AREA)
- Bakery Products And Manufacturing Methods Therefor (AREA)
Abstract
Synergistic composition and method of selectively controlling weeds, especially in cereals Abstract of the Disclosure The invention relates to a composition comprising, on the one hand,.
Description
7~6~81l Case 5-12951/-Synergistic composition and method of selectively controlling weeds~ especially in cereals The present invention relates to a synergistic composition comprising a combination of herbioides and which is most suitable for selectively controlling weeds in cereals. The invention also relates to a method of controlling weeds which comprises the use of the novel composition, especially in cereals.
The most requently encountered and most important - weeds at the presen~ ti~e in cereals are species of the genera Sinapis (mustard) and ChrysenthemLm(corn marigold), and certain Avena species (wild oats).
Excellent postemergence selectiYe herbicideY against monocot weeds are 4-~3' ,5'-dichloropyridyl-2'-oxy)-a-phenoxypropionic acid propargyl esters of the formula I
~Cl ~
Cl~ 0~ O-c~-co Z C~2 wherein Z is o~yge~ or sulfur.
The two co~pounds offormula~ viz. 4-(3',5'-dichloro-pyridyl-2~-oxy~--phenoxypropionic acid propargyl ester (Ia~
and 4-(3',5'-dichloropyridyl~2'-oxy)-a-phenox~thioFropionic acid propargyl eqter (Ib), processes for the production thereof and the us thereof as selectîve hPrbicides, are described in European paten~ publica~ion 3114.
~:
. ' ~', , .. . . .
It is known that dicot weeds, and also a number of mono- ~
cots, can o~nbe successfully controlled postemergence in cereals with 3-(3'-chloro-4'-methylphenyl)~ dimethylurea (Chlortoluron) of the formula IIa T~ C-~ ~o-N~I-CO~ ) (IIa) .~.
Cl .
or with 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (Metoxuron) of the form~la IIb 3 0 ~ NH-C0-N(C~3)2 (IIb) Cl :or with 3-(4'-isopropylphenyl)~ dimethylurea (Isoproturon) of the formula IIc ._.
7C3~ C0 ~(CS3) 2 (IIc) ., .
or with l-benzothiazol-2-yl-1,3-dimethylurea (Methabenzthiazuron) of the ormula IId N-C0-NH-Ca3 ( IId) : .
or with 4~hydroxy-3,5-diiodobenzonitrile (Ioxynil) of the .~ formula IIe ',, .
.~., j .. .
.. ~
6~8il !~ /OH
li i (IIe) or with 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',4'-dinitrophenyl)-oxime ~Bromophenoxime) of the formula IIf Br E10~ N-O-~ NO2 ~: Br ~72 ~, The compounds of the formulae IIa to IIf and their herbicidal activity are described e g. in the following publications:
Chlortoluron (compound IIa) in C.~. 5e Conf. Com. franc.:
Mauvaises Herbes (COLUMA), 1969, II3 3493 Metoxuron (compound IIb) in Z. Pflkrankh., PflPath., PflSchutz, 1968, 75, 233, Isoproturon (compound IIc~ in German Offenlegungsschrift 2 107 774, Methabenzthiazuron (compound IId) in P1Schutz-Nachr. Bayer3 1969, 22, 314, Ioxynil (compound IIe) in Nature, Lond., 1963, 200, 28~ and ; Bromofenoxime (compound IIf) in Proc, 3rd EWRC Symp.
~- "New Herbicides", Paris, 1968, S. 177.
Surprisingly3 it has now been ound that a combination o:E both classes of compound X nd II, in a ratio varing within specific limits, exerts a spe~ific synerglstic ~ action which is able to control the majority of all weeds ;~ ; in cereals without damaging these latter. The principal :;
.
. ~ .
:
~" .
S ~3 !,j weeds i.n cereals, such as species of the dicot genera Chrysenthemum and Sinapis as well as certain Avena (wild oat) species, are selec-tively destroyed in the emergent crops.
Accordingly, the invention provides a synergistic composition for selec-tively controlling weeds, which composition comprises, on the one hand, a 4-(3',~
5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester of the Eormula ~: I
Cl Cl-- ~ ~0~ O-CH-CO-Z-CH -C-CH (I) , o=1~
wherein Z is oxygen or su].fur, and, on the other, in approximately equal ratio to :~ 10 or in excess of component I, one of 3-(3'-chloro-4'-methylphenyl)-1,1-dimethyl-urea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isopro-.-. pylphenyl)-l,l-dimethylurea (IIc), l-benzothiazol-2-yl-1,3-dimethylurea (IId), . 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',4'-dinitrophenyl)-oxime (IIf), together with carriers and/or other adjuvants.
. 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 additive . . .
r enhancement of the activity spectrum against the customary weeds associated with cereals and soybeans, but gives rise to a synergistic effect which potentiates the action of both componen-ts 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 bo-th sin-gle compounds 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 cereals and soybeans, as is necessary and desirable in the event of unintentional ''' ~
.
,? ~ .
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` overapplication.
In addition to beiny used in crops of soybeans and cereals such as bar-ley, rye and, in particular, whea-t, the composition of -this invention can also be used for selectively controlling weeds in crops of othe~ monocot plants having similar sensitivity to herbicides and similar weed infestation, e.g. in mai~e and rice.
The herbicidal combination emp]oyed in the practice of -this inven-tion will contain a compound of the formula I and a compound of the Eonnula II in equal amounts or with an excess of the component II. The preferred ratio o~ com-ponen-t I to component II is 1:1 to 1:25, with the most preferred ratio being from 1:1 to 1:10.
The herbicidal combina-tion has an excellent action against weeds with-out having any noticeable effects in crops of cereals when used in the conventio~
nal rates of application of 0.2 to 4 kg/ha, preferably 0.5 to 3 kg/ha.
The following combinations have proved particularly effective synergis-tic herbicidal mixtures:
a) 4-(3',5'-dichloropyridyl-2'-oxy)--phenoxypropionic acid propargyl ester (Ia) and 3-(3'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa), b) 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxythiopropionic acid propargyl ester (Ib) and 3-(4'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa), ` c) 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl -- ester (Ia) and 3-(4'-isopropylphenyl)-1,1-dime-thylurea (IIc), and ~:i d) 4-(3',5'-dichloropyridyl-2'-oxy)-~phenoxythiopropionic acid propargyl ester (Ib) and 3-(4'-isopropylphenyl)-1,1-dimethylurea ~IIc).
The present invention also relates to the use of the composition, i.e.
to a method of selectively controlling grasses and weeds postemergence in cereals.
."' ~
~' ~
I :~ 6~8/i In addition to the novel combina-tion of active ingredients, the composi-tion of this invention also contains suitable carriers and/or other adjuvan-ts.
These can be solid or liquid and correspond to -the substances ~onventionally employed in the art of formulation, e.y. natural or regenerated mineral substan-ces, solvents, dispersants, `~, :.
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!',~
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wet~ing agents, ~acki~iers, thickeners, binders or fertilisers. Suitable formulations are therefore e.g.
emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g.
polymer substanc~s. The method~ of application, such as sprayi~g, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances, just like the nature of the co~positions~
The formulations, i.e. the compositions or preparations containing the herbi.cidal combina~ion o~ the invention and, where appropriate, a solid or liquid adjuvant, are prepared ill known manner, e~g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-ac~ive compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, prefexably the fractions cont~ning 8 to 12 carbon atoms, e.g. xylene mixtures or cubstituted naphthalenes, phthalate~ ~uch as dibutyl phthalate or dioctyl phthala~e, alipha~ic hydrocar~ons such as cyclohexane or parains, alcohols and glycols and their e~hers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketcnes such as cyclohexanone, strongly polar solvents such as N-methyl~2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconu~ oil or soybean oil; or w ter.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral filler3 such as calcite, talcum, kaolin~ montmorillonite or attapulgiteO In order to improve the phy~ical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granula~ed adsorptive carriers are porous 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 inorganic or organio 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, dispersing and wetting properties. The term "~urfactants" will also be unders~ood as comprising ~urfactant mixtures.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble 3ynthetic surface-active compounds .
Suitable soap~ are the alkali metal salts, alkaline earth metal salts or unsubs~ituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g~ the sodium or potas~um salts of oleic or stearic acid, or of natural fatty a~id mix ures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fa~ty acid methyltaurin salts.
