CA1291344C

CA1291344C - Herbicides

Info

Publication number: CA1291344C
Application number: CA000536657A
Authority: CA
Inventors: Hilmar Mildenberger; Klaus Bauer; Hermann Bieringer; Lothar Willms; Peter Langeluddeke
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1986-05-09
Filing date: 1987-05-08
Publication date: 1991-10-29
Anticipated expiration: 2008-10-29
Also published as: ZA873301B; ATE64819T1; EP0252237A3; JPH0818938B2; ES2028823T3; EP0252237A2; MY101888A; AU605484B2; AU7264087A; EP0252237B1; GR3002379T3; JPS62267211A; DE3771135D1; JP2688341B2; JPH09151105A

Abstract

Abstract of the disclosure:
Herbicides The invention relates to herbicides which contain an active ingredient of the formula I, (I) in which A1 denotes H and A2 denotes NH2, or A1 and A2 together denote an oxygen atom, V denotes O or NH, Y, in the case where V denotes O, denotes hydrogen or alkyl or, in the case where V - NH, denotes a radical of the formula -CH(CH3)-CONH-CH(CH3)-COOH or -CH(CH3)-CONH-CH-[CH2CH(CH3)2]-COOH, and W denotes hydrogen, or a salt thereof, in combination with a compound of the formula II

(II) in which R1 denotes alkyl, alkenyl or alkynyl, which may in each case be halogenated, (di)alkylamino, N-alkylsulfonyl-N-alkyl-amino, where the alkyl radicals may be halogenated, a (substituted) phenyl, benzyl, phenoxy, pyrazolyl or thienyl radical, R1 denotes H, alkyl or alkenyl, R2 and R3 denote (substituted) alkyl, (substituted) alkoxy, alkenyl, alkynyl, alkenyloxy, alkynyloxy or halogen, X
denotes O, S or NR6, and Z denotes CH or N, and the salts thereof, or with a compound of the formula III or III', or the salts thereof, (III) (III')

Description

3~ 4 IIOECHST AKTIENGESELLSCHAFT HOE 86/F 104J Dr.AU/mu Herb;cides . .

The present invention reLates to herbicides which contain an active ingredient of the formula I, ~P - CH2 - CH2 - C - CI- V Y (I) in which A1 denotes H and AZ denotes NH2, or A1 and A2 together denote an oxygen atom, V denotes O or NH, Y, where V = O, denotes hydrogen or (C1-C4)alkyl, or Y, where V = NH, denotes a radical of the formula -CH(CH3)-CONH-CH(CH3)-COOH or -CH(CH3)-CONH-CH[CH2CH(CH3)2]-COOH, and, irrespective of the meaning of V, W denotes hydrogen, or a salt thereof, in combination w;th a compound of the formula II

R - S02 ~ NH - C - N ~ ~ tII) in which : R1 denotes (C1-C4) alkyl, (C~-C6) alkenyl, (C2-C6) alkynyl, which may in each case be halo-genated, (C1-C4) alkylamino, d;(C1-C4-alkyl)-amino, [N-(C1-C4-alkylsulfonyl)-N-(C1-C4-alkyl)]-amino, where the alkyl radicals may be halogenated, phenyl, benzyl, phenoxy, pyrazolyl or thienyl which : 25 may all be substituted by (C1-C4) alkyl, (C2-C
alkenyl, (C2-C6) alkynyl or (C1-C4) alkoxy which may all be substituted by halogen or (C1-C4-alkoxy)carbonyl, .

~l.2~13~L

furthermore by halogen, CF3, nitro or a radical of the formula -CooR4, in which R4 denotes H, ~C1-C4) alkyl, (C2-C6)-alkenyl, (C2-C6) alkynyl, (C1-C4) alkoxy-(C1-C4) alkyL or halo (C1-C4) alkyl, furthermore by a radical of the formula -Sto)nR5, in which R5 denotes ~C1-C4) al.kyl, (C1-C4) alkoxy, halo (C1-C4) alkyl, (C1-C4) alkoxy-(C1-C4) alkyl, (C1-C4) alkoxy-carbonyl-(C1-C4) alkyl, di(C1-C4-alkyl)-amino~
(C1-C4) alkylamino, (C1-C4) alkoxy-(C1-C4)alkylamino, and n denotes 0, 1 or 2, R1 denotes H, (C1-C4)alkyl or (C2-C4)alkenyl, : 15 R2 and R3, independently of one another, denote (C1-C4)-alkyl or (C1-C4) alkoxy wh;ch are both opt;onally monosubstituted or polysubstituted by halogen, (C1-C4) alkoxy or (C1-C4-~ alkoxy)-carbonyl, (C2-C6) alkenyl, ; :: 20 (C2-C6) alkynyl, (C2-C6) alkenyloxy, ; (C2-C6) alkynyloxy or halogen, ; X denotes 0, S or NR6, where R6 =
(C1-C4) alkyl or (C1-C4) alkoxy, and Z denotes CH or N, or a salt thereof, or with a compound of the formula III or lll', or salts thereof, ::

