Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
  • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/24—Oxygen or sulfur atoms
  • C07D207/26—2-Pyrrolidones
  • C07D207/273—2-Pyrrolidones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D263/28—Nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D277/18—Nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

• This invention relates to chemical compounds useful as herbicides, to processes for preparing them, and to herbicidal compositions and processes utilising them.
• Y is O, S or CH 2 ;
• R' is an optionally substituted aryl or heteroaromatic ring, wherein the optional substituents are selected from halogen, C,.C 4 alkyl, C,.C 4 haloalkyl, C,.C 4 alkoxy or C,.C 4 haloalkoxy;
• R 2 and R 3 are independently selected from hydrogen or halogen
• R and R 5 are independently selected from halogen.
• alkyl refers to fully saturated straight or branched hydrocarbon chains having from one to six carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, rvbutyl, t ⁇ butyl and n ⁇ exyl. Expressions such as “alkoxy” and “haloalkyl” should be construed accordingly.
• aryl and aromatic ring system refer to ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl or phenanthrenyl.
• heteromatic ring or '"heteroaromatic ring system” refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
• single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur.
• groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1 ,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-
• halogen includes fluorine, chlorine, bromine and iodine.
• Preferred groups R 1 are optionally substituted phenyl or optionally substituted thienyl, preferably 2-thienyl Where R 1 is a substituted phenyl, substituents are suitably arranged at the 3-, 3,4- 3,5- or 3,4,5- positions and where R' is substituted 2-thienyl, substituents are suitably at the 5-, 3,5- or 4,5- positions.
• Preferred substituents for the group R 1 are trifluoromethyl, trichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, fluoromethoxy, chloromethoxy, trichloroethoxy, trifluoroethoxy, dichloroethoxy, difluoroethoxy, fluoroethoxy, ethoxy, methoxy, fluoro, chloro, bromo, iodo and methyl.
• the substituents may be the same or different.
• R' is substituted by trifluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, fluoro, chloro, bromo and methyl.
• Suitable groups for R 2 and R 3 are hydrogen or chlorine. Preferred compounds include those in which R 2 and R 3 are both the same.
• halogen groups R 4 and R 3 are both the same and in particular are chlorine.
• Y is preferably S or CH 2 , most preferably CH 2
• the formula I given above is intended to include tautomeric forms of the structure drawn, as well as physically distinguishable modifications of the compounds which may arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or from the inability of parts of the molecule to rotate freely in relation to other parts, known as “rotameric forms" or “rotamers”, or from geometrical isomerism, or from intra-molecular or inter-molecular hydrogen bonding, or otherwise.
• the compounds of the invention can exist in enantiomeric forms and some can also exist in both enantiomeric and diastereoisomeric forms.
• the invention includes all individual forms and mixtures thereof in all proportions.
• Particular examples of compounds of general formula I are listed in Tables I, II and III below.
• Me represents methyl
• Et represents ethyl
• Pr represents propyl
• Ph represents phenyl
• Bz represents benzyl
• Ac represents acetyl.
• Many of the compounds of the invention can exist in two diastereoisomeric forms and these are generally in the form of 1 : 1 mixtures unless otherwise stated;- references to A or B forms refer to separated diastereoisomers.
• compounds of general formula I may be produced by reacting a compound of general formula II
• R 2 , R 3 , R 4 and R 5 are as defined in relation to formula I, and X is a leaving group; and thereafter if desired modifying the substituents on the group R 1 .
• Preferred leaving groups for X are halogen, and in particular chlorine.
• the reaction may be carried out in an organic solvent such as chloroform, dichloromethane or toluene at a temperature of from 0 to 50°C, preferably at room temperature.
• suitable bases include amines such as 4-N,N dimethylaminopyridine (DMAP) or triethylamine, or a combination of these.
• R 1 may be carried out using conventional chemistry.
• R 1 is an optionally substituted phenyl or thienyl group
• substitutents or additional substitutents in particular halogen substitutents may be introduced subsequently, for example by reaction with halogenating agents such as N-bromosuccinimide as illustrated hereinafter.
