GB2350298A - The safening of 2-benzoylcyclohexane-1,3-dione herbicides with 1-phenyl-1,2,4-triazole, 1-phenyl-pyrazolin-3-carboxylate & 8-oxy-quinoline derivatives - Google Patents

Abstract

A method is disclosed for selectively killing weeds in a crop (eg cereals) using safened herbicides. The triketone herbicides are of formula (I) and the safeners are selected from <SL> <LI>(a) 1,1,4-triazoles of formula (II) <LI>(b) pyrazolin-3-carboxylates of formula (III) and <LI>(c) quinolin-8-oxy compounds of formula (IV) </SL> where the substituents and indices are as defined in claim 1. A herbicidal product is provided comprising a herbicide of formula (I) and at least one safener of formula (II), (III) or (IV), the herbicide being either combined with the safener in the same composition or placed in separated compartments of a two pack container. <EMI ID=1.1 HE=102 WI=84 LX=637 LY=1853 TI=CF>

Description

2350298 HERBICIDE COMPOSITION The present invention relates to a method

for selectively killing weeds in a crop plant as well as to herbicidal compositions and preparations for use in the method.

The protection of crops from weeds and other undesirable vegetation which inhibit crop growth is a constantly recurring problem in agriculture. To help combat this problem researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted growth.

Chemical herbicides of many types have been disclosed in the literature and a large 0 number are in commercial use.

For example, U.S. Pat. Nos. 4,780,127, 4,938,796, 5,006,158 and 5,089,046 disclose 2-(substituted benzoyl)-1,3-cyclohexanedione compounds having the general structure:

0 0 X (0)z - 0 Pn wherein X, Q and Z have the meanings set forth hereinafter. These dione compounds have proved to be effective pre-emergent and postemergent herbicides against a wide variety of grasses, broadleaf weeds and sedges.

It is frequently desirable that herbicides are applied to growing crops. In such cases, it is desirable to minimise any phytotoxic effects which the herbicide may have on the crop plant. Safeners are one method whereby the selectivity of a herbicide may be achieved. By applying a safener to the crop, either prior, in conjunction with, or subsequently to the herbicide, crop damage can be reduced whilst the herbicidal effect on the weeds is not significantly diminished.

0 2 However, the effect of any particular safener with any particular herbicide is not predictable. The applicants have found that only certain particular groups of safener compounds are effective when used in conjunction with the herbicides of formula (1).

Thus according to the present invention there is provided a method of killing or 5 controlling weeds amongst crop plants, said method comprising applying to the crops a t> C> C compound of formula (1) 0 0 X (Q)Z - (Z)n wherein X represents a halogen atom; a straight- or branched-chain alkyl or alkoxy group c containing up to six carbon atoms which is optionally substituted by one or more groups -OR' or one or more halogen atoms; or a group selected from nitro, cyanO, -C02 R 2 -S(O),,Rl, -O(CH2),0R1, -COR2, -OSO2R 4, -NR 2 R 3, -SOYR 2 R 3, -CONR 2 R 3 and CSNR 2 R 3; R' represents a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; R 2 and R 3 each independently represents a hydrogen atom; or a straightor 0 0 branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; R 4 represents a straight- or branched-chain alkyl, alkenyl or alkynyl group tn containing up to six carbon atoms optionally substituted by one or more halogen atoms; or a cycloalkyl group containing from three to six carbon atoms; C each Z independently represents halo, nitro, cyano, S(O) R 5 ' OS(O),,R5, (ClC6)alkyl, (Q-C6)alkoxy, (C]-C6)haloalkyl, (Cl-C6)haloalkoxy, carboxy, (ClC6)alkylcarbonyloxy, (Cl-C6)alkoxycarbonyl, (Cl-C6)alkylcarbonyl, amino, (Cl- 3 C6)alkylarnino, (Cl-C6)dialkylamino having independently the stated number of carbon 0 atoms tn each alkyl group, (Cl-C6)alkylcarbonylamino, (Cl- C6)alkoxycarbonylamino, In (Cl-C6)alkylaminocarbonylamino, (CI-C6)dialkylaminocarbonylam-ino having t> independently the stated number of carbon atoms in each alkyl group, (Cl- C6)alkoxycarbonyloxy, (Cl-C6)alkylaminocarbonyloxy, (ClC6)dialkylarninocarbonyloxy, phenylcarbonyl, substituted phenylcarbonyl, phenylcarbonyloxy, substituted ' phenylcarbonyloxy, phenylcarbonylamino, substituted phenylcarbonylan-iino, phenoxy or substituted phenoxy; R 5 represents cyano; -COR 6; -CO,R 6; or -S(O)... R 7; R6 represents hydrogen or straight- or branched-chain alk 1 group containing up to b 0 y c 0 six carbon atoms; R7 represents (Cl-C6)alkyl, (Cl-C6)haloalkyl, (Cl-C6)cyanoalkyl (C3- C8)cycloalkyl optionally substituted with halogen, cyano or (C I-C4)alkyl; or phenyl optionally substituted with one to three of the same or different halogen, nitro, cyano, (Cl- C4)haloalkyl, (Cl-C4 4D alkyl, (Cl-C4)alkoxy or -S(O) R 8; R8 represents (C 1 -C4) alkyl, (C 1 -C4) alkyl substituted with halogen or cyano, phenyl or benzyl; each Q independently represents Cl-C4 alkyl or -C0,7R9 wherein R9 is Cl- C4 alkyl; m is zero, one or two; n is zero or an integer from one to four; r is one, two or three; and z is 0 or an integer from 1 to 6; and at least one of (a) a compound of formula (II) 4 N N / R12 N (R1O)q R11 (II) or an agriculturally acceptable salt or ester thereof, I where Rcis the same or different groups selected from halogen; nitro; cyano; C> 1.13 trifluoromethyl; CI-4 alkyl, CI-4alkoxy or CI-4alkylthio, wherein the alkyl, alkoxy and alkylthio groups are optionally substituted by one or more halogen atoms, in particular C fluorine or chlorine; C3-6cycloalkyl optionally substituted by CI-4 alkyl; or phenyl or phenoxy optionally substituted by one or more trifluoromethyl groups; Z3 R" is hydrogen; C I -4alkyl which is optionally substituted by one or more halogen atoms, or by a CI-4alkoxy or C 1 -4 alkylthio group; C2-6alkenyl; C2-6 alkynyl; C3-6 cYClOaIkyI which is optionally substituted by C 1 -4 alkyl and/or a dichlorovinyl group; R 12 is hydroxy; C 1 -4 alkyl; C3-6 cycloalkoxy; phenylC 1 -6alkoxy; phenoxy; C2-6 alkenyloxy; C2-6alkynyloxy; CI-6alkoxy, CI-6alkylthio wherein the alkoxy of alkylthio groups are optionally substituted by CI-2 alkoxy mono- or di-CI-4alkylaminocarbonyl, phenylaminocarbonyl, N-(CI-4)alkylphenylaminocarbonyl, mono- or di-CI6alkylamino, Cj6alkylcarbonyloxy, CI-2alkylthio, cyano or halogen; a group of formula R14 N-7( R13 R13 or 0 where R 13 is hydrogen or Cj-4 alkyl and R 14 is as defined above in relation to R10; mono or di-C I -4alkylamino, C5-6Cycloalkylamino, piperidino, morpholino, or 2, 6 dimethylmorpholino, a group of formula R15 R16 where R' 5 and R 16 are the same or different and are C] -4alkyl groups, or R 15 and R 16 0 together form a 5-, 6- or 7-membered c cloalkyl group, 0 y and q is 0, 1, 2 or 3:

or (b) a compound of formula (III) R20 R19 N \ N-- COOR18 (R17)t where each R 17 group is independently selected from halogen or haloalkyl; t is an integer of from 1 to 3, R18 is hydrogen, alkyl, cycloalkyl, tdalkylsilyl, trialkylsilylmethyl or alkyloxyalkyl, C R19 and R20 are independently selected from hydrogen, alkyl, C3- 6CY1C10alkyl, alkenyl, tn alkynyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, optionally substituted with phenyl, halogen or cyano, or R19 and R20 together with the carbon atom to which they are attached form a ring such as an alkyl ring or (c) a compound of formula (IV) 6 R23 R24 - R25 R2 'z R2 tN R26 R27 R28 (IV) or an acid addition salt or metal complex thereof, wherein R 21, R 22 and R 23 are independently selected from hydrogen, halogen, nitro, cyano, 5 alkyl or alkoxy, R 24, R 25 and R 26 are independently selected from hydrogen, halogen or alkyl, 4D R 27 is an aliphatic, acyclic, saturated hydrocarbon radical having from I to 3 carbon atoms and R 28 is a carboxyl group or a salt thereof, a mercaptocarbonyl group or a salt thereof, a carboxylic acid ester group, a carboxylic acid thiolester group or an unsubstituted or substituted derivative of a carboxylic acid amide group or a carboxylic acid hydrazide group, or R 27 and R 28 together form an unsubstituted or substituted tetrahydrofuran-2-one D ring.

As used herein, the terms "halogen" and "halo" include fluorine, chlorine, bromine and iodine atoms. Unless stated others, the term "alkyl", "alkenyl" and "alkynyl" includes alkyl, alkenyl or alkynyl groups respectively, which have up to 6 carbon atoms. In polyhalogenated groups, the halogens may be the same or different.

r) The term "substituted" in terms of "substituted phenyicarbonyl," "substituted phenylcarbonyloxy," "substituted phenylcarbonylamino" and "substituted phenoxy" as used in relation to formula (1) means having one to five substituents, which may be the same or different, selected from the following: halo, nitro, cyano, S(O),, R 2, (CI-C6)alkyl, (CI-C6)alkoxy, (CI-C6)haloalkyl, (CI-C6)haloalkoxy, carboxy, (CIC6)alkylcarbonyloxy, (C 1 -C6)alkylcarbonyl, (C 1 -C6)alkoxycarbonyl, (C I -C6)alkylcarbonylamino, amino, (C I - 7 Q)alkylarnino and (CI-C6)dialkylamino having independently the stated number of carbon atoms in each group.

Certain compounds of formula (II) and their preparation are described in European Patent Application No. 174562, the content of which is incorporated herein by reference.

Particularly suitable compounds of formula (II) for use in the method of the invention are compounds where R10 is halogen and in particular chlorine, q is 2, R1 1 is a trihalomethyl group such as trichloromethyl, and R 12 is hydroxy of an agriculturally acceptable salt or r3 C) ester thereof. Suitable esters are C1-4 alkyl esters such as ethyl ester.

A particularly preferred compound of formula (II) is 1-(2,4dichlorophenyl-5 trichloromethyl- I H-1,2,4-triazole-3-carboxylic acid (fenchlorazole) or the ethyl ester thereof.

Compounds of formula (111) and their preparation are described in US Patent No.

5,703,008 and US Patent No. 5,700,758 the content of which is incorporated herein by reference. Particular compounds of formula (III) are those where R 17 is halogen, in particular chlorine, t is 2, R 18 is alkyl such as ethyl, R19 is alkyl such as methyl, and R 20 is alkoxycarbonyl, in particular ethoxycarbonyl.

A particularly preferred compound of formula (II) is diethyl (RS)- 1 -(2, 4 dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylate (mefenpyrdiethyl).

Compounds of formula (IV) and their preparation are described in British Patent Application No. 2120661 the content of which is incorporated herein by reference.

Preferred compounds of formula (IV) are defined more fully in this document. Particularly preferred compounds of formula (IV) for use in the present invention are compounds where R 21, R 22, R 23, R 25 and R 26 are all hydrogen, R 24 is halogen and in particular chlorine, R 27 is an alkylene group and R 28 is carboxylic ester group, in particular a C I 1 Oalkyl ester group such as a branched chain alkyl ester.

Z) A particular compound of formula (IV) is 1-methylhexyl(5-chloroquinolin-8- yloxy) acetate (cloquintocet-mexyl).