~ ~ :
: ~

~29~34~L

R7 ~ / ~ R7 ~ ~ (III') CH3 (III) N C~
¦ CH(CH3~ CH(C~2 in which R7 denotes phenyl, pyridyl, ancl quinolyl which are all optionally monosubstitutecl or polysubstituted by ~C1-C4) alkyl or (C1-C4) alkoxy, which may both be monosubstituted or polysubstituted by halogen, are further substituted by a radical of the formula -CooR9, -coo CH2R9-CooR9, -CH2R9-COO(C1~C4-alkyl) or CH2R9-CooCH2R9 CooR9, ; in which, in each case independently of one another, R denotes~ H or ~C1-C4) alkyl, or a radical of the formula -CH2-S(O)n-(C1-C4)-alkyl, where n denotes 0, 1 or 2, and R8 denot~es H or~a rad;cal of the formula -CONH(C1-C4-alkyl), -OCO(C1-C4-alkyl) or -CO(C1-C4-alkyl)~

In the case where R8 - H, the two formulae III and IIl ' ex;st in tautomeric equilibrium. Depending on the radi-cal R8 and the other substituents, the one or the other -form ~III or III:' ) can therefore be present, see German Offenlegungsschrift 3,121,636 and German Offenlegungs-schrift 2,833,274.

The compounds of the formula I~where V = O are described in U S. Pa~tent 4,168,936 and European Patent 30,424, whereas the compounds of the formula I where V = NH are ~-: : known from U.S. Patent 4,309,208, S. Omura et al., The 34~

Japanese Journal of Antibiotics, Volume YXXVIII-2, p. 542 (1985); and H~S. Seto et al., The Journal of Antibiotics, Vol. XXXVI 1, pp. 96 - 98 (1983). Of the compounds of the formula I, preferred compounds are Ia: A1 = H, A2 = NH2; V - Y = OH, W = H, and the salts thereof; monoammonium salt; common name:
glufosinate-ammonium~

Ib: A1 and A2 together = oxygen; V - Y = OH, W = H, and the salts thereof.

Ic: A1 = H, A2 = NH2; V = NH; Y = -CH(CH3)-CONH-CH(CH3)COOH, W = H, and the salts thereof; common name: bialaphos.

Id: A1 = H, A2 = NH2; V = NH; Y = -CH(CH3)-CONH-CH(CH2CH-(CH3)z)COOH, W = H, and the salts thereof; common name: phosalacine (S. Omura et al.
The Japanese Journal of Antibiotics, 37 (2), p. 542 (1985)).

Preferred compounds of the formula II are:

Type 1: Alkylaminosulfonylureas of the abovement;oned : ~ 20 formula II, ;n wh;ch R1 denotes lN-(C1-C4-alkylsulfonyl)-N-(C1-C4-alkyl)amino], where the alkyl radicals may ;n each case be halogenated, and X
denotes O, see EP-A 131,258; of these, the compound IIa in which R1 denotes ~CH3SO2~-(CH3)N-, R2 and R3 denote OCH3, and Z denotes CH are of particular importance.

Type 2: Pyrazolylsulfonylureas of the abovementioned formula II in which R1 denotes a radical of the formula in which R9 has the abovementioned meaning, R10 denotes H, (C1-C4) alkyl, (C1-C4) alkoxy, or S a radical of the formula -CooR4 or -S(o)nR5 , in wh;ch R5 = (C1-C4) alkyl, (C1-C4) alkoxy, halo (C1-C4) alkyl, (C1-C4) alkylamino or di(C1-C4-alkyllamino, and R11 denotes H, halogen, (C1-C4) alkyl or (C1-C4) alkoxy, which may both be halogenated, and X denotes O, see EP-A ~7,780.