• a substitutent such as bromine or iodine can be replaced by, for example by a C alkyl group such as methyl, by reaction with a reagent such as tetramethyl tin in the presence of a catalyst such as Pd(O) as illustrated hereinafter.
• a catalyst such as Pd(O) as illustrated hereinafter.
• R' and Y are as defined in relation to formula (I) and X 1 is a leaving group such as halogen, mesylate or tosylate and in particular iodine, with methylamine.
• X 1 is preferably bromine, iodine, mesylate or tosylate and most preferably iodide.
• Y is S or O
• X 1 can also be chlorine as well as bromine, iodide, mesylate or tosylate.
• the reaction is suitably effected in the presence of an organic solvent such as tetrahydrofuran and at elevated temperatures in the range of from 0 to 100°C.
• Preferred compounds of formula (IV) where X' is iodide can be prepared by reacting a compound of formula (IV) where X 1 is a different leaving group with a iodide salt, suitably in an organic solvent such as acetonitrile or acetone.
• X 2 , X 3 and X 4 are independently selected from leaving groups, in particular halogen such as bromine or chlorine, with a compound of formula (VI)
• reaction is suitably effected in the presence of an organic solvent and a base such as those listed above in relation to the reaction between compounds of formula (II) and (III).
• the reaction may be carried out at a temperature of from 0 to 50°C, preferably at room temperature.
• a particularly preferred compound of formula (V) is 2,4-dibromobutanoyl chloride.
• compounds of formula (IV) where Y is CH 2 may be prepared by reacting a compound of formula (VI) with a compound of formula (VII) at elevated temperature, for example of from 100-180°C, preferably 150-160°C.
• X 5 is chlorine or bromine and NMP is N-methylpyrrolidin-2-one
• (I) are suitably prepared by reacting an acid addition salt, in particular a hydrobromide salt of a compound of formula (VI) as defined above, with a compound of formula (V) as defined above.
• an acid addition salt in particular a hydrobromide salt of a compound of formula (VI) as defined above
• a compound of formula (V) as defined above in this instance, a preferred scheme for producing hydrobromide salts of formula (VI) is as follows:
• DPPA diphenylphosphoryl azide
• X6 and X 7 are suitably independently selected from halogen other than bromine, hydrogen or alkyl.
• X6 is chlorine and X 7 is hydrogen or methyl.
• a variety of co-solvents with t-butanol can, optionally, be used in the transformation of (XIX) to (XX).
• 1,4-dioxane, diglyme or monoglyme may be used in co- mixtures, provided that the quantity of t-butanol does not fall below one molar equivalent with respect to (XIX).
• a variety of combinations of these co-solvents can be employed in several different proportions, and the optional co-solvent(s) used need not necessarily be limited to those mentioned above.
• One particularly preferred procedure for this transformation is the slow, controlled addition of the DPPA reagent to a heated mixture of the other reaction components and solvents. This permits one to maintain a low concentration of potentially hazardous azide containing materials in the reaction vessel throughout the course of the reaction run, thereby enhancing the safety of the process.
• R 2 , R 3 , R 4 and R 5 are as defined in relation to formula (I), with a halogenating agent such as thionyl chloride or oxalyl chloride.
• a halogenating agent such as thionyl chloride or oxalyl chloride.
• the reaction is suitably effected in an organic solvent such as dichloromethane containing a small amount dimethylformamide at moderate temperatures of from 0-50°C, conveniently at ambient temperature.
• the compounds of the invention can exist in enantiomeric forms. Some can also exist in both enantiomeric and diastereoisomeric forms. If desired resolved forms of the compounds can be prepared by techniques known to those skilled in the art.
• chiral starting materials such as enantiomerically pure compounds of formula (XXII) can be employed in the reactions outlined above.
• an enantiomerically pure compound of formula (XXII) can suitably be prepared by reacting the corresponding racemic compound with a suitable chiral base such as cinchonine in a suitable solvent such as a mixture of ethanol and water to form two diasterometric salts. The salt of one enantiomer can then be separated out by crystallisation. The other enantiomer and be recovered by acidification of the mother liquors and extraction with a suitable solvent such as ethyl aceteate or dichloromethane.
