Triazolopyrimidine herbicides.

0001This invention concerns herbicidal triazole sulphonamides, processes for their preparation, and compositions containing them.

0002In one aspect, the invention provides the triazole sulphonamides of the formula: <chemistry id="chem0001" num="0001"><img file="EP0244948A2_D0001.tif" /></chemistry> and the salts thereof, where R^a represents hydrogen and R^b represents a group R³CONHCR²=CR¹-, or R^a and R^b together represent a chain of formula -C(R³)=N-C(R²)=C(R¹)- or -C(=Y)-N(R⁶)-C(R²)=C(R¹)-, where R¹, R² and R³, which may be the same or different, each represent hydrogen, hydroxy, mercapto, halo, cyano, amino, alkylamino, dialkylamino, or substituted or unsubstituted alkyl, aryl, aralkyl, alkoxy or alkylthio, Y is oxygen or sulphur, and R⁶ is hydrogen or a substituted or unsubstituted alkyl or aryl group; or R¹ and R² together represent -CH=CH-CH=CH- or -(CH₂)_n- where n is 3, 4 or 5; R⁴ represents substituted phenyl or a substituted or unsubstituted aralkyl or heteroaryl group; and R⁵ represents hydrogen, acyl, carboxy, alkoxycarbonyl, alkylsulphonyl, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or aralkyl group, or a group of the formula: <chemistry id="chem0002" num="0002"><img file="EP0244948A2_D0002.tif" /></chemistry> where R^a and R^b are as defined hereinbefore.

0003R^a and R^b preferably together represent a chain of formula -C(R³)=N-C(R²)=C(R¹)-.

0004When R¹, R² or R³ represents halo, it is preferably chloro or bromo.

0005When R¹, R², R³, R⁵ or R⁶ represents or contains an alkyl group, that group is preferably of 1 to 6 carbon atoms, especially of 1 to 4 carbon atoms. Specific preferred unsubstituted alkyl-containing groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, methoxy, ethoxy, n-propoxy, methylamino, dimethylamino, methylthio and ethylthio. The alkyl group may if desired be substituted, for example by one or more halogen atoms, eg fluorine, chlorine or bromine, or by alkoxy groups of 1 to 4 carbon atoms, eg methoxy or ethoxy. Specific preferred substituted alkyl-containing groups include chloromethyl, bromomethyl, dichloromethyl, trifluoromethyl, methoxyethyl and ethoxyethyl.

0006When R¹, R², R³, R⁵ or R⁶ represents an aryl or aralkyl group, it is preferably a phenyl group or an aralkyl group of 7 to 10 carbon atoms, especially benzyl, substituted for example by one or more halogen atoms, eg fluorine, chlorine or bromine, nitro groups, cyano groups, or alkyl or alkoxy groups of 1 to 4 carbon atoms, eg methyl, ethyl, methoxy or ethoxy groups.

0007R¹, R² and R³ independently preferably represent hydrogen, methyl, ethyl, phenyl, trifluoromethyl, chloro or bromo.

0008It will be appreciated that when R³ represents hydroxy or mercapto, the compounds may exist in either the keto or enol forms or as an equilibrium mixture of the two.

0009When R⁴ or R5 represents an aralkyl group, it is preferably benzyl, which may be substituted by one or more alkyl or alkoxy groups of 1 to 4 carbon atoms, halogen atoms or nitro groups.

0010When R⁴ represents a heteroaryl group, it is preferably a 5- or 6-membered heterocycle which contains one or more nitrogen, oxygen or sulphur atoms. Preferred such groups include pyridyl, pyrrolyl, furyl and thienyl.

0011R⁴ preferably represents a phenyl group substituted by one or more halogen (eg chlorine, bromine or fluorine) atoms, alkyl groups of 1 to 4 carbon atoms (eg methyl or ethyl), alkoxy or alkylthio groups of 1 to 4 carbon atoms (eg methoxy, ethoxy or methylthio) trifluoromethyl groups, alkoxycarbonyl groups of 2 to 5 carbon atoms (eg methoxycarbonyl or ethoxycarbonyl) or nitro groups.

