Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
  • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
  • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings

Definitions

• This invention relates to novel 1,3-oxazin- 4-one derivatives, processes and intermediates for their preparation, compositions containing the same, and their use as herbicides.
• W represents -NR ;
• R represents thiophene optionally substituted by one to three groups which may be the same or different selected from halogen, hydroxy,lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, -S(0) n R 7 , -C0 2 R 7 , COR 7 , cyano, nitro and phenoxy;
• R represents hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, lower alkenyl, lower haloalkenyl, alkoxyalkenyl, -CHO, -COR 7 , -C0 2 R 7 , -CH 2 NO 2 , and lower alkyl which is substituted by a group selected from -S(0) ⁇ R 7 and -OCOR 7 ;
• R 3 represents phenyl optionally substituted by one to five groups which may be the same or different selected from halogen, lower alkyl, •lower haloalkyl, lower alkoxy, lower haloalkoxy, -S(0) n R 7 , -C0 2 R 7 , -COR 7 , cyano, nitro, -OH, phenoxy, -NR 8R9 and -SF 5 ; or 9 /0 33
• R 4 and R5 independently represent lower alkyl
• R represents hydrogen
• R represents lower alkyl or lower haloalkyl
• R 8 and R9 independently represent hydrogen or R ; and m and n independently represent zero, one or two; or an agriculturally acceptable salt thereof, which possesses valuable properties.
• salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use.
• the salts are water-soluble.
• Suitable salts with bases include alkali metal (e.g. sodium and potassium), alkaline earth metal (e.g. calcium and magnesium), ammonium and amine (e.g. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts.
• Suitable acid addition salts e.g. formed by compounds of formula (I) containing an amino group, include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids for example acetic acid.
• - 'lower alkyl' means a straight- or branched- chain alkyl group having one to six carbon atoms.
• 'lower haloalkyl 1 means a straight- or branched- chain alkyl group having one to six carbon atoms, substituted by one or more halogens.
• 'lower alkoxy' means a straight- or branched- chain alkoxy group having one to six carbon atoms.
• 'lower haloalkoxy' means a straight- or branched- chain alkoxy group having one to six carbon atoms, substituted by one or more halogens.
• 'halogen' means a fluorine, chlorine, bromine or iodine atom.
• lower alkenyl means an alkenyl group containing two to six carbon atoms.
• lower haloalkenyl means an alkenyl group containing from two to six carbon atoms, substituted by one or more halogen atoms.
• 'alkoxyalkyl' means a lower alkyl group substituted by a lower alkoxy group.
• 1 alkoxyalkenyl' means a lower alkenyl group substituted by a lower alkoxy group.
• the compounds of the invention in certain aspects of their properties, for example their control of the grass species Alopecurus myosuroides. Avena fatua and Echinochloa crus- galli and their selectivity in wheat, show advantages over known compounds.
• Preferred compounds of formula (I) above include those in which:-
• R represents thiophene optionally substituted by one to three groups which may be the same or different selected from halogen, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, -S(0) n R , -C0 2 R 7 , COR 7 , cyano, nitro and phenoxy;
• R represents hydrogen, lower alkyl, lower haloaikyl, alkoxyalkyl, lower alkenyl, lower haloalkenyl, alkoxyalkenyl, -CHO, -COR 7 and -C0 2 R 7 ;
• R represents phenyl optionally substituted by one to five groups which may be the same or different selected from halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, -S(0) n R 7 , -C0 2 R 7 , -COR 7 , cyano, nitro, -OH, phenoxy and -NR R ; or a cycloalkyl group containing from three to six carbon atoms, optionally substituted by lower alkyl, lower haloalkyl or one or more halogen atoms which may be the same or different;
• R 4 and R 5 independently represent lower alkyl
• W represents -NR ;
• R 6 represents hydrogen
• R 7 represents lower alkyl or lower haloalkyl
• R 8 and R 9 independently represent hydrogen or R 7
• n is zero, one or two.
• Particularly preferred compounds of formula (I) above are those in which R 2 is lower alkyl, most preferably methyl.
• R 3 represents phenyl optionally substituted by one to three groups which may be the same or different selected from halogen, or a straight- or branched- chain alkyl group containing from one to three carbon atoms optionally substituted by one or more halogen atoms
• R represents phenyl substituted by one or two groups which may be the same or different selected from halogen (especially chlorine or fluorine) , C 1 . 3 alkyl (especially methyl) and C ! _ 3 haloalkyl (especially -CF 3 ) , are particularly preferred.
