CA1188532A - Synergistic herbicidal combination - Google Patents
Synergistic herbicidal combinationInfo
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- CA1188532A CA1188532A CA000408880A CA408880A CA1188532A CA 1188532 A CA1188532 A CA 1188532A CA 000408880 A CA000408880 A CA 000408880A CA 408880 A CA408880 A CA 408880A CA 1188532 A CA1188532 A CA 1188532A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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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:
Subject of the invention are herbicides charac-terized by a content of a compound of formula I
(I) wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is -OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of formula II
(II) wherein R is chlorine or bromine, X is oxygen or sulfur, R1 is hydrogen, alkyl or a cation equivalent, or with a compound of formula III
(III) wherein R1 is hydrogen or halogen, R2 is hydroxy, alkoxy or isopropyloxilmoxy or the group -OKat, Kat being the cation of a base, or with a compound of formula IV
(IV) wherein R is hydroxy, alkoxy or the group -OKat, Kat being the cation of a base, or with a compound of formula V
(V) or with a compound of formula VI
(VI) wherein R1 is halogen or trifluoromethyl, R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the cation of a base, or with a compound of formula VII
(VII) wherein A is -CH- or -N-, X is a halogen, n is 0, 1 or 2, R1 is hydrogen or alkyl and R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the cation of a base, the mixing ratio of the compounds of formulae I and II
to VII being in the range of from 1:0.1 to 1:5, and of use for combatting pests.
Subject of the invention are herbicides charac-terized by a content of a compound of formula I
(I) wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is -OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of formula II
(II) wherein R is chlorine or bromine, X is oxygen or sulfur, R1 is hydrogen, alkyl or a cation equivalent, or with a compound of formula III
(III) wherein R1 is hydrogen or halogen, R2 is hydroxy, alkoxy or isopropyloxilmoxy or the group -OKat, Kat being the cation of a base, or with a compound of formula IV
(IV) wherein R is hydroxy, alkoxy or the group -OKat, Kat being the cation of a base, or with a compound of formula V
(V) or with a compound of formula VI
(VI) wherein R1 is halogen or trifluoromethyl, R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the cation of a base, or with a compound of formula VII
(VII) wherein A is -CH- or -N-, X is a halogen, n is 0, 1 or 2, R1 is hydrogen or alkyl and R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the cation of a base, the mixing ratio of the compounds of formulae I and II
to VII being in the range of from 1:0.1 to 1:5, and of use for combatting pests.
Description
- 2 - HOE 81/~ 195 The present invention relates to herbicides chzracterized by a content of a compound of the formula 5}~3C \ ~O ~ O
/ P ~ C~2 ~ C}12 - CH - C \ ~I) RO NH~ X
wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is ~OH or -NH CH(CH3~-CONH-CH(CH3)-COOH, in combination with a compound of formula Il R ~ ~ O- ~ ~O-C~I-COOR1 (II) wherein ~ is chlorine or bromlne, X is oxygen or sulfur, R1 i5 hydrogen, (C1-C4)alkyl or a cation equivalent of an inorganic or organic base, or with a compound of formula III
~3C~ O ~ -O-CH-C (III) "~
wherein R1 is hydrogen or halog~n, R2 is hydroxy, (C1-C6)alkoxy or isopropyloximoxy or the group -OKat, Kat bei~g the cation of an inGrganic or organic base,
/ P ~ C~2 ~ C}12 - CH - C \ ~I) RO NH~ X
wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is ~OH or -NH CH(CH3~-CONH-CH(CH3)-COOH, in combination with a compound of formula Il R ~ ~ O- ~ ~O-C~I-COOR1 (II) wherein ~ is chlorine or bromlne, X is oxygen or sulfur, R1 i5 hydrogen, (C1-C4)alkyl or a cation equivalent of an inorganic or organic base, or with a compound of formula III
~3C~ O ~ -O-CH-C (III) "~
wherein R1 is hydrogen or halog~n, R2 is hydroxy, (C1-C6)alkoxy or isopropyloximoxy or the group -OKat, Kat bei~g the cation of an inGrganic or organic base,
3~
3 -HOE 81iF 195 or with a compound of formula IV
3C- ~ ~- ~ ~O~C~I_~ ~(I~) wherein R is hydroxy, (C~ C6)alkoxy or the group -OKatJ Kat being the cation of an inorganic or organic base, or with a compound of formula V
. . ~ C ~ 2 5 ~ ~ 3 7(n) (V) CH3-fH-CH2 .
or with a cornpound of formula VI
C~3 Rl- ~ -O ~\ ~ -O-CH-CH-CII-C \(VJ) ~2 wherein R1 is halogen or trifluoromethyl 9 R2 is hydroxy, (C1-C~)-alkoxy or the group -OKat, wherein Kat is the cation of an inorganic or organic base, or with a compound of formula VII
N ~ O _ ~ ~ O-CH-C (VII) wherein A is -CH- or -N-, X is a halogen, n is 0, l or 2, Rl is hydrogen or (Cl-C4)alkyl and R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the eation of an inorganic or organic base, the components oE formulae I and II to VII being present in synergistic proportions.
The eompound of formula I wherein R is hydrogen and X
:is ~OH is also known under the name phosphinotrieine.
Partieularly preferred is the compound of formula I
wherein R is NH4 and X is -OH (= compound Ia, the ammonium salt of phc)sphinotricine). It is disclosed in German Offenlegungssehrif-t 2,7:L7,4~0 and may be used as a raeemie eompound as well as an opt:ically aetive L-form. Preference is furtner given to eompounds oE formula :[ wherein X is -NH-CH(CH3)-CONH-CH(CH3)-COOH, whieh are clisclosed, for example in German Offenleyungsschrift 2,848,224.
The eompounds of formula II are disclosed, for example, in German Offenlegungsschrift 2,640,730. Particularly preferred are eompounds of formula II wherein X is O, R is Cl and Rl is -C2H5 (= compound IIa) as well as compounds of formula II wherein X is S, R is Cl and Rl is -C2H5 (= compound lIb).
From among compounds of formula III those are preferred . A
5;3~
wherein Rl is H and R2 is -OCH3 (= compound IIIa), which a.re dlsclosed, for example, in Zschr. krkh. Pfl. sch. SH VIII (].977), page 429, as well as the correspond.ing isopropyloxime ester, R
in formula III being hydrogen and R2 being -0-N=C(CH3)2 (= compound IIIb), -4a-,~
i3;~:
- 5 - . HOE 81/F 195 which is described, by way of example, in European Patent Specification 2246.
From among compounds of formula IV those are preferred wherein R is O~(CH2)3-CH3 (= compound IVa9 common name: fluazifopbutyl). It is described, for example, in Proc. 1980 British Crop Protection Conf., page 29.