0012When R⁵ represents an alkyl group, it is preferably methyl or ethyl. When, however it represents an alkenyl or alkynyl group, that group is preferably unsubstituted, and is preferably of 2 to 6 carbon atoms, for example vinyl, allyl or propargyl. Preferred acyl, alkoxycarbonyl and alkylsulphonyl groups which R⁵ may represent are those in which the alkyl moiety is of 1 to 4 carbon atoms, including formyl, acetyl, propanoyl, methoxycarbonyl, ethoxycarbonyl and methylsulphonyl.

0013R⁵ preferably represents hydrogen.

0014Preferred salts of the compounds of formula I are alkali-metal salts, eg sodium or potassium salts, ammonium salts, trialkylammonium salts, and salts with heterocyclic bases, eg the pyridinium salts.

0015In a particularly preferred group of compounds of formula I, R^a and R^b together represent a chain of formula -C(R³)=N-C(R²)=C(R¹)-, R¹, R² and R³ each represent hydrogen, methyl, ethyl, phenyl, trifluoromethyl or chloro, R⁴ is a phenyl group substituted by one or more halogen atoms, alkyl, alkoxy or alkylthio groups of 1 to 4 carbon atoms, trifluoromethyl groups, alkoxycarbonyl groups of 2 to 5 carbon atoms, or nitro groups, and R⁵ is hydrogen.

0016Especially preferred compounds according to the invention are those of the Examples provided hereinafter. Specific mention may be made, however, of N-(2,6-difluoro­phenyl)-5,7-dimethyl[1,2,4]triazolo[1,5-c]pyrimidine-2-­sulphonamide and 5-(2-acetamido-1-propenyl)-N-(2,6-­difluorophenyl)-1H-1,2,4-triazole-3-sulphonamide.

0017In another aspect, the invention provides a process for the preparation of a triazole sulphonamide of formula I where R^a and R^b together represent a chain of formula -C(R³)=N-C(R²)=C(R¹)- or -C(=Y)-N(R⁶)-C(R²)=C(R¹)-, where R¹, R², R³, R⁶ and Y are as defined hereinbefore, in which a sulphonyl halide of the formula: <chemistry id="chem0003" num="0003"><img file="EP0244948A2_D0003.tif" /></chemistry> where R^a and R^b are as defined hereinbefore, and Hal represents halogen, is reacted in the presence of a base with an amine of the formula R⁴R⁵NH where R⁴ and R⁵ are as defined hereinbefore to give the desired compound.

0018The reaction is conveniently effected at a temperature of from 0°C to 100°C, for example 0 to 50°C, especially at room temperature. It is preferably effected in a suitable solvent medium, especially pyridine, which may also serve as the base.

0019The reaction may be catalysed by a stronger organic base, particularly a tertiary organic base such as 4-dimethylaminopyridine.

0020The compounds of formula II may themselves be prepared by reacting a compound of the formula: <chemistry id="chem0004" num="0004"><img file="EP0244948A2_D0004.tif" /></chemistry> where R^a and R^b together represent a chain of formula -C(R³)=N-C(R²)=C(R¹)- or -C(=Y)-N(R⁶)-C(R²)=C(R¹)- where R¹, R², R³, R⁶ and Y are as defined hereinbefore, and R represents hydrogen, alkyl, aryl or aralkyl, with the appropriate halogen or sulphuryl halide in a suitable solvent medium, to give the desired compound.

0021The reaction is desirably effected with cooling to less than ambient temperature, eg to a temperature of -10°C to 5°C.

0022Where a halogen is used, it is conveniently passed into a solution or suspension of the appropriate starting material in an aqueous medium, eg aqueous acetic acid or hydrochloric acid.

0023Where a sulphuryl halide is employed, the reaction is preferably effected in the presence of wet silica gel, and in a suitable solvent medium, eg dichloromethane.