• a preferred class of compounds of formula (I) are those wherein:
• R 2 represents methyl, halogenated methyl or methoxymethyl
• R represents phenyl optionally substituted by one to three groups which may be the same or different selected from halogen, a straight- or branched- chain optionally halogenated alkyl group containing from one to four carbon atoms, a straight- or branched- chain optionally halogenated alkoxy group containing from one to four carbon atoms, or -S(0) n R 7 ; or cyclobutyl;
• R and R each represent methyl; and R represents a straight- or branched- chain optionally halogenated alkyl group containing from one to four carbon atoms.
• a particularly preferred class of compounds of formula (I) are those wherein: R 1 represents thiophene optionally substituted by one or two groups which may be the same or different selected from halogen, a straight- or branched- chain optionally halogenated alkyl group containing from one to four carbon atoms, a straight- or branched- chain optionally halogenated alkoxy group containing from one to four carbon atoms, or -S(0) n R 7 ;
• R , R 4 and R each represent methyl;
• R 3 represents phenyl optionally substituted by one or two groups which may be the same or different selected from halogen and optionally halogenated methyl; or cyclobutyl; and
• R 7 represents a straight- or branched- chain optionally halogenated alkyl group containing from one to four carbon atoms.
• a further particularly preferred class of compounds of formula (I) are those wherein: R represents thiophene;
• R 2 , R 4 and R each represent methyl; and R 3 represents phenyl optionally substituted by one or two groups which may be the same or different selected from halogen, optionally halogenated methyl; or cyclobutyl.
• R 3 represents phenyl optionally substituted by one or two groups which may be the same or different selected from halogen, optionally halogenated methyl; or cyclobutyl.
• R represents thiophene optionally substituted by lower alkyl, lower alkoxy or halogen
• R represents methyl or ethyl
• R 4 and R each represent methyl
• R represents phenyl optionally substituted by one, two or three groups which may be the same or different selected from halogen, optionally halogenated methyl, nitro or -SF 5 ; or cyclobutyl or cyclopropyl.
• Another preferred class of compounds of formula (I) above are those having one or more of the following features:
• R 1 represents 2-thienyl; 3-thienyl; 3- methoxy-2-thienyl; 5-methyl-2-thienyl or 5- chloro-2-thienyl;
• R represents methyl; ethyl or fluoromethyl; R 4 and R 5 each represent methyl; and
• R represents cyclopropyl; cyclobutyl; 3,5-difluorophenyl; 3, 5-dichlorophenyl; 2-fluoro- 5-trifluoromethylphenyl; 2-fluoro- 5-methylphenyl; 3-chlorophenyl;
• Particularly important compounds of formula (I) include the following:-
• reaction is generally performed in the presence of a base, for example a tertiary amine such as triethylamine and in an inert solvent such as dichloromethane at a temperature from 0°C to the reflux temperature of the solvent.
• a base for example a tertiary amine such as triethylamine and in an inert solvent such as dichloromethane at a temperature from 0°C to the reflux temperature of the solvent.
• reaction is performed in the presence of a coupling reagent for example N,N' -dicyclohexylcarbodiimide (DCCI) optionally in the presence of a base for example 4- dimethylaminopyridine (DMAP) and in an inert solvent such as dichloromethane at a temperature from 0 to 60°C.
• a coupling reagent for example N,N' -dicyclohexylcarbodiimide (DCCI) optionally in the presence of a base for example 4- dimethylaminopyridine (DMAP) and in an inert solvent such as dichloromethane at a temperature from 0 to 60°C.
• DCCI N,N' -dicyclohexylcarbodiimide
• DMAP dimethylaminopyridine
• compounds of formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 and W are as defined above may also be prepared by the reaction of a carboxylic acid of formula (IV) above with a phenyl carbamate of formula PhO C-NHR , wherein
• R is as defined above.
• the reaction is generally performed in the presence of a base, preferably 1,8-diazabicyclo[5.4.0] undec-7-ene, in an inert solvent for example 1,4-dioxan and at a temperature from 20-100°C.
• a base preferably 1,8-diazabicyclo[5.4.0] undec-7-ene
• an inert solvent for example 1,4-dioxan
• reaction is generally performed in the presence of a catalytic amount of a titanium (IV) salt, preferably prepared in situ from the reaction of titanium (IV) chloride and silver (I) trifluoromethanesulphonate, and in the presence of an anhydride, preferably 4- trifluoromethylbenzoic anhydride and in an inert solvent for example dichloromethane at a temperature from 0 to 60°C.
