AU605484B2

AU605484B2 - Herbicides

Info

Publication number: AU605484B2
Application number: AU72640/87A
Authority: AU
Inventors: Klaus Bauer; Hermann Bieringer; Peter Langeluddeke; Hilmar Mildenberger; Lothar Willms
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1986-05-09
Filing date: 1987-05-08
Publication date: 1991-01-17
Anticipated expiration: 2007-05-08
Also published as: EP0252237A2; JPH0818938B2; GR3002379T3; ATE64819T1; EP0252237B1; EP0252237A3; ES2028823T3; ZA873301B; MY101888A; JP2688341B2; CA1291344C; DE3771135D1; JPS62267211A; AU7264087A; JPH09151105A

Abstract

The invention relates to herbicidal agents which contain an active substance of the formula I <IMAGE> in which A<1> is H and A<2> is NH2, or A<1> and A<2> together are an oxygen atom, V is O or NH, Y is hydrogen or alkyl when V is O, or, when V is NH, is a radical of the formulae -CH(CH3)-CONH-CH(CH3)-COOH or -CH(CH3)-CONH-CH-[CH2CH(CH3)2]-COOH, and W is hydrogen, or a salt of this active substance, in combination with a compound of the formula II, <IMAGE> where R<1> represents alkyl, alkenyl or alkynyl each of which can be halogenated, (di)alkylamino, N-alkylsulphonyl-N-alkylamino, where the alkyl radicals can be halogenated, a (substituted) phenyl, benzyl, phenoxy, pyrazolyl or thienyl radical, R<1><'> is H, alkyl or alkenyl, R<2> and R<3> are (substituted) alkyl, (substituted) alkoxy, alkenyl, alkynyl, alkenyloxy, alkynyloxy or halogen, X is O, S or NR<6> and Z is CH or N, and their salts, or with a compound of the formula III or III' or salts thereof <IMAGE> where R<7> represents a (substituted) phenyl, pyridyl or quinolinyl radical, and R<8> is H, a radical of the formulae -CONH(alkyl), -OCO- and -CO(alkyl). They have advantageous effects on annual and perennial weeds.

Description

r COMMONWEALTH OF AUSTRALIA5 4- PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINALI

4 79c640 l$1 Application Number: Lodged: Complete Specification Lodged;, Acciptc4+ 4 Publishe,.

Class I nt. Class FlIelated Art: amendniitlill the nd Sectionl 49 atnd is Coi-r*cct C(' Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: HOECHST AKTIENGESELLSCHAFT Bruningstrasse, D-6230 Frankfurt/Main 80, Federal Republic of Germany HILMAR MILDENBERGE#R, KLAUS BAUER, HERMANN BIERINCER, LOTHAR WILLMS and PETER LANGELUDDEKE EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled:

HERBICIDES

The following statement is a full description of this invention, including the best mnethod of performing it known to us #0 4 -lA- HOECHST AKTIENGESELLSCHAFT HOE 86/F 104J D r A U/ m 6 Herbic ides The present invention relates to herbicides which contain an active ingredient of the formula I, HCO0

A

1 0 WozP CH 2-

C

WO A 2 i n wh ic h Al denotes H and A 2 denotes NH 2 or Al and A2 together denote an oxygen atom, V denotes 0 or NH, Y, where V denotes hydrogen or (Cl-C 4 )aLkyL, or where V NH, denotes a radlical of the formula -CHC CH 3

)-CONH-CH(CH

3 )-COOH or -CH(CH 3

)-CONH-

CHECH

2

CH(CH

3 2 J-COOH, and, irrespective of the meaning of V, W denotes hydrogen, or a salt thereof, in combination with a compound of the formula II ~rfi 10 If,, I II I I I CI I C I