• a suitable solvent such as ethyl aceteate or dichloromethane.
• compound of formulae (V), (VI), (VII), (VIII), (XIII), (XIV), (XVII), (XIX) and (XXII) are known compounds or they can be prepared from known compounds by known methods.
• compound of formula (XIV) where R 2 , R 3 , R 4 and R 5 are all halogen can be prepared by halogenation of the corresponding dihalo compound, as illustrated hereinafter.
• compounds where R 2 , R 3 , R 4 and R 5 are all chlorine can be prepared by addition of dichlorocarbene to an ester of the corresponding 2,2-dichloro-l- methyl propenoic acid, followed by hydrolysis to the acid (XIV).
• the compounds of formula I above are active as herbicides, and the invention therefore provides, in a further aspect, a process for severely damaging or killing unwanted plants, which process comprises applying to the plants, or to the growth medium of the plants, a herbicidally effective amount of a compound of formula I as hereinbefore defined.
• the compounds of formula I are active against a broad range of weed species including monocotyledonous and dicotyledonous species. They show some selectivity towards certain species; they may be used, for example, as selective herbicides in soya, maize and in particular rice crops.
• the compounds of formula I are applied directly to unwanted plants (post-emergence application) or may be applied to the soil before the unwanted plants emerge (pre-emergence application).
• the compounds of formula (I) When the compounds of formula (I) are applied to rice it is preferred to apply them in flooded i.e. paddy conditions.
• the compounds of formula I may be used on their own to kill or severely damage plants, but are preferably used in the form of a composition comprising a compound of formula I in admixture with a carrier comprising a solid or liquid diluent.
• compositions containing compounds of formula I include both dilute compositions, which are ready for immediate use, and concentrated compositions, which require to be diluted before use, usually with water.
• the compositions Preferably contain from 0.01% to 90%) by weight of the active ingredient.
• Dilute compositions ready for use preferably contain from 0.01 to 2% of active ingredient, while concentrated compositions may contain from 20 to 90%o of active ingredient, although from 20 to 70% is usually preferred.
• 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.
• a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum.
• a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite
• Liquid compositions may comprise a solution or dispersion 'of an active ingredient in water optionally containing a surface-active agent, or may comprise a solution or 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 ammonium compounds (e.g. cetyltrimethylammonium 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 dodecylbenzenesulphonate, sodium, calcium, and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid.
• Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g.
• Non-ionic agents are the partial esters derived from long chain 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 agents (water soluble surface active agents having a skeleton which comprises a siloxane chain e.g. Silwet L77TM).
• a suitable mixture in mineral oil is Atplus 41 IFTM.
• the aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent(s).
• Suitable organic solvents include, for example, ethylene di-chloride, isopropyl alcohol, propylene glycol, diacetone alcohol, 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 capable of dilution with water to form aqueous preparations which remain homogeneous for -a sufficient time to enable them to be applied by conventional
• 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.
• a preferred form of concentrated composition comprises 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 hydrophilic colloids and include, for example, polyvinylpyrrolidone and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth.
• Preferred suspending agents are those which impart thixotropic properties to, and increase the viscosity of the concentrate. Examples of preferred suspending agents include hydrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorite, saponite, and saucorite. Bentonite is especially preferred.
• Other suspending agents include cellulose derivatives and polyvinyl alcohol.
• the rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an application rate of from 0.001 to 20 kilograms per hectare is suitable while from 0.025 to 10 kilograms per hectare may be preferred.
• compositions of the invention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activity. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula I as hereinbefore defined with at least one other herbicide.
• the other herbicide may be any herbicide not having the formula I. It will generally be a herbicide having a complementary action in the particular application. Examples of useful complementary herbicides include: 1 l,2,4-triazin-5-ones such as metamitron and metribuzin
• dimethylpyrazoles such as benzofenap, pyrazolynate (pyrazolate) and pyrazoxyfen.