• a titanium (IV) salt preferably prepared in situ from the reaction of titanium (IV) chloride and silver (I) trifluoromethanesulphonate
• an anhydride preferably 4- trifluoromethylbenzoic anhydride and in an inert solvent for example dichloromethane at a temperature from 0 to 60°C.
• R represents lower alkenyl optionally substituted by halogen or lower alkoxy and wherein the double bond of the alkenyl group is located between the two carbon atoms closest to the 1,3-oxazin-4-one ring may be prepared by reaction of the corresponding compound of formula (I) in which R 2 is -CHO or -COR 7 in
• R 7 which R is defined above, with a phosphorane, typically generated by reaction of a phosphonium salt of formula Ph 3 P +" CHR 10 R 11 -X " in which X represents chlorine, bromine or iodine, R 10 represents hydrogen, alkoxy, or alkyl containing from one to four carbon atoms optionally substituted by halogen or alkoxy, and R represents hydrogen or alkyl containing from one to four carbon atoms optionally substituted by halogen with the proviso that the total number of carbon atoms in the combined alkyl groups R , R 10 and R does not exceed four.
• a phosphorane typically generated by reaction of a phosphonium salt of formula Ph 3 P +" CHR 10 R 11 -X " in which X represents chlorine, bromine or iodine, R 10 represents hydrogen, alkoxy, or alkyl containing from one to four carbon atoms optionally substituted by halogen or alkoxy, and R represents hydrogen or alkyl containing from
• the reaction is generally performed in the presence of a strong base for example n-butyl lithium and in an inert solvent for example tetrahydrofuran at a temperature from 0°C to the reflux temperature, the reaction being conducted under an inert atmosphere.
• a strong base for example n-butyl lithium
• an inert solvent for example tetrahydrofuran
• compounds of formula (I) wherein R 1, R3, R4, R5 and W are as defined above and R represents chloromethyl, bromomethyl or iodomethyl may be prepared by reaction of the corresponding compound of formula (I) in which R 2 is methyl with a chlorinating, brominating or iodinating agent, preferably the appropriate N- halosuccinimide, for example N-bromosuccinimide in an inert solvent e.g. carbon tetrachloride, optionally in the presence of a radical initiator e.g. azobis-isobutyronitrile or by irradiation with a tungsten light source, and at a temperature from ambient to the reflux temperature of the solvent.
• a chlorinating, brominating or iodinating agent preferably the appropriate N- halosuccinimide, for example N-bromosuccinimide in an inert solvent e.g. carbon tetrachloride, optionally in the presence of a radical initiator
• compounds of formula (I) in which R 1 , R , R 4 , R and W are as defined above and R 2 is -CF 2 R 12a wherein R 12a is C ⁇ -C 5 alkyl or haloalkyl may be prepared by reaction of the corresponding compound of formula (I) in which R 2 is -COR a with diethylaminosulphur trifluoride in an inert solvent, e.g. dichloromethane, at a temperature of 0 to 60°C.
• an inert solvent e.g. dichloromethane
• compounds of formula (I) in which R 1, R3, R4, R5 and W are as defined above and R 2 is lower alkyl substituted by iodine may be prepared by iodination of the corresponding compound of formula (I) in which the iodine atom in R is replaced by bromine or chlorine.
• the transhalogenation reaction is generally performed using sodium or potassium iodide in a inert solvent preferably acetone at a temperature from ambient to the reflux temperature of the solvent.
• compounds of formula (I) wherein R 2 represents a lower alkyl group substituted by a group -SR , and R , R , R , R 7 and W are as defined above, may be prepared by the reaction of the corresponding compound of formula (I) in which the -SR 7 group is replaced by a leaving group, preferably chloro or bromo, with a thiol of formula R 7 SH or alkali metal salt of the thiol R SM wherein M represents lithium or sodium.
• the reaction is generally performed in an inert solvent e.g. N,N- dimethylformamide at a temperature from 0 to 60°C.
• compounds of formula (I) wherein R , R , R 4 , R and W are as defined above and R represents a lower alkyl group substituted by -SCF3 may be prepared by the reaction of the corresponding compound of formula (I) in which the -SCF3 group is replaced by an -SCN group, with trifluoromethyltrimethylsilane according to the procedure of B.R.Langlois et. al. as described in Tetrahedron Letters, Volume 38 (1) , pages 65- 68 (1997) .
• the reaction is generally performed in the presence of a catalyst preferably tetrab ⁇ tylammonium fluoride in an inert solvent for example tetrahydrofuran and at a temperature of from -20 to 20°C.