IL

U

1~ 1X

N

NH -N-C-N

TR

3

(II)

i n wh ic h R 1denotes (Cl-C 4 aLkyL, (C 2

-C

6 aLkenyl,

(C

2

-C

6 alkynyL, which may in each case be halogenated, (Cl-C 4 alkyLamino, di(Cl-C 4 -aLkyL)amino, EN-(Cl-C 4 -aLkyLsuLfonyL )-N-(Cl-C 4 -aLkyl amino, where the aLkyl radicals may be halogenated, phenyL, benzyL, phenoxy, 4Tnaa"or thienyL which may all be substituted by (Cl-C 4 aLkyl, (C 2

-C

6 aLkenyL, (C 2

-C

6 aLkynyl or (CC-C 4 alkoxy which may all be substituted by haLogen or (Cl-C 4 aLkoxy)carbonyL, -2furthermore by halogen, CF 3 nitro or a radical of the formula -COOR in which R 4 denotes H, (C -C 4 )alkyl, (C 2

-C

6 )-alkenyl, (C 2

C

6 )alkynyl, (C 1 C 4 )alkoxy-(C 1

-C

4 )alkyl or halo S alkyl, furthermore by a radical of the formula R51 in which

R

5 denotes (C -,C,)alkyl, -C 4 )alkoxy, halo (C -C )alkyl, (C 1

-C

4 )alkoxy-(C -C 4 )alkyl, (C 1

-C

4 )alkoxycarbonyl-(C -C )alkyl, di(C 1

-C

4 -alkyl)-amino, (C -C) alkylamino, (C 1

-C

4 )alkoxy-(C 1

-C

4 )alkylamino, and n denotes 0, 1 or 2, of 6SMO&MIvljpyrazolyl which may be substituted by halogen, (C-C 4 )alkyl, (C -C 6 )alkenyl, (C-C 6 )alkinyl or I7 (C -C 4 )alkoxy which may all be substituted by halogen or

(C

1

-C

4 )-alkoxy)carbonyl 3 furthermore by halogen, CF 3 nitro or a radical of the formula R, in which R 5 has the abovementioned meaning, R' denotes H, (C -C )alkyl or (C -C 4 )alkenyl, 2 3 and R independently of one another, denote (C -C 4 )-alkyl or (C -C 4 )alkoxy which are m.oth optionally monosubstituted or polysubstituted by halogen, (C -C 4 alkoy or (C 1

C

4 alkoxy)-carbonyl,

(C

2 -C )alkenyl,

(C

2

C

6 )alkynyl, (C 2

C

6 )alkenyloxy, (C 2

C

6 )alkynyloxy or halogen, 6 ,6 X denotes 0, S or NR ,where R C 4 )a-!kyl or denotes CH or N, or a salt thereof, dor with a compound of the formula III or III', or salts thereof, 3R 8

I.R

1J i

N-

P

7 N CH 3 CH(CH 2 in which in which

N

R

CH

CH(CH

(III')

(III)

t~F L t 1 A. 4 R' denotes phenyl, pyridyl, and quinolyl which are all optionally monosubstituted or polysubstituted by

(C

1

-C

4 alkyl or (C 1

-C

4 alkoxy, which may both be monosubstituted or polysubstituted by halogen, are further substituted by a radical of the formula 9 9 9 -COOR -COO-CH 2 R -COOR 9

-CH

2

R

9

-COO(C

1

-C

4 -alkyL) or CH 2

R

9

-COOCH

2

R

9

COOR

9 in which, in each case independently of one another,

R

9 denotes H or (C 1

-C

4 alkyl, or a radical of the formula -CH2-S(O)n-(C1-C4)alkyl, where n denotes 0, 1 or 2, and

R

8 denotes H or a radical of the formula -CONH(C 1

-C

4 alkyl), -OCO(C 1

-C

4 -alkyl) or -CO(C 1

-C

4 -alkyl).

In the case where R 8 H, the two formulae III and III' exist in tautomeric equilibrium. Depending on the radical R 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 Offenlegungsschrift 2,833,274.