Of these compounds, the:following are particularly suit-able according to the invention:

Compound lIb: R1 _ H, R1 = 1,3,5-t~rimethyl-pyrazol-4 yl, X = 0, R2 = CH3, R3 = OCH3 andZ = N.
Ilc: R1 := H, R1 = 1,3,5-tr;methyl-pyrazol-4-yl, X = O, R~ = CH3, R~ = OCH3 and z = CH.
IId: R1 = H, R1 = 1,3,5-trimethyl-pyrazol-: 20 4-yl, X = O, R2 = R3 = CH3~:~and Z = CH.
IIe: R1 := H, R1 = 5-chloro-1,3-dimethyl-~ : pyrazol-4-yl, X = O, R2 = CH3, R3 =
::~ : : OCH3 and Z = N
IIf:~R1 =;H, R1 = 5-chloro-1,3-~di~ethyl-py~razol-4-yl, X = O, R2 = CH3, R3 =
: OC~H3 and Z =~CH.
:: IIg~ R1 = H, R1 = 5-chloro-1,3-dimethyl-pyrazol-4-yl, X = O, R2 = R3 =~CH3 and Z = CH.
~: :

.,, ~l ~S~3~'3~4 IIh: R1 = H, R1 = 1,5-dimethyl-pyrazol-4-yl, X = O, R2 = R3 = 0CH3 and Z = CH~
IIi: R1 = H, R1 = 1,3-dimethyl-5-difluoro-methoxy-pyrazol-4-yl, X = O, R2 = CH3, R3 = OCH3 and Z = H.
IIk: R1 = H, R1 = 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl, X = 0, R2 = R3 = CH3 and z = CH.
II(~): R1 = H, R1 = 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl, X - O, R2 = R3 = OCH3 and Z = CH.

Type 3: Thienylsulfonylureas of the abovementioned formula II, in which R denotes a radical of the formula R

;n which R1Z denotes H, halogen, tC1-C~) alkyl, (C2-C4) alkenyl or (C1-C4) alkoxy, where all three of the lastmentioned radicals may be halo-genated, a radical of the formula -CooR4 where R = H, (C1-C4) alkyl or (C2-C6)alkenyl, ~: or a radical of the formula -S(o)n-R5 , and X
denotes 0, see U.S~ Patent 4,431,029, JP-A 60/
~; ~ 197,676, JP-A 60/139,691 and JP-A 6U/193,983.

Of these compounds, examples which may be men-: tioned are the compounds IIm: Ri = 2-methoxycarbonyl-3-thienyl, R1 H, X = o,:R2 = 0CH3, R3 = CH3 and Z = N
: (thiameturon-methyl) IIn: R1:= 3-(pentafluoro-1-propenyl)-2-; thienyl, R1 =~H, X = O, R2 and R3 ~
: OCH3, Z = N or CH
IIo: R = 3-(2-chloro-1,2-difluoroethenyl)-2-:~

3~A~
~ 7 --thienyl, R1 = H, X - O, R2 and R3 =
OCH3 and Z = N or CH
IIp: R1 = 3-(2-chloro-1,2-difluoroethenyl)-2-thienyl, R1 = H, X = O, R2 = CH3, R3 = OCH3 and Z = N or CH
Ilq: R1 = 3-(pentafluoro-1-propenyl~-2-thienyl, R1 = H, X = O, R2 = CH3, R3 = OCH3 and Z = N or CH

Type 4: Phenyl-, phenoxy- and ben~ylsulfonylureas of the formula II, in which R1 denotes phenyl, phenoxy or benzyl which may both be substituted by halogen, (C1-C4) alkyl or (C1 C4) alkoxy which may both be halogenated, or a radical of the formula -CooR4 or -S(o)nR5 , and X denotes 0, see EP-A 51,466, EP-A 113,956 EP-A 7,687 and U.S. Patent 4,514,212.

Amongst these, the following compounds may be mentioned as examples:

IIs: R1 = H, R1 = 2-ethoxycarbonyl-phenyl, X = 0, RZ = Cl, R3 = OCH3 and Z = CH

IIt: R1 _ H, R1 = 2-methoxycarbonyl-phenyl-methyl, X = O, R2 = R3 = OCH3 and Z = CH.