The compound V is.described, for example, in EWRS-Symposium, Mainz, page 317.
From among the compounds of formula VI those are pre-ferred wherein R1 i.s -CF3 and R2 is -OC2H5 (= com-pound VIa, common name: difenopentene). It is described, for example, in Japanese laid-open patent application 7g/154723.
The compounds of formula VII are known, for example, from German Offenlegungsschrift 3, 004, 770 .
The compounds of formula I are active in combatting annual and perennial weeds of many botanical families in doses of from 0.5 to 1.5 kg/ha of active substance, pre~
ferably~ ln perennial T,Jeeds this action may last partially f`or a considerable period of time. In perennial Gramineae, the action i5 not always satisfactory. There is obtained, certainly, a relatively rapid short-time "burning effect~' on the green plant parts (stems and leaves), the action frequently does not last for a very long time, however.
On the other hand it is known from compounds of formu-la II to VII that they have a specific action against annual and perennial weed grasses. This biological action is relatively uniformous for said substances, although they have a different chemical structure~ They are more-over advantageous in that they can be used for combatting selectively weed grasses in dicotyledonous crops such as sugar beets, rape, beans, soybeans and cotton. They may be highly efficient in the treatment of emerged weed grasses and they are likewise very efficient in many cases in soil treatment, that means, in preventive appli-cation against plants germinating from seed.sO Depending on the soil humidity or on the positiuon of the seeds, their i3~
action may a~so be unsatisfactory. They arc more or less inefficient for combatting spacious sprout and root systems in the soil. The doses required depend on the preparation used. For example, for combatting couch-grass (Agropyron repens) compound IIb is used in dosesof from 0.72 to 1.0 kg/ha and compound IIIb is used in doses of from 1.44 to 2.16 kg/ha, while compound IIa has to be applied in doses of far more than 2 kg/ha. To combat effectively Lolium species or Avena fatua 9 com-pound IIb has to be used in doses of from 0.5 to 0.75 kg/ha, while compound IIa, when applied i~ doses of from 0.2 to 0.3 kg/ha, is particularly effective in combatting Digitaria sang_inalis or Sorghum halepense. Similar differences also apply to substances of formuale IV to VII.
It has now been found that combinations of compounds of formula I with compounds of formulae II to VII are disti.nguished by surprising synergistic effects, especial-ly in combatting perennial weed grasses, in particular Grarnineae. For example J they-may be used ~dvantageously in cornbatting said weed grasses in open non-agricultural sites, on stubble-fields 9 in forests, in sites provided ror permanent crop plantations or under similar con-ditions.
In non-agricultural sites or on .stubble~fields, the compounds according to the invention are used, for example, for eombatting Agropyron rep_ns or Sorghum hal pense; in sites provided for permanent crop plantations, they are suitable for combatting the following Gramineae species:
Agrostis, Alopecurus, Bromus, Dactylis, Festuca 7 olium or Poa 9 and, under tropical conditions, in particular Imperata eylindrica. In forests they are active, for example, against the species Deschampsia flexuosa, Deschampsia eaespitosa Holcus lanatus, Holcus mollis, -~l ~ _ . . _ .
Calamagrostis epigeios or the genus Carex brizoides of the family Cyperaceae.
The mixing ratio of components I to VII to com-ponent II in the synergistic combinations according to the invention may ~ary w;thin wide limits. For example, it ranges generally from 1:0.1 to 1:5, preferably ~rom 1:0.2 to 1:2.
The combinatlons according to the invention of compounds of ~ormula I with compounds of formulae II to VII can be applied either in the for~ of tank mixtures, ~here ~he active ingredients prepared individually are mixed iMmediately before their application, or in the form of ready-for-use formulations. In thi~ latter case, ; 10 they are rormulated as wettable powders, emulsifiable concentrates, solutions, dispersions~ dusting agents, or granules, and may contain the usual formulation auxilia-rles ~uch as wetting agents, adhesives, emulsif~ers) dispersing agents, solid or liquid inert substances and grinding auxiliaries or solvents.
Wettable powders are ~ormulat.ions which are uni-formly dispersible in water and which, in addition to the active compound and a diluent or inert materi.al, also contain wetting agents, for example, polyoxethylated alkylphenols, polyoxethylated oleylamines or stearyl-amines, alkylsulfonates or alkylphenylsulfonates and disper~ing agents, for example sodium ligninsulfonate, ~odium 2,2'-dinaphthylmethane-6 7 6'-disulfonate, sodium dibutylnaphthalen0-sulfonate or the sodium salt of oleoyl-methyl-taurine.
; Emulsifiable concentrates are obtained by dis-~olving the active compound in an organic solvent~ for example, butanol, cyclohexanone, dimethylformamide, xylene~isophorone or even higher boiling aromztics 7 and adding one or several emulsifiers. Suitable emul~
sifiers are, for example: calcium salts of alkylaryl-sulfonic acid, fatty acid polyglycol esters, alkylaryl~
polyglycol ethers, fatty alcohol polyglycol ethers, polyoxethylated oleyl or stearylamines, condensation products based on propylene oxide and ethylene oxide, alkylpolyethers, sorbitan~fatty.acid esters, conden-~a~ion products based on alkylaryl, propylene oxide and 153~
- 8 - E F, 81/F 195 e~hylene oxide and the like.
Dus~ing agents are obtained by grinding the active compound with firaly divided solids, for example talc, natural clays, such as kaolin, bentonite, pyrophilite or diatomaceous earth~
Granules can be manufactured either by spraying a solution o~ the active compound onto absorbent 9 granular inert material or by applyir.g active compound concen-trates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate, methylhydroxyethyl cellulose or even mineral oils 9 onto the surface of carriers, such as sand, ~aolinites or granular inert rnaterial. Suitable for~ulations can also be manufactured by the customary methods of manufacture of fertilizer granules, if desired, in admixture with fertilizers.
The synergistic mixtures of active substances accordin~ to the invention of compounds of formula I
with compounds of formulae II to VII may be present in the form of the usual formulations, in particular as wettable powders, emulsifiable concentrations, solutions, dispersior.s, dusting ag2nts or granules. The total con--tent of act.ve substances of the marketable formulations is from about 2 to 95 weight %, preferably from about 5 to 80 weight %, the remainder consisting of the usual formulation auxiliaries such as adhesives, wetting agent~, emulsifiers, dispersing a~ents, fillers, sol~ents and carniers.
In wsttable powders~ the total concentration of active compounds varies, for example, between about 10 and 80 ~, the remainder consisting of the above-mentioned 40rmulation additives. In the case of emulsi-fiable concentrates, the total concentration of the active compounds is ~bout 10 % to 70 ~. Sprayable solu-tiOIlS contain about 2 ~ 20 % of active compounds. In the case of granules, the total content of active compounds is about 2 to 10 weight % and dust formulation3 usually contain ~ro~ 5 to 20 weight ~ of active substances.