The compounds of the formula I where V 0 are described in U.S. Patent 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 -4- Japanese JournaL of Antibiotics, Volume XXXVIII-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: A H, A NH 2 V Y OH, W H, and the salts thereof; monoammonium salt; common name: glufosinate-ammonium.

Ib: A and A together oxygen; V Y OH, W H, and the salts thereof.

Ic: A 1 H, A 2

NH

2 V NH; Y -CH(CH 3

)-CONH-

CH(CH

3 )COOH, W H, and the salts thereof; common Sname: bialaphos.

it l SId: A H, A NH 2 V NH; Y -CH(CH 3

)-CONH-

CH(CH

2

CH-(CH

3 2 )COOH, W H, and the salts 15 thereof; common name: phosalacine Omura et al.

I The Japanese Journal of Antibiotics, 37 p. 542 (1985)).

Preferred compounds of the formula II are: Type 1: Alkylaminosulfonylureas of the abovementioned formula II, in which R denotes CN-(C 1

-C

4 -aLkylsulfonyl)-N-(C 1

C

4 -alkyl)amino3, where the alkyl radicals may in each case be halogenated, and X ~denotes 0, see EP-A 131,258; of these, the compound IIa in which R denotes (CH 3

SO

2

(CH

3

R

2 and R 3 denote OCH 3 and Z denotes CH are of particular importance.

Type 2: Pyrazolylsulfonylureas of the abovementioned formula II in which R denotes a radical of the formula

A

I

PR

10 in wh ich R 9has the abovementioned meaning,

I

Ii t ft t t R 0denotes H, (Cl-C 4 aLkyL, (Cl-C 4 aLkoxy, or 4 5' a radicaL of the formuLa -COOR 4 or -S(O)nR ,in which R 5

(CC-C

4 aLkyL, (Cl-C 4 alkoxy, haLo (Cl-C 4 aLkyL, (Cl-C 4 aLkyLamino or di (Cl-C 4 -aLkyL)amino, and Rldenotes H, haLogen, (Cl-C 4 atkyL or (Cl-C 4 aLkoxy, which may both be haLogenated, and X denotes 0, see EP-A 87,780.

Of these compounds, the folLowing are particuLarly suitable according to the invention: Compound I~b: R H, F? 1,3,5-trimethyL-pyrazoL-4-yL, X 0, R 2

-CH

3 R 3= OCH 3 andlZ =N.

IIc: R H, R 1 1,3,5-trimethyL-pyrazoL- 4-yL, X 0, R 2 CH 3 R 3= OCH 3 and Z C H I~d: R 1 H, R 1 1,3,5-trimethyL-pyrazoL- 4-yL, X R- R 3= CH 3 and Z CH.

lie: R if= H, Ri= 5-chLoro--1,3-dimethyLpyrazoL-4-yL, X 0, R 2 CH 3 ,R3

OCH

3 and Z =N.

Ilf: R i H, R 5-chLoro-1,3-dimethyLpyrazoL-4-yL, X 0, R2=CH 3

R-

OCH

3 and Z =CH.

Ihg: R -f H, R 5-chLoro-1,3-dimethyLpyrazoL-4-yL, X 0, R2= R3= CH 3 and Z CH.

4 4 -6a 04 6 15 4 1 I1h: 1 H, Ri= 1,5-dimethyL-pyrazoL-4yL, X 0, R 2=R 3= OCH 3 and Z CH.

Ili: R 1= H, -i 1,3-dimethyL-5--difLuoromethoxy-pyrazoL-4-yL, X 0, R 2

CH

3 3 R =OCH 3 and Z H.