IIu: R1 = H, R1 = 2-methoxycarbonyl-phenyl, : :: 25 X = O, R2 and R3 = CH3 and Z = CH;
common name: sulfometuron-methyl IIv: R1 - CH3, R1 = 2-methoxycarbonyl-phenyl, X = O, R2 = CH3, R3 = OCH3 and . Z = N

:. 30 IIw: R1 = H, R1 = 2-me:thoxycarbonyl-phenyl, X = O, R~ = CH3, RJ a OCH3 and Z = N
:: (metsulfuron-methyl) ~: :

~9~34~

IIx: R1 = H, R1 = 2-(2-chloroethoxy)-phenyl~
X = O, R2 = CH3, R3 = OCH3 and Z = N

lIy: R1 = H, R1 = Z-chlorophenyL, X = 0, R = CH3~ R3 = OCH3 and Z = N
(chlorsuLfuron) Compounds which may be mentioned as being preferred amongst the compounds of the formula III or IlI ' are those in which R7 = pyridyl which may be substituted by (C1-C4)-alkyl, or a radical of the formula -CooR9, -CooCH2R9 CooR9, -CH2R9-COO(C1-C4-alkyl), -CH2(R9)-CooCH2R9-CooR9 or -CH2-S(0)n-(C1-C4 alkyl), and R8 has the abovementioned meaning.
(see Japanese Offenlegungsschrift 59/225,180, EP-A 133,311 and EP-A 41,624).

; 0f these compounds III and III', compounds which may be mentioned as examples are IIIa: R7 = 3-methoxycarbonyl-2-pyr;dyl and R8 = methylaminocarbonyl.

IIIb: R7 = 3-methoxycarbonyl-2-pyridyl and R8 = ethylaminocarbonyl.

: ~ IIIc: R7 = 3-methoxycarbonyl-2-pyridyl and ;~ R8 = methoxycarbonyl4 ~ 25 IIId: R7 = 3-carboxy-Z~pyridyL and ; R8 = H; the isopropyLammon;um salt has the common name: ;mazap;r.

Amongst the compounds of the formulae III and III', the 34~

following compound is furthermore of particular import-ance:

IIIe: R7 = 2-methoxycarbonyl-5-methyl-phenyl and R8 =

The combinations according to the invent;on also cover the salts of the compounds of the formulae I to III
which can be employed for agriculture.

Su;table as such are, for example, the conventional alkali metal salts, alkaline~earth metal salts, substi-tuted or unsubstituted ammonium salts, phosphonium salts or sulfonium salts. Amongst the alkaline-earth metal salts and alkali metal salts, the Na, K, Mg or Ca salts are to be mentioned primar;ly.

Furthermore, the compounds of the formula I can also form acid-addition salts with ;norganic acids, such as HCl, H~r, HzS04 or ~3P04, or w;th organ;c acids, such as tC1-C4) carboxylic acids, chlorinated acetic acids, tartaric ac;d or citric acid; these are likewise covered by the invention.

Furthermore, formula I and formula III or III' also cover all corresponding stereoisomers and the mixtures thereof, so that these likewise come under the combinations according to the invention.

The present invention also relates to three-component combinations of compounds of the general formula I with two different active ingredients of the general formula II or III.

The herbicidal active ingredient combinations mentianed exhibit a surprisingly high act;vity which is greater than could have been expected as a result of the actions of the individual components.

The active ingredient combinations according to the 34~

invention cover a broad range of weeds. They are suit-able, for example, for combating annual and perennial weeds, such as, for example, Agropyron, Paspalum, Cynodon, Imperata, Pennisetum, ConvolvuLus, Cirsium, Rumex and others.

The combinations according to the invention can be employed for selective combating of harmful plants in pLantation crops, such as oil palm, coconut palm, rubber tree, citrus fruit, pineapple, cotton, coffee, cocoa inter alia, and also in fruit growing and viticulture.
Likewise, the combinations according to the invention can be employed in arable farm;ng in the so-called "no till" or "zero till" methods~ However, they can also be used non-selectively on paths, squares, industrial works etc. in order to keep these areas free of undesired vegetat;ve growth.

The ratios of the compounds of the formula I to the com-pounds of the formula II or III in the mixtures can vary within broad limits, in particular between about 500:1 to 1:10. The choice of mixture ratio depends on various parameters, such as the type of mixture partners, stage of development of the weeds and the range of weeds.
Mixture ratios from 100:1 to 1:5 are preferably selected.