8 The 2-(substituted benzoyl)- 1,3-cyclohexanedione compounds of formula I are described, inter alia, in U.S. Patent Nos. 4,780,127, 4,938,796, 5, 006,158 and 5,089,046, the disclosures of which are incorporated herein by reference. Herbicidal 2-(substituted benzoyl)-1,3-cyclohexanedione compounds for use in this invention may be prepared by the methods described in the aforementioned patent publications, or by the application and adaptation of known methods used or described in the chemical literature.

Especially preferred 2-(substituted benzoyl)-1,3-cyclohexanedione compounds useful in the present invention include those in which z is zero; X is chloro, bromo, nitro, cyano, CI-C4 alkyl, -CF3, -S(O) R1 or OR'; n is one or two; and each Z is independently chloro, bromo, nitro, cyano, CI-C4 alkyl, -CF3, -OR', -OS(O),nR5 or -S(O). R 5. Examples of preferred cyclohexanedione compounds are 2-(2'-nitro-4'methylsulfonylbenzoyl)-1,3cyclohexanedione, 2-(2'-nitro-4'methylsulfonyloxybenzoyl)-1,3-cyclohexanedione and 2-(2'-chloro-4'methylsulfonylbenzoyl)- 1,3-cyclohexanedione.

Other preferred compounds of formula (1) are those where z is one, Q is CI-C4 alkyl, X is chloro, bromo,'nitro, cyano, CI-C4 alkyl, -CF3, -S(O)rnR' or - ORI; n is one or two; and each Z is independently chloro, bromo, nitro, cyano, CI-C4 alkyl, -CF3, -OR,, -OS(O),,,R 5 or -S(O),nR 5. An example of a preferred cyclohexanedione compound of this type is 2-(2'-chloro-3'ethoxy-4'ethylsulfonylbenzoyl)-5-methyl-1,3-cyclohexanedione.

Compounds of formula (1) may exist in enolic tautomeric forms that may give rise to geometric isomers. Furthermore, in certain cases, the various substituents may contribute to optical isomerism and/or stereoisomerism. All such forms are embraced within compounds useful in the present invention.

These compounds may be in the form of metal chelates. Copending patent application, U.S. Serial No. 08n92,340, discloses that metal chelates of 2-(substituted benzoyl)-1,3-cyclohexanedione compounds have proved to be chemically stable for Iong periods of time under normal as well as extreme temperature conditions. It has now been discovered that by formulating the compound of formula (I) as a metal chelate, the phytotoxic effect of the compound on the crop itself can be reduced.

9 Suitable crops include zgraminaceous crops such as wheat and barley. The method of the invention may be applied to the crops post- or preemergently but is preferably applied post emergently.

0 The ratio of the compound of formula (1) to the compound of formula (I1), (Ill) or (IV) will vary depending upon factors such as the precise nature of the compounds, 0 the crops being treated and their growth stage. However, in general, the ratio will be of the Z:1 Z order of 1: 1 to 20: 1 suitably at a ratio of about 4: 1.

The amount of herbicide applied in any particular case again will depend :n upon the particular compound of formula (I) being used as well as the nature of the weed 0 condition being treated, the type of crops, the growth stage etc. However, in general, CI t> application rates of from 10-250g/ha would be used.

Herbicides may be applied in admixture with other herbicidal compounds not of formula (1) as is well known in the art. Examples of other herbicides include:

A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as'bentazone; B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (ea. salts, esters and amides); C. 1,3 dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap; D. Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, dinoseb and its ester, dinoseb acetate; E. dinitroaniline herbicides such as dinitramine, trifluralin, ethalflurolin, pendimethalin, oryzalin; F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorbromuron, daimuron, methabenzthiazuron; G. phenylcarbamoyloxyphenylcarbamates such as phenmedipham. and desmedipham; H. 2-phenylpyridazin-3-ones such as chloridazon and norflurazon; 1. uracil herbicides such as lenacil, bromacil and terbacil; J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn; K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos; L. thlocarbamate herbicides such as prosulfocarb, cycloate, vernolate, molinate, thiobencarb, butylate'., EPTC, tri-allate, di-allate, esprocarb, tiocarbazil, pyridate, and dimepiperate; M. 1,2,4-triazin-5-one herbicides such as metamitron and metribuzin; N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben; 0. anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor; P. dilialobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil; Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof, R. diphenylether herbicides such as lactofen, fluroglycoferi or salts or ester thereof, nitrofen, bifenox, aciflurofen and salts and esters thereof, oxyfiuorfen, fornesafen, chlornitrofen and chlomethoxyfen; S. aryloxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof, fenoxaprop and esters thereof such as the ethyl ester and clodinofop and esters thereof; T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, tralkoxydim, and clethodim; U. other sulfonyl urea herbicides such as chlorsulfuron, sulforneturon, metsulfuron and esters thereof., bensulfuron and esters thereof such as DPX-M6313, chlorimuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof, 2-[3-(4-methoxy-6-methyl-1,3,5-triazin-zyl)-3-methylureido-sulphonyl) benzoic acid esters such as the methyl ester thereof (DPX-L5300) and pyrazosulfuron; 11 V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr; W. arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican; X. amino acid herbicides such as glyphosate and glufosinate and their salts and esters, such as glyphosate trimesium, and bialaphos; Y. organoarsenical herbicides such as monosodium methanearsonate (MSMA); 0 Z. herbicidal amide derivative such as napropamide, propyzarnide, carbetamide, tebutam., bromobutide, isoxaben, naproanilide and naptalam; AA. herbicidal triketones which are not of formula (I) such as sulcotrione; AB. herbicidal benzoylisoxazoles such as AB. miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinclorac, dithiopyr and mefanacet, diflufenican and These compounds are preferably employed in combination with a safener such as dichlorn-fid, fenchlorazole or cloquintocet.

Preferably however, the compound of formula (II), (IH) or (IV) will exert a safening effect on any herbicidal mixture partners used in the method of the invention.

Particular examples of herbicides which can be used in combination with the mixtures of the invention include dihalobenzonitrile herbicides in particular, bromoxynil.

