CA1188533A - Herbicidal agents - Google Patents
Herbicidal agentsInfo
- Publication number
- CA1188533A CA1188533A CA000412534A CA412534A CA1188533A CA 1188533 A CA1188533 A CA 1188533A CA 000412534 A CA000412534 A CA 000412534A CA 412534 A CA412534 A CA 412534A CA 1188533 A CA1188533 A CA 1188533A
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- Prior art keywords
- compound
- iii
- formula
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
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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)
Abstract
Abstract of the disclosure:
The invention relates to herbicidal agents which contain a compound of the formula I
(I) in which R denotes H, NH4, Na, K or 1/2 Ca, and X denotes OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of the formula II
(II) in which X denotes Cl or CH3 and Y denotes H, an alkali metal, optionally substituted NH4 or alkyl, d with the compound of the formula III
(III) or the compound of the formula IV
The invention relates to herbicidal agents which contain a compound of the formula I
(I) in which R denotes H, NH4, Na, K or 1/2 Ca, and X denotes OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of the formula II
(II) in which X denotes Cl or CH3 and Y denotes H, an alkali metal, optionally substituted NH4 or alkyl, d with the compound of the formula III
(III) or the compound of the formula IV
Description
.~ ;3~
~ 2 - HC. 81/F 2~2 Th~ present invention relates to hPrbicid3l ~ents ~hich contain ~A~ a compound of the formula I
H3C ~ ~
, P C~2 CH2 - f~ ~ C ~I) RO ~H2 X
in ~hich R deno~es hydrogen, NH~ tla, K or lt2 Ca and X
denotes OH or -NH-~H(CH3)--CONH~CH(CH3)-COOH, in ~ombin~
at;on with (B) a compound of the formula II
Cl~ CH2 -- C~ tII) \OY
X.
in ~hich ~ denotes Cl or CH3 and Y denotes h)dro~cl1, an ~lk~li metal, N~14, NH3-CH3~ N~l2(C2H~)2 NH2~C1'13)2~ N~3-C2H4()H, Nlt2~c2H~oo~l) Nll(C2H~DoH~3 or (C1-C~-alkyl, and ~C~ the compound of the ~ormula III
Cl ~)\ ?~ 7.
Cl or the ~ompound of the formul~ IV
~ ' C2H5-NH N ~ N~I-C2H5 IV
wherein the ratio by weight of the components of the formulae I:II:III or IV is 1:(1 to 4):(0.5 to 6).
The compound of the formula I in which R -- hydrogen and X = -OH has also been disclosed under the name Phosphinotricin.
The compound of the formula I in which R = NH4 and X --~OH (= compound Ia, the ammonia salt of Phosphinotricin) is particu-larly preferred. It is described, for example, in German Offenlegungsschrift 2,717,440 and can be employed both as the racemate and as the optically active L-form. Compounds of the formula I in which X = -NH-CH(CH3)-CONH-CH(CH3)-COOH, such as are described, for example, in German Offenlegungsschrift 2~848,224, are also preferred.
Compounds of the formula II in which X denotes either chlori.ne (= compound :[Ia, common name: 2,4-D) or methyl (= compound I-Cb, common name: MCP~) are already known as growth regulators.
~oth are clescrihed, for example, in the "Pesticide Manual", edited by C.~. Worthing (1979), page 145 (IIa) and page 326 (IIb). They are preferably used in the form of alkali metal (sodium or potassium) or magnesium or amine salts, and in some cases also as esters (Y =
(Cl-C~)-alkyl) r for example as isopropyl or isobutyl esters.
The compounds of the formula III (common name: diuron) and of the formula IV (common name: simazine) are 4 ~
already known as her~;cides. Both are described, for example~ in th~ Pest;cide Manua~l, edited by ~.R~ Worthing ~1~79), page ~24 ~IIX) and page 474 tIY).
- At dosages of, preferablr~ O.S to ~5 kg~hectare of acti ~ compound, compounds of the formula I combat annual and perennial ~eeds belonging to various bo~anical - families, and the after-effects canf in so~e cases~ be considerable in the case of perennial specie~. In the case of perenniaL ~ramineae~ hohe~er~ the effect is no.
al~3ys satisfactory in some casesn Although a relatively rapid~ short~term burning-off effect is achieved on the green parts of the plants ~stalks and leaves)f a p,olonged effect of longer duration ;s frequently no~ ach;eved~
Compounds of the formula II make it possible to comoat numerous broad-leaved species of ueeds~ specific-ally bot~ a~nual and perennial species~ They are ~re~
~uently ernployed in cereai crops at dosages of less than 1 kg/hectare of active compoundu Another main area of use is in applicat;on ;n perennial crops, above all tree-like or shrub~like crops, such 3S vines~ fru;~ trees or citrus trees and var;ous tropical plantation crops~ such as rubber~ coffee, cocoa and the lil;e, or in bush-like crops, such as sugar cane or bananas. The dosayes here, ~hen used alone, are in most cases more than 1 kg/hectare, ;n come cases more than 2 kg~hectare~ of active co~po~nd.
In these crops, o~;ng to the lo~Jer volatility and the lower risk of possible damage to ~he crop plants caused there~y, it is preferab~e to use the salts o~ the ccmpour~ds of the fornula II, and ~he corresponding esters only to a 5 _ small extent. The said active compounds of the formula II are ab-sorbed via the leaf and are transported within the plant both to-wards the roots and towards the tips of the shoots.
The compounds of the formulae III and IV are also employed in the permanent plantations mentioned above, specifically in a wide range of dosage which can be betueen 0.5 and 5 kg/hectare of active compound, depending on the crop. Although they have a certain action on the weed flora present, they do not prevent, above all through their long-term action in the soil, the new emergence of weeds from seeds, while they have only a slight effect on re-sprouting from sur-viving parts of plants below ground (roots, tubers and rhi~omes).
It has also been disclosed that combinations of compounds of the formula I with compounds of the formulae III or IV, and also, on the other hand, combinations of compo~mds of the formula I with compounds of the formula II, exhibit a synergistic herbicidal action (cf., for example, German Offenlegungsschriften 2,839,087 and
~ 2 - HC. 81/F 2~2 Th~ present invention relates to hPrbicid3l ~ents ~hich contain ~A~ a compound of the formula I
H3C ~ ~
, P C~2 CH2 - f~ ~ C ~I) RO ~H2 X
in ~hich R deno~es hydrogen, NH~ tla, K or lt2 Ca and X
denotes OH or -NH-~H(CH3)--CONH~CH(CH3)-COOH, in ~ombin~
at;on with (B) a compound of the formula II
Cl~ CH2 -- C~ tII) \OY
X.
in ~hich ~ denotes Cl or CH3 and Y denotes h)dro~cl1, an ~lk~li metal, N~14, NH3-CH3~ N~l2(C2H~)2 NH2~C1'13)2~ N~3-C2H4()H, Nlt2~c2H~oo~l) Nll(C2H~DoH~3 or (C1-C~-alkyl, and ~C~ the compound of the ~ormula III
Cl ~)\ ?~ 7.
Cl or the ~ompound of the formul~ IV
~ ' C2H5-NH N ~ N~I-C2H5 IV
wherein the ratio by weight of the components of the formulae I:II:III or IV is 1:(1 to 4):(0.5 to 6).
The compound of the formula I in which R -- hydrogen and X = -OH has also been disclosed under the name Phosphinotricin.