0024The compounds of formula I where R^a represents hydrogen and R^b represents R³CONHCR²=CR¹- may be prepared by a process which comprises subjecting the corresponding compounds of formula I where R^a and R^b together represent -C(R³)=N-C(R²)=C(R¹)- to the action of a base under mild conditions to give the desired compound.

0025The base is desirably an inorganic base, especially an alkali-metal hydroxide, eg sodium or potassium hydroxide, and is desirably employed in aqueous solution.

0026The reaction is desirably effected at a temperature of from 0°C to 50°C, particularly at room temperature. At higher temperatures, or under more severe conditions, the reaction proceeds a stage further as described hereinafter.

0027The compounds of formula I where R^a and R^b together represent a chain -C(R³)=N-C(R²)=C(R¹)- where R³ is other than hydroxy, mercapto or amino may alternatively be prepared by a process in which a compound of the formula: <chemistry id="chem0005" num="0005"><img file="EP0244948A2_D0005.tif" /></chemistry> where R¹, R², R⁴, and R⁵ are as defined hereinbefore is reacted with an amide of formula R³CONH₂ where R³ is as defined herinbefore to give the desired compound.

0028The reaction is conveniently carried out by heating a mixture of the reactants, eg to 50°C to 200°C.

0029The compounds of formula I in which R^a and R^b together represent a chain -C(R³)=N-C(R²)=C(R¹)- where R³ is hydroxy, mercapto or amino may be prepared by reacting a compound of formula IV as defined hereinbefore respectively with urea, thiourea or guanidine, to give the desired compound.

0030The reaction is conveniently carried out by heating a mixture of the reactants, eg to 50°C to 200°C.

0031The compounds of formula IV may in turn be prepared by a process in which a compound of formula I in which R^a represents hydrogen and R^b represents a group R³CONHCR²=CR¹- is subjected to the action of a suitable base under suitable conditions to give the desired compound.

0032The base employed is conveniently an alkali-metal base, eg an alkali-metal hydroxide, and the reaction is desirably effected in a suitable solvent medium, eg water, and with heating to a temperature of from 60°C to 100°C.

0033The compounds of formula III in which R^a and R^b together represent a chain of formula -C(=Y)-N(R⁶)-C(R²)=C(R¹)-, where Y, R¹, R² and R⁶ are as defined herinbefore are themselves novel compounds which may be prepared from the corresponding compounds in which R^a is hydrogen and R^b is a group R²COCHR¹- by reaction thereof with an isocyanate or isothiocyanate of formula R⁶NCY where R⁶ and Y are as defined hereinbefore. In turn these staring materials may be made by.reacting thiosemicarbazide with a compound of the formula: <chemistry id="chem0006" num="0006"><img file="EP0244948A2_D0006.tif" /></chemistry> where R¹ and R² are as defined hereinbefore, reacting the product, if desired, with a compound of formula RHal where R is as defined hereinbefore and removing the protecting group by means of acid.

0034Salts of the compounds of formula I may be prepared by reaction thereof with a suitable base containing the desired cation, eg the appropriate trialkylamine.

0035The comounds of formula I may also be interconverted by methods known per se. For example, the compounds of formula I in which R⁵ is other than hydrogen may be prepared from the corresponding compounds of formula I where R⁵ is hydrogen by reaction thereof in the presence of a strong base, for example sodium hydride, with a halide of formula R⁵Hal.

0036Carboxy groups present in the compounds of formula I may be esterified, ester groups present may be hydrolysed to give the corresponding acids, and cyano or ester groups may be converted to amido or substituted amido groups. Such transformations, as well as many others, may be effected by techniques well-known to those skilled in the art, and various examples of such transformations are provided hereinafter.

0037Particular mention may be made of the conversion of compounds of formula I in which R² or R³ is hydroxy into the corresponding compounds in which R³ is chloro by reaction of the former with phosphorus oxychloride, and the subsequent reaction of the chloro compounds in the presence of a base with an appropriate alcohol, alkanethiol, amine or cyanide to give the corresponding compounds of formula I in which R³ respectively represents alkoxy, alkylthio, amino or cyano.