• compounds of formula (I) wherein R 1, R3, R4, R5 and W are as defined above and R represents a lower alkyl group substituted by -OC(0)R 7 wherein R 7 is as defined above may be prepared by the reaction of the corresponding compound of formula (I) in which the -0C(0)R 7 group i.s replaced by a leavi.ng group, with a salt of formula R -C ⁇ 2 ⁇ M_ + , wherein Mi , represents sodium or potassium.
• the leaving group is preferably chlorine or bromine.
• the reaction is typically performed in an inert solvent preferably N,N-dimethylformamide, at a temperature from ambient to 120°C.
• Compounds of formula (I) in which R 2 represents a lower alkyl group substituted by -OR 7 and R 1 , R 3 , R 4 , R 5 , R 7 and W are as defined above, may be prepared by reaction of the corresponding compound of formula (I) in which -OR is replaced by a hydroxy group, with an alcohol of formula R OH in the presence of a trialkylphosphine, e.g. tri-n-butylphosphine and 1, 1'- (azodicarbonyl)piperidine, in an inert solvent (e.g. toluene at a temperature from 20°C to the reflux temperature) .
• a trialkylphosphine e.g. tri-n-butylphosphine and 1, 1'- (azodicarbonyl)piperidine
• an inert solvent
• compounds of formula (I) in which R 2 is -CHFR 7 and R 1 , R 3 , R 4 , R 5 , R 7 and W are as defined above may be prepared by reaction of the corresponding compound of formula (I) in which R 2 is -CH(0H)R 7 with diethylaminosulphur trifluoride in an inert solvent, e.g. dichloromethane at a temperature from 0 to 60°C.
• an inert solvent e.g. dichloromethane
• compounds of formula (I) wherein R 1 , R 3 , R 4 , R 5 and W are as defined above and R 2 represents a fluoromethyl group may be prepared by the fluorination of the corresponding compound of formula (I) in which R 2 is replaced by a hydroxymethyl group, most preferably with diethylaminosulphur trifluoride in an inert solvent for example dichloromethane at a temperature from 0 to 60°C.
• compounds of formula (I) wherein R 1 , R 3 , R 4 , R 5 and W are as defined above and R 2 represents a difluoromethyl group may be prepared by the fluorination of the corresponding compound of formula (I) in which R 2 is -CHO, most preferably with diethylaminosulphur trifluoride in an inert solvent for example dichloromethane at a temperature from 0 to 60°C.
• compounds of formula (I) wherein R 1, R3, R4, R5 and W are as defined above and R represents alkoxyalkyl may be prepared by the reaction of the corresponding compound of formula (I) in which R is replaced by hydroxyalkyl, with an alkyl iodide in the presence of silver (I) oxide and in an inert solvent for example acetonitrile at a temperature from ambient to the reflux temperature.
• the general procedure is as described in J. Org.Chem. 4£, 206 (1975) .
• aldehydes of formula (I) wherein R 1, R3, R4, R5 and W are as defined above and R represents a -CHO group may be prepared by oxidation of the corresponding compounds of formula (I) in which R 2 is replaced by hydroxymethyl using for example pyridinium chlorochromate in dichloromethane at 0°C to the reflux temperature.
• compounds of formula (I) in which R 2 represents -COR 7 and R 1 , R 3 , R 4 , R 5 , R 7 and W are as defined above, may be prepared by oxidation of the corresponding compounds of formula (I) in which R 2 is replaced by -
• compounds of formula (I) in which R 2 represents -C0 2 R 7 and R 1 , R 3 , R 4 , R 5 , R 7 and W are as defined above, may be prepared by esterification of the corresponding compound of formula (I) in which R 2 is replaced by -C0 2 H.
• the reaction is preferably performed using an alcohol of formula R OH and diethylazodicarboxylate in an inert solvent for example ether, at a temperature from 0°C to the reflux temperature of the solvent.
• the above conversion may be performed by chlorination of the corresponding compound of formula (I) in which R is replaced by -C0 2 H using for example oxalyl chloride, in an inert solvent for example dichloromethane or 1,2-dichloroethane, optionally in the presence of a catalyst such as N,N-dimethylformamide at a temperature from 20°C to the reflux temperature of the mixture to give the corresponding acid chloride, which is subsequently reacted with an alcohol of formula R OH in an inert solvent for example tetrahydrofuran at a temperature from 0°C to the reflux temperature of the solvent.