The compound of the formula I in which R = NH4 and X --~OH (= compound Ia, the ammonia salt of Phosphinotricin) is particu-larly preferred. It is described, for example, in German Offenlegungsschrift 2,717,440 and can be employed both as the racemate and as the optically active L-form. Compounds of the formula I in which X = -NH-CH(CH3)-CONH-CH(CH3)-COOH, such as are described, for example, in German Offenlegungsschrift 2~848,224, are also preferred.
Compounds of the formula II in which X denotes either chlori.ne (= compound :[Ia, common name: 2,4-D) or methyl (= compound I-Cb, common name: MCP~) are already known as growth regulators.
~oth are clescrihed, for example, in the "Pesticide Manual", edited by C.~. Worthing (1979), page 145 (IIa) and page 326 (IIb). They are preferably used in the form of alkali metal (sodium or potassium) or magnesium or amine salts, and in some cases also as esters (Y =
(Cl-C~)-alkyl) r for example as isopropyl or isobutyl esters.
The compounds of the formula III (common name: diuron) and of the formula IV (common name: simazine) are 4 ~
already known as her~;cides. Both are described, for example~ in th~ Pest;cide Manua~l, edited by ~.R~ Worthing ~1~79), page ~24 ~IIX) and page 474 tIY).
- At dosages of, preferablr~ O.S to ~5 kg~hectare of acti ~ compound, compounds of the formula I combat annual and perennial ~eeds belonging to various bo~anical - families, and the after-effects canf in so~e cases~ be considerable in the case of perennial specie~. In the case of perenniaL ~ramineae~ hohe~er~ the effect is no.
al~3ys satisfactory in some casesn Although a relatively rapid~ short~term burning-off effect is achieved on the green parts of the plants ~stalks and leaves)f a p,olonged effect of longer duration ;s frequently no~ ach;eved~
Compounds of the formula II make it possible to comoat numerous broad-leaved species of ueeds~ specific-ally bot~ a~nual and perennial species~ They are ~re~
~uently ernployed in cereai crops at dosages of less than 1 kg/hectare of active compoundu Another main area of use is in applicat;on ;n perennial crops, above all tree-like or shrub~like crops, such 3S vines~ fru;~ trees or citrus trees and var;ous tropical plantation crops~ such as rubber~ coffee, cocoa and the lil;e, or in bush-like crops, such as sugar cane or bananas. The dosayes here, ~hen used alone, are in most cases more than 1 kg/hectare, ;n come cases more than 2 kg~hectare~ of active co~po~nd.
In these crops, o~;ng to the lo~Jer volatility and the lower risk of possible damage to ~he crop plants caused there~y, it is preferab~e to use the salts o~ the ccmpour~ds of the fornula II, and ~he corresponding esters only to a 5 _ small extent. The said active compounds of the formula II are ab-sorbed via the leaf and are transported within the plant both to-wards the roots and towards the tips of the shoots.
The compounds of the formulae III and IV are also employed in the permanent plantations mentioned above, specifically in a wide range of dosage which can be betueen 0.5 and 5 kg/hectare of active compound, depending on the crop. Although they have a certain action on the weed flora present, they do not prevent, above all through their long-term action in the soil, the new emergence of weeds from seeds, while they have only a slight effect on re-sprouting from sur-viving parts of plants below ground (roots, tubers and rhi~omes).
It has also been disclosed that combinations of compounds of the formula I with compounds of the formulae III or IV, and also, on the other hand, combinations of compo~mds of the formula I with compounds of the formula II, exhibit a synergistic herbicidal action (cf., for example, German Offenlegungsschriften 2,839,087 and
2,856,260).
It has now been fo~md that combinations of the known mix-ture3 of compounds oE the formulae I and II with compounds of the 2() -formulae :[II or IV, as well as comb:inations of compo~olds o:E the fOrlllUla I [ W:itll the known mixtures o:E compounds of the formulae I
and III or I and IV exhibit a surprising additional synergistic herbicidal action.
This surprising additional synergism of triple S3~
combinations according to the invention can also be confirmed, for example, by using the calculation Eormulae of S.R. Colby which are customary in connection with the discovery of synergism, by compar ing the action found experimentally (in % of damage) o:E a triple combination with the calculable total action of the individual effects of the components. If the latter is less than the former, synergism is indicated.
The ratios by weight of the components T~ III or IV
in the combinations according to the invention can vary within wide limits, but are within the range comprising 1:(1 to 4):(0.5 to 6), preferably within the range comprising 1:(1.5 to 2.5):(1 to 4).
The triplecombinations according to the invention can be used particularly advantageously to combat in a lasting manner an existing broad spectrum of weeds composed of annual and perennial species, and at the same time to keep the treated areas free for a prolonged period from weeds which emerge later (long-term prolonged effect). Depending on the dosage and on the proportion of the individual components, they can be employed in tree-like shrub-like c.rops oE the temperate and tropical zones, for example in vines, ~0 citrus Eruit, apples, pears, plums, cherries, soft fruit shrubs, rubber, oil palms, coffee or cocoa; in addition they can also be used in bush like crops, such as bananas or sugar cane.
The combinations according to the invention can be applied either as tank mixtures in which the individually formulated active compound components are only mixed _ 7 _ uith one another immediately before application, or as finished mixtures. As finished mixtures, they can be formulate~ or example~ in the forrn o~ eraulsifi~ble con-centrates or pre~erably, for exarnple~ in the form of ~et-S table po~ders~ and they then contain, if appropriate, thecust~rnary ~ormul;Jtion auxiliaries~ such asf for example, ~etting agents, adhesives, ~mulsifiers~ diso~rsing agents, sol;d incrt substances~ ~rinding auxiliaries and solvents.
The concentrations of the active cornpound combin~
acions according to t~e invention in the forrnulat-ions to be used car vary. In general, they are 2 to 95% by ~e;ght, pre~era~ly S to 80X by weight.
The inv~ntiorl also relates~ therefore, to herbi cidal agents containing 7 ~0 ~5-~ by weight, preferably 5 to ~OX by ~eight~ of an active compound combination colnposed of cornpounds of the iorrnulae I + II ~ I or IV
ancl also custornary ~ormulation auxiliaries~
In the we~table po~ders, the tot.~l concentration of ~ctive compound tI ~ III or I~ aries ~I;thirl the 2~ ran~ from about 10 to 8UX by h~eight; the rer,1air,der up ~o 100% by w~i~ht is cornposed of customary for~nulation additi~es.
For application~ the active compound concentrates accordil-g to the ir,venlion aref ;f appropriate~ diluted 2~ in a customary Manner, for e~mple ~ith ~ater in the case o~ wcttal)le powders and emulsion concentrates. The re-~quired application rate of the agents according to the in~ent;on also varies ~J;th the external conditions~ s(ch a5 ter,1perat(lre, humidity and other conditionsn I~ can ' vary ~/ithin ~ide li~;~s and is genera~y bet~een 0.5 and 20 kg~hectare of triple combination of active compounds, pre1ferably 1 ~o 10 kg/hectare.
_~ Formulation ex~æ~
S ~e~able powders con~aining triple combinations, accor~ing to the ;nvention~ of active compounds are pre-ferably prepared by vigorously m;xing, with the exclusion of r,~oisture, advantageously in a hammer mill~ the active compounds which are sparingly soluble in uater, such as, ~0 for example, the compound III (- diuron) in a finely ground form and already formulated as a wettable po~der, ~;th the water-soluble act;ve compounds, such as~ for example~ the compound la t- a~monium Phosphino~ricin~ and the sodium salt or dimethylamine sa~t of the compound IIb t- MCPA) or IIa t-~ 2,4 D) and ~ith the necessary ~Jettin~
agents and dispersing 2gents~ As a result of this the water-solub~e active compounds are very vigorously homogenized with the active compounds ~hich are sparingly solubLe ;n water and uith thesurface-active compounds, so that it is possible to achieve optimum wettability and suspendabil;ty in the resulting ~ettable po~ders.