0038The compounds of formula I are herbicidally-active against a wide range of broad-leaved and grassy weeds, but are comparatively safe to certain crop species. They may thus be of use as selective herbicides, particularly in the control of a range of weeds in cereals or other crops, eg wheat, barley, maize, soya beans, oilseed rape, cotton or sugar beet.

0039In another aspect, the invention provides a herbicidal composition which comprises one or more compounds of the invention in association with a suitable carrier and/or surface active agent.

0040The compositions usually contain from 0.01 to 99% by weight of the present compounds, and are normally produced initially as concentrates containing from 0.5 to 99%, preferably from 0.5 to 85%, and especially from 10 to 50% by weight thereof. Such concentrates are diluted if necessary before application to the locus to be treated such that the active ingredient comprises from 0.01 to 5% by weight of the formulation applied.

0041The carrier may be water, in which case an organic solvent may also be present, though this is not usually employed. A flowable suspension concentrate may be formed by grinding the compound with water, a wetting agent and a suspending agent, e.g. xanthan gum.

0042The carrier may alternatively be a water immiscible organic solvent, e.g. a hydrocarbon which boils within the range 130-270°C, e.g. xylene, in which the compound is dissolved or suspended. An emulsifiable concentrate containing a water immiscible solvent may be formed with a surface active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water.

0043The carrier may alternatively be a water-miscible organic solvent e.g. 2-methoxy ethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or dimethylformamide.

0044The carrier may alternatively be a solid, which may be finely divided or granular. Examples of suitable solids are limestone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulphonates and solid fertilizers. The carrier can be of natural or synthetic origin or can be modified natural material.

0045Wettable powders soluble or dispersible in water may be formed by admixing the compound in particulate form with a particulate carrier or spraying molten compound on to the particulate carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture.

0046An aerosol composition may be formed by admixing the compound with a propellant, e.g. a polyhalogenated alkane such as dichlorofluoromethane, and suitably also with a solvent.

0047The term 'surface active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.

0048The surface active aqents used may comprise anionic surface active agents, for example mono- or di-esters of phosphoric acid with a fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulphates such as sodium dodecyl sulphate, ethoxylated fatty alcohol sulphates, ethoxylated alkylphenol sulphates, lignin sulphates, petroleum sulphonates, alkylaryl sulphonates such as alkyl-benzene sulphonates or lower alkylnaphthalene sulphonates, salts of sulphonated naphthaleneformaldehyde condensates, salts of sulphonated phenolformaldehyde condensates, or more complex sulphonates such as the amide sulphonates, e.g. the sulphonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulphosuccinates e.g. the sodium sulphonate of dioctyl succinate.

0049The surface active agents may also comprise non-ionic agents, for example condensation products or fatty acid esters, fatty alcohols, fatty acid amides or alkyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-­decyn-4,7-diol, or ethoxylated acetylenic glycols.

0050The surface active agents may also comprise cationic agents, for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl trimethylammonium bromide, or ethoxylated tertiary fatty amines.

0051Preferred surface active agents include ethoxylated fatty alcohol sulphates, lignin sulphonates, alkyl-aryl sulphonates, salts of sulphonated naphthaleneformaldehyde condensates, salts of sulphonated phenolformaldehyde condensates, sodium oleoyl N-methyltauride, dialkyl sulphosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.

0052The present active compounds, especially those of the Examples provided hereinafter, and particularly N-(2,6-difluorophenyl)-5,7-dimethyl[1,2,4]triazolo[1,5-c]­pyrimidine-2-sulphonamide and 5-(2-acetamido-1-propenyl)-N-­(2,6-difluoropheny1)-1H-1,2,4-triazole-3-sulphonamide, may be admixed with another pesticide, eg a herbicide, fungicide or insecticide, or a plant growth regulator, particularly another herbicide. Suitable further herbicides include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metolachlor, fluometuron, oxyfluorfen, fomesafen, bentazone, prometryne, norflurazon, chlomazone, EPTC, imazaquin, and especially isoproturon, methabenzthiazuron, trifluralin, ioxynil, bromoxynil, benazolin, mecoprop, fluroxypyr, alachlor, acifluorfen, lactofen, metribuzin and pendimethalin.