R

2 R3and Z CH I1(L): R H, R oxycarbonyL-1-methyLpyra -yL, X 0, R 2 R 3 0CH 3 and Type 3: ThienyLsuLfonyLureas of the abovementioned formula II, in which Rdenotes a radical of the formula R 1 i n wh ic h R 12 denotes H, halogen, (Cl-C 4 aLkyL,

(C

2

-C

4 alkenyL or (Cl-C 4 aLkoxy, where aLl three of the Lastmentioned radicals may be halogenated, a radicaL of the formula -COOR 4 1 where R 1= H, (Cl-C 4 aLkyL or (C 2

-C

6 )aLkenyL, or a radical of the formula -S(0)n-R 5 and X denotes 0, see U.S. Patent 4,431,029, JP-A 197,676, JP-A 60/139,691 and JP-A 60/193,983.

Of these compounds, examples which may be mentioned are the compounds 41 Irn R' 2-methoxycarbonyL-3-thienyL, R 1 H, X R 2

OCH

3

R

3

CH

3 and Z =N (thiameturon-methyL) Iun: R 3-(pentafLuoro-l-propenyL)-2thienyL, R f= H, X 0, R 2 and R3

OCH

3 Z N or CH Ilo: Ri= 3-(2-chLoro-1,2-difLuoroethenyL)-2-

I

Itt 4$ 04 4 44 4 41 4 S 444 .4 44 4 4 @0 -7- 2 3 thienyL, R H, X RandR

OCH

3 and Z =N or CH I Ip: R =3-(2-chLoro-1,2-difLuoroethenyL)- 2-thienyL, R H, X R 2=CH 3 R =OCH 3 and Z =N or CH I I q R1 3-(pentafLuoro-l-pr-openyL)-2thienyL, R H, X 0, R H 3 3 R 3 0CH 3 and Z =N or CH Type 4: PhenyL-, phenoxy- and benzyLsuLfonyLureas of the formuLa II, in which [R denotes phenyL, phenoxy or benzyL which may both be substituted by haLogen, (Cl-C 4 aLkyL or (Cl-C 4 aLkoxy which may both be haLogenated, or a radlicaL of the formuLa -C00R 4 o r -S(0 )nR 5 and 4X 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: Ius: R H, R xycarbonyL-phenyL, 2 3 X R 2 CL, R OCH 3 and Z CH It: R 1 14H, R 2-methoxycarbonyL-phenyLmethyL, X =0 =0C 3 and Z =CH.

fjIIu: R H, R 1 2-methoxycarbonyL-phenyL, X 0 and R CH 3 and Z CH; common name: suLfometuron-methyL IIv: R CH 3

R

1 2-methoxycarbonytphenyL, X R 2

CH

3 R3= 0CH 3 and Z =N 11w: R H, R 2-methoxycarbonyL-phenyL, X 0, R= CH 3 R3= OCH 3 and Z N (metsu Ifuron-methyl) I~x: R H, -i 2-(2--chLoroethoxy)-phenyL, X R 2 CH 3 R 3=OCH 3 and Z =N Ily: R Hi, R 2-chLorophenyL, X =0, R 2

=CH

3 R 3 0CH 3 and Z N (chLorsuLfuron) Compounds which may be mentioned as being preferred amongst the compounds of tile formuLa III or III' are those in which R 7 pyridyL which may be substituted by (Cl-C 4 9 aLkyL, or a radicaL of the formuLa -COOR

-COOCH

2

R

9 COOR 9

CH

2 R 9 C00(C 1

-C

4 -aLkyL

-CH

2 (R 9 )-COO CH 2 R 9-COOR 9or (Cl-C 4 -aLkyL and R 8 has the abovementioned meaning.

(see Japanese OffenLegungsschrift 59/225,180, EP-A 133,311 and EP-A 41,624).

'4 t I t Cr'' C C

CC

Of these compounds III and III', compounds mentioned as examples are which may be II a

R

7 R 8 I I b: R 7 R 8 R 8 3-methoxycarbonyL-2-pyridyL and methyLaminocarbonyL.

3-methoxycarbonyL -2-pyr idyL and ethyLaminocarbonyL.