In order to increase the free-flol~ing properties of the wettable powders, the latter can ad~antageously contain~ as carriers, for example, fine synthetic silica, kieselgUhr clay or bentonite powder. Examples of suitable dispersing agents are soclium dinaphthylm~thanedisulfonate, lignin sulfonates, condensatiorl proclucts of alkylnapthal-enesulfonic acids wi~h cresols, sodium sulfite ancl form-aldehyde~ oleoyl ~methylcaurides, polyvinyl alcohols or _ 9 ~
polyY;nylpyrrolidones~ ~hi(e examples of suitable wettincJ
agents are sod;u~ d;bu~ylnaphthalenesulfonate, sodium a~kylnaphthalenesulfonates~ aiky~sulfatcs~ preferabLy, fo~ example, alkali metal salts and ammonium salts of S the sulfuric ac;d half-ester of aliphatic ~C12-C16~-a~coho~ polyglycol ethers con~ainin~ 2~6 units of ethyl-ene oxide ~= wet~ing agent FES)u ~ iquid cr iow-meiting surface-active substances are advantageously first absorbed on adsorptive silica ?0 to 91ve pu~verulent dry concentrates and are mixed into th~ ~ettable powder in the forrn of powder. Suitable anti-foaming agents, if requirecl, are sod;um or potassium salts of ~atty acids and also sil;cones.
E m~_e 1 Preparation of a wettable powder having 53.Z~ by ~eiyht of a triple combination of active cornpounclsr con-~ai"incl 1ax by ueigh~ of compound Ia t 16.6~ by weigh~ of sodium compound IIb + 2b.6% by weicJht of compound III.
1.1 The form lation of a ~_ttable powder conta nu~g roo~ by we_cJht of com~nd III;
A mixture of 80.0~ by ~eight of compound III, 1~.0% by weight of synthetic silica, 6.0~ by weight o~
soa'ium dinaphthylmethanedisulfonate, 1.8% by weight of a sodium alkylnaphthalenesulfonate and 0.2% by weic~ht of sodiu~ oleoyl-N-methyltauridewas ground on a hiqh-speed p-lnnea'-d;sk milltO give a fine powder of particle size less than 44 rnicrons.
1u2 ~he Formulat1On of a wettincl ~ent a~Qu~LiQ~_ concentra_~_coMposed o~ a pas~y, aqueous sodium (C12_ f~tty alcohol polyglycol ether-sulfate ~= FFS~ and adsorp~
tive synttletic siLica:
~ 0 parts by weight of a 70X by weight ~S paste and 40 parts by ~eight of colloidal syn~hetic silica were vigorously mixed at a s~irrer speed of approximately 150 r.pOm. in a high-efficiency mixer containing a stirrer sha~t fitted ~;th circulating paddles, uhereby a pulveru~
~en~ adsorbate containing 42X by weight of FES active substance ~asobtained.
1.3 Preparation of the wettable Powder con_ainin~
53.2% by weiqht of t~!e triple combination of active_ c oMpoun ~s:
33.25 par.s by weight of 80% strength wettable powder of compound IIIr prepared in accordance uith 1.1 and containing 26.6 parts by Height of compound III, 10.00 parts by wei~ht of compound Ia~ 16.60 parts by ~ei~ht of the sodium salt of compound IIb~ 2-~ 80 parts by e;~ht of FES adsorbate wetting agent, prepared in accord-ance with 1~2 and contain;ng 10 parts by wei~ht of FES, 5~15 parts by wei~ht of sodium dtnaphthylmethanedisulfon~
ate, 2.00 parts by wei~ht of sodium dibutyLnaphthaLene-sulfonate, 1.~0 part by ueight o~ soap fla~es and ~o2U
par~s by weight of synthetic siLica weremixed ~lith exclusion of rnoisture and were then ground on a cross-hammer mill to give a finely pulverized product.
Example 2 __ __ ratior) of a wet able_po~lder havin~_~næ b~
ei~ t of a trie~e combination of_active co~o~lnds~_so~-tain~ 10% by~_~e~ght of_ ~m~Q~_Ia~ ~D~y--wei~h~-~f-sodium compou~1 I`3 1q~h~ p urld I I I r ; 12~5 parts by weigl)t of an 80X strength ~!ettable pouder of compound IIX, prepared in accordance ~ h Example 1~1 and containing 10 parts by ~eight of compound III, 10~0 parts by ~eight of compound Ia, 20~0 par~s ~y weight o~ the sodium salt o~ compound lIa~ 23.8 parts by wei~ht of FES adsorbate ~etting agent, prepared in accordance k'ith EXaMpLe 1.2 and contair,;ng 10 parts by ~eight of FE~, 5.~ parts b)~ ~eight of soc1ium dinaph~hylm2thanedisulfon atc, 3.0 parts by ~eight of sodium dibutylnaphthalene~sul~onate, 200 parts by ~eight of soap tlakes and 13.U
parts by ~ei~ht of synthetic silica 1~re mixed wi~h er~clus1on o~ moisture in a high-efficiency ~ixer analogously ~o Example 1, and the mixture ~as then ground on a cross--1~ hammer mill to give a finely pulverized productOB. Biological examples the biological examples I to IV which follow, a distinction is dra~Jn, for the ac~ive compound com~in-ations tested, be~ween the calculated degree of ac~ion an~ the degree of act;on found, on the weeds mentionecl~
~hc dcgree of action is calculated using the formulae of s.i'.Cl~Yr Calcula~ing synerg-istic and an~agonistic rcsponses of herbicide combinations ~Weeds 15 pages 20 Z2, 1~67) from the effects of the constituents of the combinations ~hen the latter are applied individually.
Formula (1) for the comb;nat,on of 2 active compounds is as follows:
y~ ~ Y
- X -~ Y
in ~hi~t~ X denotes % dama~e caused by herbicide A at an appltcation rate o~ x kgJhectare, Y denotes X damage caused by l-~rbic;de B ~t an app~ication rate of y kg~hectare and E denotes the ~xpected dar~age caus~d by ~he herbicides 5 A ~ æ at appl;cation rates clf x ~ y kyJhect~re~
For the combination of 3 actiYe com"ounclsO for-mula ~2) is given in the sarne p~biication f~r ça~culating the degree of acticn-(XY ~ X~ ~ YZ~ XY2 ~ ~ - (2 1 00 ~ O, 00~
1~ in ~h;ch Z denotes X damaae caused by herbicide C a~ an application rate of z kg/hectare and X and Y have th~ sar,le meaoings as in formu~a (1).
If the actual dama~e, ie. the damage determined ~x~rimentally, i~ srea.er thar, .hat caltula~ed, ~he action of the cornbination is more than additive, ie. a synerg;stic effect is present. In the biological examples ~hich follo~1, this evidence is presented for the combi-nations according to the invention~ the v~lues of aclion calculated from the above formulae being also shown in 2~ brackets in each case for the treatments with com~inations according to the invent;on, ~hile the action actually achie~ed agairlst the part;cular ~eeds m~ntioned is l;st~d after these ~i~ures.
~n biolo~ical examples I tc I`l~ coniparison ,s ~5 made not only ~ the action of the combination I
II ~ III or I~/ w;th that o~ the 3 individual acti~.~e com-pounds, but also ~;th the action of the cor,binatioos I -) II and I ~ IIX or ~'~', which are already l~no~!n~ ~hese - ~3 use ~xamples rela~e ~o field test~ ~hich ~ere carrie~l out under ~ar;o~s cl-imatie cond;~îons. The results are shown in summary form in Tables I to IV~ All the te~ts were carried out in plots of area lD to 20 m .