Preparations or compositions for use in the method of the invention form a further aspect of the invention.

Thus the invention further provides a herbicidal preparation comprising a C> compound of formula (I) as defined above and at least one of a compound of formula (II), (III) or QV) as defined above.

The preparation may take the form of a single pre-mix composition, or a twin pack or combination arrangement where compositions of the compound of formula (I) and 12 the compound of formula (11), (111) and (IV) are stored in separate compartments, ready for mixture at the site of application.

Where the mixture contains additional components such as other herbicides, these may be contained separately or pre-mixed either with the compound of formula (1) as defined above or with the compound of formula (II), (III) or (IV). Examples of the latter are available commercially, for example the mixtures sold under the trade name "Puma" and "Proper".

Compositions of the invention may further comprise agriculturally acceptable carriers as is known in the art. For example, compositions of the invention may be in the form of either a dilute composition which is ready for immediate use, or a concentrated compositions which require dilution before use, usually with water. Preferably the compositions contain from 0.01% to 90% by weight of the active ingredient. Dilute compositions ready for use preferably contain from 0.0 1% to 2% of active ingredient, while concentrated compositions may contain from 20% to 90% of active ingredient, althouoFh from 20% to 70% is usually preferred.

0 The solid compositions may be in the form of granules, or dusting powders wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.

Microencapsulated formulations (microcapsule suspensions CS) or other controlled release formulations may also be used, particularly for slow release over a period of time.

Liquid compositions may comprise a solution or dispersion of an active ingredient in C) water optionally containing a surface-active agent, or may comprise a solution or Z.1.1 z:1 dispersion of an active ingredient in a water-immiscible organic solvent which is dispersed as droplets in water.

Surface-active agents may be of the cationic, anionic, or non-ionic type or mixtures thereof. The cationic agents are, for example, quaternary anunoniurn compounds (e.o, ZD Z:) 13 cetyltrimethylammoniurn bromide). Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenes ul phonate, sodium,calcium, and ammonium lignosul phonate, butyl naphthalene sulphonate, and a mixture of the Z-:) sodium salts.of diisopropyl and triisopropylnaphthalenesulphonic acid. Suitable non-Ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl zn (RTMI alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g. Agra Z__ 11 1/ 90) or octyl-cresol. Other non-ionic agents are the partial esters derived from long chain 0 C) fatty acids and hexitol anhydrides, for example sorbitan monolaurate; the condensation products of the partial ester with ethylene oxide; the lecithins; and silicone surface active ao,ents (water soluble surface active agents having a skeleton which comprises a siloxane tD Wrl, z:1 Z3 (0er"') chain e.g. Silwet L77. A suitable mineral oil is for use in mixture is Atplus 41 IF.

X TM Preferably the mixture is an adjuvant such as Turbocharge 0 The aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing z:- r.:1 ZD agent(s) and then, when organic solvents are used, adding the mixture so obtained to water 0 optionally containing wetting or dispersing agent(s). Suitable organic solvents include, for Z) C) example, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, t toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.

The compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use. The concentrates are usually required to withstand storage for prolonged periods and after such storage, to be zn 1 tn capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.

Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active ingredient(s). Dilute preparations ready for use may contain varying amounts of the active ingredient(s) depending upon the intended purpose; amounts of 0.01% to 10. 0% and preferably 0. 1% to 2%, by weight of active ingredient(s) are normally used.

Z;' C 14 A preferred form of concentrated composition compfises the active ingredient which has been finely divided and which has been dispersed in water in the presence of a surface-active agent and a suspending agent. Suitable suspending agents are hydrophille ZI) I-) Z C) Z:) colloids and include, for example, polyvinylpyrrolidone and sodium carboxymethy1cellulose, and the vegetable gums, for example gum acacia and gum Z:> C) ZD tragacanth. Preferred suspending agents are those which impart thixotropic properties to, C) 0 and increase the viscosity of the concentrate. Examples of preferred suspending agents C> 4n include hydrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorite, saponite, and saucorite. Bentonite is especially preferred. Other suspending 10 agents include cellulose derivatives and polyvinyl alcohol.

The compositions of the invention may comprise, in addition to a compound of formula (1), one or more additional compounds which possess biological activity. The additional compounds may be, for example, other herbicides, fungicides, insecticides (optionally with an insecticide synergist) or plant growth regulators. Other herbicides are, 15 however, particularly preferred ingredients.

The invention will now be particularly described by way of Example. In the following Examples, the compounds referred to are shown in the following Table.

Compound No Structure 0 02 0 S02CH3 2 02 C 0 S02CH2CH3 Example I

Post-emergence effects of treatments on Temperate Crovs In this glasshouse trial, active ingredients in the desired concentrations were formulated as C> ZD either a 5% or a 10% emulsifiable concentrate (EQ in a standard blank comprising:

(P-) 0 Span 80 21.8g/l X (ai") Tween,20 78.2g/l Methylcyclohexanone 900g/1 The concentrates were then diluted into to form an aqueous solution which was sprayed with 0.5% of the adjuvant TurbochargeTm available from Zeneca Ltd. at an application rate of 2001/ha with a spray volume of 25ml, onto post emergent plants, grown in pots, at the 2-4 leaf growth stage.

The species used in this test were Winter wheat (Prinqual), Spring wheat (Katepwa), Winter barley (Plaisant), Spring barley (Bedford), Alopecurus myosuroides (ALOMY), Avenafatua (AVEFA), Lolium rigidum (LOLRI), Setaria viridis (SETVI), Chenopodium album (CHEAL) and Stellaria media (STEME).

In this case the active ingredients were Compound I and Compound 2 above, which were applied alone and in mixture with the safeners fenchlorazole and cloquintet at a ratio of 4:1 (herbicide: safener).

Assessments were carried out 7 days after treatment (7 DAT) when early crop phytotoxicity was recorded and 27 days after test (27 DAT) when both crops and weeds were assessed.

The results are shown in Tables I and 2 hereinafter.