More frequently, however, so-called syntheti~
surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimida201e derivatives or alkyl-arylsulfonategJ
q The fatty sulfonates or sulfates are usually in the form o~ alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety o~
acyl radicals, e.g. the sodium or calcium salt o~ ligno-sulfonic acid, of dodecylsulfate or of a mixtuxe of fatty alcohol sulfates obtained from natural ~atty acids. These compounds also comprise the salts of sulfuric acid esters and sul~onic acids of adduct~ of fatty alcohols and ethylene oxide. The ~ulfonated benzimidazole derlvatives preerably contain 2 sul~onic acid groups and one fatty ac~d radical containing 8 to 22 carbon atoms. Exampl s o~ alkylarylsulf~
onates are the sodium, calcium or triethanolamine salts o~
docecylbenzenesul~onic acid, dibutylnaphthalenesulfonic acid, or o~ a naphthalenesulfonic acid/formaldehyde condensatio~
product~ Also suitable are corresponding pho~phates, e.g.
salts of the phosphoric acid ester o an adduct of p-nonylphenol with 4 to 14 moles of ethylene o~ide.
~ on-ionic surfac~ants are pre~erably polyglycol ether derivatives o~ aliphatic or cycloaliphatic alcohols, or sat~rated or unsatura~ed fatty acids and alkylphenols, ~ald derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in ~he (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylph nols.
Further ~uitable non-ionic Qurfactants are t~e water~solu~le adducts of polyethylene oxide with poly-propyle~e glycol, ethylenediamlnepolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the aIkyl chain, which adduc s contain 20 to 250 ethylene glycol ether group and 10 to 100 propylene glycol ether 3 8 ~
g group3. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples o~ nPn-ionic s~rfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylenelpolyethylene o~ide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxypolyethoxyethanol. Fatty acld esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic suractants.
Catio~ic ~ur~actants are preferably ~uaternary ammonium salts which contain, as N-sub~tituent, at least one polyglycol ether or C8-C22alkyl radical and, a further sub~ituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxylalkyl radicals. The salts are preferably in the ~orm of halide~ methylsulate3 or ethylsul~ates, e.g. stearyltrimethyLammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The sur~actants customarily employed in the art of formulation are described e~g. in th~ following publications: "McCu~cheo~'~ Detergents aad ~mulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, lg79;
Sisaly and Wood, I'Encyclopedia of Surfac~ Active Agents", Chemical Publishing Co. Inc., ~ew York, 1964.
The concentration of active ingredient in commercial compssitions is from 0.1 to 95 % by weight, prPferably from 1 to 80 % by weight.
Pre~erred formulations are composed in par~icular of ~he following constituent~ (/0 ~ perc~n~age 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%
active ingredient:10% to 50%, pref~rably 10 to 40%
surfactant:5% to 40%, preferably 10 to 20%
liquid carrier:20% to 95%, preferably 40 ~o 80%
Dust active ingredient:0.5 to 10%, preferably 2 to 8%
solid carrier:99.S to 90%, preerably 98 o 2%
active ingredient:5 to 75%, preferably 10 to 50/0 wa~er:94 to 25%, pre~erably 90 to 30%
surfactant:1 ~o 40%, preferably 2 to 30%
Wet~ablel~owders active ingredient:5 to 90%, pre~erably 10 ~o 80% and, most preferably, 20 to 60~
surfactant:0. 5 to 20%, preferably 1 to 15%
solid carrier:5 to 90%, preferably 30 'co 70%
Granulates aotive ingredient:0.5 to 30%, preferably 3 to 15%
solid carrier:9905 to 70%, prefer~bly 97 to 85%.
~ ~6~3~38ll Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formulations. The ~ormulations can be diluted to a concentration as low as 0.001%.
The compositions of the invention can be mdxed wlth other biocidal compounds or compositions. Accordingly, in addition to containing the comlpounds of the general formula I and ~ormula II~the compositions o~ the invention can also contain e.g. insecticide,s, fungicides, bactericides, fungistats~ bacteriostats, or nematocides7 in order to broaden the activity spectrum.
Herbicides ~lways have a ~ynergistic effect if the herbicidal action of the c~mbination of I + II is greater than the sum of the action of the individual active ingredient~.
The expeeted plant growth E for a give~ combinatio~
of two herbicides can be calculated as follows (cf. COLBY, S.R., "Calcula~ing ~ynergistic and antagonis~ic respon~es of herbicide compo~itions'9, Weeds 15, pages 20-22~1967~:
wherein 100 X - the percentage grawth (compared with untreated plants) after treatment with a herbicide I at a rate of application of p kg per hectare, Y ~ the percentage growth after ~reatment with a herbicide II at a rate of application of q kg per hectare, and E - the expected percentage growth (compared with the control pla~ts) after treatment with the herbicidal mixture of :C ~ II at a rate o application of p ~ q kg of active ingredient per hectare~
~ ~ 6~3~ li If the actually observed value is lower than the expected value E, then thare is s~nergism.
The synergistic effect of the combinations of compounds I and II is demonstrated in the following Examples.
.~ 6 ~ 8 ~ 13 -Example 1:
The test plants are sown, in a greenhouse, in plastic containers fil~ed with 30 litres of sterilised garden soil.
The plants are then sprayed pos~emergence in the 2- to 3-leaf s~age with an aqueous dispersion of the com~ination of herbicides. The rat~ of application of the di~persion is 50 ml/m2 . Evaluation is made after 20 days at 18 i-20C
and a relativs 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 S - medium damage 9 - n~rmal s~ate.
The following results are obtained with different mixture ratios and total am~unts of active ingredient:
a) Table l:Tolerance and activity o~ 4-(3',5'-dichloro-pyridyl-2'-oxy)-a-phenoxypropionic acid propargyl ester (compound Ia) and compounds lIa to IIf, and mixtures thereof, when applied pos~-em~rgence: , __ _~ l _~ _ ~ ~ :`~ . - 14-C1 . _ ~ __ _ _ _ ~ o _, ~ ~ C`~ ~ ,~ _ .u O ~ C~ ~ a~ ~ ~
Q~ -- u~ . _ : ~ __ _ _ 3 o . ~ C`J ~ ~:r ~ ~
~ Ul . ~ ~ ~ ~ ~ _-e o -~~ __ _ _ _ _ _ _o . C~ ~ ~ O Cl ~
~ O`O ~4 ~ G~ ~ ~
~ o o . _ _ _ __ _ U~, . _ _ _ _ C~l U~ o . _ _ _ _ _ _ o . ~ _, ~I _, _ _, O a~ cr o~ ~ ~ cr W _ U~ l __ .,. ' .; _ _ 'w . ~ ~ _, C~ ~ ~
~ U~ o ' . _ _ _ _ _ ~ . . C~ ~ _l _, ~ ~, ~ o _, . _ _ ~ _ _ W _ ~ . C~ Cr~ CJ _ ~ 01 ~ o o . ~ ;.. _, ~ ~ ~
U~ ~ ~ ~ _. C~l _ ~
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~ o C`~ ~I C`~ ~'I ~ ~`I
O O . __ _ _ _ ~`I
l _ Ul. ~ _ _ _ _ ; C`~
:1 U~ O . _ . ; _ _ ~`I
_~ ~ . _ . _ _ .
_ .... .. . C~ C`l C~ ~.. C~l _Y
u~ ¢~ ~ a~ o~ a~ s~
O O . .,.. , ~.~ ~- _ _ . O cr ~ ~ 5~ c~ ol _ ___ . _ .. .~ _ _ _ c~ ~ o~ cl~ o~ ~ a~
U7 --O' . _ _ _ ..
_ O O . ~ a~ ~ e~ ,~ ~
~ -- U~ . ~ . _ .. . _ c~ O O . ~o ~o ~ r~ D ~
O__ C~ I;~ ~ ~ ~ ~
O --O- _ _ __ ~ C~ 3 ~, ~ æ~ w ., _ : .
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~6~ 3 - 15 ~
If the valuesrelating to the additi~e action calculated by the method of Colby are compared with the results reported in Table 1, then it is evident that the observed growth figures given for Sinapis arvensis and Chrysanthemum are lower than those calculated. The synergistic effect of the combination of 4-(3',5'-dichloro-pyridyl-2'-oxy)--phenoxypropionic acid propargyl ester and compounds IIa to IIf is thus demonstrated (cf. Table 2).
Table 2: Values calculated by the method of Colby for demonstrating the synergism of 4--(3',5'-dichlo~opyridyl-
The most requently encountered and most important - weeds at the presen~ ti~e in cereals are species of the genera Sinapis (mustard) and ChrysenthemLm(corn marigold), and certain Avena species (wild oats).
Excellent postemergence selectiYe herbicideY against monocot weeds are 4-~3' ,5'-dichloropyridyl-2'-oxy)-a-phenoxypropionic acid propargyl esters of the formula I
~Cl ~
Cl~ 0~ O-c~-co Z C~2 wherein Z is o~yge~ or sulfur.
The two co~pounds offormula~ viz. 4-(3',5'-dichloro-pyridyl-2~-oxy~--phenoxypropionic acid propargyl ester (Ia~
and 4-(3',5'-dichloropyridyl~2'-oxy)-a-phenox~thioFropionic acid propargyl eqter (Ib), processes for the production thereof and the us thereof as selectîve hPrbicides, are described in European paten~ publica~ion 3114.