Example 1 Xn a test under trop;cal conditions on the ~eed Mikania corda1a in a rubber plantation, ~he ir,d;vidual eorrlpounds Ia, IIa and III ~ere ~ested alongsicle Grle another~
as was the kno~n comb;nation Ia + III. Botll ~/hen compared with 10 the ind;vidual produc's and when compared ~;th the known combination, combinations accurding to the invent;on, composed of these thlee active compounds~ produced a considerable ;ncrease in the ~ction, si~nificantly exceeding ~-he degree to be expected~ The action of the ~riple combinatiorls can, accordingly, be desicJrla~eci synergistic. ~-he result is sho~n ir, ~ummary forM in Table I belo~.
~able I
.
Combating Mikania cordata in a rubber plantation.
.~ ~ _~
Dosac~e of Action (% damage) on Mi~ania Treatrnent act;ve cordata (field test) S weeks after with active compound, treàtment compound kcJ/hectare calculated founcl , ,.. _ _.__. ___ ~ ______ _ a) Individual active compounds , .. .-_ ____ Compound Ia 0.4 5D
Cornpound IIa 0.8 60 Compound IIa 0.4 4û
Compound III 0.4 10 b) _no~n comb;nat;on Cornpounds Ia ~- III 0~4 ~ 0.4 70 3n c) Combinat;ons _ccording to the irvert_ n Compound~ Ia-lIIa-~ o.4ln~4+o~h ¦ (73~/82*^) 90 1:1 1 Compounds Ia1IIatIII¦0.4~0.X~O.h L (82*/88**) 96 1:2:1 . ~
It has now been fo~md that combinations of the known mix-ture3 of compounds oE the formulae I and II with compounds of the 2() -formulae :[II or IV, as well as comb:inations of compo~olds o:E the fOrlllUla I [ W:itll the known mixtures o:E compounds of the formulae I
and III or I and IV exhibit a surprising additional synergistic herbicidal action.
This surprising additional synergism of triple S3~
combinations according to the invention can also be confirmed, for example, by using the calculation Eormulae of S.R. Colby which are customary in connection with the discovery of synergism, by compar ing the action found experimentally (in % of damage) o:E a triple combination with the calculable total action of the individual effects of the components. If the latter is less than the former, synergism is indicated.
The ratios by weight of the components T~ III or IV
in the combinations according to the invention can vary within wide limits, but are within the range comprising 1:(1 to 4):(0.5 to 6), preferably within the range comprising 1:(1.5 to 2.5):(1 to 4).
The triplecombinations according to the invention can be used particularly advantageously to combat in a lasting manner an existing broad spectrum of weeds composed of annual and perennial species, and at the same time to keep the treated areas free for a prolonged period from weeds which emerge later (long-term prolonged effect). Depending on the dosage and on the proportion of the individual components, they can be employed in tree-like shrub-like c.rops oE the temperate and tropical zones, for example in vines, ~0 citrus Eruit, apples, pears, plums, cherries, soft fruit shrubs, rubber, oil palms, coffee or cocoa; in addition they can also be used in bush like crops, such as bananas or sugar cane.
The combinations according to the invention can be applied either as tank mixtures in which the individually formulated active compound components are only mixed _ 7 _ uith one another immediately before application, or as finished mixtures. As finished mixtures, they can be formulate~ or example~ in the forrn o~ eraulsifi~ble con-centrates or pre~erably, for exarnple~ in the form of ~et-S table po~ders~ and they then contain, if appropriate, thecust~rnary ~ormul;Jtion auxiliaries~ such asf for example, ~etting agents, adhesives, ~mulsifiers~ diso~rsing agents, sol;d incrt substances~ ~rinding auxiliaries and solvents.
The concentrations of the active cornpound combin~
acions according to t~e invention in the forrnulat-ions to be used car vary. In general, they are 2 to 95% by ~e;ght, pre~era~ly S to 80X by weight.
The inv~ntiorl also relates~ therefore, to herbi cidal agents containing 7 ~0 ~5-~ by weight, preferably 5 to ~OX by ~eight~ of an active compound combination colnposed of cornpounds of the iorrnulae I + II ~ I or IV
ancl also custornary ~ormulation auxiliaries~
In the we~table po~ders, the tot.~l concentration of ~ctive compound tI ~ III or I~ aries ~I;thirl the 2~ ran~ from about 10 to 8UX by h~eight; the rer,1air,der up ~o 100% by w~i~ht is cornposed of customary for~nulation additi~es.
For application~ the active compound concentrates accordil-g to the ir,venlion aref ;f appropriate~ diluted 2~ in a customary Manner, for e~mple ~ith ~ater in the case o~ wcttal)le powders and emulsion concentrates. The re-~quired application rate of the agents according to the in~ent;on also varies ~J;th the external conditions~ s(ch a5 ter,1perat(lre, humidity and other conditionsn I~ can ' vary ~/ithin ~ide li~;~s and is genera~y bet~een 0.5 and 20 kg~hectare of triple combination of active compounds, pre1ferably 1 ~o 10 kg/hectare.
_~ Formulation ex~æ~
S ~e~able powders con~aining triple combinations, accor~ing to the ;nvention~ of active compounds are pre-ferably prepared by vigorously m;xing, with the exclusion of r,~oisture, advantageously in a hammer mill~ the active compounds which are sparingly soluble in uater, such as, ~0 for example, the compound III (- diuron) in a finely ground form and already formulated as a wettable po~der, ~;th the water-soluble act;ve compounds, such as~ for example~ the compound la t- a~monium Phosphino~ricin~ and the sodium salt or dimethylamine sa~t of the compound IIb t- MCPA) or IIa t-~ 2,4 D) and ~ith the necessary ~Jettin~
agents and dispersing 2gents~ As a result of this the water-solub~e active compounds are very vigorously homogenized with the active compounds ~hich are sparingly solubLe ;n water and uith thesurface-active compounds, so that it is possible to achieve optimum wettability and suspendabil;ty in the resulting ~ettable po~ders.
In order to increase the free-flol~ing properties of the wettable powders, the latter can ad~antageously contain~ as carriers, for example, fine synthetic silica, kieselgUhr clay or bentonite powder. Examples of suitable dispersing agents are soclium dinaphthylm~thanedisulfonate, lignin sulfonates, condensatiorl proclucts of alkylnapthal-enesulfonic acids wi~h cresols, sodium sulfite ancl form-aldehyde~ oleoyl ~methylcaurides, polyvinyl alcohols or _ 9 ~
polyY;nylpyrrolidones~ ~hi(e examples of suitable wettincJ
agents are sod;u~ d;bu~ylnaphthalenesulfonate, sodium a~kylnaphthalenesulfonates~ aiky~sulfatcs~ preferabLy, fo~ example, alkali metal salts and ammonium salts of S the sulfuric ac;d half-ester of aliphatic ~C12-C16~-a~coho~ polyglycol ethers con~ainin~ 2~6 units of ethyl-ene oxide ~= wet~ing agent FES)u ~ iquid cr iow-meiting surface-active substances are advantageously first absorbed on adsorptive silica ?0 to 91ve pu~verulent dry concentrates and are mixed into th~ ~ettable powder in the forrn of powder. Suitable anti-foaming agents, if requirecl, are sod;um or potassium salts of ~atty acids and also sil;cones.
E m~_e 1 Preparation of a wettable powder having 53.Z~ by ~eiyht of a triple combination of active cornpounclsr con-~ai"incl 1ax by ueigh~ of compound Ia t 16.6~ by weigh~ of sodium compound IIb + 2b.6% by weicJht of compound III.