0053The present compounds may be applied to plants, the soil, land or aquatic areas, and particularly to a locus at which a crop is growing or is about to grow. The compounds are active both pre- and post-emergence.

0054The invention is illustrated by the following Examples, in which Me = methyl, Et = ethyl and Ph = phenyl.

Preparative Example A

N-(2-chlorophenyl)-5,7-dimethyl[1,2,4]triazolo[1,5-c]­pyrimidine-2-sulphonamide (Compound Al)

(a)

5,7-dimethyl[1,2,4]triazolo[1,5-c]pyrimidine-2-­sulphonyl chloride

0055Chlorine gas was passed into a suspension of 5,7-dimethyl[1,2,4]triazolo[1,5-c]pyrimidine-2-thiol (5.4g) in water (50ml) at 5-10°C with vigorous stirring for 30 minutes. The solid was filtered off and dissolved in dichloromethane (80ml). The organic solution was washed with water (10ml), dried over magnesium sulphate and concentrated in vacuo to give a yellow gummy solid, 2.7g, shown to be the desired product by spectroscopy.

(b)

N-(2-chlorophenyl)-5,7-dimethyl[1,2,4]triazolo[1,5-c]­pyrimidine-2-sulphonamide

0056A solution of the sulphonyl chloride (2.7g) in dichloromethane (10ml) was slowly added at 10-15°C to a stirred solution of 2-chloroaniline (1.54g) in pyridine (20 ml). The temperature was maintained at below 15°C. After the addition was complete, the mixture was allowed to return to ambient temperature and was stirred overnight. It was then concentrated in vacuo and 5% hydrochloric acid (15ml) and ether (10ml) were added to the residue. The resulting solid was filtered and flash chromatographed on silica using petroleum ether (bp 60-80°C)/ethyl acetate 1:1 as eluent. The desired sulphonamide was obtained as a cream solid, mp 190-192°C, in a yield of 1g.

Examples A2-A49

0057The following compounds of formula I where R⁵ represents hydrogen were prepared by methods analogous to that of Example A: <tables id="tabl0001" num="0001"><img file="EP0244948A2_D0007.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0244948A2_D0008.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0244948A2_D0009.tif" /></tables>

0058The following compound of formula I was also prepared by a method analogous to that of Example A: <tables id="tabl0004" num="0004"><img file="EP0244948A2_D0010.tif" /></tables>

0059The following compound of formula I where R⁴ represents 2-pyridyl was also prepared by a method analogous to that of Example A: <tables id="tabl0005" num="0005"><img file="EP0244948A2_D0011.tif" /></tables>

Examples A49-A52

0060The following compounds of formula I where R⁵ represents a group of formula A where R¹, R² and R³ are the same as the corresponding groups in the remainder of the molecule were prepared by methods analogous to those of Example A: <tables id="tabl0006" num="0006"><img file="EP0244948A2_D0012.tif" /></tables>

Preparative Example B

5-(2-Acetamido-1-propenyl)-N-(2,6-difluorophenyl)-1H-­1,2,4-triazole-3-sulphonamide (Compound B1)

0061A solution of the product of Example 4 (2.4g) in 5% aqueous sodium hydroxide solution (20ml) was stirred at room temperature for 1.5 hours and was left to stand for a further 18 hours. The solution was then acidified to pH=2 with concentrated hydrochloric acid to precipitate a solid. This was filtered off, washed with water (2 × 10ml) and ether (2 × l0ml) to give 2.1g of the desired product as a white solid, mp 226-228°C.