353:2 9 - H~E 81~F 195 If necessary or desired the commercial concentrate3 may bc diluted prior to application in the u~ual manner, for example by means of water in the case of wettable pow-ders 9 emulsifiable concentrates and dispcrsions. Dusts, granules and sprayable solutions are generally ready for use without further dilution. The amount of active ingre-dient necessary for obtaining the desired result depends on external conditions such as temperature, humidity and the like. It may vary within wi~e limits and is generally in the range from 0.1 to 10.0 kg/ha, preferably of from 0.3 to 5 kg/ha.
The following examples illustrate the invention:
A. Formulation Examples Example 1 A wettable powder easily dispersi~le in water is obtained by mixing thoroughly in a drum miY.er 300 weight parts of compound Ia, 100 weight parts of compound IIb, 350 weight parts of synthetic si'ici.c acid 9 ~0 weight parts of calcium ligninesulfonate!
50 weight parts of polyarylsulfonate (Na-salt), 50 weight parts of the ~odium salt of o3.eoy:Lmetllyl-tauri.c acid, 40 weight parts of polyYinyl alcohol, 30 weight parts of basic aluminum silicate (kaolinite) and ~ub~equently crushing the result.ing mixture in a disk attr~tion mill at 3,000 rpm. The ground material is mixed anew ~nd ground to fine particles at 12,000 rpm.
Example 2 A wettable powder easily dispersible in water is obtained by mixing thoroughly i.n a drum mixer l~oo weight parts of compound Ia 9 100 weight parts of compound IIa, 300 weight parts of synthetic silicic ac.d, 70 weight part~ of potassium lignosulfonate, 50 wei.ght parts of polyacrylsulfo!late (Na-salt), 40 weight parts of the sodium salt of oleoylmeth~l ~8853~
- 10 ~ - HOE_81/F 195 tauric acid and 40 weight par~s of polyvinyl alcchol and grinding the resulting mixture in the manner described in Example 1 at 3,000 rpm and at 12,000 rpm subsequently.
Examples 3 to 5 Wettable powders of combinations of active substances according to the invention may alternatively be obtained by melting the compounds IIa and IIb, respectively 9 and by absorbing the melt obtained in a rapid mixer in l.iquid form on finely divided silicic acid to obtain a powder con-centrate, which is subsequently ground in a cross~beater mill to obtain a high fineness and homogeneity.
The resulting powder concentrate is subsequently mixed with the compound Ia as well as with dispersing agents and wetting agents selected from the group con~
sisting of sodium dinaphthylmethanedisulfonate, sodium lignosulfonate, sodium 2,2-dinaphthylmethane 6,6l-di sulfonate, sodium dibutylnaphthalenesulfona~e or sodîum oleoylmethyltaurate. The compounds prepared according to this method in Examples 3 to 5 have the f'ollowing compositions:
Formulation component Composition (in weight parts) Example 3 _Rxample ll Example 5 Compound I 40 40 45 25 Compound IIa 10 20 ~
Compound IIb -- __ 15 Silicic acid 38 20 28 Sodium oleoyl-N-methyltauride 2 2 2 30 Sodium dinaphthyl-methanesulfonate 10 8 ~0 B. Biological Examples The followlng biological examples differenciate between the additive activity calculated fro~l the indi-vidual activity of the components of active subst~ncewhen applied alone and between the experimentally prove~
degree of activi$y of the combinations of active substance 353~
~ HOE 81/F 195 The additive degree of activity is calculated by the formula of S.R~ Colby ~cf. Calculating ~ynergistic and antagonistic responses of herbicide combinations, Weeds, 15, 1967, pages 20-22).
This formula is as follows:
X Y
E = X + Y - lOO
X denoting the damage in % by herbicide A in the case of x kg/ha of quantity applied, Y denoting the damage in % by herbicide B in the case of y kg/ha of quantity applied, E denoting the expected damage by the herbicides A~B in the case o~ x+y kg/ha o~ quantity applied.
The activity of the combination of active substances is greater than the additive activity~ if the actual damage i9 greater than the damage calculated, that means, a synergistic effect is observed. This is demonstrated in the following Examples I to III, the right column and the next-to~right column of Tables I to III indicating the result of the combination treatment and, in brackets9 the additive activity calculated by the above formula.
~xam~le I
A field test is conducted, wherein the compourlds Ia, IIa, IIb, IIIa, IIIb, IVA and VIa present as marketable rormulations and in formulated combinations of Ia*IIa, Ia~IIb, Ia-~IIIa, Ia~IIIb, Ia~IVa, Ia+V and Ia-~VIa 9 respectively, are sprayed onto an area of well de~eloped Johnson gras~ ~Sorghurn halepense) individually in separate tests in the form of aqueous spray liquors in the quantities of active substance indicated in Table I
(per unit o~ area) and at the mixing ratios indicated.
The activity is evaluated 3 and 8 weeks after the treat-ment. It is found that nei.ther compound Ia nor the other active substances tested, when applied alone, have a satisfactory action on the green plant parts at the dose~
used in eaeh case, and vn the further growth.
When applying the combinations according to the in~
3~
Yention of compou-sd Ia and the individual weed grass herbicides, the leaves and stem.s have been destroyed completely after 3 weeks and the permanent acti.on, measured by the action on a second growth, is in all tests somewhat higher than 85 % and, consequently, higher than the values to be calculated by the formula of Colby. Hence, a synergistic effect is obvious. The results are sur.1marized in the following Table I:
Table I
Test on Sorghum ha _pense Treatment with Dose of Activity (% of damage) active substance active substance on Sorghum halepense _ _ ~ __ __ __~ after weeks Comp~und Ia 0.5 75 50 Compound IIa 0.12 60 50 Compound IIb 0. 6 55 20 Compound IIIa 0. 5 65 45 Compound IIIb 0. 5 70 60 Compound IVa 0. 5 75 55 Compound V 0.2 70 60 Compout1d VIa 0. 5 53 40 Compounds lalIIa 0.5 ~ 0.12 100 (90) 90 (75) Compounds Ia~IIb 0O5 ~ 0.6 100 (89) 88 (60) Compounds Ia-~IIIa 0.5 -~ 0.5 l00 (91) 90 (72) Compound.s Ia~IIIb 0.5 t 0.5 100 (9~) 93 (80) Compounds Ia-~IVa 0.5 -~ 0.5 100 (94) 90 (77) Compounds Ia~V 0.5 + 0.2 100 (92) 95 (80) Compounds Ia~VIa 0.5 ~ 0.5 l 00 (87) 85 (70) ~ Action on a second growth Example II
In a test conducted on the species of weeds Deschampsia flexuosal Calamagrostis epigeios and Carex . . .
brizoides ir. a forest, the compounds Ia and IIb present as market.able formlllations are sprayed onto the weed area i.ndivi.dually and in tne form of ~he combination Ia+IIb, respectively in the form of aqueous spray liquors in the 3~
- 13 - EIOE 81~F 195 quantities of active substances indicated in Table II (per unit of area) and at the mixing ratios indic~ted. The action ls evaluated 2~7 and 50 weeks after ~he treatment.