1.1 The form lation of a ~_ttable powder conta nu~g roo~ by we_cJht of com~nd III;
A mixture of 80.0~ by ~eight of compound III, 1~.0% by weight of synthetic silica, 6.0~ by weight o~
soa'ium dinaphthylmethanedisulfonate, 1.8% by weight of a sodium alkylnaphthalenesulfonate and 0.2% by weic~ht of sodiu~ oleoyl-N-methyltauridewas ground on a hiqh-speed p-lnnea'-d;sk milltO give a fine powder of particle size less than 44 rnicrons.
1u2 ~he Formulat1On of a wettincl ~ent a~Qu~LiQ~_ concentra_~_coMposed o~ a pas~y, aqueous sodium (C12_ f~tty alcohol polyglycol ether-sulfate ~= FFS~ and adsorp~
tive synttletic siLica:
~ 0 parts by weight of a 70X by weight ~S paste and 40 parts by ~eight of colloidal syn~hetic silica were vigorously mixed at a s~irrer speed of approximately 150 r.pOm. in a high-efficiency mixer containing a stirrer sha~t fitted ~;th circulating paddles, uhereby a pulveru~
~en~ adsorbate containing 42X by weight of FES active substance ~asobtained.
1.3 Preparation of the wettable Powder con_ainin~
53.2% by weiqht of t~!e triple combination of active_ c oMpoun ~s:
33.25 par.s by weight of 80% strength wettable powder of compound IIIr prepared in accordance uith 1.1 and containing 26.6 parts by Height of compound III, 10.00 parts by wei~ht of compound Ia~ 16.60 parts by ~ei~ht of the sodium salt of compound IIb~ 2-~ 80 parts by e;~ht of FES adsorbate wetting agent, prepared in accord-ance with 1~2 and contain;ng 10 parts by wei~ht of FES, 5~15 parts by wei~ht of sodium dtnaphthylmethanedisulfon~
ate, 2.00 parts by wei~ht of sodium dibutyLnaphthaLene-sulfonate, 1.~0 part by ueight o~ soap fla~es and ~o2U
par~s by weight of synthetic siLica weremixed ~lith exclusion of rnoisture and were then ground on a cross-hammer mill to give a finely pulverized product.
Example 2 __ __ ratior) of a wet able_po~lder havin~_~næ b~
ei~ t of a trie~e combination of_active co~o~lnds~_so~-tain~ 10% by~_~e~ght of_ ~m~Q~_Ia~ ~D~y--wei~h~-~f-sodium compou~1 I`3 1q~h~ p urld I I I r ; 12~5 parts by weigl)t of an 80X strength ~!ettable pouder of compound IIX, prepared in accordance ~ h Example 1~1 and containing 10 parts by ~eight of compound III, 10~0 parts by ~eight of compound Ia, 20~0 par~s ~y weight o~ the sodium salt o~ compound lIa~ 23.8 parts by wei~ht of FES adsorbate ~etting agent, prepared in accordance k'ith EXaMpLe 1.2 and contair,;ng 10 parts by ~eight of FE~, 5.~ parts b)~ ~eight of soc1ium dinaph~hylm2thanedisulfon atc, 3.0 parts by ~eight of sodium dibutylnaphthalene~sul~onate, 200 parts by ~eight of soap tlakes and 13.U
parts by ~ei~ht of synthetic silica 1~re mixed wi~h er~clus1on o~ moisture in a high-efficiency ~ixer analogously ~o Example 1, and the mixture ~as then ground on a cross--1~ hammer mill to give a finely pulverized productOB. Biological examples the biological examples I to IV which follow, a distinction is dra~Jn, for the ac~ive compound com~in-ations tested, be~ween the calculated degree of ac~ion an~ the degree of act;on found, on the weeds mentionecl~
~hc dcgree of action is calculated using the formulae of s.i'.Cl~Yr Calcula~ing synerg-istic and an~agonistic rcsponses of herbicide combinations ~Weeds 15 pages 20 Z2, 1~67) from the effects of the constituents of the combinations ~hen the latter are applied individually.
Formula (1) for the comb;nat,on of 2 active compounds is as follows:
y~ ~ Y
- X -~ Y
in ~hi~t~ X denotes % dama~e caused by herbicide A at an appltcation rate o~ x kgJhectare, Y denotes X damage caused by l-~rbic;de B ~t an app~ication rate of y kg~hectare and E denotes the ~xpected dar~age caus~d by ~he herbicides 5 A ~ æ at appl;cation rates clf x ~ y kyJhect~re~
For the combination of 3 actiYe com"ounclsO for-mula ~2) is given in the sarne p~biication f~r ça~culating the degree of acticn-(XY ~ X~ ~ YZ~ XY2 ~ ~ - (2 1 00 ~ O, 00~
1~ in ~h;ch Z denotes X damaae caused by herbicide C a~ an application rate of z kg/hectare and X and Y have th~ sar,le meaoings as in formu~a (1).
If the actual dama~e, ie. the damage determined ~x~rimentally, i~ srea.er thar, .hat caltula~ed, ~he action of the cornbination is more than additive, ie. a synerg;stic effect is present. In the biological examples ~hich follo~1, this evidence is presented for the combi-nations according to the invention~ the v~lues of aclion calculated from the above formulae being also shown in 2~ brackets in each case for the treatments with com~inations according to the invent;on, ~hile the action actually achie~ed agairlst the part;cular ~eeds m~ntioned is l;st~d after these ~i~ures.
~n biolo~ical examples I tc I`l~ coniparison ,s ~5 made not only ~ the action of the combination I
II ~ III or I~/ w;th that o~ the 3 individual acti~.~e com-pounds, but also ~;th the action of the cor,binatioos I -) II and I ~ IIX or ~'~', which are already l~no~!n~ ~hese - ~3 use ~xamples rela~e ~o field test~ ~hich ~ere carrie~l out under ~ar;o~s cl-imatie cond;~îons. The results are shown in summary form in Tables I to IV~ All the te~ts were carried out in plots of area lD to 20 m .
Example 1 Xn a test under trop;cal conditions on the ~eed Mikania corda1a in a rubber plantation, ~he ir,d;vidual eorrlpounds Ia, IIa and III ~ere ~ested alongsicle Grle another~
as was the kno~n comb;nation Ia + III. Botll ~/hen compared with 10 the ind;vidual produc's and when compared ~;th the known combination, combinations accurding to the invent;on, composed of these thlee active compounds~ produced a considerable ;ncrease in the ~ction, si~nificantly exceeding ~-he degree to be expected~ The action of the ~riple combinatiorls can, accordingly, be desicJrla~eci synergistic. ~-he result is sho~n ir, ~ummary forM in Table I belo~.
~able I
.
Combating Mikania cordata in a rubber plantation.
.~ ~ _~
Dosac~e of Action (% damage) on Mi~ania Treatrnent act;ve cordata (field test) S weeks after with active compound, treàtment compound kcJ/hectare calculated founcl , ,.. _ _.__. ___ ~ ______ _ a) Individual active compounds , .. .-_ ____ Compound Ia 0.4 5D
Cornpound IIa 0.8 60 Compound IIa 0.4 4û
Compound III 0.4 10 b) _no~n comb;nat;on Cornpounds Ia ~- III 0~4 ~ 0.4 70 3n c) Combinat;ons _ccording to the irvert_ n Compound~ Ia-lIIa-~ o.4ln~4+o~h ¦ (73~/82*^) 90 1:1 1 Compounds Ia1IIatIII¦0.4~0.X~O.h L (82*/88**) 96 1:2:1 . ~
3~
..._.. 14 ~
~ calculated frorn the action of the indi~ dual prod~lcts ** calcl~lated frorn the action of the kno~n coMbination and IIa .