3-methoxycarbonyL-2-pyridyL and methoxycarbonyl.

3-carboxy-2-pyridyL and H; the isopropyLammonium salt has the common name: imazapir.

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

X

I'

9 following compound is furthermore of particuLar importance: IIIe: R 2-methoxycarbonyL-5-methyL-phenyL and R H The combinations according to the invention aLso cover the salts of the compounds of the formulae I to III which can be employed for agriculture.

Suitable as such are, for example, the conventional alkali metal salts, alkaline-earth metal salts, substituted 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 S are to be mentioned primarily.

S Furthermore, the compounds of the formula I can also form acid-addition salts with inorganic acids, such as HCI, HBr, H 2 S0 4 or H 3 P0 4 or with organic acids, such as (C 1

-C

4 carboxylic acids, chlorinated acetic acids, tartaric acid 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 SII or III.

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

The active ingredieit combinations according to the 10 invention cover a broad range of weeds. They are suitable, 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 farming in the so-called "no till" or "zero till" methods. However, they can also be S used non-selectively on paths, squares, industrial works S 15 etc. in order to keep these areas free of undesired S vegetative growth.

The ratios of the compounds of the formula I to the compounds 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 present both in the form of mixed formulations wettable powders, emulsion concentrates which are then used in a conventional 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

F.I.

11 Compounds of the formula III, 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. i ./ha type 3 0.01 and 0.5 kg of a.i./ha type 4 0.05 and 2.0 kg of a. i ./ha and compounds of the formuLa III 0.05 and 2.0 kg of a.i./ha S The agents according to the invention can be marketed in 15 the conventional formuLations which are known to those skilled in the art, for example as wettable powders, t, dusting agents, granules, dispersion concentrates, emulsifiable concentrates or sprayable solutions. In this S case, the formulated agents generaLLy contain the active ingredient in concentrations from 2 to 95% by weight.

T Wettable powders are preparations, uniformLy dispersibLe in water, which contain, besides the active ingredient and in addition to a diluent or inert material, wetting agents, for example polyoxyethylated alkylphenols, polyoxyethyLated oleylamines or stearyLamines, alkyLsuLfonates or alkyLphenyL sulfonates, and dispersing agents, for example sodium Ligninsulfonate, sodium dinaphthyLmethanesuLfonate or also sodium oLeyLmethyltaurinate.

Emulsifiable concentrates are obtained by dissolving the active ingredient mixture in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or alternatively higher-boiling aromatics, and adding a nonionic wetting agent, Tor example a polyoxyethylated alkylphenol or a polyoxyethylated oleylamine or stearylamine.

i -12 In wettable powders, the total concentration of active ingredient is between about 10% and 95%, and the rest comprises the abovementioned formulation additives. In the case of emulsifiable concentrates, the active ingredient concentration is about 10% to 80%. Dust-Like formulations 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 ingredients 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 I t example using water in the case of wettabLe powders and 9 t t t 15 emulsifiable concentrates.

T 4T ,r Dust-Like and granulated formulations and sprayable soLu- Stions are not diluted with further inert substances before use.

SA. Formulation Examples a) The dusting agent is obtained by mixing 10 parts by weight of active ingredient 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 kaolin-containing quartz as inert material, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetting and dispersing agent, and grinding in a pin disc mill.

c) The dispersion concentrate which is easily dispersible in water is prepared by mixing 20 parts by S weight of active ingredient mixture with 6 parts by r -13weight of alkylphenoL poLygLycoL ether (Triton X 207), 3 parts by weight of isotridecanoL polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example about 255 to above 377°C), and grinding in a ball mill 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 of oxyethylated nonylphenol (10 EO) as emulsifier.

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

This formula is:

X

E X Y E=X+Y 100 where X denotes the damage by herbicide A at an apnlication rate of x kg/ha, Y denotes the damage by herbicide B at an application rate of y kg/ha, E denotes the expected damage by herbicides A B at an application rate of x y kg/ha.