16 It is clear from these tables that when used alone, Compound 1 and Compound 2 were damacina, to the cereals. The addition of the safeners increased the tolerance of wheat 0 0 and barley to the herbicides 17 Table 1 (7 DAT) Trt Component 1 Rate Component 2 Rate TP TK HP HB No. ailha g. ai/ba 1 fenchlorazole 125 - 0 0 0 0 2 10% EC 250 - 0 0 0 0 3 500 - 0 0 0 0 4 cloquintocet 125 - 0 0 0 0 10% EC 250 - - 0 0 0 0 6 500 - - 0 0 0 0 7 Compound 1 125 - - 3 5 37 17 14 8 5% EC 250 - - 47 57 35 22 9 500 - 62 63 57 57 1000 - 67 65 65 62 11 2000 - 67 65 68 68 12 Compound 1 125 fenchlorazole 31.25 12 20 10 11 13 5% EC 250 10% EC 62.5 21 23 20 14 14 500 125 40 42 30 25 1000 250 52 50 52 43 16 2000 500 63 60 63 58 17 Compound 1 125 cloquintocet 31.25 13 25 4 8 18 5% EC 250 10% EC 62.5 23 33 10 11 19 500 125 37 43 22 17 1000 250 47 53 28 30 21 2000 500 62 60 63 60 22 Compound 2 125 62 62 62 60 23 5% EC 250 62 65 68 65 24 500 67 65 72 67 1000 67 70 75 68 26 2000 72 70 70 73 27 Compound 2 125 fenchlorazole 31.25 65 63 65 63 28 5% EC 250 10% EC 62.5 65 65 67 69 29 500 125 67 65 73 67 1000 250 65 67 73 70 31 2000 500 73 70 72 73 32 Compound 2 125 fenchlorazole 31.25 63 62 65 60 33 5% EC 250 10% EC 62.5 67 67 67 63 34 500 125 67 65 68 67 1000 250 67 65 70 70 36 2000 500 67 67 72 69 All treatments applied in combination with 0. 1 % vIv Agral 90 ZD Data mean of 3 replicates and are percentage scores TP = TUAW PRINQUAL; TK = MAS KATEPWA; HP=HORW PLAISANT; HB= HORVS BEDFORD Table 2 27 DAT TRT Component Rate Component Rate TK TP HB HP ALO AVE LOLRI SETV1 STE CHE No. 1 9 2 9 MY FA ME AL ai/ha ailha 1 fenchchlorazole 125 0 0 0 0 0 0 0 0 0 0 2 10% EC 250 0 0 0 0 0 0 0 0 0 0 3 500 0 0 0 0 0 0 0 0 0 0 4 cloquintocet 125 0 0 0 0 0 0 0 0 0 0 10% EC 250 0 0 0 0 0 0 0 0 0 0 6 500 0 0 0 0 0 0 0 0 0 0 7 125 14 25 2 2 2 7 6 13 100 100 8 Compound 1 250 55 58 7 5 37 5 22 93 100 100 9 5% EC 500 70 72 18 10 52 55 48 100 100 100 1000 90 88 45 60 85 83 72 100 100 100 11 2000 94 99 80 68 97 100 96 100 100 100 12 125 31.25 23 40 0 0 4 0 6 38 100 100 13 Compound 1 250 fenclichlorazole 62.5 28 45 10 5 8 9 22 65 100 100 14 5% EC 500 10% EC 125 62 68 15 12 50 53 55 95 100 1001000 250 70 70 40 37 80 80 72 100 100 100 16 2000 500 80 85 68 63 96 98 99 100 100 100 17 125 31.25 8 30 0 0 2 2 3 47 100 100 18 Compound 1 250 cloquintocet 62.5 28 35 3 7 10 5 12 70 100 100 19 5% EC 500 10% EC 125 50 65 7 7 45 60 32 100 100 100 1000 250 72 73 43 38 76 83 75 100 100 100 21 2000 500 78 78 63 62 90 100 93 100 100 100 -i 00 Table 2 contd

TRT Component Rate Component Rate TK TP HB HP ALOM AVE LOLRI SETVI STE CHE No. 1 9 2 9 y FA ME AL ai/ha ai/ha 22 125 52 38 ' 12 22 37 58 23 100 100 1-1-00 23 Compound 2 250 87 70 62 47 75 85 68 100 100 100 24 5% EC 500 94 95 98 82 96 100 79 100 100 100 1000 99 99 100 100 100 98 98 100 100 100 26 2000 100 100 100 ' 99 100 100 100 100 1 100 100 27 125 fenchchlorazole 31.25 77 45 22 18 47 83 32 100 100 100 28 Compound 2 250 10% EC 62.5 89 67 63 53 79 95 55 100 100 100 29 5% EC 500 125 100 94 100 89 89 98 62 100 100 100 1000 250 100 100 100 100 100 98 94 100 100 100 31 2000 500 100 100 100 100 100 100 99 100 100 100 32 125 31.25 75 53 33 27 58 72 30 100 100 100 33 Compound 2 250 cloquintocet 62.5 93 67 73 57 58 85 40 100 100 100 34 5% EC 500 10% EC 125 99 94 100 73 90 97 78 100 100 100 1000 250 99 99 100 92 98 100 89 100 100 100 36 2000 500 100. 100 100 100. 100 100 ' 98 100 100 100 where TIC is TRZAS KATEPWA; TP is TIZZAW PRINQUAL; HB is HORVS BEDFORD and HP is HORM PLAISANT Example 2 Efficacy of treatments in glasshouse trials on Spring wheat Makwa spring wheat was seeded in 4" square pots by 4" deep filled with a loam soil, t placed on a bench in the glasshouse and watered. Shortly after emergence the plants were 4:1 0 thinned to five plants per pot. Application was made at l0gal/a when the plants were 4-5" 0 tall prior to tillering.

Compound I was formulated as a suspension concentrate (SC) comprising 480c,/1 of the C> gn acid form of compound I and was applied alone and in combination with a mixture of containing 69g/l fenoxaprop and 39g/I fenchlorazole, sold under the trade name "Puma In S"Tm, and a safener comprising the potassium salt of naphthalic anhydride, at various rates as well as in mixture with a compound of formula A Oy CHC12 >( N 0 DIIX A Compound A is known to be an effective safener for thiolcarbamate herbicides and acetochlor.