~ Examp!e II
~able II sho~ls the results ~ith three weeds~which are d-i~ficuL~ to combat, from a series of tests in Yine and app~e plantations ~hich was dra~n up in ac~ordance with a uniform test plan; in particuLar~ side b~ side tests ~ere carried out siith the compound IIb and the known com-binations Ia ~ III and Ia ~ IV and also the combinations~
~ccording to the in~ention~ Ia ~ XIb ~- IXI and Ia ~ llb YV~ ~he herbicidal acti~n of the triple coalhir,ations mentioned was distinctly better than would have been expected from the calculations of the Colby ~ormula, the known comb;nations be;n3 rated in each case as single treatments, ~hich sign;fies a synergistic increase in ~he action. ~he result is shos~!n in summary form in Table II below.
5~3 ~ 15 ~
.~ ~
~n C
~ ., C ~ L
C) ~ t~' ~J ~ r~
C O n 6t~ ~n E O O O
C~ ;C)~`~
tn ~ , t ~
t 6I C~
O :' C ~ L ~ tt~
W ._ L ~ O ~_ ~ O t L
Q ~ ~ C C~_ t~ S ~ ~ ~ ._ nt~ _,~ 3`. ___ __ ~Utn w, c~
r r L -- ~ D
O ~ ~ ~
~ ~?
.,. o n. ~ o o o ~ ~
~_ aJ o ,~ o c o o .. - tn 6J tn tn C ~- ~
t~_ t~ _C tn Ln ' . ~ n) o t.~ o .C
.,. _ ~ . .~
3 ~_o t-l ~ ~ .
. ~ ~;~'J _O
al c .o ~n~tn ~0 ~U
tJ\ tU ~ 1Co ;-1 ~_1 ~1 C_ o~ ~ ' C~
~ L ~ ~ 1 C
QJ I;) ~_ ~J O OO ~-- C~ O
_ n ~ n n Q_~l QQ
.0 ' . . O O O OE ~= .
:1, 3~
Exanple III
Tl7e kno~fn combination Ia ~ was testcd as a mixture t~ith the compound III in a f~rther test on tl1e s~eed Rumex acetosa ;n a cherry plan~at;on. An increase ;n action ~hich markediy exceeded tl~e amount to be eY~pected ~as found in the case of the triple combination according to ~he invent;on, ie. a synergistic increase ;n action is present~ The result is shos~n in summary form ir, Table III below.
~able III
.
Combating Rumex acetosa in a cherry plan-at;on ~ . .~_ ~ . .. ~
Dosage of Action t% dama~e) on Kumex Treatment ~;th active compound acetosa ~field test) active compound kg/hectare 6 weeks af-ter treatment calc~lated j found , __ __ . ~ .~
Cornpoun~,Ia~IIb 0.5~1.25 80 Compound lII 2~0 20 Compounds 15 I~IIb~III 0.5~1.25~2.0 ~84) ~5 1 : 2.5 : 4 Exarnple IV
. __.
~ he preparations Ia, IIa and III ~lere tested on thcir own and also in the known comb;nat;ons 1a -~ IIa ancl la ~ III and aLso in tr;pLe combinations accordin~ ~o tile invention, in a young plantat;on of oil palms in ~Jhich the rows of trees were very severely infes~ed slith Mikania cordata, Pueraria sp. and various grasses, pr;ncipally Paspalu~n conjugat(Jm. The action on the sJeeds and also ~5 thc danlarge ~o cro? plal1ts were assessed aiter S and 10 weel~s. In the case of the actiol1 on Pas?alum it llas ~ 17 ~
found that the com~ound Ia at 0.4 kgthectare of active compound s~lfficed co~ple~ely, as such,.to ach;eve a 100X
~ction on th` weed plants prescnt. However~ after 10 weeks nunerous Paspalum pLants had re-emer~ed from seeds present ;n the soil~ s~nce the compound Ia has no effect on the SOt l~ On the other hand~ in plo~s uhich had been ~reated with compound III the plants which had re~emeryed fror,l seeds had been destroyed~ whereas the weed plants a(reao'y present ~ere onLy slightly damaged. Iloslever, the plots which i1ad been treated with cornbinations according tQ the ;nvention llere sinlilarly free from old plants, ie.
pLants present at the t;me of application, and also from freshly yerminated plants. In tlle case ~f Pueraria and Mikania, all the treatments with the cornpounds Ia or Ila 1~ had an ;nitial action which was in some cascs very good, but the after-effect 10 weeks after the treatment was complctcly unsatisfactory. The kno~n combinations ~lere also no longer adequ%tely effective at this point in tirne~
Us ln~ thc triple combinations according to ~he inven~
~0 tion, however, it was founcl that, above all, the after effect was particularly good, an effect which uould not have been expected to be so marked and ~hich rDust there-fore be designated as synergistic~ A good after-effect could admittedly also be achieved using the known combi~
~5 nation Ia ~ IIa at ~.4 t 1.2 ky/hectare; however, in this case distinct damage. caused by groslth substances (leaf ts~tist;ng~ s~as found on young trees which had comc into c.ontact ~tith the spray liquor on the bark or on parts of the palm -frond~ On the other hand, in the case of the 3S3~
combination according to the invention, ;n ~hich the pro-portion of the substance IIa had been reduced markedly, this lea~ da~lage could no longer be observed. The dosage of the combination could even be reduced by one quarter in S order to reduce the risk o~ leaf damage still further~
~ithout the action against ~eeds, in particular the after~
e~fect 10 ~leeks after treatn~ent~ being reduced to a con-siderable extent tcf. Table IV~ las~ line). Triple com b;nations according to the invention thus make it possible 10 to ensure that ~he use of the herbicide becomes more reliable arld tha~ a markedly increased and thus su~icicntly lon~ after~effect is achieved at the same ~ime; the result o~ this under practical conditions is that the time of ~he next treatment w;th herbic;de can be postpon~d; this also ~ects a saving in the costs of labor and productSr aMongst other things. The resul~ is shown in summary fOrln itt Table IY below~
;3.3 , ~ ~ .
..- C~
C
1~-0 ~ ' ~ J __ _.~
. CJ
O ~ O ~ ~ ~
' O`
. ~ j 5.
;~ __ _~_~
.,_ ~ .
3~ C~. 00 ~ ~ O C:~ O C ~ O
~ ~0 . `
O ____ . ~
1~ Q . `,~
F ~ .c) O 0~ o~ o O` ul o _~ ) t ~
Q.O ~ :~ ~ .
.J~ .1 O L
0JJ Q ~ CO
C .~ ~ O ~ '' C~`
.- . L O O~ r~ O~ O~
~r-l r~
c r~ ~7 _~ __ ~ - . r_ I
Q C ~1 ::~ o r2 ~ ~J ~o ~s o~7 O ~J O ~ ~ 7 `
a (~ l o ~- o o ~ ~ ~ ~ o .C o.~, cl I o o r? -u o r V) _ ,_____ W El ~
-u ~ ~ ~,~ cl ~ ~ ~u~l ~)~ ~ ~ J 7 8 t ~ t * O I
1 ~ o ~1 ~on~ ~I El O ra a ,1 rL ~ ~1 01 E ~1 ~1 ~-1 ~ ~ t.~l ~1 r~ r ~1 -o ~ ~ ~ I u u~-I u' ~ u' ~, ~, ~1 r` ~ ~ ~ ol ~ ~ ~El ~ a .~ n~
~- ~ ~ ~ cl o o o o r l o o oo~ o i . O ,-~
_.r~ c~ ~ ~-11 rl rl c2. r.~ ~I rlrlr~ ~I rL ~I Q 1-1 .0E _ ~ I F: E E F: I E E E I E ~ '-;
~ .. _.