It is observed that the activit~ of the combination according to the invention after ~ and 7 weeks on 2 of three plant species is distinctly better than the activity to be expected by the formula of Colby. The activity of the comblnation according to the invention, 50 months later, on all of the three plant species, two of which belonging to the botanical family Gramineae and one be longing to the botanical family Cyperaceae, is likewise distinctly better than that reached upon application of the individual active substances. The cGmbination is hence dis~inguished by a distinct synergistic effect and by a decisively improved permanent action. The results are summarized in the following Table II:
~q ~ u~
~ Q) L~ a C~ ~ C ~_ -- a) c) oo o o o .~ ~ L~
~_ ~ ~ ~_ 00 ~ ~o o o o X C~
~ a) a) _, o - a~ s~ _____ 5~ ~ ~ ~~ C~
v ~ a~ o~
_, _ _ _~
~ oo o o o o o ~_ __ O _~
bO ~ a) a~
e ~ . _ ~-O co `~O
U ~ ~ ~ C~
-- _ o * _~
o o In o u~
~ ~ L~ ~ a _~~rl _~
:~,Q. td _ ~__ ~ e ~ ~ o ~0 co O
d O o~ o X __ ~q a) ~ ;
c~ a) ~
~ 1 ~_ ~ ~_ t~
a r~
C~
~'~ a) ~ ~r t~ o ~ O ~ 5 a)tH C .. ~
~O ~d ~ ~~ ~ 3 O ~ O
a) tn s~
t/~
tD O
1:~ t~
_ . . . - - O
r~ tD C) .,1 t~ ~ tl~
H t~
tn~ tt~ H
~1 a) ,2t,~ t~ H(d H HH S~
~ 5 O
H !::~ t/~'~
1~ S~ ~
O~; O ~ 3 ~ O
a) ~ ~ o o o ~1 ,1 t/~a) ~ ~ o td tD ~ C) O O O eq ~, E~ d t) t~
15 ~ HOE 81/F 195 Example III
. _ In this test, the compounds Ia, IIa 9 IIb and IIIa each present in marketable formulations are sprayed in-dividually in separate tests and the combinations Ia+IIa, Ia+IIb and Ia+IIIa likewise present in marketable formu~
lations are likewise sprayed onto an area of the well developed forest weed C amagrostis from aqueous spray liquors in the quantities of active substance in-dicated in Table III (per unit of area) or at the mixing ratios indicated. The activity is evaluated after 4 weeks.
It is observed that the combinations according to the invention have a far higher activity on the green plant parts (leaves and stems) than the individual components applied separateIy and that this activity is distinctly higher than that calculated by the formula of Colby. The combinations according to the invention are, consequent~
ly, distinguished by a clear synergistic effect. The results are summarized in the following Table III:
Table III
Test conducted on Calama rostis in the ~orest Treatment with Dose of active Activity (% of damage) active substance substance (kg/ha) on Calamagrostis ~ _ _ __ after ~ weelcs Compound Ia 0.5 60 25 Compound IIIa 0.75 7o Compound IIa 0.75 50 Compound IIb 0.75 50 Compound Ia~IIIa 0.5 ~ 0.75100 (88) Compounds Ia-~IIa 0.5 + 0.75 90 (80) Compounds Ia~IIb 0.5 + 0.75 95 (80)
3 -HOE 81iF 195 or with a compound of formula IV
3C- ~ ~- ~ ~O~C~I_~ ~(I~) wherein R is hydroxy, (C~ C6)alkoxy or the group -OKatJ Kat being the cation of an inorganic or organic base, or with a compound of formula V
. . ~ C ~ 2 5 ~ ~ 3 7(n) (V) CH3-fH-CH2 .
or with a cornpound of formula VI
C~3 Rl- ~ -O ~\ ~ -O-CH-CH-CII-C \(VJ) ~2 wherein R1 is halogen or trifluoromethyl 9 R2 is hydroxy, (C1-C~)-alkoxy or the group -OKat, wherein Kat is the cation of an inorganic or organic base, or with a compound of formula VII
N ~ O _ ~ ~ O-CH-C (VII) wherein A is -CH- or -N-, X is a halogen, n is 0, l or 2, Rl is hydrogen or (Cl-C4)alkyl and R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the eation of an inorganic or organic base, the components oE formulae I and II to VII being present in synergistic proportions.
The eompound of formula I wherein R is hydrogen and X
:is ~OH is also known under the name phosphinotrieine.
Partieularly preferred is the compound of formula I
wherein R is NH4 and X is -OH (= compound Ia, the ammonium salt of phc)sphinotricine). It is disclosed in German Offenlegungssehrif-t 2,7:L7,4~0 and may be used as a raeemie eompound as well as an opt:ically aetive L-form. Preference is furtner given to eompounds oE formula :[ wherein X is -NH-CH(CH3)-CONH-CH(CH3)-COOH, whieh are clisclosed, for example in German Offenleyungsschrift 2,848,224.
The eompounds of formula II are disclosed, for example, in German Offenlegungsschrift 2,640,730. Particularly preferred are eompounds of formula II wherein X is O, R is Cl and Rl is -C2H5 (= compound IIa) as well as compounds of formula II wherein X is S, R is Cl and Rl is -C2H5 (= compound lIb).
From among compounds of formula III those are preferred . A
5;3~
wherein Rl is H and R2 is -OCH3 (= compound IIIa), which a.re dlsclosed, for example, in Zschr. krkh. Pfl. sch. SH VIII (].977), page 429, as well as the correspond.ing isopropyloxime ester, R
in formula III being hydrogen and R2 being -0-N=C(CH3)2 (= compound IIIb), -4a-,~
i3;~:
- 5 - . HOE 81/F 195 which is described, by way of example, in European Patent Specification 2246.
From among compounds of formula IV those are preferred wherein R is O~(CH2)3-CH3 (= compound IVa9 common name: fluazifopbutyl). It is described, for example, in Proc. 1980 British Crop Protection Conf., page 29.
The compound V is.described, for example, in EWRS-Symposium, Mainz, page 317.
From among the compounds of formula VI those are pre-ferred wherein R1 i.s -CF3 and R2 is -OC2H5 (= com-pound VIa, common name: difenopentene). It is described, for example, in Japanese laid-open patent application 7g/154723.