Each treatment was replicated three times. All spray solutions contained a non-ionic adjuvant (X-77) at 0.25%v/v. After spraying the plants were set on a bench in the glasshouse. Percent injury, primarily chlorosis (bleaching) and stunting, was recorded at 5, 14 and 25 DAT.

The results are shown in Table 3.

21 Table 3

Treatment Rate LB ai/a 5 DAT 14 DAT 25 DAT Untreated control 0.000 0 0 0 PumaTm + X-77 @ 0.016 0 0 0 0.25% 0.031 1 0 0 Compound 1 + X-77 0.016 53 93 20 @ 0.25% 0.031 63 47 43 Puma + Compound 1 0.016 + 0.016 2 3 4 + X-77 @0.25% 0.031 +0.016 4 5 6 Puma + Compound 1 0.016 +0.031 8 22 27 +X-77@ 0.25% 0.031 + 0.031 6 17 15 Compound 1 + Kna 0.016+0.25 40 12 15 + X-77 @ 0.25% 0.031+0.25 53 37 20 Compound 1 + Kna 0.016+0.50 30 10 12 + X-77 @ 0.25% 0.031+0.50 50 33 20 Compound 1 + 0.016+0.50 53 20 18 Compound A + X-77 0.031 +'030 60 47 47 @0.25% Kna is the potassium salt of napthalic anhydride Injury symptornology at 5 DAT was chlorosis (bleaching); injury at 14 and 25 DAT was 5 primarily stunting.

22 The results show that when in mixture with the safener fenchlorazole, Compound 1 was significantly less damaging to wheat. Early injury, chlorosis, was reduced more than late c 0 injury (growth reduction). Although the potassium salt of napthalic anhydride reduced the 0 C injury, the reduction was less than with fenchlorazole. Finally compound A was ineffective as a safener for Compound 1 on wheat.

Example 3

Comparative treatment with usinz mixtures of herbicides The method of Example 1 was repeated using Compound 1 either alone, in the form of a copper chelate, or in mixture with the herbicide bromoxynil (BNIX). The effects of the addition of various compounds and safeners was investigated by including these in the mixtures applied to the plants.

The safeners/mixture partners used were; a. 1-(2,4-dichlorophenyl)-5trichloromethyl-IH-1,2,4-triazole-3-carboxylic acid (fenchlorazole); b. 1-methylhexyl (5-chloroquinolin-8-yloxy)acetate (cloquintocet-mexyl); C. dichlorn-fid - (available from Zeneca Ltd) d. Compound A of structure given above. e. Piperonyl butoxide 20 f. A mixture containing 55g11 fenoxaprop and 30g/1 mefenpyr sold under the trade name "Proper Energy'Tm. g. A mixture containing 69g/1 fenoxaprop and 39g/1 fenchlorazole, sold under the trade name"Puma S1ITM.

Tables 4 and 5 present data for an 8 DAA(days after application) assessment of crop phytotoxicity and 21 DAA assessment of crop damage/weed control respectively. Figure 1 is a bar chart showing mean wheat damage across all 3 varieties for the mixture of 10g/ha Compound 1 + 20g/ha BNIX with or without safener.

23 Plant species used in this test were were Spring wheats (Roblyn, Makwa and ID Katepwa), and as weed species Ainaranthus retroflexits (AMARE), canola (BRSNS) and Polygonum convolvidus (POLCO).

-upon variety, and Compound I alone caused 7-11 % damage to wheat, dependin,, Compound I/bromoxynil caused 14-21 % damage. Bromoxynil (BMX) alone at 20g/ha was C> completely safe to wheat so addition of bromoxynil to Compound I acid increases the wheat damage by a factor of 2x.

Compound I in the form of a copper chelate was much safer to wheat than the acid, causing no damage at 100g/ha and up to 14% at 200g/ha. This damage had increased at the 21 DAA assessment, unlike the acid where recovery occurred, indicating root uptake of Compound I at the higher rates of the chelate employed. There was some evidence that addition of BMX increased wheat damage with the chelate but it was much less obvious than with the acid.

When mixed with safeners however, only fenchlorazole, cloquintocet and mixtures including the safener mefenpyr produced any safening effects wheat.

C, Trt Herbicide 1 Rate Herbicide 2 Rate Safener/ Rate MEAN No (g ai/lia) (g aillia) Herbicide 3 (g ai/lia) RESULTS TRZAS TRZAS TIZZAS Roblyn' 'Makwa' 'Katepwa' GS:2.25 GS:2.25 GS:2.25 1 Compound 1(acid) 2.5 0 0 0 2 it 5 1 0 0 3 it 10 - 11 7 8 4 Compound 1 (acid) 2.5 Bromoxyllil 20 4 1 1 99 5 12 8 9 6 It 10 21 14 20 7 Bronioxynil 20 0 0 0 8 Compound 1 Cu 50 0 0 0 chelate 9.1 100 - - - - 0 0 0 11 200 - 14 5 9 11 Compound 1 CU 50 Brornoxynil 20 0 0 0 chelate 12 100 11.1 - - 6 0 6 13 11 200 11 #1 - - 14 4 4 14 Compound 1 (acid) 2.5 Bromoxynil 20 fenchlorazole 2.5 0 0 1 5 0 4 2 16 10 9 8 10 K) A.

Table 4 contd.