..._.. 14 ~
~ calculated frorn the action of the indi~ dual prod~lcts ** calcl~lated frorn the action of the kno~n coMbination and IIa .
~ Examp!e II
~able II sho~ls the results ~ith three weeds~which are d-i~ficuL~ to combat, from a series of tests in Yine and app~e plantations ~hich was dra~n up in ac~ordance with a uniform test plan; in particuLar~ side b~ side tests ~ere carried out siith the compound IIb and the known com-binations Ia ~ III and Ia ~ IV and also the combinations~
~ccording to the in~ention~ Ia ~ XIb ~- IXI and Ia ~ llb YV~ ~he herbicidal acti~n of the triple coalhir,ations mentioned was distinctly better than would have been expected from the calculations of the Colby ~ormula, the known comb;nations be;n3 rated in each case as single treatments, ~hich sign;fies a synergistic increase in ~he action. ~he result is shos~!n in summary form in Table II below.
5~3 ~ 15 ~
.~ ~
~n C
~ ., C ~ L
C) ~ t~' ~J ~ r~
C O n 6t~ ~n E O O O
C~ ;C)~`~
tn ~ , t ~
t 6I C~
O :' C ~ L ~ tt~
W ._ L ~ O ~_ ~ O t L
Q ~ ~ C C~_ t~ S ~ ~ ~ ._ nt~ _,~ 3`. ___ __ ~Utn w, c~
r r L -- ~ D
O ~ ~ ~
~ ~?
.,. o n. ~ o o o ~ ~
~_ aJ o ,~ o c o o .. - tn 6J tn tn C ~- ~
t~_ t~ _C tn Ln ' . ~ n) o t.~ o .C
.,. _ ~ . .~
3 ~_o t-l ~ ~ .
. ~ ~;~'J _O
al c .o ~n~tn ~0 ~U
tJ\ tU ~ 1Co ;-1 ~_1 ~1 C_ o~ ~ ' C~
~ L ~ ~ 1 C
QJ I;) ~_ ~J O OO ~-- C~ O
_ n ~ n n Q_~l QQ
.0 ' . . O O O OE ~= .
:1, 3~
Exanple III
Tl7e kno~fn combination Ia ~ was testcd as a mixture t~ith the compound III in a f~rther test on tl1e s~eed Rumex acetosa ;n a cherry plan~at;on. An increase ;n action ~hich markediy exceeded tl~e amount to be eY~pected ~as found in the case of the triple combination according to ~he invent;on, ie. a synergistic increase ;n action is present~ The result is shos~n in summary form ir, Table III below.
~able III
.
Combating Rumex acetosa in a cherry plan-at;on ~ . .~_ ~ . .. ~
Dosage of Action t% dama~e) on Kumex Treatment ~;th active compound acetosa ~field test) active compound kg/hectare 6 weeks af-ter treatment calc~lated j found , __ __ . ~ .~
Cornpoun~,Ia~IIb 0.5~1.25 80 Compound lII 2~0 20 Compounds 15 I~IIb~III 0.5~1.25~2.0 ~84) ~5 1 : 2.5 : 4 Exarnple IV
. __.
~ he preparations Ia, IIa and III ~lere tested on thcir own and also in the known comb;nat;ons 1a -~ IIa ancl la ~ III and aLso in tr;pLe combinations accordin~ ~o tile invention, in a young plantat;on of oil palms in ~Jhich the rows of trees were very severely infes~ed slith Mikania cordata, Pueraria sp. and various grasses, pr;ncipally Paspalu~n conjugat(Jm. The action on the sJeeds and also ~5 thc danlarge ~o cro? plal1ts were assessed aiter S and 10 weel~s. In the case of the actiol1 on Pas?alum it llas ~ 17 ~
found that the com~ound Ia at 0.4 kgthectare of active compound s~lfficed co~ple~ely, as such,.to ach;eve a 100X
~ction on th` weed plants prescnt. However~ after 10 weeks nunerous Paspalum pLants had re-emer~ed from seeds present ;n the soil~ s~nce the compound Ia has no effect on the SOt l~ On the other hand~ in plo~s uhich had been ~reated with compound III the plants which had re~emeryed fror,l seeds had been destroyed~ whereas the weed plants a(reao'y present ~ere onLy slightly damaged. Iloslever, the plots which i1ad been treated with cornbinations according tQ the ;nvention llere sinlilarly free from old plants, ie.
pLants present at the t;me of application, and also from freshly yerminated plants. In tlle case ~f Pueraria and Mikania, all the treatments with the cornpounds Ia or Ila 1~ had an ;nitial action which was in some cascs very good, but the after-effect 10 weeks after the treatment was complctcly unsatisfactory. The kno~n combinations ~lere also no longer adequ%tely effective at this point in tirne~
Us ln~ thc triple combinations according to ~he inven~
~0 tion, however, it was founcl that, above all, the after effect was particularly good, an effect which uould not have been expected to be so marked and ~hich rDust there-fore be designated as synergistic~ A good after-effect could admittedly also be achieved using the known combi~
~5 nation Ia ~ IIa at ~.4 t 1.2 ky/hectare; however, in this case distinct damage. caused by groslth substances (leaf ts~tist;ng~ s~as found on young trees which had comc into c.ontact ~tith the spray liquor on the bark or on parts of the palm -frond~ On the other hand, in the case of the 3S3~
combination according to the invention, ;n ~hich the pro-portion of the substance IIa had been reduced markedly, this lea~ da~lage could no longer be observed. The dosage of the combination could even be reduced by one quarter in S order to reduce the risk o~ leaf damage still further~
~ithout the action against ~eeds, in particular the after~
e~fect 10 ~leeks after treatn~ent~ being reduced to a con-siderable extent tcf. Table IV~ las~ line). Triple com b;nations according to the invention thus make it possible 10 to ensure that ~he use of the herbicide becomes more reliable arld tha~ a markedly increased and thus su~icicntly lon~ after~effect is achieved at the same ~ime; the result o~ this under practical conditions is that the time of ~he next treatment w;th herbic;de can be postpon~d; this also ~ects a saving in the costs of labor and productSr aMongst other things. The resul~ is shown in summary fOrln itt Table IY below~
;3.3 , ~ ~ .
..- C~
C
1~-0 ~ ' ~ J __ _.~
. CJ
O ~ O ~ ~ ~
' O`
. ~ j 5.
;~ __ _~_~
.,_ ~ .
3~ C~. 00 ~ ~ O C:~ O C ~ O
~ ~0 . `
O ____ . ~
1~ Q . `,~
F ~ .c) O 0~ o~ o O` ul o _~ ) t ~
Q.O ~ :~ ~ .