• acylanilides such as propanil amide herbicides such as benfluamid, bromobutide, carbetamide, flufenacet, isoxaben, naproanilide, napropamide, naptalam, propyzamide and tebutam
• amino acids and salts and esters thereof such as bialaphos and salts and esters thereof, glufosinate salts and esters thereof, glyphosate and salts and esters thereof, and sulfosate.
• aryloxypropionates including the optically active isomers thereof, such as clodinafop- propargyl, cyhalofop-butyl, diclofop & esters thereof eg methyl ester, fenoxaprop & esters thereof eg ethyl ester, fluazifop-butyl, haloxyfop and esters thereof, propaquizafop, quizalofop and esters thereof and quizalofop-p-tefuryl
• arylanilides such as diflufenican, flamprop, fiamprop-M and esters thereof
• arylureas such as chlorbromuron, chlorotoluron, cumyluron, daimuron (dymron), dimefuron, diuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, methyldymron, metobromuron, metoxuron, monolinuron, neburon and tebuthiuron
• benzoic acids such as 2,3,6-trichlorobenzoic acid, chloramben and dicamba
• bipyridyliums such as diquat and salts thereof, and paraquat and salts thereof.
• carbamates such as chlorpropham and propham, and phenylcarbamoyloxyphenyl carbamates such as desmedipham and phenmedipham
• acetamides such as acetochlor, alachlor, butachlor, dimethachlor, dimethenamid and isomers thereof, metazachlor, metolachlor and isomers thereof, pretilachlor, propachlor, propisochlor and thenylchlor.
• cyclohexanediones such as alloxydim and salts thereof, butroxydim, clethodim, cycloxydim, sethoxydim, tepraloxydim and tralkoxydim.
• dihalobenzonitriles such as dichlobenil dinitrophenols such as dinoterb and dintro ortho-cresol (DNOC)
• diphenyl ethers such as aciflurofen and salts and esters thereof, aclonifen, bifenox, chlomethoxyfen, chlornitrofen, fluroglycofen or salts or ester thereof, fomesafen, lactofen and oxyfluorfen.
• dinitroanilines such as dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin.
• haloalkanoic herbicides such as dalapon and trichloroacetic acid and salts thereof.
• HBN hydroxybenzonitrile herbicides
• bromoxynil and ioxynil hydroxybenzonitrile herbicides
• HBN precursors such as bromofenoxim
• herbicides such as 2,4,5-trichlorophenoxyacetic acid, 2,4- dichlorophenoxyacetic acid, 2,4-dichlorophenoxybutyric acid, clopyralid, dichlorprop
• MCPA 4-chloro-2-methoxyacetic acid
• MCPA- thioethyl 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB)
• mecoprop & mecoprop- p picloram
• thiazopyr and triclopyr.
• imidazolinones such as imazapic, imazamox, imazamethabenz-methyl, imazapyr & isopropylammonium salts thereof, imazaquin and imazethapyr.
• methyl isothiocyanate precursors such as dazomet.
• miscellaneous herbicides such as ammonium sulfamate, asulam, azafenidin, benazolin, benzobicyclon/benbiclon, cinmethylin, clomazone, difenzoquat & salts thereof eg methyl sulphate salt, diflufenzopyr-sodium (SAN-835H), dimethipin, dimexyflam, diphenamid, dithiopyr, epoprodan, ethofumesate, etobenzanid, fluazolate, fentrazamide, flucarbazone, flumiclorac-pentyl, flumioxazin, flupoxam, flurenol-butyl, flurochloridone, flurtamone, fluthiacet-methyl, hexazinone, mefenacet, oxadiazon, oxaziclomefone, pentoxazone, pyraflufen-ethy
• organophosphorus herbicides such as anilofos and fosamine-sodium
• phosphorothioates such as butamifos, bensulide and piperophos
• pyridazinones such as chloridazon and norfiurazon
• pyrimidinyloxybenzoic acids and salts and esters thereof such as pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl and pyribenzoxim.