The combinations according to the invention can be pre-sent both in the form of mixed formulations - wettable powders, emulsion concentrates - which are then used in a convent;onal fashion diluted with water; however, they can also be prepared as so-called tank mixes by common dilution of the separately formulated components with water The application rates of the herbicide of the formula I
in the active ingredient mixtures generally vary between 0.25 and 4.0 kg/ha, whereas the application rates of the compounds of the formula II or III can be in the range between 0.01 and 5.0 kg/ha, specifically for ~ ~9~344 of the formula IIJ, between 0.01 and 2.0 kg of a.i./ha " type 1 " 0.01 and 1.0 kg of a.i./ha " type 2 " 0.01 and 0.5 kg of a.;./ha " type 3 " 0.01 and 0.5 kg of a.i./ha " type ~ " 0.05 and 2.0 kg of a~i~/ha and compounds of the formula III " 0.05 and 2.0 kg o~
a.i./ha The agents according to the invention can be marketed in the conventional formulations which are known to those skilled in the art, for example as wettable powders, dusting agents, granules, dispersion concentrates, emul-s;f;able concentrates or sprayable solut;ons. In this case, the formulated agents generally contain the active ingredient in concentrations from 2 to 95% by weight.

Wettable powders are preparations, uniformly dispersible in water, ~hich contain, besides the active ingredient and in addition to a diluent or inert material, wetting agents, for example polyoxyethylated alkylphenols, poly-oxyethylated oleylamines or stearylamines, alkylsulfon-ates or alkylphenyl sulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium dinaphthyl-methanesulfonate or also sodium oleylmethyltaurinate~

Emulsifiable concentrates are obtained by dissolving the active ;ngred;ent mixture in an organic solvent, for example butanol, cyclohexanone, dimethylformam;de, xylene or alternatively higher-boiling aromatics~ and adding a nonionic wetting agent, for example a polyoxyethylated alkylphenol or a polyoxyethylated oleylamine or stearyl-amine.

:~

In wettable powders, the total concentration of act;ve ingredient is between about 10% and 95%, and the rest comprises the abovement;oned formulation additives. In the case of emulsifiable concentrates, the active ingredi-ent concentration is about 10% to 80%. Dust-like formu-lations usually contain 5% to 20% of active ingredients, sprayable solutions about 2% to 20%. In the case of granules, the active ingredient content depends partly on the form (liquid or solid) in which the active ingred;-ents are present and on which granulation auxiliaries,fillers etc. are used.

For use, the commercially available concentrates are, if appropriate, diluted in a conventional fashion, for example using water in the case of wettable powders and emulsifiable concentrates.

Dust-like and granulated formulations and sprayable solu-tions are not d;luted with further inert substances before use.

A. Formulation Examples a) The dusting agent ;s obtained by m;xing 10 parts by weight of act;ve ;ngredient mixture and 90 parts by weight of talc as inert material, and comminuting in a hammer mill.

b) The wettable powder which is easily dispersible in water is obtained by mixing 25 parts by weight of active ingredient mixture, 64 parts by weight of kaol;n-containing quartz as inert material, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetting and dispersin~q agent, and grinding in a p;n disc mill.

c) The dispersion concentrate which is easily d;spers-ible ;n water is prepared by mixing 20 parts by weight of active ingredient mixture with 6 parts by ~.Z9~34~

weight of alkylphenol polyglycol ether ~ riton X
207), 3 parts by we;ght of isotridecanol polyglycol ether (8 E0) and 71 parts by we;ght of paraff;nic mineral oil (boiling range, for example about 255 to above 377C), and grind;ng ;n a ball m;ll to a fineness of below 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient mixture, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight o~ oxyethylated nonylphenol ~10 E0) as emul-sifier.

B. Biological Examples Synergism is detected in the following examples by com-paring ~he additive degree of act;on calculated from the actions of individual components with the experimentally found degree of action of the active ingredient combina-tions. The additive degree of action ;s calculated according to the formula of S.R. Colby (cf. Calculating synergistic and antagonistic responses of herbicide com-binations, Weeds~ 15, 1967, pp. 20 to 22).

This formula is:

X . Y
E = X ~ r -where X denotes the ~ damage by herbicide A at an application rate of x kg/ha, Y denotes the % damage by herbicide B at an application rate of y kg/ha, E denotes the ~xpected % damage by herbicides A + B at an appl;cation rate of x + y kg/ha.