If the actual damage is greater than that calculated, the

I

1A action of the active ingredient combination is more than additive, i.e. there is a synergistic effect.

Example 1 Seeds of various weed grasses and weeds were sown in sandy Loam in plastic pots 9 cm) and raised for 3 4 weeks in a greenhouse under good growth conditions. The compounds of the formula I, formulated as aqueous solutions, water-dispersible powders or emulsion concentrates, and the combination partners were subsequently sprayed, alone and in combination, in the form of sprayable solutions onto the above-ground parts of the plants. The amount of water used in this corresponded to 400 I/ha.

After standing for about 3 weeks in the greenhouse under ideal growth conditions, the herbicidal action was assessed visually. The results ar- reproduced in Table 1 below.

Table 1: Herbicidal tion under action of the mixtures according to the invengreenhouse conditions (according to Example 1) Product Dosage, kg of a.i./ha actio'n

PMI

Ii: *4 4 4

ECG

IIu Ia IIu 0.125 0.060 0.008 0.125 0.008 0.060 0.008 10 0 30 90 (37) 75 (30) 95 (84) 80 (68) Abbreviations:

ECG

PMI

a.i.

Ia Echinochloa crus-galli Panicum miliaceum active ingredient glufosinate 1 IIa sulfometuron-methyL expected value according to Colby The results show that an unexpectedly high herbicidal activity which is considerably better than could have been expected as a result of the sum of the individual 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 in combination in a crop of the gramineae Imperata cylindrica. At the time of application, this species of gramineae had a growth height of to 120 cm; the inflorescence had already formed. The experimental area was not shaded by trees. A standard knapsack sprayer was used for the treatment; the experimental plots had an area of 16 m 2 Each treatment was repeated three times. Evaluation was carried out by visual estimation of the damage.

The results are shown in Table 2 below, the actions t, having been determined as average values for the damage S(in from three experiments in each case. The values in 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 la 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 combined use of Ia and IIId, where the low and r YIII-(--- 16 average dosages for both products were used, it became apparent that both the initial and the long-term action were considerably better than for the individual components; they were markedly greater than the actions calculated according to the Colby formula. Synergism is therefore present.

Table 2: Action on Imperata cylindrica Product la IIld Dosage, kg of a.i./ha 1.5 0.25 0.375 1.5 0.25 0.375 0.25 0.375 action 28 53 82 89 after days 84 140 (d) 34 13 39 62 54 Ia IIId 68 (55.35) 83 (56.29) 85 (82.9) 88 (83.26) 93 (57.1) 97 (67.1) 98 (60.35) 98 (69.5) 74 (47.8) 87 (60.85) 82 (49.0) 89 (69.75) a.i. active ingredient la glufosinate-ammonium IIId imazapir d days Example 3 Under field conditions, a crop of various annual and perennial weeds having a growth height of 5 to 15 cm was divided into plots of 8 m 17 These plots were then treated with the mixtures according to the invention and with the individual components forming these mixtures on their own at various application rates using the post-emergence method. The amount of water applied here was 400 I/ha. After 30 days, the plant damage compared to untreated experimental samples was assessed visually.

The activities of the mixtures and of the individual components against the various weeds are collated in Table 3.

The experimental results shown clearly prove the synergistic actions of the mixtures according to the invention compared to the activities of the individual components.

This synergism can be seen particularly clearly on perennial weeds which are difficult to combat, such as, for example, Agropyron or Cirsium.

Table 3: ~4

V

Product Dosage, action kg of a.i./ha AGR SIA CAR Ia 0.5 0 0 27 55 IIu 0.0125 23 70 0 Ia IIu 0.5 0.0125 63 (23) 80 (70) 65 0.0125 68 (43) 92 (86) 85 Abbreviations: AGR Agropyron repens SIA Sinapis arvensis CAR Cirsium arvense a.i. active ingredient Example 4 Plants of Commelina communis and Amaranthus retroflexus II I 18 were raised analogously to Example 1 in pots (0 10 cm) and, at a growth height of about 25 cm, treated with the mixtures according to the invention and the individual components on their own with a water application 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.