• quinolinecarboxylic acids such as quimerac and quinclorac
• herbicide antidotes such as benoxacor, cloquintocet-mexyl, dichlormid, fenchlorazole- ethyl, fenclorim, fluxofenim, furilazole, naphthalic anhydride, oxabentrinil, mefenpyr- diethyl, N-(dichloroacetyl)-l -oxa-4-azaspirobicyclo-(4,5)-decane (AD-67), 3- dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148) and 2-dichloromethyl-2-methyl- l ,3-dioxolane (MG-191).
• herbicide antidotes such as benoxacor, cloquintocet-mexyl, dichlormid, fenchlorazole- ethyl, fenclorim, fluxofenim, furilazole, naphthalic anhydride, ox
• sulfamoylureas such as cyclosulfamuron.
• sulfonanilides such as chloransulam-methyl, diclosulam, florasulam, flumetsulam and metosulam.
• sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron and esters thereof, chlorimuron & esters eg ethyl ester thereof, chlorsulfuron, cinosulfuron, ethametsulfuron-methyl, flazasulfuron, flupyrsulfuron and salts thereof, halosulfuron- methyl, ethoxysulfuron, imazosulfuron, iodosulfuron, metsulfuron and esters thereof, nicosulfuron, oxasulfuron, primisulfuron & esters eg methyl ester thereof, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron- methyl, triasulfuron, tribenuron, tribenuron-methyl
• thiocarbamates such as butylate, cycloate, dimepiperate, 5-ethyl dipropylthiocarbamate (EPTC), esprocarb, molinate, orbencarb, pebulate, prosulfocarb, thiobencarb, tiocarbazil, tri-allate and vernolate.
• triazine herbicides such as ametryn, atrazine, cyanazine, dimethametryn, prometon, prometryn, propazine, simazine, simetryn, terbuthylazine, terbutryn and trietazine.
• uracils such as bromacil, lenacil and terbacil.
• Particularly suitable complimentary herbicides for use in mixtures containing compounds of formula (I) are dimethylpyrazoles such as pyrazolate, amide herbicides such as bromobutide and naproanilide, triketones such as sulcotrione, arylureas such as cumyluron and sulfonylureas such as ethoxysulfuron. Some of these mixtures may show synergy or other useful effects.
• NMR spectrum nuclear magnetic resonance spectrum which were recorded at 270 or 400 MHz. (This refers to the proton magnetic resonance spectrum unless otherwise stated).
• the following abbreviations are used to indicate the multiplicity of the peaks in the NMR spectrum: s (singlet); d (doublet); t (triplet); q (quartet) quin (quintet) m (multiplet; br (broad).
• IR spectrum infra-red absorption spectrum.
• the apparatus was then fitted with a CO2/acetone condenser and chlorodifluoromethane was bubbled into the reaction mixture for 1 hour yielding a dark red emulsion (39g of chlorodifluoromethane was used in this process as judged by the cylinder's weight loss).
• the reaction mixture was allowed to rise to room temperature (introduction of the gas had led to a fall in temperature in the reaction mixture) and then allowed to stand at room temperature overnight.
• the reaction mixture was diluted with dichloromethane (120 ml) and poured into water. After shaking in a separating funnel the organic layer was separated, washed with water twice, and dried (MgSO .
• 2,2-dichloro-l- methylcyclopropyl carbonyl chloride ( 0.5g) (prepared as described in Example 7 hereinafter) was then added and then after 20 minutes triethylamine (0.5g), dropwise, over a further 20 minutes.
• the reaction mixture was allowed to rise to room temperature and then stood at room temperature for 2 days.
• the reaction mixture was diluted with dichloromethane (30 ml), washed with water (x3), washed with IM hydrochloric acid, water, and then brine.
• EXAMPLE 2 Preparation of diastereoisomers of 3 (( ⁇ (2,2-dichloro- 1 -methylcvclopropy lcarbonv Dmethyl- aminoVl(4-bromo-3- triifluoromethoxyphenyl)pyrrolidin-2-one (Compound 37 in Table 1) 3((N(2,2-dichloro-l-methylcyclopropylcarbonyl)methylamino)-l(3- trifluoromethoxyphenyl)pyrrolidin-2-one (prepared as described in Example 7 hereinafter) (lg) was stirred in dry DMF (25 ml) and N-bromosuccinimide (0.4g) added.