~:
. ' ~', , .. . . .
It is known that dicot weeds, and also a number of mono- ~
cots, can o~nbe successfully controlled postemergence in cereals with 3-(3'-chloro-4'-methylphenyl)~ dimethylurea (Chlortoluron) of the formula IIa T~ C-~ ~o-N~I-CO~ ) (IIa) .~.
Cl .
or with 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (Metoxuron) of the form~la IIb 3 0 ~ NH-C0-N(C~3)2 (IIb) Cl :or with 3-(4'-isopropylphenyl)~ dimethylurea (Isoproturon) of the formula IIc ._.
7C3~ C0 ~(CS3) 2 (IIc) ., .
or with l-benzothiazol-2-yl-1,3-dimethylurea (Methabenzthiazuron) of the ormula IId N-C0-NH-Ca3 ( IId) : .
or with 4~hydroxy-3,5-diiodobenzonitrile (Ioxynil) of the .~ formula IIe ',, .
.~., j .. .
.. ~
6~8il !~ /OH
li i (IIe) or with 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',4'-dinitrophenyl)-oxime ~Bromophenoxime) of the formula IIf Br E10~ N-O-~ NO2 ~: Br ~72 ~, The compounds of the formulae IIa to IIf and their herbicidal activity are described e g. in the following publications:
Chlortoluron (compound IIa) in C.~. 5e Conf. Com. franc.:
Mauvaises Herbes (COLUMA), 1969, II3 3493 Metoxuron (compound IIb) in Z. Pflkrankh., PflPath., PflSchutz, 1968, 75, 233, Isoproturon (compound IIc~ in German Offenlegungsschrift 2 107 774, Methabenzthiazuron (compound IId) in P1Schutz-Nachr. Bayer3 1969, 22, 314, Ioxynil (compound IIe) in Nature, Lond., 1963, 200, 28~ and ; Bromofenoxime (compound IIf) in Proc, 3rd EWRC Symp.
~- "New Herbicides", Paris, 1968, S. 177.
Surprisingly3 it has now been ound that a combination o:E both classes of compound X nd II, in a ratio varing within specific limits, exerts a spe~ific synerglstic ~ action which is able to control the majority of all weeds ;~ ; in cereals without damaging these latter. The principal :;
.
. ~ .
:
~" .
S ~3 !,j weeds i.n cereals, such as species of the dicot genera Chrysenthemum and Sinapis as well as certain Avena (wild oat) species, are selec-tively destroyed in the emergent crops.
Accordingly, the invention provides a synergistic composition for selec-tively controlling weeds, which composition comprises, on the one hand, a 4-(3',~
5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester of the Eormula ~: I
Cl Cl-- ~ ~0~ O-CH-CO-Z-CH -C-CH (I) , o=1~
wherein Z is oxygen or su].fur, and, on the other, in approximately equal ratio to :~ 10 or in excess of component I, one of 3-(3'-chloro-4'-methylphenyl)-1,1-dimethyl-urea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isopro-.-. pylphenyl)-l,l-dimethylurea (IIc), l-benzothiazol-2-yl-1,3-dimethylurea (IId), . 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',4'-dinitrophenyl)-oxime (IIf), together with carriers and/or other adjuvants.
. 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 additive . . .
r enhancement of the activity spectrum against the customary weeds associated with cereals and soybeans, but gives rise to a synergistic effect which potentiates the action of both componen-ts 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 bo-th sin-gle compounds 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 cereals and soybeans, as is necessary and desirable in the event of unintentional ''' ~
.
,? ~ .
J :~ B ~
` overapplication.
In addition to beiny used in crops of soybeans and cereals such as bar-ley, rye and, in particular, whea-t, the composition of -this invention can also be used for selectively controlling weeds in crops of othe~ monocot plants having similar sensitivity to herbicides and similar weed infestation, e.g. in mai~e and rice.
The herbicidal combination emp]oyed in the practice of -this inven-tion will contain a compound of the formula I and a compound of the Eonnula II in equal amounts or with an excess of the component II. The preferred ratio o~ com-ponen-t I to component II is 1:1 to 1:25, with the most preferred ratio being from 1:1 to 1:10.
The herbicidal combina-tion has an excellent action against weeds with-out having any noticeable effects in crops of cereals when used in the conventio~
nal rates of application of 0.2 to 4 kg/ha, preferably 0.5 to 3 kg/ha.
The following combinations have proved particularly effective synergis-tic herbicidal mixtures:
a) 4-(3',5'-dichloropyridyl-2'-oxy)--phenoxypropionic acid propargyl ester (Ia) and 3-(3'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa), b) 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxythiopropionic acid propargyl ester (Ib) and 3-(4'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa), ` c) 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl -- ester (Ia) and 3-(4'-isopropylphenyl)-1,1-dime-thylurea (IIc), and ~:i d) 4-(3',5'-dichloropyridyl-2'-oxy)-~phenoxythiopropionic acid propargyl ester (Ib) and 3-(4'-isopropylphenyl)-1,1-dimethylurea ~IIc).
The present invention also relates to the use of the composition, i.e.
to a method of selectively controlling grasses and weeds postemergence in cereals.
."' ~
~' ~
I :~ 6~8/i In addition to the novel combina-tion of active ingredients, the composi-tion of this invention also contains suitable carriers and/or other adjuvan-ts.
These can be solid or liquid and correspond to -the substances ~onventionally employed in the art of formulation, e.y. natural or regenerated mineral substan-ces, solvents, dispersants, `~, :.
:
r;~
~'..;
!',~
., .
:, ~
''' ',~' ., : - 5a -' ~ :
wet~ing agents, ~acki~iers, thickeners, binders or fertilisers. Suitable formulations are therefore e.g.
emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g.
polymer substanc~s. The method~ of application, such as sprayi~g, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances, just like the nature of the co~positions~
The formulations, i.e. the compositions or preparations containing the herbi.cidal combina~ion o~ the invention and, where appropriate, a solid or liquid adjuvant, are prepared ill known manner, e~g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-ac~ive compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, prefexably the fractions cont~ning 8 to 12 carbon atoms, e.g. xylene mixtures or cubstituted naphthalenes, phthalate~ ~uch as dibutyl phthalate or dioctyl phthala~e, alipha~ic hydrocar~ons such as cyclohexane or parains, alcohols and glycols and their e~hers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketcnes such as cyclohexanone, strongly polar solvents such as N-methyl~2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconu~ oil or soybean oil; or w ter.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral filler3 such as calcite, talcum, kaolin~ montmorillonite or attapulgiteO In order to improve the phy~ical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granula~ed adsorptive carriers are porous 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 inorganic or organio 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, dispersing and wetting properties. The term "~urfactants" will also be unders~ood as comprising ~urfactant mixtures.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble 3ynthetic surface-active compounds .
Suitable soap~ are the alkali metal salts, alkaline earth metal salts or unsubs~ituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g~ the sodium or potas~um salts of oleic or stearic acid, or of natural fatty a~id mix ures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fa~ty acid methyltaurin salts.
More frequently, however, so-called syntheti~
surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimida201e derivatives or alkyl-arylsulfonategJ
q The fatty sulfonates or sulfates are usually in the form o~ alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety o~
acyl radicals, e.g. the sodium or calcium salt o~ ligno-sulfonic acid, of dodecylsulfate or of a mixtuxe of fatty alcohol sulfates obtained from natural ~atty acids. These compounds also comprise the salts of sulfuric acid esters and sul~onic acids of adduct~ of fatty alcohols and ethylene oxide. The ~ulfonated benzimidazole derlvatives preerably contain 2 sul~onic acid groups and one fatty ac~d radical containing 8 to 22 carbon atoms. Exampl s o~ alkylarylsulf~
onates are the sodium, calcium or triethanolamine salts o~
docecylbenzenesul~onic acid, dibutylnaphthalenesulfonic acid, or o~ a naphthalenesulfonic acid/formaldehyde condensatio~
product~ Also suitable are corresponding pho~phates, e.g.
salts of the phosphoric acid ester o an adduct of p-nonylphenol with 4 to 14 moles of ethylene o~ide.
~ on-ionic surfac~ants are pre~erably polyglycol ether derivatives o~ aliphatic or cycloaliphatic alcohols, or sat~rated or unsatura~ed fatty acids and alkylphenols, ~ald derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in ~he (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylph nols.
Further ~uitable non-ionic Qurfactants are t~e water~solu~le adducts of polyethylene oxide with poly-propyle~e glycol, ethylenediamlnepolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the aIkyl chain, which adduc s contain 20 to 250 ethylene glycol ether group and 10 to 100 propylene glycol ether 3 8 ~
g group3. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples o~ nPn-ionic s~rfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylenelpolyethylene o~ide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxypolyethoxyethanol. Fatty acld esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic suractants.