If the actual damage is greater than that calculated, the ~'3i~3~L

act;on of the active ;ngredient combination is more than additive, i.e. there ;s a synerg;st;c effect.

Example 1 . _ _ Seeds of var;ous weed grasses and weeds were sown ;n sandy loam in plastic pots (~ 9 cm) and raised for 3 - 4 weeks ;n a greenhouse under good growth cond;t;ons. The compounds of the formula I, formulated as aqueous solu-t;ons, water-d;spersible powders or emulsion concentrates, and the combinat;on partners were subsequently sprayed, alone and in combination, ;n the form of sprayable solu-t;ons onto the above-ground parts of the plants~ The amount of water used in this corresponded to 400 l/ha.

After standing for about 3 weeks ;n the greenhouse under ;deal growth conditions, the herb;c;dal act;on was assessed visually. The results are reproduced ;n Table 1 below.

Table 1:

Herb;c;dal action of the mixtures accord;ng to the ;nven-tion under greenhouse conditions (according to E%ample 1) 20 ProductDosage, ~ act;on kg of a.;./ha ECG PMI

Ia 0.125 10 65 0.060 o 30 IIu 0.008 30 55 25 Ia + IIu0.1Z5 ~ 0.008 90 (37) 95 ~84) 0.060 + O.Q08 75 (30) 80 (68) Abbreviations:

ECG = Echinochloa crus-gall;
PMI = Panicum miliaceum a.i. = active ingredient Ia = glufosinate ~l ~9~l~349~

IIa a sulfometuron-methyl ( ) = expected value according to Colby The results show that an unexpectedly h;gh herbic;daL
activity which is considerably better than could have been expected as a result of the sum of the indiv;dual actions of the active ingredients was achieved using the active ingredient combination.

Example 2 In a field experiment under tropical conditions, the preparations glufosinate-ammonium (Ia) and imazapyr (IIId) were tested alone and ;n combination in a crop of the gramineae Imperata cylindrica. At the time of applica-tion, this species of gramineae had a growth height of 80 to 1Z0 cm; the inflorescence had already formed. The experimental area was not shaded by trees~ A standard knapsack sprayer was used for the treatment; the experi-mental plots had an area of 16 m2.

Each treatment was repeated three t;mes. Evaluation was carried out by visual estimation of the damage.

The results are shown ;n Table 2 below, the actions having been determined as average vaLues for the damage (in %) from three experiments in each case. The values ;n parentheses represent the values to be expected according to the Colby formula.

It can be seen from the results that Ia on its own achieved an average to good initial action at the dosages tested; however, the action of Ia feLl off in the course of 12 to 20 weeks since resprouting occurs from the below-ground rhizomes. In contrast, herbicide IIId has a weak initial action, and the action was not compLetely satisfactory even 12 weeks after application.

For comb;ned use of Ia and IIld, where the low and ~C31344 average dosages for both products were used, ;t became apparent that both the init;al and the long-term action were considerably better than for the individual compon-ents; they were markedly greater than the actions cal-culated according to the Colby formula. Synerg;sm ;stherefore present.

Table 2:

Action on lmperata cyl;ndr;ca _ _ Product Dosage, % action after ~. days kg of a.i./ha 28 84 140 (d) Ia 1.5 53 34 13 2.0 82 39 15 3.0 89 62 54 IIId 0.25 5 35 40 0.375 7 50 55 0.5 14 72 76 Ia ~ IIId 1.5 + 0.25 68 93 74 t55.35) (57.1) (47.8) 1.5 + 0.375 83 97 87 (56.29) (67.1) (60.85) 200 + O.~S 85 98 ~2 (82.9) (60035) t49.0) 2.0 ~ 0.375 88 98 ~9 t83.26) (69.5) (69.7S) - _ .

a~;. = active ingredient Ia = glufosinate-ammonium IIId = imazapir d = days Exam Under field condit;ons, a crop of various annual and per-ennial weeds having a growth height of 5 to 15 cm was divided into plots of 8 m2.

9~L34 These plots were then treated with the mixtures accord;ng to the invention and with the individual components form;ng these mixtures on their own at var;ous applica-tion rates using the post-emergence method. The amount of water applied here was 400 l/ha. After 30 days, the plant damage compared to untreated experimentaL samples was assessed visually.