The compounds of formula VII are known, for example, from German Offenlegungsschrift 3, 004, 770 .
The compounds of formula I are active in combatting annual and perennial weeds of many botanical families in doses of from 0.5 to 1.5 kg/ha of active substance, pre~
ferably~ ln perennial T,Jeeds this action may last partially f`or a considerable period of time. In perennial Gramineae, the action i5 not always satisfactory. There is obtained, certainly, a relatively rapid short-time "burning effect~' on the green plant parts (stems and leaves), the action frequently does not last for a very long time, however.
On the other hand it is known from compounds of formu-la II to VII that they have a specific action against annual and perennial weed grasses. This biological action is relatively uniformous for said substances, although they have a different chemical structure~ They are more-over advantageous in that they can be used for combatting selectively weed grasses in dicotyledonous crops such as sugar beets, rape, beans, soybeans and cotton. They may be highly efficient in the treatment of emerged weed grasses and they are likewise very efficient in many cases in soil treatment, that means, in preventive appli-cation against plants germinating from seed.sO Depending on the soil humidity or on the positiuon of the seeds, their i3~
action may a~so be unsatisfactory. They arc more or less inefficient for combatting spacious sprout and root systems in the soil. The doses required depend on the preparation used. For example, for combatting couch-grass (Agropyron repens) compound IIb is used in dosesof from 0.72 to 1.0 kg/ha and compound IIIb is used in doses of from 1.44 to 2.16 kg/ha, while compound IIa has to be applied in doses of far more than 2 kg/ha. To combat effectively Lolium species or Avena fatua 9 com-pound IIb has to be used in doses of from 0.5 to 0.75 kg/ha, while compound IIa, when applied i~ doses of from 0.2 to 0.3 kg/ha, is particularly effective in combatting Digitaria sang_inalis or Sorghum halepense. Similar differences also apply to substances of formuale IV to VII.
It has now been found that combinations of compounds of formula I with compounds of formulae II to VII are disti.nguished by surprising synergistic effects, especial-ly in combatting perennial weed grasses, in particular Grarnineae. For example J they-may be used ~dvantageously in cornbatting said weed grasses in open non-agricultural sites, on stubble-fields 9 in forests, in sites provided ror permanent crop plantations or under similar con-ditions.
In non-agricultural sites or on .stubble~fields, the compounds according to the invention are used, for example, for eombatting Agropyron rep_ns or Sorghum hal pense; in sites provided for permanent crop plantations, they are suitable for combatting the following Gramineae species:
Agrostis, Alopecurus, Bromus, Dactylis, Festuca 7 olium or Poa 9 and, under tropical conditions, in particular Imperata eylindrica. In forests they are active, for example, against the species Deschampsia flexuosa, Deschampsia eaespitosa Holcus lanatus, Holcus mollis, -~l ~ _ . . _ .
Calamagrostis epigeios or the genus Carex brizoides of the family Cyperaceae.
The mixing ratio of components I to VII to com-ponent II in the synergistic combinations according to the invention may ~ary w;thin wide limits. For example, it ranges generally from 1:0.1 to 1:5, preferably ~rom 1:0.2 to 1:2.
The combinatlons according to the invention of compounds of ~ormula I with compounds of formulae II to VII can be applied either in the for~ of tank mixtures, ~here ~he active ingredients prepared individually are mixed iMmediately before their application, or in the form of ready-for-use formulations. In thi~ latter case, ; 10 they are rormulated as wettable powders, emulsifiable concentrates, solutions, dispersions~ dusting agents, or granules, and may contain the usual formulation auxilia-rles ~uch as wetting agents, adhesives, emulsif~ers) dispersing agents, solid or liquid inert substances and grinding auxiliaries or solvents.
Wettable powders are ~ormulat.ions which are uni-formly dispersible in water and which, in addition to the active compound and a diluent or inert materi.al, also contain wetting agents, for example, polyoxethylated alkylphenols, polyoxethylated oleylamines or stearyl-amines, alkylsulfonates or alkylphenylsulfonates and disper~ing agents, for example sodium ligninsulfonate, ~odium 2,2'-dinaphthylmethane-6 7 6'-disulfonate, sodium dibutylnaphthalen0-sulfonate or the sodium salt of oleoyl-methyl-taurine.
; Emulsifiable concentrates are obtained by dis-~olving the active compound in an organic solvent~ for example, butanol, cyclohexanone, dimethylformamide, xylene~isophorone or even higher boiling aromztics 7 and adding one or several emulsifiers. Suitable emul~
sifiers are, for example: calcium salts of alkylaryl-sulfonic acid, fatty acid polyglycol esters, alkylaryl~
polyglycol ethers, fatty alcohol polyglycol ethers, polyoxethylated oleyl or stearylamines, condensation products based on propylene oxide and ethylene oxide, alkylpolyethers, sorbitan~fatty.acid esters, conden-~a~ion products based on alkylaryl, propylene oxide and 153~
- 8 - E F, 81/F 195 e~hylene oxide and the like.
Dus~ing agents are obtained by grinding the active compound with firaly divided solids, for example talc, natural clays, such as kaolin, bentonite, pyrophilite or diatomaceous earth~
Granules can be manufactured either by spraying a solution o~ the active compound onto absorbent 9 granular inert material or by applyir.g active compound concen-trates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate, methylhydroxyethyl cellulose or even mineral oils 9 onto the surface of carriers, such as sand, ~aolinites or granular inert rnaterial. Suitable for~ulations can also be manufactured by the customary methods of manufacture of fertilizer granules, if desired, in admixture with fertilizers.
The synergistic mixtures of active substances accordin~ to the invention of compounds of formula I
with compounds of formulae II to VII may be present in the form of the usual formulations, in particular as wettable powders, emulsifiable concentrations, solutions, dispersior.s, dusting ag2nts or granules. The total con--tent of act.ve substances of the marketable formulations is from about 2 to 95 weight %, preferably from about 5 to 80 weight %, the remainder consisting of the usual formulation auxiliaries such as adhesives, wetting agent~, emulsifiers, dispersing a~ents, fillers, sol~ents and carniers.
In wsttable powders~ the total concentration of active compounds varies, for example, between about 10 and 80 ~, the remainder consisting of the above-mentioned 40rmulation additives. In the case of emulsi-fiable concentrates, the total concentration of the active compounds is ~bout 10 % to 70 ~. Sprayable solu-tiOIlS contain about 2 ~ 20 % of active compounds. In the case of granules, the total content of active compounds is about 2 to 10 weight % and dust formulation3 usually contain ~ro~ 5 to 20 weight ~ of active substances.