Catio~ic ~ur~actants are preferably ~uaternary ammonium salts which contain, as N-sub~tituent, at least one polyglycol ether or C8-C22alkyl radical and, a further sub~ituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxylalkyl radicals. The salts are preferably in the ~orm of halide~ methylsulate3 or ethylsul~ates, e.g. stearyltrimethyLammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The sur~actants customarily employed in the art of formulation are described e~g. in th~ following publications: "McCu~cheo~'~ Detergents aad ~mulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, lg79;
Sisaly and Wood, I'Encyclopedia of Surfac~ Active Agents", Chemical Publishing Co. Inc., ~ew York, 1964.
The concentration of active ingredient in commercial compssitions is from 0.1 to 95 % by weight, prPferably from 1 to 80 % by weight.
Pre~erred formulations are composed in par~icular of ~he following constituent~ (/0 ~ perc~n~age 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%
active ingredient:10% to 50%, pref~rably 10 to 40%
surfactant:5% to 40%, preferably 10 to 20%
liquid carrier:20% to 95%, preferably 40 ~o 80%
Dust active ingredient:0.5 to 10%, preferably 2 to 8%
solid carrier:99.S to 90%, preerably 98 o 2%
active ingredient:5 to 75%, preferably 10 to 50/0 wa~er:94 to 25%, pre~erably 90 to 30%
surfactant:1 ~o 40%, preferably 2 to 30%
Wet~ablel~owders active ingredient:5 to 90%, pre~erably 10 ~o 80% and, most preferably, 20 to 60~
surfactant:0. 5 to 20%, preferably 1 to 15%
solid carrier:5 to 90%, preferably 30 'co 70%
Granulates aotive ingredient:0.5 to 30%, preferably 3 to 15%
solid carrier:9905 to 70%, prefer~bly 97 to 85%.
~ ~6~3~38ll Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formulations. The ~ormulations can be diluted to a concentration as low as 0.001%.
The compositions of the invention can be mdxed wlth other biocidal compounds or compositions. Accordingly, in addition to containing the comlpounds of the general formula I and ~ormula II~the compositions o~ the invention can also contain e.g. insecticide,s, fungicides, bactericides, fungistats~ bacteriostats, or nematocides7 in order to broaden the activity spectrum.
Herbicides ~lways have a ~ynergistic effect if the herbicidal action of the c~mbination of I + II is greater than the sum of the action of the individual active ingredient~.
The expeeted plant growth E for a give~ combinatio~
of two herbicides can be calculated as follows (cf. COLBY, S.R., "Calcula~ing ~ynergistic and antagonis~ic respon~es of herbicide compo~itions'9, Weeds 15, pages 20-22~1967~:
wherein 100 X - the percentage grawth (compared with untreated plants) after treatment with a herbicide I at a rate of application of p kg per hectare, Y ~ the percentage growth after ~reatment with a herbicide II at a rate of application of q kg per hectare, and E - the expected percentage growth (compared with the control pla~ts) after treatment with the herbicidal mixture of :C ~ II at a rate o application of p ~ q kg of active ingredient per hectare~
~ ~ 6~3~ li If the actually observed value is lower than the expected value E, then thare is s~nergism.
The synergistic effect of the combinations of compounds I and II is demonstrated in the following Examples.
.~ 6 ~ 8 ~ 13 -Example 1:
The test plants are sown, in a greenhouse, in plastic containers fil~ed with 30 litres of sterilised garden soil.
The plants are then sprayed pos~emergence in the 2- to 3-leaf s~age with an aqueous dispersion of the com~ination of herbicides. The rat~ of application of the di~persion is 50 ml/m2 . Evaluation is made after 20 days at 18 i-20C
and a relativs 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 S - medium damage 9 - n~rmal s~ate.
The following results are obtained with different mixture ratios and total am~unts of active ingredient:
a) Table l:Tolerance and activity o~ 4-(3',5'-dichloro-pyridyl-2'-oxy)-a-phenoxypropionic acid propargyl ester (compound Ia) and compounds lIa to IIf, and mixtures thereof, when applied pos~-em~rgence: , __ _~ l _~ _ ~ ~ :`~ . - 14-C1 . _ ~ __ _ _ _ ~ o _, ~ ~ C`~ ~ ,~ _ .u O ~ C~ ~ a~ ~ ~
Q~ -- u~ . _ : ~ __ _ _ 3 o . ~ C`J ~ ~:r ~ ~
~ Ul . ~ ~ ~ ~ ~ _-e o -~~ __ _ _ _ _ _ _o . C~ ~ ~ O Cl ~
~ O`O ~4 ~ G~ ~ ~
~ o o . _ _ _ __ _ U~, . _ _ _ _ C~l U~ o . _ _ _ _ _ _ o . ~ _, ~I _, _ _, O a~ cr o~ ~ ~ cr W _ U~ l __ .,. ' .; _ _ 'w . ~ ~ _, C~ ~ ~
~ U~ o ' . _ _ _ _ _ ~ . . C~ ~ _l _, ~ ~, ~ o _, . _ _ ~ _ _ W _ ~ . C~ Cr~ CJ _ ~ 01 ~ o o . ~ ;.. _, ~ ~ ~
U~ ~ ~ ~ _. C~l _ ~
__ ~ . _ _ _ _ _ _ .
. . o, . ~ ~. ~ ~ ~
~ o C`~ ~I C`~ ~'I ~ ~`I
O O . __ _ _ _ ~`I
l _ Ul. ~ _ _ _ _ ; C`~
:1 U~ O . _ . ; _ _ ~`I
_~ ~ . _ . _ _ .
_ .... .. . C~ C`l C~ ~.. C~l _Y
u~ ¢~ ~ a~ o~ a~ s~
O O . .,.. , ~.~ ~- _ _ . O cr ~ ~ 5~ c~ ol _ ___ . _ .. .~ _ _ _ c~ ~ o~ cl~ o~ ~ a~
U7 --O' . _ _ _ ..
_ O O . ~ a~ ~ e~ ,~ ~
~ -- U~ . ~ . _ .. . _ c~ O O . ~o ~o ~ r~ D ~
O__ C~ I;~ ~ ~ ~ ~
O --O- _ _ __ ~ C~ 3 ~, ~ æ~ w ., _ : .
.
~6~ 3 - 15 ~
If the valuesrelating to the additi~e action calculated by the method of Colby are compared with the results reported in Table 1, then it is evident that the observed growth figures given for Sinapis arvensis and Chrysanthemum are lower than those calculated. The synergistic effect of the combination of 4-(3',5'-dichloro-pyridyl-2'-oxy)--phenoxypropionic acid propargyl ester and compounds IIa to IIf is thus demonstrated (cf. Table 2).
Table 2: Values calculated by the method of Colby for demonstrating the synergism of 4--(3',5'-dichlo~opyridyl-
2'-oxy)--phenoxypropionic. acid propargyl ester (com~ound I~) and compounds IIa to IIf.
3 ~ li . _ ul arr~A pa~ ~a dxa ~ ~ o o ~ ~'_ u~ O a~A pa~a~ap ~ ~ u~ ,~ u~ ~
a~ ~ . - _ _ _ . _ ~ o o an[~A pa~a dxa ~_ ~ ~ ~ ~ _, e ,, ~rrre~ par~la ~3p ~ ~ ~ ~ ,, ___ ~ __ _ _ _ _ _ ~e u~ ~rr@~, a dxa ~o_ ~ o ~ ~
o ~n~ p3u~ a~ap ,~ ~ ~ ~ ~ ul ~ u~ _ ............ . __ _ . c _ _ :~ O O rl[BI~ p~ d~ l ~ ~ o ~ ,.
. ____ __ _ _ _ _ __ar~eA p~ 3~aF . _ ~ ~ r~ c~l _ arr[~A pal ~adxa ~o_ ~ _, u~
o 3~ pau~la~ap ~ ~ _, . __ __ __ _ _ _ _ o o an~ pa~aaxa u~ ~ ~ c~ _, _, ar~ ~u~ a~aF __ _ _ _ _ _ _ __ ~__ _ _ _ _ anl~A pa~,oa~xa ~o ~ _, o r~ ap ~ u~ ~ ~ -~
~u~ ~ _ _ _ _ ~ O O 3~ p~ dx~ ~ ~ ,, ~ _, ~
c~ r~~ a~ BA pall~ ~ ~`1 _ _ _ _ __ ~_ __ _ _ __ _ _ u~ all~2A pa~:~adx- ~ ~ ~ ~ ~ ~
O ~A p3tT~mla:lap ~ C~l ~1 C~l c~ ~1 . . . , _ . _ _ ~ _ _ O O II~A pa~,~adxa ~ ~ ~ ~ ~ ~
,~ ~_ _ _ _ _ all~ p~la3,ap ~ ~ ~ ~ ~ _, .- _ __ ~ _ ta u~ al~A pa~axa w o ~ _, _, ~_, _, ........... -~
C 3tll~?A ~ p~wla~ap ~ ~ c~l ~ ~ _~
c, u~ __ ~_ _ _ _ _ _ .3 O O arrreA pa~adxa ~ ~ ~ C~l ~
_, a~ A pa~,m~ 3p c~ ~ ~ ~ ~
_ _ __ __ _ _ _ _ _ _ u~ 3n~ pa~adxa u~ u~ ~ u~ ~ u~
. __ _ __ . . . . _ u~ O ~eA p~mla~a ~ 8 o o o o .