The activities of the mixtures and of the ind;v;dual components aga;nst the var;ous weeds are collated ;n Table 3.

The experimental results shown clearly prove the syner-g;stic actions of the m;xtures accord;ng to the ;nvent;on compared to the act;vities of the ;nd;v;dual components.
Th;s synergism can be seen particularly clearly on per-ennial weeds which are difficult to combat, such as, forexample, Agropyron or Cirsium.

Table 3:
. . .

Product Dosage, % action kg of a.i./ha A6R _IA CAR
20 Ia 0.5 40 1.U 27 55 55 IIu 0.0125 23 70 0 Ia ~ IIu 0.5 + 0.0125 63 (23) 80 (70) 65 (40) 1.0 + 0.0125 68 (43) 92 (86) 85 (55) , . . ~

Abbreviations.

AGR = Agropyron repens SIA = Sinapis arvensis CAR - Cirsium arvense a.i. = active ingredient Example 4 Plants of CommeLina communis and Amaranthus retroflexus 1 2~'-3~l34~

were ra;sed analogously to Example 1 ;n pots (~ 10 cm) and, at a growth height of about 25 cm, treated with the mixtures according to the ;nvent;on and the individual components on their own with a water appl;cation rate of 1,000 l/ha.

Evaluation by means of visual assessment occurred after about 3 weeks.

The results of this experiment are collated in TabLe 4.
As the data illustrated clearly show, the mixtures of glufosinate-ammonium and various sulfonylurea derivatives exhibit clearly synergistic actions, since in all cases the degrees of action of the mixtures are considerably greater than the values calculated according to Colby for additive effects.

34~

Table 4:

Product Dosage ~ action __ _k,~ a . i . /ha COMC0 _ AMARE
Ia 0, 4 40 5 IIu 0,1 0 5 0,05 0 5 0,1 o 5 0,5 o lO
IIy 0.0l 5 IIm 0,01 - 12 0,05 - lO
o,l _ 10 0,5 _ lO
IIw 0,01 - 5 0,05 - 5 0,1 - 5 0.5 _ 5 Ia + IIu 0,4 + 0,01 - 86 ( lO) 0,4 + 0,05 7~ (40) 92 (10) 0,4 + 0,1 63 (40) 99 (lO) 0,4 + 0,5 90 (40) 99 (15) Ia + IIy 0,4 ~ 0,01 60 (40) 95 (10) Ia + IIm 0,4 + 0,01 ~ _ 85 (16) 0,4 + 0,05 - 83 (l 5) 0,4 + 0~ l _ 8~ (l 5) 0,4 + 0,5 - 88 (l 5) Ia ~ IIw 0,4 + 0,01 - 80 (l Oj 094 + 0,05 - ~0 (1 0) o, 4 + o, 1 - 80 ( l 0) 0,4 + 0,5 - 85 (10) Abbreviations:

COMCO = Commelina communis AMARE = Amaranthus retroflexus a.;. = actlve ingredient ~91~4~
- 20 ~
~ ) = expected values accord;ng to Colby Ia = glufos;nate-ammonium lIm = Th1ameturon-methyl IIu = sulfometuron-methyl S IIw = metsulfuron-methyl IIy = chlorsulfuron : :

Claims

1. A herbicidal composition comprlsing an active ingredient of the formula I

(I) in which A1 denotes H and A2 denotes NH2, or A1 and A2 together denote an oxygen atom, V denotes O or NH, Y, where V = O, denotes hydrogen or (C1-C4)alkyl, or Y, where V = NH, denotes a radical of the formula -CH(CH3)-CONH-CH(CH3)-COOH or -CH(CH3) CONH-CH[CH2CH(CH3)2]-COOH, and, irrespective of the meaning of V, W denotes hydrogen, or a salt thereof, in combination with a compound of the formula II