353:2 9 - H~E 81~F 195 If necessary or desired the commercial concentrate3 may bc diluted prior to application in the u~ual manner, for example by means of water in the case of wettable pow-ders 9 emulsifiable concentrates and dispcrsions. Dusts, granules and sprayable solutions are generally ready for use without further dilution. The amount of active ingre-dient necessary for obtaining the desired result depends on external conditions such as temperature, humidity and the like. It may vary within wi~e limits and is generally in the range from 0.1 to 10.0 kg/ha, preferably of from 0.3 to 5 kg/ha.
The following examples illustrate the invention:
A. Formulation Examples Example 1 A wettable powder easily dispersi~le in water is obtained by mixing thoroughly in a drum miY.er 300 weight parts of compound Ia, 100 weight parts of compound IIb, 350 weight parts of synthetic si'ici.c acid 9 ~0 weight parts of calcium ligninesulfonate!
50 weight parts of polyarylsulfonate (Na-salt), 50 weight parts of the ~odium salt of o3.eoy:Lmetllyl-tauri.c acid, 40 weight parts of polyYinyl alcohol, 30 weight parts of basic aluminum silicate (kaolinite) and ~ub~equently crushing the result.ing mixture in a disk attr~tion mill at 3,000 rpm. The ground material is mixed anew ~nd ground to fine particles at 12,000 rpm.
Example 2 A wettable powder easily dispersible in water is obtained by mixing thoroughly i.n a drum mixer l~oo weight parts of compound Ia 9 100 weight parts of compound IIa, 300 weight parts of synthetic silicic ac.d, 70 weight part~ of potassium lignosulfonate, 50 wei.ght parts of polyacrylsulfo!late (Na-salt), 40 weight parts of the sodium salt of oleoylmeth~l ~8853~
- 10 ~ - HOE_81/F 195 tauric acid and 40 weight par~s of polyvinyl alcchol and grinding the resulting mixture in the manner described in Example 1 at 3,000 rpm and at 12,000 rpm subsequently.
Examples 3 to 5 Wettable powders of combinations of active substances according to the invention may alternatively be obtained by melting the compounds IIa and IIb, respectively 9 and by absorbing the melt obtained in a rapid mixer in l.iquid form on finely divided silicic acid to obtain a powder con-centrate, which is subsequently ground in a cross~beater mill to obtain a high fineness and homogeneity.
The resulting powder concentrate is subsequently mixed with the compound Ia as well as with dispersing agents and wetting agents selected from the group con~
sisting of sodium dinaphthylmethanedisulfonate, sodium lignosulfonate, sodium 2,2-dinaphthylmethane 6,6l-di sulfonate, sodium dibutylnaphthalenesulfona~e or sodîum oleoylmethyltaurate. The compounds prepared according to this method in Examples 3 to 5 have the f'ollowing compositions:
Formulation component Composition (in weight parts) Example 3 _Rxample ll Example 5 Compound I 40 40 45 25 Compound IIa 10 20 ~
Compound IIb -- __ 15 Silicic acid 38 20 28 Sodium oleoyl-N-methyltauride 2 2 2 30 Sodium dinaphthyl-methanesulfonate 10 8 ~0 B. Biological Examples The followlng biological examples differenciate between the additive activity calculated fro~l the indi-vidual activity of the components of active subst~ncewhen applied alone and between the experimentally prove~
degree of activi$y of the combinations of active substance 353~
~ HOE 81/F 195 The additive degree of activity is calculated by the formula of S.R~ Colby ~cf. Calculating ~ynergistic and antagonistic responses of herbicide combinations, Weeds, 15, 1967, pages 20-22).
This formula is as follows:
X Y
E = X + Y - lOO
X denoting the damage in % by herbicide A in the case of x kg/ha of quantity applied, Y denoting the damage in % by herbicide B in the case of y kg/ha of quantity applied, E denoting the expected damage by the herbicides A~B in the case o~ x+y kg/ha o~ quantity applied.
The activity of the combination of active substances is greater than the additive activity~ if the actual damage i9 greater than the damage calculated, that means, a synergistic effect is observed. This is demonstrated in the following Examples I to III, the right column and the next-to~right column of Tables I to III indicating the result of the combination treatment and, in brackets9 the additive activity calculated by the above formula.
~xam~le I
A field test is conducted, wherein the compourlds Ia, IIa, IIb, IIIa, IIIb, IVA and VIa present as marketable rormulations and in formulated combinations of Ia*IIa, Ia~IIb, Ia-~IIIa, Ia~IIIb, Ia~IVa, Ia+V and Ia-~VIa 9 respectively, are sprayed onto an area of well de~eloped Johnson gras~ ~Sorghurn halepense) individually in separate tests in the form of aqueous spray liquors in the quantities of active substance indicated in Table I
(per unit o~ area) and at the mixing ratios indicated.
The activity is evaluated 3 and 8 weeks after the treat-ment. It is found that nei.ther compound Ia nor the other active substances tested, when applied alone, have a satisfactory action on the green plant parts at the dose~
used in eaeh case, and vn the further growth.
When applying the combinations according to the in~
3~
Yention of compou-sd Ia and the individual weed grass herbicides, the leaves and stem.s have been destroyed completely after 3 weeks and the permanent acti.on, measured by the action on a second growth, is in all tests somewhat higher than 85 % and, consequently, higher than the values to be calculated by the formula of Colby. Hence, a synergistic effect is obvious. The results are sur.1marized in the following Table I:
Table I
Test on Sorghum ha _pense Treatment with Dose of Activity (% of damage) active substance active substance on Sorghum halepense _ _ ~ __ __ __~ after weeks Comp~und Ia 0.5 75 50 Compound IIa 0.12 60 50 Compound IIb 0. 6 55 20 Compound IIIa 0. 5 65 45 Compound IIIb 0. 5 70 60 Compound IVa 0. 5 75 55 Compound V 0.2 70 60 Compout1d VIa 0. 5 53 40 Compounds lalIIa 0.5 ~ 0.12 100 (90) 90 (75) Compounds Ia~IIb 0O5 ~ 0.6 100 (89) 88 (60) Compounds Ia-~IIIa 0.5 -~ 0.5 l00 (91) 90 (72) Compound.s Ia~IIIb 0.5 t 0.5 100 (9~) 93 (80) Compounds Ia-~IVa 0.5 -~ 0.5 100 (94) 90 (77) Compounds Ia~V 0.5 + 0.2 100 (92) 95 (80) Compounds Ia~VIa 0.5 ~ 0.5 l 00 (87) 85 (70) ~ Action on a second growth Example II
In a test conducted on the species of weeds Deschampsia flexuosal Calamagrostis epigeios and Carex . . .
brizoides ir. a forest, the compounds Ia and IIb present as market.able formlllations are sprayed onto the weed area i.ndivi.dually and in tne form of ~he combination Ia+IIb, respectively in the form of aqueous spray liquors in the 3~
- 13 - EIOE 81~F 195 quantities of active substances indicated in Table II (per unit of area) and at the mixing ratios indic~ted. The action ls evaluated 2~7 and 50 weeks after ~he treatment.