O O ~nlBA pa1 ~dx. ,~ ,~ ,~ u~ u~ r~
3 . _~ an~eA p3~WIa~aF ~` ~ ~ ~ ~
~nleA pa~,~a x._ ~ ~ ~ ~ ~.
o an~A pa~a~ap u~ ~ ~ ~ co ~
r~~ .~ _ _ _ _ _ . I
O O tl~BA pa ~ ~a dx~ ~ ~ ~ ~ ~o c~ oa~rrLeA paul,n:Ia~aF u~ ~ ~0 u~ ,~ ~3 _ ~ E~__ ~ ~ H ~_1 H u~
L~ a ~ 9 o ~ __ a~ a a~ a~ ~a~ ~
~ 8~/A
b) TabLe 3:Tolerance and activity of 4~(3',5'-dichloro-pyridyl-2'-axy)-~-pheno~thiopropionic acid propargyl ester (compound Ih) and compounds IIa to IIf, and mdx~ure~
thereaf, when applied post-emergence:
3 8 ~
_ _ ~ _ _ __ _ - 18 -~ ~ ~ I ~ ~ ~
U~ . . . _ _ _ . _ _ ~ . ~r ,~ ~ ~o c~l _~
6 O _. . _ _ _ _ _ c~ a~ cl ~ ~ ~1 o~
~ _ U~ . __ _ _ _ _ o . ~ ~ I C~l `O c~ ~'1 U=~ _. _ j. . _ __ ~ U~. C`~ ~ C~l ~o ~ _~
O _~ . __ __ _-.
.~ C~ :J~ C~ ~ 5~ ~ Cl~
C _ ~ l _ _ _ _. __ ~ . ~.:3 ~ V~ ~ ~r ~
~C:l , _ _ _ _, . _ I~ O ~
. ~ ~ ~ `t O~ ~
_-- u~ : __ _ _. _ _ O ~ ~ _~ ~ _~ ~
Ul ,. , __ _ _. . .
e~ . C~l ~ _l _l _l O _~ , . _ _ _ _~ .. . _ O c~ ci~ a~ cr~ a~ ~
o~ -- U~ l _ _ _ _. _ _ ._~ . ~ ~'7 _ ~ ~ ~1 C U~ ~ . _ , _. _ ~ .. C~l ~ ~ _~ _I ~
~ O ,_1 . _ _ . __ ~
o~ ~ a~ ~ 5~ o~
__ __ l _ _ _ _ _ _ .~ Ul ~o ~ ,-1 ~ C~l ,C O' ~. __ _ . _ V~ . ~ C`~ ~ ~ _~ ~
__ ~1 , _ __ ,,._. _ _ . c`J ~ ~ ~ ~ c`l u~ o ~ - - - :- -- -~ . c`l c`l ~ ~ ~ ~
~~ ~------ ----o c`~
- ~ l - - - - - -. c`l ~ ~ c'~ ~ ~
~ ~ o ~ ~- - - -~ . . ~ ~ ~ c`l ~ ~
'3 o -~ l - - - - - -o ~ c`
~ --~--l----~ --cC~ u~ a~ ~ cn O~ :n ~ o o l------------o c~ ~ l~ ~ ~ o~
~ -- ~ l----~
a~ ~ ~ co u~ o l - ~- - - -. . ~ ~ ~ c~ cr~ o~
o -l ~ - - -~ ~ ~ r~ r~ ,~ r~ ~
~ - u~ l - - - - - -a~ . ,~ cr. a~ ~ ~ 5~
~ u~ o~ ~ - - - -- o -~ ~ ~ x ~ ~ cr~
., S~ O r. I~ r~ r~ r~ I~
~ - u~ l - - - - - -o a~ a~
c~ o - - - - - - - -_ . ~ ~ a~ ~ ~ ~
-----l ~ ----~ su - s~ ~ ~ u ~ c) u~
~ a ~ ~ cO, ~ ~ ~ ~ ~ ~ ~ ~
~l ~1 O hn O O hD O O O O O O
; ~ ~_ c~5~ c~ '~ ~ ~ ~ c~ Q~
1 3 B~3~3li 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 Sinapis arvensis and Chrysanthmum segetum are lower than those calculated. The synergistic effect o~ the combination of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxythiopropionic acid ester (compound Ib) and compounds IIa to IIf is thus demonstrated (cf. Table 4).
Table 4: Values calculated by the method of Colby for demonstrating the synergism o~ 4-(3',51-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and compounds IIa to IIf.
- ~ 3 ~3~/i - 20 ~
_~ _ __ ~ _ ~ _ _ u~ ~ p~adx~ ~ ~ ~ ~ ,~ u~
~ o ~P _ _ _ o ' _ _ U U~ . ~ _ ~ ~ ~ ~ .~ C`J
~,o ~ an~l~ p~aaxa ~ ~ r- ~3 ~
o o__ ~O_ _, ~ . _, _, ~ _ _1~ P~ P ~ _ ~ ~o ~ _,-an~ pa~ aa dxa ~ ~ o ~1 ~ ~
~ u~ ~ ~L ~o u~ . ~ .. ~_ u O i~lleA ~3~11;~;3p . u~ ~1 ~ e~l ~`1 ~ U~ __. __ __ __ _ 8 O O ~ A pe~ dx~ ~_ ~ ~ 8 - - ~ ~ ~ ~ ~ ~
o an~eA_p~ dx~
~T~?A Feu~;E:ap ~ ~ _, . __ _ _ _ . _ v. o o 3rr[~A pa~oadxa ~ ~ _. ~ _ , e anleA pa~m3la~al ~ ~7 _, _~ _, ~ .
an~pA pa~oa a ~ u~ ~ u~ ~ u O aT~A E~:l~;~
o~~ - - ~ - - ~ - - -e o o an eA pa~oadxa ~ ~ _, ~ _, _-u~ _~ ar~ peul~a~p ~ . ~ _~ _, _. ~
_ _ __ __ _ _ _ _ _ _ ~ arrreA pa~ dxa c~l ~ ~ ~L
Ul --ar[ eA pau~3~ap c~ ~ _~ _; ~
O O 7rl~A pa~,~adxa ~ ~ ~ ~ ~ ~
. ~ _____ ~ _, a~A p~a:~3p ~ ~ ~ ~ ~ e~l 3 _ . _. ~_ _ _ ___ n~ p~adx~ ~ ~ ~ ~ ~ ~
0 o ar~BA P~F _ _ _ ~ _ _ C It7 _~ ,___~_ d _ _ _'1 d _I
:~ . arE~A pa~aaxa C~l ~ ~ . c~
<d O O ~ _~ _l c~ ~ _~ _l __ _ an~A paUI~ =;aF ~ ~ _, ~ ~ _.
U~ a~A pa:~adx~ U~ U~ ~ ~ u~
U ~ O ~n~BA E~3Ullll:l~p oo O o ~ O 8 ~d o o ~ 7~ U~ _;~ o U~
_- ~r{ eA E~ a~ap o _~ o r~ _~ 8 _ __ __ _ _ _ . _ _ _ _ u~ ~nlsA p~aax~ u~ ~ u~ u~ u~ u~
P u~ o a~[eA pa~m~a~ r~ ~ ,~ _~
o o all~A pa~dx F ~1_ ~ ~i oo ~ ~ 5 ~ ~ ~ ~, ~ ~ ~ ~ ~
~ ~ ~ ~ e ~ ~ ~ ~ ~
E~ ~ 0 00 O 0 ~0 O O O O O O
:; _ ~ ~ __ ~ C~ C~ ~ ~ ~
~6 Example 2: Field tests in wheat ~ields yielded the following results. The growth figures are reported as percentages compared with the untreated control field.
a) Field test in Cisse/France.
Applica~ion on March 18, 1980.
Evaluation 85 days after application (June 10, 1980).