.J~ .1 O L
0JJ Q ~ CO
C .~ ~ O ~ '' C~`
.- . L O O~ r~ O~ O~
~r-l r~
c r~ ~7 _~ __ ~ - . r_ I
Q C ~1 ::~ o r2 ~ ~J ~o ~s o~7 O ~J O ~ ~ 7 `
a (~ l o ~- o o ~ ~ ~ ~ o .C o.~, cl I o o r? -u o r V) _ ,_____ W El ~
-u ~ ~ ~,~ cl ~ ~ ~u~l ~)~ ~ ~ J 7 8 t ~ t * O I
1 ~ o ~1 ~on~ ~I El O ra a ,1 rL ~ ~1 01 E ~1 ~1 ~-1 ~ ~ t.~l ~1 r~ r ~1 -o ~ ~ ~ I u u~-I u' ~ u' ~, ~, ~1 r` ~ ~ ~ ol ~ ~ ~El ~ a .~ n~
~- ~ ~ ~ cl o o o o r l o o oo~ o i . O ,-~
_.r~ c~ ~ ~-11 rl rl c2. r.~ ~I rlrlr~ ~I rL ~I Q 1-1 .0E _ ~ I F: E E F: I E E E I E ~ '-;
~ .. _.
Claims (5)
1. A herbicidal agent which contains (A) a compound of the formula I
(I) in which R denotes hydrogen, NH4, Na, K or 1/2 Ca and X
denotes OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combin-ation with (B) a compound of the formula II
(II) in which X denotes Cl or CH3 and Y denotes hydrogen, an alkali metal, NH4, NH3-CH3, NH2(C2H5)2, NH2(CH3)2, NH3-C2H4?OH, NH2(C2H4?OH)2, NH(C2H4?OH)3 or (C1-C4)-alkyl, and (C) the compound of the formula III
(III) or the compound of the formula IV
IV
wherein the ratio by weight of the components of the formulae I:II:III or IV is 1:(1 to 4):(0.5 to 6).
(I) in which R denotes hydrogen, NH4, Na, K or 1/2 Ca and X
denotes OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combin-ation with (B) a compound of the formula II
(II) in which X denotes Cl or CH3 and Y denotes hydrogen, an alkali metal, NH4, NH3-CH3, NH2(C2H5)2, NH2(CH3)2, NH3-C2H4?OH, NH2(C2H4?OH)2, NH(C2H4?OH)3 or (C1-C4)-alkyl, and (C) the compound of the formula III
(III) or the compound of the formula IV
IV
wherein the ratio by weight of the components of the formulae I:II:III or IV is 1:(1 to 4):(0.5 to 6).
2. A herbicidal agent as claimed in claim 1, wherein the ratio of the components of the formulae I:II:III or IV is 1:(1.5 to 2.5):(1 to 4).
3. A herbicidal agent which contains 2 to 95% by weight of an active compound combination as claimed in claim 1, the remainder up to 100% by weight being composed of customary formulation auxiliaries.
4. A process for combating weeds, which comprises applying an active compound combination as claimed in claim 1, 2 or 3 to the area infested by the weeds, in a quantity of 0.5 to 20 kg of active compound combination per hectare.
5. A process for combating weeds in a tree-like, shrub-like or bush-like permanent plantation which comprises applying an active compound combination as claimed in claim 1, 2 or 3 to the plantation in a quantity of 0.5 to 20 kg of active compound combination per hectare.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3139060.9 | 1981-10-01 | ||
| DE19813139060 DE3139060A1 (en) | 1981-10-01 | 1981-10-01 | HERBICIDAL AGENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1188533A true CA1188533A (en) | 1985-06-11 |
Family
ID=6143152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412534A Expired CA1188533A (en) | 1981-10-01 | 1982-09-30 | Herbicidal agents |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0076470A1 (en) |
| JP (1) | JPS5867609A (en) |
| KR (1) | KR840001242A (en) |
| AU (1) | AU8890682A (en) |
| BR (1) | BR8205721A (en) |
| CA (1) | CA1188533A (en) |
| DD (1) | DD210196A5 (en) |
| DE (1) | DE3139060A1 (en) |
| DK (1) | DK434582A (en) |
| GR (1) | GR77663B (en) |
| IL (1) | IL66874A0 (en) |
| NZ (1) | NZ202035A (en) |
| OA (1) | OA07221A (en) |
| PH (1) | PH18242A (en) |
| PT (1) | PT75632A (en) |
| ZA (1) | ZA827171B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0412577A1 (en) * | 1986-05-09 | 1991-02-13 | Hoechst Aktiengesellschaft | Herbicidal agent |
| JPS6341407A (en) * | 1986-08-08 | 1988-02-22 | 明治製菓株式会社 | Herbicidal composition |
| GB8626246D0 (en) * | 1986-11-03 | 1986-12-03 | Monsanto Europe Sa | Compositions containing glyphosate &c |
| DE3719264A1 (en) * | 1987-06-10 | 1988-12-29 | Hoechst Ag | LIQUID PESTICIDAL MIXTURE |
| US6586367B2 (en) | 1996-09-05 | 2003-07-01 | Syngenta Crop Protection, Inc. | Process for the control of weeds |
| DE19836659A1 (en) | 1998-08-13 | 2000-02-17 | Hoechst Schering Agrevo Gmbh | Use of synergistic herbicide combination including glufosinate- or glyphosate-type, imidazolinone, protoporphyrinogen oxidase inhibitory azole or hydroxybenzonitrile herbicide, to control weeds in cotton |
| JP5051569B2 (en) * | 2006-09-11 | 2012-10-17 | 丸和バイオケミカル株式会社 | Mixed herbicide absorbed from foliage |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2007976B (en) * | 1977-11-08 | 1982-06-09 | Meiji Seika Kaisha | Herbicidal composition and herbicidal processes |
| GB2011416B (en) * | 1977-12-28 | 1982-10-20 | Meiji Seika Kaisha | Herbicidal compositions |
| DE2839087A1 (en) * | 1978-09-08 | 1980-03-20 | Hoechst Ag | HERBICIDAL AGENTS |
-
1981
- 1981-10-01 DE DE19813139060 patent/DE3139060A1/en not_active Withdrawn
-
1982
- 1982-09-24 IL IL66874A patent/IL66874A0/en unknown
- 1982-09-29 GR GR69394A patent/GR77663B/el unknown
- 1982-09-29 KR KR1019820004411A patent/KR840001242A/en unknown
- 1982-09-29 OA OA57813A patent/OA07221A/en unknown
- 1982-09-29 NZ NZ202035A patent/NZ202035A/en unknown
- 1982-09-29 PH PH27929A patent/PH18242A/en unknown
- 1982-09-29 DD DD82243609A patent/DD210196A5/en unknown
- 1982-09-30 AU AU88906/82A patent/AU8890682A/en not_active Abandoned
- 1982-09-30 BR BR8205721A patent/BR8205721A/en unknown
- 1982-09-30 EP EP82109039A patent/EP0076470A1/en not_active Withdrawn
- 1982-09-30 CA CA000412534A patent/CA1188533A/en not_active Expired
- 1982-09-30 PT PT75632A patent/PT75632A/en unknown
- 1982-09-30 ZA ZA827171A patent/ZA827171B/en unknown
- 1982-09-30 DK DK434582A patent/DK434582A/en not_active Application Discontinuation
- 1982-09-30 JP JP57169933A patent/JPS5867609A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IL66874A0 (en) | 1982-12-31 |
| DD210196A5 (en) | 1984-06-06 |
| DE3139060A1 (en) | 1983-04-21 |
| BR8205721A (en) | 1983-09-06 |
| ZA827171B (en) | 1983-08-31 |
| GR77663B (en) | 1984-09-25 |
| NZ202035A (en) | 1985-02-28 |
| DK434582A (en) | 1983-04-02 |
| AU8890682A (en) | 1983-04-14 |
| PH18242A (en) | 1985-05-03 |
| PT75632A (en) | 1982-10-01 |
| OA07221A (en) | 1984-04-30 |
| JPS5867609A (en) | 1983-04-22 |
| EP0076470A1 (en) | 1983-04-13 |
| KR840001242A (en) | 1984-04-30 |
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