• compounds of formula (I) in which R 1 , R , R 4 , R and W are as defined above and R 2 represents -CH 2 N0 2 may be prepared by reaction of the corresponding compound in which R 2 is bromomethyl or iodomethyl, with an alkali metal nitrite preferably sodium nitrite, or silver nitrite in a solvent such as N,N- dimethylformamide or dimethylsulphoxide, and at a temperature from -20 to 50 C.
• compounds in which m and/or n are one or two are generally prepared by the oxidation of the sulphur atom of the corresponding compounds in which m and/or n are zero or one. The oxidation of the sulphur atom is generally carried out using for example 3- chloroperbenzoic acid in an inert solvent such as dichloromethane at a temperature from -40°C to room temperature.
• the reaction may be performed in an inert solvent for example ether or tetrahydrofuran at a temperature from 20 to 60°C.
• Acid chlorides of formula (II) may be prepared by the reaction of an acid of formula (IV) above with a chlorinating agent, for example oxalyl chloride or a mixture of triphenylphosphine and carbon tetrachloride.
• a chlorinating agent for example oxalyl chloride or a mixture of triphenylphosphine and carbon tetrachloride.
• the reaction with oxalyl chloride may be performed in an inert solvent for example dichloromethane optionally in the presence of a catalyst, for example N,N-dimethylformamide, at a temperature from 0 to 50°C.
• the reaction with triphenylphosphine and carbon tetrachloride may be performed in an inert solvent, for example toluene or excess carbon tetrachloride, and at a temperature from 20 to 120°C.
• Carboxylic acids of formula (IV) may be prepared by the hydrolysis of an ester of formula (VI) :
• R 1 , R 2 , R 4 and R 5 are as defined above and R 8a represents an alkyl group, preferably methyl or ethyl.
• the reaction is performed in the presence of a base for example sodium or potassium hydroxide and in a solvent, e.g. aqueous alcohol at a temperature from 0°C to the reflux temperature of the solvent.
• Carboxylic acids of formula (IV) may also be prepared by the reaction of a benzyl ester of formula (VII) :
• Carboxylic acids of formula (IV) may also be prepared from benzyl esters of formula (VII) by catalytic hydrogenation.
• the reaction may be performed at normal or elevated pressure in an inert solvent, for example ethanol, preferably at room temperature and in the presence of a suitable catalyst, for example 5% palladium or activated carbon.
• Esters of formula (VI) or (VII) may be prepared by the reaction of a compound of formula (VIII) :
• Esters of formula (VI) or (VII) may also be prepared by the reaction of a compound of formula (IX) :
• the reaction is performed utilising similar conditions to those used for the preparation of compounds of formula (VI) or (VII) from compounds of formula (VIII) above and preferably with removal of the alcohol R 12OH formed in the reaction.
• Intermediate alcohols of formula (I) wherein
• R 2 is replaced by a hydroxymethyl group
• R 2 is replaced by a hydroxymethyl group
• R 2 is replaced by a -CH 2 OCOR 13 group in which R 13 represents lower alkyl preferably methyl.
• the reaction is generally performed using a base for example potassium carbonate in an aqueous alcohol solution at 0 to 50°C.
• compositions suitable for herbicidal use comprising one or more of the 1,3-oxazin-4-one derivative of formula (I) or an agriculturally acceptable salt thereof, in association with, and preferably homogeneously dispersed in, one or more compatible agriculturally- acceptable diluents or carriers and/or surface active agents [i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula (I)].
• compatible agriculturally- acceptable diluents or carriers and/or surface active agents i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula (I)].
• compositions in which the compounds of formula (I) are dissolved in other components.
• the term "herbicidal compositions” is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use.
• the compositions contain from 0.05 to 90% by weight of one or more compounds of formula (I) .
• the herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent.
• Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g.
• nonyl- or octyl-phenols or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and di ⁇ ctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.
• the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g. from 0.05% to 10% by weight, of surface-active agent but, if desired, herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to 15% by weight in liquid emulsifiable suspension concentrates and up to 25% by weight in liquid water soluble concentrates.
• suitable solid diluents or carriers are aluminium silicate, microfine silicon dioxide, talc, chalk, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite.
• the solid compositions are preferably prepared by grinding the compounds of formula (I) with solid diluents or by impregnating the solid diluents or carriers with solutions of the compounds of formula (I) in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders.
• Granular formulations may be prepared by absorbing the compounds of formula (I) (dissolved in suitable solvents, which may, if desired, be volatile) onto the solid diluents or carriers in granular form and, if desired, evaporating the solvents, or by granulating compositions in powder form obtained as described above.