Compound ~wth of AVENA FATU~ Growth of rate of appl~- ~bserved expected accord- WHEAT
cation in g/ha _ ing to COLBY __ Ia: 150 50 _ 100 Ib: 200 55 ~ 100 IIa:2000 60 _ 100 IIc:1250 90 _ 100 Ia +}Ia: (150 + 2000) 12 30 100 Ia +IIc: (150 ~ 1250) 6 45 100 Ib +IIa: (200 + 2000) 12 33 100 Ib ~IIc: t200 ~ 12S0) S 50 _ ___ b) Field test in Pouant/France.
Application on ~arch 19, 1980.
Evaluation 84 days after application (June 10, 1980~.
. _ . . . ~ ~
Gompound Growth of AVENA FATU~ ~rowth of rate of appli~ observed expected accord- WHEAT
- _ in~to COLBY ____________ Ia: 150 15 _ 100 Ib: 200 20 _ 100 IIa: 2000 80 _ 100 IIc: 1250 70 _ 100 Ia + lIa:(150 + 2000) 2 12 100 la + IIc: (150 t- 1250) O 10.5 100 Ib I IIa: (200 + 2000) 3 16 100 Ib + IIc: (200 + 1250) 2 12 100 . .. _ .. ,, __. . ...
Formulation Examples Exampl _ Forcu~l~ [l~ c6~ for syner~istic mixtures of the ~ormulae I and II (throughout1 percentages are by weight) a) Wettable powders a) b) c) d) compound Ia or Ib 10 % 20 % 5 % 30 %
one of compounds IIa to IIf 10 % 40 % 15 % 30 %
sodium lignosulfonate S % 5 % S % 5 %
sodium laurylsulfate 3 ~/0 - 3 %
sodium diisobutylnaphthalene-sulfonate - 6 % - 6 %
octylphenol polyethylene glycol ether (7-8 moles o ethylene oxide) - 2 % - 2 %
highly dispersed silicic acid 5 % 27 % 5 % 27 %
kaolin 67 % - 67 %
The active ingredient mixture is t ~ oughly mixed with the adjuvants and the mixture ~ ~roughly 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 %
one of compounds IIa to IIf 5 % 20 % 13 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 3 % 3 %
calcium dodecylbenzenesulfonate3 % 3 % 3 %
castor oil polyglycol ether (36 moles o~ ethylene oxide) 4 % 4 % 4 %
cyclohexanone 30 % 30 % 30 ~/0 xylene mixture 50 % 35 % 35 %
Emulsions of any required concentration can be obtained from these concentrates by dilution with water.
I~ --~) Dusts a) b) c~ d) compound Ia or Ib 2 % 4 % 2 % 4 %
one of compounds IIa to IIf 3 % 4 % 4 ~/0 8 %
talcum 95 % - 94 %
kaolin - 92 % - 88 %
Dusts which are ready for use are obtained by mixing the active ingredient mixture with the carriers~ and grînding the mixture in a suitable mill.
d) Extruder ~ranulates a) b) c) compound Ia or Ib 5 % 3 % 5 %
one of compounds IIa to IIf 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 %
one of compounds IIa to II 1.5 % S %
polyethylene gly~ol 200 3.0 % 3 %
kaolin 94.0 % 89 %
The finely ground active ingredient mixture is uniformly applied, in a mixer, to the kaoLin moistened with poly-ethylene glycol. Non-dusty coated granulates are obtained in this manner.
..
.
I ~
`` I 3 ~ 8 '~
f) ~ es a) b) compound Ia or Ib 20 % 20 %
one of compounds IIa to IIf 20 % 40 %
ethylene glycol . 10 % 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % 6 %
sodium lignosulfonate 10 % 10.0 %
carboxymethylcellulose 1 % 1.0 %
37 % aqueous formaldehyde solut:ion 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 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 o any desired concentration can be obtained by dilution with water.
,.
a~ ~ . - _ _ _ . _ ~ o o an[~A pa~a dxa ~_ ~ ~ ~ ~ _, e ,, ~rrre~ par~la ~3p ~ ~ ~ ~ ,, ___ ~ __ _ _ _ _ _ ~e u~ ~rr@~, a dxa ~o_ ~ o ~ ~
o ~n~ p3u~ a~ap ,~ ~ ~ ~ ~ ul ~ u~ _ ............ . __ _ . c _ _ :~ O O rl[BI~ p~ d~ l ~ ~ o ~ ,.
. ____ __ _ _ _ _ __ar~eA p~ 3~aF . _ ~ ~ r~ c~l _ arr[~A pal ~adxa ~o_ ~ _, u~
o 3~ pau~la~ap ~ ~ _, . __ __ __ _ _ _ _ o o an~ pa~aaxa u~ ~ ~ c~ _, _, ar~ ~u~ a~aF __ _ _ _ _ _ _ __ ~__ _ _ _ _ anl~A pa~,oa~xa ~o ~ _, o r~ ap ~ u~ ~ ~ -~
~u~ ~ _ _ _ _ ~ O O 3~ p~ dx~ ~ ~ ,, ~ _, ~
c~ r~~ a~ BA pall~ ~ ~`1 _ _ _ _ __ ~_ __ _ _ __ _ _ u~ all~2A pa~:~adx- ~ ~ ~ ~ ~ ~
O ~A p3tT~mla:lap ~ C~l ~1 C~l c~ ~1 . . . , _ . _ _ ~ _ _ O O II~A pa~,~adxa ~ ~ ~ ~ ~ ~
,~ ~_ _ _ _ _ all~ p~la3,ap ~ ~ ~ ~ ~ _, .- _ __ ~ _ ta u~ al~A pa~axa w o ~ _, _, ~_, _, ........... -~
C 3tll~?A ~ p~wla~ap ~ ~ c~l ~ ~ _~
c, u~ __ ~_ _ _ _ _ _ .3 O O arrreA pa~adxa ~ ~ ~ C~l ~
_, a~ A pa~,m~ 3p c~ ~ ~ ~ ~
_ _ __ __ _ _ _ _ _ _ u~ 3n~ pa~adxa u~ u~ ~ u~ ~ u~
. __ _ __ . . . . _ u~ O ~eA p~mla~a ~ 8 o o o o .
O O ~nlBA pa1 ~dx. ,~ ,~ ,~ u~ u~ r~
3 . _~ an~eA p3~WIa~aF ~` ~ ~ ~ ~
~nleA pa~,~a x._ ~ ~ ~ ~ ~.
o an~A pa~a~ap u~ ~ ~ ~ co ~
r~~ .~ _ _ _ _ _ . I
O O tl~BA pa ~ ~a dx~ ~ ~ ~ ~ ~o c~ oa~rrLeA paul,n:Ia~aF u~ ~ ~0 u~ ,~ ~3 _ ~ E~__ ~ ~ H ~_1 H u~
L~ a ~ 9 o ~ __ a~ a a~ a~ ~a~ ~
~ 8~/A
b) TabLe 3:Tolerance and activity of 4~(3',5'-dichloro-pyridyl-2'-axy)-~-pheno~thiopropionic acid propargyl ester (compound Ih) and compounds IIa to IIf, and mdx~ure~
thereaf, when applied post-emergence:
3 8 ~
_ _ ~ _ _ __ _ - 18 -~ ~ ~ I ~ ~ ~
U~ . . . _ _ _ . _ _ ~ . ~r ,~ ~ ~o c~l _~
6 O _. . _ _ _ _ _ c~ a~ cl ~ ~ ~1 o~
~ _ U~ . __ _ _ _ _ o . ~ ~ I C~l `O c~ ~'1 U=~ _. _ j. . _ __ ~ U~. C`~ ~ C~l ~o ~ _~
O _~ . __ __ _-.
.~ C~ :J~ C~ ~ 5~ ~ Cl~
C _ ~ l _ _ _ _. __ ~ . ~.:3 ~ V~ ~ ~r ~
~C:l , _ _ _ _, . _ I~ O ~
. ~ ~ ~ `t O~ ~
_-- u~ : __ _ _. _ _ O ~ ~ _~ ~ _~ ~
Ul ,. , __ _ _. . .