• reaction mixture was stirred at room temperature for 1 hour and then allowed to stand overnight. GLC revealed incomplete reaction and the reaction mixture was heated to 60°C for 2 hours. Two further portions of N-bromosuccinimide (0.9g in total) were added and the reaction mixture again heated at 60°C for 2 hours. The reaction mixture was allowed to cool to room temperature and then poured into water. The product was extracted with ether (x3) and the combined layers washed with water, dried (MgS0 4 ), filtered and evaporated to give an orange oil.
• Tetramethyltin (0.1 ml) was then added followed by tetrakis(triphenylphosphine)palladium(0) (0.58g). The mixture was stirred and heated to 100°C giving a gentle reflux of the added tetramethyl tin. Heating was continued for 3 hours when GLC analysis revealed about 33% conversion to the title compound. More tetrakis(triphenylphosphine)palladium(0) (0.58g) and tetramethyltin (0.1 ml) were added and refluxing continued for a further 2 hours, whereupon analysis suggested 66%o conversion.
• 5-Chlorothiophene-2-carboxylic acid (64.8g) was dissolved in dry 1 ,4-dioxane (320 ml) and stirred at room temperature. Dry t-butanol (35.7g) was added, and the solution treated with triethylamine (44.44g) giving an exotherm to 30°C. The solution was then heated to gentle reflux (97°C internal temperature, 120°C oil bath temperature). Diphenylphosphoryl azide (DPPA) (86.2 ml) was added, dropwise, using a nitrogen pressured bottle/Teflon line over 5h, with the volume of nitrogen evolved from the reaction measured by collection of the gas over water in a large measuring cylinder.
• DPPA diphenylphosphoryl azide
• the crude material was purified by chromatography on silica gel using ethyl acetate/ hexane (2:3) yielding a sticky beige solid. This material was triturated with hexane/ether (9/1) to give a brown solid comprising a mixture of 3-bromo- l(5-chloro-4-methylthien-2-yl)pyrrolidin-2-one and 3-chloro-l(5-chloro-4-methylthien-2- yl)pyrrolidin-2-one which was then added, portionwise, over 30 minutes to a solution of sodium iodide (2g) in dry acetonitrile (30 ml). The reaction mixture was gently refluxed with stirring for 3 hours and allowed to stand at room temperature overnight.
• Aluminium chloride 55g was stirred in a dry 250 ml 3-necked flask and 2-Acetyl-5- methylthiophene (23.5g) was added, dropwise, giving a modest exotherm. Chlorine gas was passed onto the slurry from a wide inlet tube for 4 hours during which time the mixture became dark brown; the reaction mixture was then stoppered and left at room temperature overnight. The reaction mixture was added slowly to a mixture of excess ice and concentrated hydrochloric acid (50 ml) and the stirring continued until the ice had melted. The mixture was extracted with ether, and the ether washed with water (x3), and brine.
• sodium hypochlorite solution ('Haychlor Agricultural' sodium hypochlorite, label said: i >5% ⁇ X6% available chlorine') (100 ml), with stirring at 60°C and 2-acetyl-4-chloro-4-methylthiophene (10.87g) was added in small portions over 30 minutes. After a further 30 minutes more of the sodium hypochlorite solution (110 ml) was added and the reaction mixture stirred and heated at 70°C for 90 minutes.
• EXAMPLE 7 Preparation of 3((N(2.2-dichloro-l -methylcvclopropyl carbonyl)methylamino)-l(3- trifluoromethoxyphenvDpyrrolidin-2-one ( Compound No. 2 in Table 1)
• a solution of 2,2-dichloro-l-methylcyclopropyl carbonyl chloride was prepared as follows: A stirred solution of 2,2-dichloro-l-methylcyclopropyl carboxylic acid (0.12 g) in dichloromethane (5 ml) was treated with oxalyl chloride (0.10 g), followed by dimethylformamide (1 drop), and the resultant solution was stirred at room temperature for 6 hours.