MEAN RESULTS TUAS TRZAS TRZAS Trt Herbicide 1 Rate Herbicide 2 Rate Safenerl Rate 'Roblyn' 'Makwa' 'Katepwa' No (g ai/ha) (g ai/ba) 1 Herbicide 3 (g ailha) ii GS:2.25 GS:2.25 GS:2.25 17 Compound 1 acid 2.5 Bromoxynil 20 fenchlorazole 25 0 0 0 18 5 0 0 0 19 10 3 5 4 Compound 1 (acid) 2.5 Bromoxynil 20 cloquintocet 2.5 0 0 0 21 5 0 0 0 22 10 3 0 3 26 Compound 1 (acid) 2.5 Bromoxynil 20 dichlormid 250 4 0 1 N) 27 5 23 15 19 28 10 43 38 29 29 Compound 1 (acid) 2.5 Bromoxynil 20 Compound A 250 7 1 6 5 19 14 17 31 10 40 25 35 32 Compond 1 (acid) 2.5 Bromoxynil 20 Piperonyl butoxide 2250 13 4 10 33 5 34 23 24 34 10 54 41 48 Compound 1 acid 2.5 Broinoxynil 20 Proper Energy 10 0 0 0 36 5 0 0 0 37 10 4 2 6 Table 4 Contd 2 ME AN- MEAN AN RES RESULTS U T SULTS ULTS L Ti.t Herbi Rate Herbicide 2 Rate 11 Tit ide 1 RZAS Herbicide 1 TRZAS C 1 TRZAS, TRZAS TRZAS TRZAS rRZAS No (g ailha) (g ai/lia) Safenerl Rate 'Roblyn, No 'Roblyn' 'Makwa' Rob y n' 'K te a Roblyn 'Katepwa' 1 a pw Herbicide 3 (a ailha) S ' C GS..2,25 S2 5 1 '.2 GS:2.25 GS:2.25 GS:2.25 T 38 COMPOUNDI 2.5 Bromoxynil 20 Puma S P U 0 cid 10 0 0 0 aC 9 5 39 An 10 0 4 0 2 NJ M Table 5 21 DAT TRT Herbicide 1 Rate Herbicide 2 Rate Safener Rate TRZAS TRZAS TIZZAS AMARE BRSNS POLCO No. 0.15/ha plillia 'Roblyn' 'Makwa' 'Kitel)xva' 'Goicit.tisli' GS 2.25 GS: 2.25 _GS: 2.25 G S:16 GS: 2.35 G S 2). 3 5 1 Compound 1 2.5 2 1 28 65 29 2 $1 5 0 0 1 29 89.51 3 it 10 1 1 56 100 60 4 Compound 1 2.5 Bronloxyllil 20 1 2 2 61 96 78 1. 5 20 1 2 2 71 96 85 6 it 1 () 20 7 8 5 74 100 99 7 Bromoxynil 20 1 4 9 61 66 8 Compound 1 50 Bromoxynil 20 3 1 3 23 87 42 9 Cti chelate 100 20 2 4 3 36 96 80 1 () 11 200 20 24 21 22 51 100 92 11 Compound 1 50 BrommYnil 20 0 2 64 100 93 12 Cu chelate 100 20 14 5 1 () 81 100 100 13 1. 200 20 28 24 24 80 100 100 14 compound 1 2.5 Bromoxynil 20 fenchlorazole 2.5 1 2 5 50 99 80 6. 5 20 11 11 1 3 75 100 95 16 it 10 20 41 1. 0 2 6 86 100 95 17 compound 1 2.5 B1.0111OXY1)d 20 f'eiicliloritzole 2.5 1 0 5 62 96 100 18 4. 5 11 20 41 1. 2 2 5 68 100 9') 19 10 20 2 2 2 78 100 100 compound 1 2.5 Bi.oiiioxyjiii 20 cloquintocet 2.5 0 2 59 99 90 21 5 41 20 0 3 70 99 79 22 10 91 20 1 1 6 78 100 100 23 Compound 1 2.5 Bromoxynfl 20 cloquilltocct 12.5 1 1 3 66 100 77 24 5 20 11 0 3 1 73 100 93 1 () 20 41 0 2 5 79 100 100 26 Compound 1 2.5 Bromoxynil 20 (licillol-oliliti 250 2 1 1 75 100 89 27 5 4, 20 1 3 6 78 96 100 28 10 41 20 9 18 4 89 100 100 K) Table 5 21 DAT Contd.

TR-F Herbicide 1 Rate Herbicide 2 Rate Saferier Rate TRZAS TRZAS TRZAS AMARE, BRSNS POLCO No. g.-,i.illlil g.ai/J1,1 g.aillia 'Roblyn' 'Makwa' 'Kitei)wit' 'Gol(li. tisli' GS 2.25 GS: 2.25 GS: 2.25 G S:16 GS: 2.35 GS 2.35 29 Compound 1 2.5 13roliloxynit 20 Compound A 250 0 0 2 77 96 100 5 19 20 11 5 4 10 80 100 100 31 10 it 20 61 6 10 9 81 100 100 32 Compound 1 2.5 Brornoxynil 20 piperonyl 2250 3 1 3 36 99 60 33 5 20 butoxide 16 8 7 4 70 100 94 34 10 20 d$ 41 16 13 14 72 100 97 C0111p0Und 1 2.5 Brornoxynil 20 Proper 10 0 0 1 69 98 92 36 5 11 20 energy""' 3 2 4 81 95 95 37 10 91 20 11 1 1 1 85 100 100 38 Coillp nd 2,5 Bronloxyllil 20 Purna S",, 10 1 4 2 59 93 48 L40 210 39 5 20 1 71 98 78 11 2 3 5 61 100 98 bi co 29

Claims (3)