1 r r

F

V.

S

19 TabLe 4: Product Dosage kg a.i./ha 0,4 Ia I Iu Ily I Tm

IIW

Ia IIu 0,1 0,05 0,1 0,01 0,01 0,05 0,1 0,01 0,05 0,1 0 [+0 L+ 0 a ct ior CONMC 0 40 0 0 0 0

AMARE

12 86 (1( 92 (iC 99 (ic 99 95 (iC 85 (OE 83 88 88 80 (ic (1c (1c 85 Ta Hly Ia IIm

V

0,4 0,4 o,ze 0,0 0,01 0,05 0,15 0,5 0,01 0,05 0,15 0,5 '01 ,05 ,l (40) (40) (40) Ia 11w Abbreviations: COMCO CommeLina conimunis AMARE Amaranthus retrofLexus a.i. =active ingredient 1 =expected values according to CoLby la gLufosinate-ammonium IIn Thiameturon-methyL IIu suLforneturon-methyL 11w retsuLfuron-rnethyL IIy chLorsuLfuron

Claims

1.A herbicidal- composition comprising an active ingredient of the formula I H C 0 A P -CH -CH 2 -C-C-v Y M 2 '2 WO A2 I in which A A 1 denotes H and Adenotes NH 2 or A 1and A2 together denote an oxygen atom, V denotes 0 or NH, Y, where V 0, denotes hydrogen or (Cl-C 4 )aLkyL, or Y, where V NH, denotes a radicaL of the formuLa -CH(CH 3 )-CONH--CH(CH 3 )-COQH or -CH( CH 3 )-CONH- I a f tiesCHECH 2 CH(CH 3 2 J-COOH, and, irrespective of the meaning of V, W denotes hydrogen, sit., it t or a saLt thereof, *1 in combiination with a compound of the formuLa II R 2 22 4* R 3 in wh ich R 1denotes (Cl-C 4 aLkyL, (C 2 -C 6 aLkenyL, CC 2 -C 6 alkynyL, which may in each case be haLo- genated, (CC-C 4 alkylamino, di(CC-C 4 -aLkyL)- amino, CN-(Cl-C 4 -aLkyLsuLfonyL )-N-(Cl-C 4 -alkyL amino, where the aLkyl radicals may be haLogenated, phenyL, benzyL, phenoxy, paai or thienyL which may aLL bp substituted by (Cl-C 4 aLkyL, (C 2 -C 6 aLkenyL, (C 2 -C 6 aVxynyL or (CC-C 4 aLkoxy which may all be substituted by halogen or (Cl-Cj+- aLkoxy)carbonyL, furthermore by halogen, CF 3 nitro or a radical Sof the formula -COOR in which Rdenotes H, (Cl-C 4 aLkyL, ,I t s -22- (C 2 -C 6 )alkenyl, (C 2 C 6 )alkynyl, (C 1 -C 4 )alkoxy-(Cl -C 4 alkyl or halo (C 1 -C 4 )alkyl, furthermore by a radical of the formula in which R 5 denote (C 4 )alkyl, (C 1 -C 4 )alkoxy, hl (C 1 C 4 )alkyl, (C 1 -C 4 )alkoxy-(C.-C 4 )alkyl, (Cl-C 4 )alkoxy- carbonyl-(C 1 C 4 )alkyl, di(C 1 -C 4 -alkyl)-amino, (C 1 -C 4 alkylamino, (C 1 -C 4 )alkoxy-(C 1 -C 4 )alkylamino, and n denotes 0, 1 or 2,orR ercm F hpyrazolyl which may be substituted by halogen, (C 1 -C 4 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkinyl or C 1 -C 4 )alkoxy which may all be substituted by halogen or C 1 -C 4 -alkoxy)-carbonyl, furthermore by halogen, CF 3 nitro or a radical of the formula 5 in which R 5 has the abovementioned meaning, R 1 denotes H, (C 1 -C 4 )alkyl or (C 2 -C 4 )alkenyl, 2 3 R and R independently of one another, denote (C 1 -C 4 )-alkyl or C 1 -C 4 )alkoxy which are both optionally monosubstituted or polysubstituted by halogen, (C 1 -C 4 )alkoxy or (C 1 -C 4 -alkoxy)-carbonyl, (C 2 C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 2 C 6 )alkenyloxy, (C 2 -C 6 )alkynyloxy or halogen, X denotes 0, S or NR6, where R 6= (C 1 C 4 )alkyl or (C I- C 4 )alkoxy, and Z denotes CH or N, or a salt thereof, or with a compound of the formula III or III, or salts thereof f 0 R 7 R R (III) R8 R R CH (CH 3 2 (III I) 23 in which or R denotes phenyL, pyridyL,Aa4 quinoLyL which are aLL optionally monosubstituted or polysubstituted by (C 1 -C 4 alkyL or (C 1 -C 4 aLkoxy, which may both be monosubstituted or polysubstituted by halogen, are further substituted by a radical of the formula 9 9 9 -COOR -COO-CH 2 R -COOR, -CH 2 R 9 -CO(C 1 -C 4 -alkyL) or CH 2 R 9 -COOCH 2 R 9 9 COOR, in which, in each case independently of one another, 9 R denotes H or (C 1 -C 4 alkyL, or a radical of the formuLa -CH2-$(0)n-(C1-C4)- alkyl, where n denotes 0, 1 or 2, and It 4 r ct 8 c R denotes H or a radical of the formula -CONH(C 1 -C 4 alkyl), -OCO(C 1 -C 4 -aky) or -CO(C 1 -C 4 -alky).