e~ . C~l ~ _l _l _l O _~ , . _ _ _ _~ .. . _ O c~ ci~ a~ cr~ a~ ~
o~ -- U~ l _ _ _ _. _ _ ._~ . ~ ~'7 _ ~ ~ ~1 C U~ ~ . _ , _. _ ~ .. C~l ~ ~ _~ _I ~
~ O ,_1 . _ _ . __ ~
o~ ~ a~ ~ 5~ o~
__ __ l _ _ _ _ _ _ .~ Ul ~o ~ ,-1 ~ C~l ,C O' ~. __ _ . _ V~ . ~ C`~ ~ ~ _~ ~
__ ~1 , _ __ ,,._. _ _ . c`J ~ ~ ~ ~ c`l u~ o ~ - - - :- -- -~ . c`l c`l ~ ~ ~ ~
~~ ~------ ----o c`~
- ~ l - - - - - -. c`l ~ ~ c'~ ~ ~
~ ~ o ~ ~- - - -~ . . ~ ~ ~ c`l ~ ~
'3 o -~ l - - - - - -o ~ c`
~ --~--l----~ --cC~ u~ a~ ~ cn O~ :n ~ o o l------------o c~ ~ l~ ~ ~ o~
~ -- ~ l----~
a~ ~ ~ co u~ o l - ~- - - -. . ~ ~ ~ c~ cr~ o~
o -l ~ - - -~ ~ ~ r~ r~ ,~ r~ ~
~ - u~ l - - - - - -a~ . ,~ cr. a~ ~ ~ 5~
~ u~ o~ ~ - - - -- o -~ ~ ~ x ~ ~ cr~
., S~ O r. I~ r~ r~ r~ I~
~ - u~ l - - - - - -o a~ a~
c~ o - - - - - - - -_ . ~ ~ a~ ~ ~ ~
-----l ~ ----~ su - s~ ~ ~ u ~ c) u~
~ a ~ ~ cO, ~ ~ ~ ~ ~ ~ ~ ~
~l ~1 O hn O O hD O O O O O O
; ~ ~_ c~5~ c~ '~ ~ ~ ~ c~ Q~
1 3 B~3~3li 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 Sinapis arvensis and Chrysanthmum segetum are lower than those calculated. The synergistic effect o~ the combination of 4-(3',5'-dichloro-pyridyl-2'-oxy)-~-phenoxythiopropionic acid ester (compound Ib) and compounds IIa to IIf is thus demonstrated (cf. Table 4).
Table 4: Values calculated by the method of Colby for demonstrating the synergism o~ 4-(3',51-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester (compound Ia) and compounds IIa to IIf.
- ~ 3 ~3~/i - 20 ~
_~ _ __ ~ _ ~ _ _ u~ ~ p~adx~ ~ ~ ~ ~ ,~ u~
~ o ~P _ _ _ o ' _ _ U U~ . ~ _ ~ ~ ~ ~ .~ C`J
~,o ~ an~l~ p~aaxa ~ ~ r- ~3 ~
o o__ ~O_ _, ~ . _, _, ~ _ _1~ P~ P ~ _ ~ ~o ~ _,-an~ pa~ aa dxa ~ ~ o ~1 ~ ~
~ u~ ~ ~L ~o u~ . ~ .. ~_ u O i~lleA ~3~11;~;3p . u~ ~1 ~ e~l ~`1 ~ U~ __. __ __ __ _ 8 O O ~ A pe~ dx~ ~_ ~ ~ 8 - - ~ ~ ~ ~ ~ ~
o an~eA_p~ dx~
~T~?A Feu~;E:ap ~ ~ _, . __ _ _ _ . _ v. o o 3rr[~A pa~oadxa ~ ~ _. ~ _ , e anleA pa~m3la~al ~ ~7 _, _~ _, ~ .
an~pA pa~oa a ~ u~ ~ u~ ~ u O aT~A E~:l~;~
o~~ - - ~ - - ~ - - -e o o an eA pa~oadxa ~ ~ _, ~ _, _-u~ _~ ar~ peul~a~p ~ . ~ _~ _, _. ~
_ _ __ __ _ _ _ _ _ _ ~ arrreA pa~ dxa c~l ~ ~ ~L
Ul --ar[ eA pau~3~ap c~ ~ _~ _; ~
O O 7rl~A pa~,~adxa ~ ~ ~ ~ ~ ~
. ~ _____ ~ _, a~A p~a:~3p ~ ~ ~ ~ ~ e~l 3 _ . _. ~_ _ _ ___ n~ p~adx~ ~ ~ ~ ~ ~ ~
0 o ar~BA P~F _ _ _ ~ _ _ C It7 _~ ,___~_ d _ _ _'1 d _I
:~ . arE~A pa~aaxa C~l ~ ~ . c~
<d O O ~ _~ _l c~ ~ _~ _l __ _ an~A paUI~ =;aF ~ ~ _, ~ ~ _.
U~ a~A pa:~adx~ U~ U~ ~ ~ u~
U ~ O ~n~BA E~3Ullll:l~p oo O o ~ O 8 ~d o o ~ 7~ U~ _;~ o U~
_- ~r{ eA E~ a~ap o _~ o r~ _~ 8 _ __ __ _ _ _ . _ _ _ _ u~ ~nlsA p~aax~ u~ ~ u~ u~ u~ u~
P u~ o a~[eA pa~m~a~ r~ ~ ,~ _~
o o all~A pa~dx F ~1_ ~ ~i oo ~ ~ 5 ~ ~ ~ ~, ~ ~ ~ ~ ~
~ ~ ~ ~ e ~ ~ ~ ~ ~
E~ ~ 0 00 O 0 ~0 O O O O O O
:; _ ~ ~ __ ~ C~ C~ ~ ~ ~
~6 Example 2: Field tests in wheat ~ields yielded the following results. The growth figures are reported as percentages compared with the untreated control field.
a) Field test in Cisse/France.
Applica~ion on March 18, 1980.
Evaluation 85 days after application (June 10, 1980).
Compound ~wth of AVENA FATU~ Growth of rate of appl~- ~bserved expected accord- WHEAT
cation in g/ha _ ing to COLBY __ Ia: 150 50 _ 100 Ib: 200 55 ~ 100 IIa:2000 60 _ 100 IIc:1250 90 _ 100 Ia +}Ia: (150 + 2000) 12 30 100 Ia +IIc: (150 ~ 1250) 6 45 100 Ib +IIa: (200 + 2000) 12 33 100 Ib ~IIc: t200 ~ 12S0) S 50 _ ___ b) Field test in Pouant/France.
Application on ~arch 19, 1980.
Evaluation 84 days after application (June 10, 1980~.
. _ . . . ~ ~
Gompound Growth of AVENA FATU~ ~rowth of rate of appli~ observed expected accord- WHEAT
- _ in~to COLBY ____________ Ia: 150 15 _ 100 Ib: 200 20 _ 100 IIa: 2000 80 _ 100 IIc: 1250 70 _ 100 Ia + lIa:(150 + 2000) 2 12 100 la + IIc: (150 t- 1250) O 10.5 100 Ib I IIa: (200 + 2000) 3 16 100 Ib + IIc: (200 + 1250) 2 12 100 . .. _ .. ,, __. . ...
Formulation Examples Exampl _ Forcu~l~ [l~ c6~ for syner~istic mixtures of the ~ormulae I and II (throughout1 percentages are by weight) a) Wettable powders a) b) c) d) compound Ia or Ib 10 % 20 % 5 % 30 %
one of compounds IIa to IIf 10 % 40 % 15 % 30 %
sodium lignosulfonate S % 5 % S % 5 %
sodium laurylsulfate 3 ~/0 - 3 %
sodium diisobutylnaphthalene-sulfonate - 6 % - 6 %
octylphenol polyethylene glycol ether (7-8 moles o ethylene oxide) - 2 % - 2 %
highly dispersed silicic acid 5 % 27 % 5 % 27 %
kaolin 67 % - 67 %
The active ingredient mixture is t ~ oughly mixed with the adjuvants and the mixture ~ ~roughly 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 %
one of compounds IIa to IIf 5 % 20 % 13 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 3 % 3 %
calcium dodecylbenzenesulfonate3 % 3 % 3 %
castor oil polyglycol ether (36 moles o~ ethylene oxide) 4 % 4 % 4 %
cyclohexanone 30 % 30 % 30 ~/0 xylene mixture 50 % 35 % 35 %
Emulsions of any required concentration can be obtained from these concentrates by dilution with water.
I~ --~) Dusts a) b) c~ d) compound Ia or Ib 2 % 4 % 2 % 4 %
one of compounds IIa to IIf 3 % 4 % 4 ~/0 8 %
talcum 95 % - 94 %
kaolin - 92 % - 88 %
Dusts which are ready for use are obtained by mixing the active ingredient mixture with the carriers~ and grînding the mixture in a suitable mill.
d) Extruder ~ranulates a) b) c) compound Ia or Ib 5 % 3 % 5 %
one of compounds IIa to IIf 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 %
one of compounds IIa to II 1.5 % S %
polyethylene gly~ol 200 3.0 % 3 %
kaolin 94.0 % 89 %
The finely ground active ingredient mixture is uniformly applied, in a mixer, to the kaoLin moistened with poly-ethylene glycol. Non-dusty coated granulates are obtained in this manner.
..
.
I ~
`` I 3 ~ 8 '~
f) ~ es a) b) compound Ia or Ib 20 % 20 %
one of compounds IIa to IIf 20 % 40 %
ethylene glycol . 10 % 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % 6 %
sodium lignosulfonate 10 % 10.0 %
carboxymethylcellulose 1 % 1.0 %
37 % aqueous formaldehyde solut:ion 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 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 o any desired concentration can be obtained by dilution with water.