1. A method of killing or controlling unwanted plants, which method comprises C applying to the unwanted plant or to the locus thereof, a herbicidal compound of formula C> 0 X (Q)Z (Z)n wherein X represents a halogen atom; a straight- or branched-chain alkyl or alkoxy group 10 containing up to six carbon atoms which is optionally substituted by one or more groups C1 -OR' or one or more halogen atoms; or a group selected from nitro, cyano, -CO, R 2 -S(O) R', -O(CH,),0R1, -COR 2, -OSO2R 4, -NR 2 R 3, -S02NR 2 R 3, -CONR 2 R 3 and -CSNR 2 R 3; R' represents a straightor branched-chain alkyl group containing up to six carbon Z:1 atoms which is optionally substituted by one or more halogen atoms; R 2 and R 3 each independently represents a hydrogen atom; or a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; R 4 represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms; or a cycloalkyl group containing from three to six carbon atoms; each Z independently represents halo, nitro, cyano, S(O).. R 5 ' OS(O),, R5, (ClC6)alkyl, (Cl-C6)alkoxy, (Cl-C6)haloalkyl, (Cl-C6)haloalkoxy, carboxy, (C[C6)alkylcarbonyloxy, (Cl-C6)alkoxycarbonyl, (Cl- C6)alkylcarbonyl, amino, (Cl- C6)alkylamino, (Cl -Qdi alkyl amino having independently the stated number of carbon atoms in each alkyl group, (C] -C6)alkylcarbonyl amino, (Cl- C6)alkoxycarbonylamino, 1 (Cl-C6)alkylaminocarbonylamino, (Cl-C6)dialkylaminocarbonylamino having Zn independently the stated number of carbon atoms in each alkyl group, (Cl - C C6)alkoxycarbortyloxy, (Cl-C6)alkylarflinocarbonyloxy, (Cl- C6)dialkylaminocarbonyloxy, phenylcarbonyl, substituted phenylcarbonyl, phenylearbonyloxy, substituted phenylcarbonyloxy, phenylcarbonylamino, substituted phenylcarbonylamino, phenoxy or substituted phenoxy; R 5 represents cyano; -COR'; -CO,R 6; or -S(O)... R 7; R 6 represents hydrogen or straight- or branched-chain alkyl group containing up to six carbon atoms; R 7 represents (Cl-C6)alkyl, (Cl-C6)haloalkyl, (Cl-C6)cyanoalkyl (C3- C8)cycloalkyl optionally substituted with halogen, cyano or (Cl -C4)alkyl; or phenyl optionally substituted with one to three of the same or different halogen, nitro, cyano, (C 1 - C4)haloalkyl. (C 1 -C4 is alkyl, (C I -C4)alkoxy or -S (0),,R8; R 8 represents (C 1 -C4) alkyl, (C 1 -C4) alkyl substituted with halogen or cyano, phenyl or benzyl; each Q independently represents Cl-C4 alkyl or -COR9 wherein R9 is Cl-C4 alkyl; m is zero, one or two; n is zero or an integer from one to four; r is one, two or three; and z is 0 or an integer from 1 to 6, and and at least one of (a) a compound of formula (II) 31 N /N R12 N (R1O)q R" or an agriculturally acceptable salt or ester thereof; 4:

where R10 is the same or different groups selected from halogen; nitro; cyano; zn I:, trifluoromethyl; Cj-4 alkyl, Cj-4alkoxy or CI-4alkylthio, wherein the alkyl, alkoxy and alkylthio groups are optionally substituted by one or more halogen atoms, in particular ZD ZD fluorine or chlorine; C3-6CYCloalkyl optionally substituted by CI-4 alkyl; or phenyl or phenoxy optionally substituted by one or more trifluoromethyl groups; R' 1 is hydrogen; CI-4alkyl which is optionally substituted by one or more halogen atoms, or by a CI-4alkoxy or C 1 -4 alkylthio group; C,)-6,alkenyl; C2-6 alkynyl; C3-6 cycloalkyl which is optionally substituted by CI-4alkyl and/or a dichlorovinyl group; 0 R 12 is hydroxy; Cl-4alkyl;C3-6cycloalkoxy; phenylCI-6alkoxy; phenoxy; C,- 6alkenyloxy; C'7-6alkynyloxy;CI-6alkoxy,C 1-6alkylthio wherein the alkoxy of alkylthio groups are CP optionally substituted byCI-2alkoxy mono- or di-CI-4alkylaminocarbonyl, phenylarriinocarbonyl, N-(CI-4)alkylphenylan-iinocarbonyl, mono- or di-CI- 6alkylamino, C I 6alkylcarbonyloxy,Cl-2alkylthio, cyano or halogen; a group of formula R14 N- N I R13 or -kot- R13 where R 13 is hydrogen or C I -4alkyl and R 14 is as defined above in relation to R'(); mono or di-CI-4alkylamino,C5-6Cycloalkylamino, piperidino, morpholino, or 2,6 dimethylmorpholino, a group of formula C 32 R15 R16 where R 15 and R' 6 are the same or different and are C I -4alkyl groups, or R 15 and R 16 together form a 5-, 6- or 7-membered cycloalkyl group, and q is 0, 1, 2 or 3:

or (b) a compound of formula (III) R20 R19 N COOR18 (R17)t where each R 17 group is independently selected from halogen or haloalkyl; t is an integer of from I to 3, R 18 is hydrogen, alkyl, cycloalkyl, trialkylsilyl, trialkylsilylmethyl or alkyloxyalkyl, R 19 and R 20 are independently selected from hydrogen, alkyl, C3- 6cylcloalkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, optionally substituted with phenyl, halogen or cyano, or R19 and R 20 together with the carbon atom to which they are attached form a rin., such as an alkyl ring, or (c) a compound of formula (IV) 33 R23 R24 R2 R25 1 z R2 N R26 R27 R28 (M or an acid addition salt or metal complex thereof, wherein R 21, R 22 and R 23 are independently selected from hydrogen, halogen, nitro, cyano, C alkyl or alkoxy, 24, R 25 and R 26 are independently selected from hydrogen, halogen or alkyl, 27 is an aliphatic, acyclic, saturated hydrocarbon radical having from 1 to 3 carbon atoms CI and R 28 is a carboxyl group or a salt thereof, a mercaptocarbonyl group or a salt thereof, a carboxylic acid ester group, a carboxylic acid thiolester group or an unsubstituted or substituted derivative of a carboxylic acid amide group or a carboxylic acid hydrazide group, or R 27 and R 28 together form an unsubstituted or substituted tetrahydrofuran-2-one ring.

2. A herbicidal composition comprising a compound of formula (I) as defined in claim 1 and at least one of a compound of formula (H), (HI) or (IV) as defined in claim 1, together with an agriculturally acceptable carrier or diluent.

3. A two pack container having in one compartment a compound of formula (I) as defined in claim 1, and in the second compartment, at least one of a compound of formula (11), (HI) or (IV) as defined in claim 1.