It is observed that the activit~ of the combination according to the invention after ~ and 7 weeks on 2 of three plant species is distinctly better than the activity to be expected by the formula of Colby. The activity of the comblnation according to the invention, 50 months later, on all of the three plant species, two of which belonging to the botanical family Gramineae and one be longing to the botanical family Cyperaceae, is likewise distinctly better than that reached upon application of the individual active substances. The cGmbination is hence dis~inguished by a distinct synergistic effect and by a decisively improved permanent action. The results are summarized in the following Table II:
~q ~ u~
~ Q) L~ a C~ ~ C ~_ -- a) c) oo o o o .~ ~ L~
~_ ~ ~ ~_ 00 ~ ~o o o o X C~
~ a) a) _, o - a~ s~ _____ 5~ ~ ~ ~~ C~
v ~ a~ o~
_, _ _ _~
~ oo o o o o o ~_ __ O _~
bO ~ a) a~
e ~ . _ ~-O co `~O
U ~ ~ ~ C~
-- _ o * _~
o o In o u~
~ ~ L~ ~ a _~~rl _~
:~,Q. td _ ~__ ~ e ~ ~ o ~0 co O
d O o~ o X __ ~q a) ~ ;
c~ a) ~
~ 1 ~_ ~ ~_ t~
a r~
C~
~'~ a) ~ ~r t~ o ~ O ~ 5 a)tH C .. ~
~O ~d ~ ~~ ~ 3 O ~ O
a) tn s~
t/~
tD O
1:~ t~
_ . . . - - O
r~ tD C) .,1 t~ ~ tl~
H t~
tn~ tt~ H
~1 a) ,2t,~ t~ H(d H HH S~
~ 5 O
H !::~ t/~'~
1~ S~ ~
O~; O ~ 3 ~ O
a) ~ ~ o o o ~1 ,1 t/~a) ~ ~ o td tD ~ C) O O O eq ~, E~ d t) t~
15 ~ HOE 81/F 195 Example III
. _ In this test, the compounds Ia, IIa 9 IIb and IIIa each present in marketable formulations are sprayed in-dividually in separate tests and the combinations Ia+IIa, Ia+IIb and Ia+IIIa likewise present in marketable formu~
lations are likewise sprayed onto an area of the well developed forest weed C amagrostis from aqueous spray liquors in the quantities of active substance in-dicated in Table III (per unit of area) or at the mixing ratios indicated. The activity is evaluated after 4 weeks.
It is observed that the combinations according to the invention have a far higher activity on the green plant parts (leaves and stems) than the individual components applied separateIy and that this activity is distinctly higher than that calculated by the formula of Colby. The combinations according to the invention are, consequent~
ly, distinguished by a clear synergistic effect. The results are summarized in the following Table III:
Table III
Test conducted on Calama rostis in the ~orest Treatment with Dose of active Activity (% of damage) active substance substance (kg/ha) on Calamagrostis ~ _ _ __ after ~ weelcs Compound Ia 0.5 60 25 Compound IIIa 0.75 7o Compound IIa 0.75 50 Compound IIb 0.75 50 Compound Ia~IIIa 0.5 ~ 0.75100 (88) Compounds Ia-~IIa 0.5 + 0.75 90 (80) Compounds Ia~IIb 0.5 + 0.75 95 (80)
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Herbicides characterized by a content of a compound of formula I
(I) wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is -OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of formula II
(II) wherein R is chlorine or bromine, X is oxygen or sulfur, R1 is hydrogen, (C1-C4)alkyl or a cation equivalent of an inorganic or organic base, or with a compound of formula III
(III) wherein R1 is hydrogen or halogen, R2 is hydroxy, (C1-C6)alkoxy or isopropyloximoxy or the group -OKat, Kat being the cation of an inorganic or organic base, or with a compound of formula IV
(IV) wherein R is hydroxy, (C1-C6)alkoxy or the group -OKat, Kat being the cation of an inorganic or organic base, or with a compound of formula V
(V) or with a compound of formula VI
(VI) wherein R1 is halogen or trifluoromethyl, R2 is hydroxy, (C1-C4)-alkoxy or the group -OKat, wherein Kat is the cation of an inorganic or organic base, or with a compound of formula VII
(VII) wherein A is -CH- or -N-, X is a halogen, n is 0, 1 or 2, R1 is hydrogen or (C1-C4)alkyl and R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the cation of an inorganic or organic base, the components of formulae I and II to VII being present in synergistic proportions.
(I) wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is -OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of formula II
(II) wherein R is chlorine or bromine, X is oxygen or sulfur, R1 is hydrogen, (C1-C4)alkyl or a cation equivalent of an inorganic or organic base, or with a compound of formula III
(III) wherein R1 is hydrogen or halogen, R2 is hydroxy, (C1-C6)alkoxy or isopropyloximoxy or the group -OKat, Kat being the cation of an inorganic or organic base, or with a compound of formula IV
(IV) wherein R is hydroxy, (C1-C6)alkoxy or the group -OKat, Kat being the cation of an inorganic or organic base, or with a compound of formula V
(V) or with a compound of formula VI
(VI) wherein R1 is halogen or trifluoromethyl, R2 is hydroxy, (C1-C4)-alkoxy or the group -OKat, wherein Kat is the cation of an inorganic or organic base, or with a compound of formula VII
(VII) wherein A is -CH- or -N-, X is a halogen, n is 0, 1 or 2, R1 is hydrogen or (C1-C4)alkyl and R2 is hydroxy, alkoxy or the group -OKat, wherein Kat is the cation of an inorganic or organic base, the components of formulae I and II to VII being present in synergistic proportions.
2. Herbicides according to claim 1, wherein the ratio of the component of formula I to the component(s) of formulae I
to VII is from 1:0.1 to 1:5 by weight.
to VII is from 1:0.1 to 1:5 by weight.
3. Herbicides according to claim 1, wherein the ratio of the component of formula I to the component(s) of formulae II to VII is from 1:0.2 to 1:2 by weight.
4. Herbicides according to claim 1, 2 or 3 characterized by a content of from 2 to 95 weight % of a combination of components of formulae I and II to VII, the remainder to 100 weight % consisting of the usual formulation auxiliaries.
5. A process for combating plant pests, which comprises applying a herbicide according to claim 1 to the area infested by such pests in an amount corresponding to 0.1 to 10 kg/ha of the combination of the components of formulae I and II to VII.
6. A process according to claim 5 wherein the ratio of the component of formula I to the component(s) of formulae II to VII
is from 1:0.1 to 1:5 by weight.
is from 1:0.1 to 1:5 by weight.