Examples B2-B7

0062The following compounds of formula I where R⁵ and R^a are hydrogen and R^b represents a group R³CONHCR²=CR¹- were prepared by methods analogous to those of Example B. <tables id="tabl0007" num="0007"><img file="EP0244948A2_D0013.tif" /></tables>

Preparative Example C

N-(2,6-difluorophenyl)-5,6-dihydro-7-methyl-5-oxo[1,2,4]­triazolo[1,5-c]pyrimidine-2-sulphonamide

0063An aqueous solution of the product of Example 4 (15g) in 5% sodium hydroxide (25ml) was heated at reflux for 4 hours. The solution was then cooled, and acidified to pH=4 with concentrated hydrochloric acid to precipitate a cream solid. This was filtered off and washed with water and ether to give 11g of N-(2,6-difluorophenyl)-5-(2-­oxopropyl)-1H-1,2,4-triazole-3-sulphonamide, mp 182-184°C.

0064An intimate mixture of the produced sulphonamide (2g) and urea 10g, were stirred at 150°C for 3 hours, after which the mixture was cooled to 70°C and water (40ml) was added. The solution was acidified to pH=1 by the addition of concentrated hydrochloric acid to precipitate a solid which was removed by filtration. The solid was extracted with boiling acetonitrile, filtered hot and left to cool, which gave a solid precipitate. This was filtered off to give 0.48g of the desired product as a white solid, mp >350°C which was identical to the product of Example 26.

Preparative Example D

(a)

5-(2-Methyl-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-triazole-­3-thiol

0065Ethyl (2-methyl-1,3-dioxolan-2-ylmethyl)acetate (43.5g) was added dropwise to a suspension of thiosemicarbazide (22.8g) in sodium ethoxide solution (6.04g sodium in 500ml absolute alcohol) at room temperature. The suspension was heated at reflux for 18 hours. After cooling, the solid was removed by filtration, and the filtrate was concentrated in vacuo. The oily residue was dissolved in water (60ml), acidified to pH=5 with acetic acid, and concentrated in vacuo. Trituration of the residue with propan-2-ol (50ml) and filtration gave 11.6g of the desired product, mp 168-173°C, as a white solid.

(b)

3-Benzylthio-5-(2-methyl-1,3-dioxolan-2-ylmethyl)-1H-­1,2,4-triazole

0066Benzyl chloride (8.07g) was added dropwise at room temperature to a solution of the product of stage (a) (11.6g) in sodium ethoxide solution (1.4g sodium in 100ml absolute alcohol) and the mixture was stirred for 18 hours. The precipitated solid was removed by filtration, and the filtrate was concentrated in vacuo. The resulting oil was partitioned between water (60ml) and petroleum ether (bp 60-80) (50ml), and the solid was removed by filtration. This gave 13.9g of the desired product, mp 96-98°C, as a white solid.

(c)

1-(5-Benzylthio-1H-1,2,4-triazol-3-yl)propan-2-one

0067A suspension of the product of stage (b) (9.9g) in 1% hydrochloric acid (110ml) was heated at reflux for 30 minutes. The mixture was then cooled, and the solid removed by filtration. This solid was identified as the desired product, 7.6g, mp 125°C-127°C.

Preparative Example E

N-acetyl-N-(2,6-difluorophenyl)-5,7-dimethyl[1,2,4]tri­azolo[1,5-c]pyrimidine-2-sulphonamide

0068The product of Example A4 (2g) was heated with acetic anhydride (12ml) at reflux for 2 hours, after which the reaction mixture was allowed to cool. The precipitated solid was removed by filtration to give 1.2g of the desired product, mp 171-173°C.

Preparative Example F

0069Ethyl ch;oroformate (1.3g) was added dropwise to a suspension of the product of Example A4 (2.5g) in pyridine (13ml) at 22°C, and the mixture was stirred at room temperature for 2 days. After filtering off the remaining solid, the filtrate was acidified with hydrochloric acid, and the resulting solid was removed by filtration, washed with dilute ammonia (20ml) and recrystallised from ethyl acetate to give 1.9g of the desired product, mp 155-157°C.

FORMULATION EXAMPLES

0070A 10% suspension concentrate formulation was prepared from the following ingredients: <tables id="tabl0008" num="0008"><img file="EP0244948A2_D0014.tif" /></tables>

0071Corresponding formulations containing 5, 10, 25, 50, 200 and 500 g/l of the compounds of Examples A1-A53, B1-B7, C, D and E were also prepared.