(II) in which R1 denotes (C1-C4) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, which may in each case be halo-genated, (C1-C4) alkylamino, di(C1-C4 alkyl)-amino, [N-(C1-C4-alkylsulfonyl)-N-(C1-C4-alkyl)]-amino, where the alkyl radicals may be halogenated, phenyl, benzyl, phenoxy, pyrazolyl or thienyl which may all be substituted by (C1-C4) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl or (C1-C4) alkoxy which may all be substituted by halogen or (C1-C4-alkoxy)carbonyl, furthermore by halogen, CF3, nitro or a radical of the formula -COOR4, in which R4 denotes H, (C1-C4) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, (C1-C4) alkoxy-(C1-C4) alkyl or halo (C1-C4) alkyl, furthermore by a radical of the formula -S(O)nR5, in which R5 denotes (C1-C4) alkyl, (C1-C4) alkoxy, halo (C1-C4) alkyl, (C1-C4) alkoxy-(Cl-C4) alkyl, (C1-C4) alkoxy-carbonyl-(C1-C4) alkyl, di(C1-C4-alkyl)-amino, (C1-C4) alkylamino, (C1-C4) alkoxy-(C1-C4)alkylamino, and n denotes 0, 1 or 2, R1 denotes H, (C1-C4)alkyl or (C2-C4)alkenyl, R2 and R3, independently of one another, denote (C1-C4)-alkyl or (C1-C4) alkoxy which are both optionally monosubstituted or polysubstituted by halogen, (C1-C4) alkoxy or (C1-C4-alkoxy)-carbonyl, (C2-C6) alkenyl, (C2-C6) alkynyl, (C2-C6) alkenyloxy, (C2-C6) alkynyloxy or halogen, X denotes 0, S or NR6, where R6 =
(C1-C4) alkyl or (C1-C4) alkoxy, and Z denotes CH or N, or a salt thereof, or with a compound of the formula III or III', or salts thereof, (III') (III) in which R7 denotes phenyl, pyridyl, and quinolyl which are all optionally monosubstituted or polysubstituted by (C1-C4) alkyl or (C1-C4) alkoxy, which may both be monosubstituted or polysubstituted by halogen, are further substituted by a radical of the formula -COOR9, -COO-CH2R9-COOR9, -CH2R9-COO(C1-C4-alkyl) or CH2R9-COOCH2R9-COOR9, in which, in each case independently of one another, R9 denotes H or (C1-C4) alkyl, or a radical of the formula -CH2-S(O)n-(C1-C4)-alkyl, where n denotes 0, 1 or 2, and R8 denotes H or a radical of the formula -CONH(C1-C4-alkyl), -OCO(C1-C4-alkyl) or -CO(C1-C4 alkyl).

2. A herbicidal composition as claimed in claim 1, comprising an active ingredient of the formula I, in which A1 denotes H, A2 denotes NH2 and V, Y and W have the meanings of claim 1, or the salts thereof, in combination with a compound of the formula II, where, in the formula II, R1 denotes (C1-C4) alkoxycarbonyl-thienyl, (C1-C4) alkoxycarbonylphenyl or chlorophenyl, R1 denotes H or CH3, R2 and R3 denote (C1-C4) alkyl or (C1-C4) alkoxy, X denotes O and Z denotes N or CH.

3. A herbicidal composition, as claimed in claim 1, comprising a compound of the formula I, in which A1 denotes H, A2 denotes NH2, V-Y denotes OH and W denotes H, or the salt thereof;
in combination with a compound of the formula II, in which R1 denotes 2-methoxycarbonyl-3-thienyl, 2-methoxycarbonylphenyl or 2-chlorophenyl; R1 denotes H; R2 and R3 denote OCH3 or CH3, X denotes O and Z denotes N or CH.

4. A herbicidal composition as claimed in claim 1, comprising, besides the compound of the formula I, a compound of the formula III or III', or a salt thereof, where, in the formula III or III', R7 denotes carboxypyridyl or (C1-C4-alkoxy)-carbonyl-pyridyl and R8 denotes H or -CONH(C1-C4)-alkyl.

5. A herbicidal composition as claimed in any one of claims 1 to 4, wherein the ratio of the compounds of the formula I to the compounds of the formula II or III varies in the range between 500:1 to 1:10.

6. A herbicidal composition as claimed in any one of claims 1 to 4, wherein the ratio of the compounds of the formula I to the compounds of the formula II or III varies in the range between 100:1 and 1:5.

7. A proeess for combating harmful plants, wherein a herbicidal composition as claimed in any one of claims 1 to 4 is applied to the plants or to a cultivated area containing the plants in an effective amount.

8. A process ior combating harmful plants, wherein a herbicidal composition as claimed in claim 5 is applied to the plants or to a cultivated area containing the plants in an effective amount.

9, The use of a herbicidal composition as claimed in any one of claims 1 to 4 for combating harmful plants.

10. The use of a herbicidal composition as claimed in claim 5 for combating harmful plants.