7. A process according to claim 5 wherein the ratio of the component of formula I to the component(s) of formulae II to VII is from 1:0.2 to 1:2 by weight.
8. A process for combating weeds, which comprises applying to such weeds or to a habitat thereof a herbicide according to claim 1, 2 or 3, char-acterized by a content of from 2 to 95 weight % of a combination of components of formulae I and II to VII, the remainder to 100 weight % consisting of the usual formulation auxiliaries, the herbicide being applied in an amount cor-responding to 0.1 to 10 kg/ha of the combination of the components of formulae I and II and VII.
9. Herbicides characterized by a content of a compound of formula I
(I) wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is -OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of formula II
(II) wherein R is chlorine or bromine, X is oxygen or sulfur, R1 is hydrogen, (C1-C4)alkyl or a cation equivalent of an inorganic or organic base, wherein the compounds of formulae I and II are present in synergistic proportions.
(I) wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is -OH or -NH-CH(CH3)-CONH-CH(CH3)-COOH, in combination with a compound of formula II
(II) wherein R is chlorine or bromine, X is oxygen or sulfur, R1 is hydrogen, (C1-C4)alkyl or a cation equivalent of an inorganic or organic base, wherein the compounds of formulae I and II are present in synergistic proportions.
10. Herbicides according to claim 9, wherein the ratio of the component of formula I to the component of formula II is from 1:0.1 to 1:5 by weight.
11. Herbicides according to claim 9, wherein the ratio of the component of formula I to the component of formula II is from 1:0.2 to 1:2 by weight.
12. Herbicides according to claim 9, characterized by a content of from 2 to 95 weight % of a combination of components of formulae I and II, the remainder to 100 weight % consisting of the usual formulation auxiliaries.
13. Herbicides according to claim 9, 10 or 12, wherein in formula (I) X is -NH-CH(CH3)-CONH-CH(CH3)-COOH.
14. Herbicides according to claim 9, 10 or 12, wherein in formula (II) X is O, R is Cl and R1 is -C2H5.
15. Herbicides according to claim 9, 10 or 12 wherein in formula (I) X is -NH-CH(CH3)-CONH-CH(CH3)-COOH and in formula (II) X is O, R is Cl and R1 is -C2H5.
16. A process for combating plant pests, which comprises applying a herbicide according to claim 9, 10 or 12 to the area infested by such pests in an amount corresponding to 0.1 to 10 kg/ha of the combination of the com-ponents(s) of formulae I and II.
17. A process for combating weeds, which comprises applying to such weeds or to a habitat thereof a herbicide according to claim 9, 10 or 12, characterized by a content of from 2 to 95 weight % of a combination of components of formulae I and II, the remainder to 100 weight % consisting of the usual formulation auxiliaries, the herbicide being applied to an amount corresponding to 0.1 to 10 kg/ha of the combination of the components of formulae I and II.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3131495.3 | 1981-08-08 | ||
| DE19813131495 DE3131495A1 (en) | 1981-08-08 | 1981-08-08 | "HERBICIDAL AGENTS" |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1188532A true CA1188532A (en) | 1985-06-11 |
Family
ID=6138938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000408880A Expired CA1188532A (en) | 1981-08-08 | 1982-08-06 | Synergistic herbicidal combination |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0071973B1 (en) |
| JP (1) | JPS5841807A (en) |
| AU (1) | AU8696482A (en) |
| BR (1) | BR8204637A (en) |
| CA (1) | CA1188532A (en) |
| DE (2) | DE3131495A1 (en) |
| ES (1) | ES514627A0 (en) |
| IL (1) | IL66488A (en) |
| ZA (1) | ZA825710B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140121107A1 (en) * | 1998-08-13 | 2014-05-01 | Bayer Intellectual Property Gmbh | Herbicidal compositions for tolerant or resistant rice crops |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6341407A (en) * | 1986-08-08 | 1988-02-22 | 明治製菓株式会社 | Herbicidal composition |
| EP0334041A3 (en) * | 1988-02-23 | 1990-03-28 | Mitsubishi Petrochemical Co., Ltd. | Herbicidal composition |
| EP1348336A1 (en) * | 1998-03-09 | 2003-10-01 | Monsanto Technology LLC | Mixtures for weed control in glyphosate tolerant soybeans |
| DE19836673A1 (en) * | 1998-08-13 | 2000-02-17 | Hoechst Schering Agrevo Gmbh | Use of a synergistic herbicidal combination including a glufosinate- or glyphosate-type or imidazolinone herbicide to control weeds in sugar beet |
| JP3749439B2 (en) * | 1998-12-15 | 2006-03-01 | ビーエーエスエフ アクチェンゲゼルシャフト | Cyclohexenone oxime ether / (glyphosate / glufosinate) concentrated suspension |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2007976B (en) * | 1977-11-08 | 1982-06-09 | Meiji Seika Kaisha | Herbicidal composition and herbicidal processes |
| US4265654A (en) * | 1977-12-28 | 1981-05-05 | Meiji Seika Kaisha Ltd. | Herbicidal compositions |
-
1981
- 1981-08-08 DE DE19813131495 patent/DE3131495A1/en not_active Withdrawn
-
1982
- 1982-08-02 ES ES514627A patent/ES514627A0/en active Granted
- 1982-08-04 DE DE8282107028T patent/DE3268399D1/en not_active Expired
- 1982-08-04 EP EP82107028A patent/EP0071973B1/en not_active Expired
- 1982-08-06 BR BR8204637A patent/BR8204637A/en unknown
- 1982-08-06 IL IL66488A patent/IL66488A/en unknown
- 1982-08-06 AU AU86964/82A patent/AU8696482A/en not_active Withdrawn
- 1982-08-06 ZA ZA825710A patent/ZA825710B/en unknown
- 1982-08-06 CA CA000408880A patent/CA1188532A/en not_active Expired
- 1982-08-07 JP JP57136846A patent/JPS5841807A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140121107A1 (en) * | 1998-08-13 | 2014-05-01 | Bayer Intellectual Property Gmbh | Herbicidal compositions for tolerant or resistant rice crops |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5841807A (en) | 1983-03-11 |
| EP0071973A1 (en) | 1983-02-16 |
| EP0071973B1 (en) | 1986-01-08 |
| ES8308473A1 (en) | 1983-09-16 |
| AU8696482A (en) | 1983-02-17 |
| DE3268399D1 (en) | 1986-02-20 |
| ZA825710B (en) | 1983-06-29 |
| DE3131495A1 (en) | 1983-03-03 |
| IL66488A (en) | 1985-10-31 |
| ES514627A0 (en) | 1983-09-16 |
| BR8204637A (en) | 1983-07-26 |
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