HERBICIDAL EXAMPLE A (Pre-Emergence)

0072Seeds of the weed species listed below were sown in anodised aluminium pans 19 cm long × 9.5 cm wide × 6 cm deep, containing sterilized sandy loam. They were watered and then sprayed with the compounds of the Examples listed below formulated as a solution/suspension in 1:1 by volume of acetone and the wetting agent polyoxyethylene (20 mols) monolaurate solution (2 g per litre).

0073The concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 450 litres per hectare. After 3 to 4 weeks growth in the controlled environment room (20°C; 75-95% relative humidity; 14 hours per day artificial illumination) the plants were visually assessed for any herbicidal response.

0074All differences from an untreated control were scored accordingly to an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below, the following letters are used to denote the plant species: <ul id="ul0001" list-style="none"><li>a - <u style="single">Polygonum lapathifolium</u> (Pale persicaria)</li><li>b - <u style="single">Galium aparine</u> (cleavers)</li><li>c - <u style="single">Chrysanthemum segetum</u> (corn marigold)</li><li>d - <u style="single">Alopecurus myosuroides</u> (blackgrass)</li><li>e - <u style="single">Elymus repens</u> (Couchgrass)</li><li>f - <u style="single">Avena fatua</u> (wild oat)</li><li>g - <u style="single">Abutilon theophrasti</u> (velvetleaf)</li><li>h - <u style="single">Cyperus rotundus</u> (purple nutsedge)</li><li>i - <u style="single">Pharbitis purpurea</u> (morningglory)</li><li>j - <u style="single">Echinochloa crus-galli</u> (barnyardgrass)</li><li>k - <u style="single">Setaria viridis</u> (green foxtail)</li><li>l - <u style="single">Solanum nigrum</u> (black nightshade)</li></ul>

0075The results obtained were as follows: <tables id="tabl0009" num="0009"><img file="EP0244948A2_D0015.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0244948A2_D0016.tif" /></tables>

HERBICIDAL EXAMPLE B (Post-Emergence)

0076Seeds of the plant species listed below were sown in anodised aluminium pans, 19 cm long × 9.5 cm × 6 cm deep containing sterilised sandy loam. They were then watered and placed in a controlled environment room (20°C; 75-95% relative humidity; 14 hours per day artificial illumination). Fourteen or twenty one days after sowing (depending on the species but when most plants had 2 to 3 true leaves) the seedlings received a foliar spray of the compounds of the Examples listed below, formulated as a solution/suspension in 1:1 by volume of acetone and the wetting agent polyoxyethylene (20 mols) monolaurate solution (2 g per litre).

0077The concentration of each test compound was calculated to give the desired rate of application of the compound in 450 litres per hectare. After 2 to 3 weeks growth in the controlled environment room the plants were visually assessed for any herbicidal response.

0078All differences from an untreated control were scored according to an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below, the following letters are used to denote the plant species: <ul id="ul0002" list-style="none"><li>a - <u style="single">Polygonum lapathifolium</u> (Pale persicaria)</li><li>b - <u style="single">Galium aparine</u> (cleavers)</li><li>c - <u style="single">Chrysanthemum segetum</u> (corn marigold)</li><li>d - <u style="single">Alopecurus myosuroides</u> (blackgrass)</li><li>e - <u style="single">Elymus repens</u> (Couchgrass)</li><li>f - <u style="single">Avena fatua</u> (wild oat)</li><li>g - <u style="single">Abutilon theophrasti</u> (velvetleaf)</li><li>h - <u style="single">Cyperus rotundus</u> (purple nutsedge)</li><li>i - <u style="single">Pharbitis purpurea</u> (morningglory)</li><li>j - <u style="single">Echinochloa crus-galli</u> (barnyardgrass)</li><li>k - <u style="single">Setaria viridis</u> (green foxtail)</li><li>l - <u style="single">Solanum nigrum</u> (black nightshade)</li></ul>

0079The results obtained were as follows: <tables id="tabl0011" num="0011"><img file="EP0244948A2_D0017.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0244948A2_D0018.tif" /></tables>