2. A herbicidal composition as claimed in claim 1, comprising an active ingredient of the formula I, in which 1 2 A denotes H, A denotes NH 2 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, 3 in the formula II, R denotes (C 1 -C 4 alkoxycarbonyl-thienyl, (C 1 1' C 4 alkoxycarbonylphenyl or chlorophenyl, R denotes 2 3 H or CH 3 R and R denote (C 1 -C 4 alkyL or (C 1 -C 4 alkoxy, X denotes 0 and Z denotes N or CH.

3. A herbicidal composition, as claimed in claim 1 or 2, comprising a compound of the formula I, in which Al denotes H, A 2 denotes NH 2 V-Y denotes OH and W denotes H, or the salt thereof; in combination with a compound of the formula II, in which R denotes 2-methoxycarbonyl-3-thienyl, 2- methoxycarbonylphenyL or 2-choropheny; R denotes H; R and R denote OCH 3 or CH 3 X denotes 0 and 24 Z denotes N or CH.

4. A herbicidai 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', R 7 denotes carboxypyridyL or (C 1 -C 4 -alkoxy)- P carbonylpyridyL and R denotes H or -CONH(C 1 -C 4 alkyL. A herbicidal composition as claimed in claims 1 to 4, wherein the Sratio of the compounds of the formuLa I to the com- pounds of the formula II or III varies in the range between 500 1 to 1

6. A herbicidal composition as claimed in claims 1 to 5, wherein the ratio of the compounds of the formuLa I to the com- pounds of the formuLa II or III varies in the range I between 100 1 and 1 S7. A process for combating harmful plants, wherein a herb i c i dal composition as claimed in claims 1 to 6 is applied to these plants or to the cultivated area in an effec- tive amount.

8. The use of herbicides as claimed in claims 1 to 6 for combating harmful plants. DATED this 7th day of May 1987. HOECHST AKTIENGESELLSCHAFT M EDWD. WATERS SONS PATENT ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000. i i