• diastereoisomer A ⁇ (CDC1 3 ): 1.41 (IH, d), 1.62 (3H, s), 2.11 (IH, d), 2.15 (IH, m), 2.49 (IH, m), 3.17 (3H, s), 3.78 - 3.96 (2H, m), 5.26 (IH, dd), 6.78 (IH, s) diastereoisomer B: ⁇ (CDC1 3 ; mixture ofrotamers): 1.39 & 1.45 (IH, 2 x d), 1.60 & 1.68 (3H, 2 x s), 2.07 & 2.15 (IH, 2 x d), 2.22
• diastereoisomer A ⁇ (CDC1 3 ): 1.41 (IH, d), 1.63 (3H, s), 2.1 1 (IH, d), 2.15 (IH, m), 2.52 (IH, m), 3.12 (3H, s), 3.91 (IH, m), 4.1 1 (IH, m), 5.26 (IH, t), 6.63 (IH, s) diastereoisomer B: ⁇ (CDC1 3 ; mixture ofrotamers): 1.38 & 1.45 (IH, 2 x d), 1.61 & 1.69 (3H, 2 x s), 2.07 & 2.13 (IH, 2 x d), 2.20
• diastereoisomer B ⁇ (CDC1 3 ; mixture ofrotamers): 1.39 & 1.45 (IH, 2 x d), 1.61 & 1.67 (3H, 2 x s), 2.08 & 2.17 (IH, 2 x d), 2.23 - 2.83 (5H, m), 2.91 & 3.28 (3H, 2 x s), 3.73 - 3.98 (2H, m), 4.45 & 4.85 (IH, 2 x t), 7.21 - 7.37 (IH, m), 7.74 - 7.94 (2H, m) EXAMPLE 24
• Ethyl 2,2-dichloro-l -methylpropenoate (1.02 g) was heated to 145°C (bath temperature) and sodium trichloroacetate (excess) was added portionwise. The reaction was allowed to cool to room temperature, and was left to stand for 16 hours. The mixture was then heated again to 145°C (bath temperature) and more sodium trichloroacetate (vast excess) was added portionwise over 7 hours. The reaction was allowed to cool to room temperature, and left to stand for 16 hours, before being heated again to 145°C (bath temperature) and more sodium trichloroacetate (vast excess) was added portionwise over 4 hours. The mixture was then cooled, and water was added.
• step 1 The product from step 1 was heated under reflux in thionyl chloride for 2 hours. This was then evaporated under reduced pressure, and the residue was dissolved in dichloromethane. This acid chloride solution was then reacted with 3(methylamino)-l(3- trifluoromethoxyphenyl)pyrrolidin-2-one as described in example 1 to afford, after purification by silica-gel chromatography (eluting with ethyl acetate/hexane mixtures (1 :2), the title compound.
• diastereoisomer A ⁇ (CDC1 3 ): 1.41 (IH, d), 1.67 (3H, s), 2.10 (IH, m), 2.1 1 (IH, d), 2.26 (3H, d), 2.48 (IH, m), 3.15 (3H, s), 3.70 - 3.88 (2H, m), 5.35 (IH, dd), 7.17 (IH, t), 7.23 (IH, d), 7.50 (IH, d) diastereoisomer B: ⁇ (CDC1 3 ): 1.
• Step 1 Prep, of l(5-bromothien-2-yl)pyrrolidin-2-one.
• diastereoisomer A mp 173 - 174°C; ⁇ (CDC1 3 ): 1.40 (IH, d), 1.63 (3H, s), 2.1 1 (IH, d), 2.15 (IH, m), 2.58 (IH, m), 3.12 (3H, s), 3.76 (IH, m), 3.90 (IH, m), 5.35 (IH, t), 6.30 (IH, d), 6.87 (lH, d) diastereoisomer B: mp 185 - 186°C; ⁇ (CDC1 3 ): 1.38 & 1.44 (IH, 2 x d), 1.60 & 1.69 (3H, 2 x s), 2.05 & 2.14 (IH, 2 x
• the flocculent solid suspension was stirred overnight at ambient temperature.