,.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A synergistic composition for selectively controlling weeds, which com-position comprises, on the one hand, a 4-(3',5'-dichloropyridyl-2'-oxy)-.alpha.-phenoxy-propionic acid propargyl ester of the formula I
(I) , wherein Z is oxygen or sulfur, and, on the other, in approximately equal ratio to or in excess of component I, one of 3-(3'-chloro-4'-methylphenyl)-1,1-dimethyl-urea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isoprop-ylphenyl)-1,1-dimethylurea (IIc), 1-benzothiazol-2-y1-1,3-dimethylurea (IId), 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',-4'-dinitrophenyl)-oxime (IIf), together with carriers and/or other adjuvants.
(I) , wherein Z is oxygen or sulfur, and, on the other, in approximately equal ratio to or in excess of component I, one of 3-(3'-chloro-4'-methylphenyl)-1,1-dimethyl-urea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isoprop-ylphenyl)-1,1-dimethylurea (IIc), 1-benzothiazol-2-y1-1,3-dimethylurea (IId), 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',-4'-dinitrophenyl)-oxime (IIf), together with carriers and/or other adjuvants.
2. A composition according to claim 1 which comprises 4-(3',5'-dichloropy-ridyl-2'-oxy)-.alpha.-phenoxypropionic acid propargyl ester (Ia) and 3-(3'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa).
3. A composition according to claim 1 which comprises 4-(3',5'-dichloropy-ridyl-2'-oxy)-.alpha.-phenoxythiopropionic acid propargyl ester (Ib) and 3-(4'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa).
4. A composition according to claim 1 which comprises 4-(3',5'-dichloropy-ridyl-2'-oxy)-.alpha.-phenoxypropionic acid propargyl ester (Ia) and 3-(4'-isopropyl-phenyl)-1,1-dimethylurea (IIc).
5. A composition according to claim 1 which comprises 4-(3',5'-dichloropy-ridyl-2'-oxy)-.alpha.-phenoxythiopropionic acid propargyl ester (Ib) and 3-(4'-isopro-pylphenyl)-1,1-dimethylurea (IIc).
6. A composition according to claim 1, wherein the ratio of component (I) to component (II) is 1:1 to 1:25.
7. A composition according to claim 1, wherein the ratio of component (I) to component (II) is 1:1 to 1:10.
8. A method of selectively controlling weeds in cereals, which method com-prises treating weed-infested cereal crops postemergence with a herbicidally effective amount of a composition according to claim 1.
9. A method according to claim 8, wherein the weeds to be controlled are dicot weeds of the genera Chrysanthemum and Sinapis and Avena species.
10. A method according to claim 8 or 9, which method comprises treating the cereals crops at rates of application corresponding to 0.2 to 4 kg of total active ingredient per hectare.
11. A method according to claim 8 or 9, which method comprises treating the cereals crops 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 |
|---|---|---|---|
| CH5253/80-4 | 1980-07-09 | ||
| CH525380 | 1980-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168884A true CA1168884A (en) | 1984-06-12 |
Family
ID=4290492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381247A Expired CA1168884A (en) | 1980-07-09 | 1981-07-07 | Synergistic composition and method of selectively controlling weeds, especially in cereals |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0043802B1 (en) |
| AT (1) | ATE6336T1 (en) |
| AU (1) | AU7266281A (en) |
| CA (1) | CA1168884A (en) |
| CS (2) | CS221841B2 (en) |
| DD (1) | DD201967A5 (en) |
| DE (1) | DE3162368D1 (en) |
| DK (1) | DK302081A (en) |
| ES (1) | ES9000017A1 (en) |
| GR (1) | GR74323B (en) |
| IL (1) | IL63255A (en) |
| MA (1) | MA19203A1 (en) |
| NZ (1) | NZ197643A (en) |
| PL (2) | PL130694B1 (en) |
| PT (1) | PT73332B (en) |
| TR (1) | TR21038A (en) |
| ZA (1) | ZA814620B (en) |
| ZW (1) | ZW15681A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8357629B2 (en) | 1998-07-16 | 2013-01-22 | Bayer Cropscience Ag | Herbicidal compositions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3263881D1 (en) * | 1981-07-08 | 1985-07-04 | Ciba Geigy Ag | Synergistic agent and process for the selective control of weeds, especially in crops |
| DE3202440A1 (en) * | 1982-01-26 | 1983-07-28 | Bayer Ag, 5090 Leverkusen | HERBICIDES CONTAINING METHABENZTHIAZURON IN COMBINATION WITH PARTICULAR PHENOXYPROPIONIC ACID ESTERS |
| DE3415069A1 (en) * | 1983-11-19 | 1985-05-30 | Hoechst Ag, 6230 Frankfurt | HERBICIDAL AGENTS |
| DE3406655A1 (en) * | 1984-02-24 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | HERBICIDES CONTAINING METHABENZTHIAZURON IN COMBINATION WITH PARTICULAR PYRIDINYLOXYACETIC ACID DERIVATIVES |
| US5231071A (en) * | 1987-07-10 | 1993-07-27 | Hoechst Aktiengesellschaft | Herbicidial agents |
| EP0298901B1 (en) * | 1987-07-10 | 1992-01-15 | Hoechst Aktiengesellschaft | Herbicidal agents |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004414B1 (en) * | 1978-03-01 | 1985-07-24 | Imperial Chemical Industries Plc | Mixtures of herbicidal pyridyloxyphenoxypropanoic acid derivatives with other herbicides, and processes of killing unwanted plants therewith |
-
1981
- 1981-07-01 MA MA19403A patent/MA19203A1/en unknown
- 1981-07-03 EP EP81810270A patent/EP0043802B1/en not_active Expired
- 1981-07-03 CS CS815155A patent/CS221841B2/en unknown
- 1981-07-03 AT AT81810270T patent/ATE6336T1/en not_active IP Right Cessation
- 1981-07-03 DE DE8181810270T patent/DE3162368D1/en not_active Expired
- 1981-07-07 CA CA000381247A patent/CA1168884A/en not_active Expired
- 1981-07-07 GR GR65436A patent/GR74323B/el unknown
- 1981-07-07 PL PL1981241460A patent/PL130694B1/en unknown
- 1981-07-07 PL PL1981232076A patent/PL128326B1/en unknown
- 1981-07-07 ZW ZW156/81A patent/ZW15681A1/en unknown
- 1981-07-08 ES ES503777A patent/ES9000017A1/en not_active Expired
- 1981-07-08 IL IL63255A patent/IL63255A/en unknown
- 1981-07-08 TR TR21038A patent/TR21038A/en unknown
- 1981-07-08 DK DK302081A patent/DK302081A/en not_active Application Discontinuation
- 1981-07-08 PT PT73332A patent/PT73332B/en unknown
- 1981-07-08 DD DD81231584A patent/DD201967A5/en unknown
- 1981-07-08 AU AU72662/81A patent/AU7266281A/en not_active Abandoned
- 1981-07-08 NZ NZ197643A patent/NZ197643A/en unknown
- 1981-07-08 ZA ZA814620A patent/ZA814620B/en unknown
- 1981-07-30 CS CS819945A patent/CS221842B2/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8357629B2 (en) | 1998-07-16 | 2013-01-22 | Bayer Cropscience Ag | Herbicidal compositions |
| US8765638B2 (en) | 1998-07-16 | 2014-07-01 | Bayer Intellectual Property Gmbh | Herbicidal compositions |
| US8791050B2 (en) | 1998-07-16 | 2014-07-29 | Bayer Intellectual Property Gmbh | Herbicidal compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| GR74323B (en) | 1984-06-22 |
| ATE6336T1 (en) | 1984-03-15 |
| IL63255A (en) | 1984-03-30 |
| TR21038A (en) | 1983-05-27 |
| NZ197643A (en) | 1984-09-28 |
| AU7266281A (en) | 1982-01-14 |
| PL232076A1 (en) | 1982-03-01 |
| DE3162368D1 (en) | 1984-03-29 |
| EP0043802A1 (en) | 1982-01-13 |
| CS221841B2 (en) | 1983-04-29 |
| PL130694B1 (en) | 1984-08-31 |
| ZA814620B (en) | 1982-07-28 |
| PT73332A (en) | 1981-08-01 |
| ES9000017A1 (en) | 1990-05-16 |
| CS221842B2 (en) | 1983-04-29 |
| ZW15681A1 (en) | 1982-02-10 |
| PL128326B1 (en) | 1984-01-31 |
| IL63255A0 (en) | 1981-10-30 |
| PT73332B (en) | 1983-06-20 |
| EP0043802B1 (en) | 1984-02-22 |
| DK302081A (en) | 1982-01-10 |
| MA19203A1 (en) | 1982-04-01 |
| DD201967A5 (en) | 1983-08-24 |
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