• the crude hydrated aldehyde product of the Pummerer reaction (72.5 gms) was divided into two equal portions, and each 36 grm aliquot separately dissolved in dioxan (350 ml), in which hydrogen chloride (ca. 80 grm) had been dissolved, at ca. 4 °C with ice-bath cooling. The temperature was allowed to slowly rise to 20 °C and stirring continued for 4 hours.
• the hydroxy-oxazolidinone obtained from step 3 (7.0 gms, 0.0302 mole) was dissolved in dry dichloromethane (50 ml) and two drops of dimethylformamide added. Oxalyl chloride (4.2 gms, 1.1 eq) was slowly added by syringe, and the solution stirred at room temperature for 4 hours, by which time degassing had ceased. The solution was evaporated to dryness to give the 5-chlorooxazolidin-4-one as a pale brown oil (7.7 gms).
• Methylamine (33.4 mis of a 2.0 mole solution in tetrahydrofuran: 2.2 eq) was added dropwise over 15 mins, during which time a white solid forms and the temperature was maintained below 22 °C. After stirring for 2 hours at room temperature, the reaction was refrigerated overnight.
• Step 1 Preparation of 3-Bromo- 1 (3-methoxy-4-methoxyphenyl)pyrrolidin-2-one.
• 3-Methoxy-4-methylaniline (3.5 gms) was dissolved in dry dichloromethane (50 ml) and cooled under nitrogen to 5 °C (ice - water bath).
• Triethylamine (14.2 ml, 4 eq) was added followed by 2,4-dibromobutyryl bromide containing a known proportion of 2,4- dibromobutyryl chloride (9.5 g, 1.2 eq).
• Step 2 Preparation of 3-methylamino -l (3-methoxy-4-methylphenyl)pyrrolidin-2-one.
• the product from step 1 (3.3 gms) was dissolved in dry tetrahydrofuran (50 ml) and treated with one equivalent of sodium iodide (1.75 gms). The solution was stirred at room temperature, becoming cloudy after a short period. After 5 minutes stirring, methylamine (20 mis of a 2M solution in tetrahydrofuran) was added and stirring continued at room temperature for 5 hours. After standing at room temperature overnight, solvent was removed under reduced pressure and the residue partitioned between ethyl acetate and water.
• Example 41 The following compounds were prepared using a method analogous to that described in
• Span 80 is a Trade Mark for a surface-active agent comprising sorbitan mono-laurate. If the chemical did not dissolve, the volume was made up to 5cm ⁇ with water, glass beads were added and this mixture was then shaken to effect dissolution or suspension of the chemical, after which the beads were removed. In all cases, the mixture was then diluted with water to the required spray volume. If sprayed independently, volumes of 10cm J and 14cm J were required for pre-emergence and post-emergence tests respectively; if sprayed together, 20cm- 3 was required.
• the sprayed aqueous emulsion contained 4%> of the initial solvent/surfactant mix and the test chemical at an appropriate concentration.
• the spray compositions so prepared were sprayed onto young pot plants (post-emergence test and flooded conditions test) at a spray volume equivalent to 400 litres per hectare.
• the flooded conditions test was used for species which are of relevance to the growth of paddy-rice crops.
• the plant species were contained in 4cm diameter Aqua pots which had been kept moist for a minimum of 48 hours before spraying.
• the tubs were then kept moist for a further 24 hours after spraying and then flooded to a depth of approximately 2cm. This water level was maintained for the duration of the test.
• Damage to plants was assessed 13 days after spraying for the post-em test and 20 days for the flooded conditions by comparison with untreated plants, on a scale of 0 to 9 where 0 is 0% damage, 1 is 1-5% damage, 2 is 6-15% damage, 3 is 16-25%) damage, 4 is 26-35% damage, 5 is 36-59% damage, 6 is 60-69% damage, 7 is 70-79% damage, 8 is 80-89% damage and 9 is 90-100% damage.
• PC Polygonum convolvulus
• CA Chenopodium album
• GA Galium aparine
• AR Amaranthus retroflexus

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