• Solid herbicidal compositions may contain wetting or dispersing agents (for example of the types described above) , which may also, when solid, serve as diluents or carriers.
• Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may incorporate a surface-active agent.
• Suitable liquid diluents for incorporation in the liquid compositions include water, glycols, glycol ethers, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, N-alkyl pyrrolidones, toluene, xylene, mineral, animal and vegetable oils, esterified vegetable oils and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents) .
• Surface-active agents which may be present in the liquid compositions, may be ionic or non-ionic (for example of the types described above) and may, when liquid, also serve as diluents or carriers.
• Powders, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
• suitable diluents for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
• liquid compositions of the compound of formula (I) may be used in the form of self-emulsifying concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of such concentrates to water producing compositions ready for use.
• Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
• Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, spreading agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents. Unless otherwise specified, the following percentages are by weight. Preferred herbicidal T 9 /01733
• compositions according to the present invention are: aqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of formula (I) , from 2 to 10% of surface-active agent, from 0.1 to 5% of thickener and from 15 to 87.9% of water; wettable powders which comprise from 10 to 90% of one or more compounds of formula (I), from 2 to 10% of surface-active agent and from 8 to 88% of solid diluent or carrier,- water dispersible granules which comprise from 1 to 75%, e.g. 50 to 75% of one or more compounds of formula (I) , from 2 to 10% of surface-active agent and from 1 to 20%, e.g.
• liquid emulsifiable suspension concentrates which comprise from 10 to 70% of one or more compounds of formula (I) from 5 to 15% of surface-active agent, from 0.1 to 5% of thickener and from 10 to 84.9% of organic solvent; granules which comprise from 1 to 90%, e.g. 2 to 10% of one or more compounds of formula (I) from 0.5 to 7%, e.g. 0.5 to 2%, of surface- active agent and from 3 to 98.5%, e.g.
• Herbicidal compositions according to the present invention may also comprise the compounds of formula (I) in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
• nicosulfuron e.g. synthetic pyrethroids, e.g. permethrin and cypermethrin
• fungicides e.g. carbamates, e.g. methyl N- (1-butyl-carbamoyl- benzimidazol-2- yl)carbamate, and triazoles e.g. l-(4-chloro- phenoxy) -3,3- dimethyl-1- (1,2,4-triazol-l-yl) - butan-2-one.
• Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions of the present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilised in the form of conventional derivatives, for example alkali metal and amine salts and esters.
• an article of manufacture comprising at least one of the 1,3- oxazin-4-one derivative of formula (I) or, as is preferred, a herbicidal composition as hereinbefore described, and preferably a herbicidal concentrate which must be diluted before use, comprising at least one of the 1,3- oxazin-4-one derivative of formula (I) within a container for the aforesaid derivative or derivatives of formula (I) , or a said herbicidal composition, and instructions physically associated with the aforesaid container setting out the manner in which the aforesaid derivative or derivatives of formula (I) or herbicidal composition contained therein is to be used to control the growth of weeds.
• the containers will normally be of the types conventionally used for the storage of chemical substances which are solid at normal ambient temperatures and herbicidal compositions particularly in the form of concentrates, for example cans and drums of metal, which may be internally lacquered, and plastics materials, bottles or glass and plastics materials and, when the contents of the container is a solid, for example granular, herbicidal compositions, boxes, for example of cardboard, plastics materials and metal, or sacks.
• the containers will normally be of sufficient capacity to contain amounts of the N- substituted pyrazole derivative or herbicidal compositions sufficient to treat at least one acre of ground to control the growth of weeds therein but will not exceed a size which is convenient for conventional methods of handling.
• the instructions will be physically associated with the container, for example by being printed directly thereon or on a label or tag affixed thereto.
• the directions will normally indicate that the contents of the container, after dilution if necessary, are to be applied to control the growth of weeds at rates of application between 0.5 g and 5000 g of active material per hectare in the manner and for the purposes hereinbefore described.
• An emulsifiable concentrate is formed from: Active ingredient (Compound 1) 20% w/v N-Methylpyrrolidone (NMP) 25% w/v
• CaDDBS Calcium dodecylbenzenesulphonate
• Nonylphenol ethylene oxide propylene oxide condensate (Synperonic NPE 1800)
• Aromatic solvent by stirring NMP, active ingredient (Compound 1) , CaDDBS, NPEOPO and 90% Aromatic solvent until a clear solution is formed, and adjusting to volume with Aromatic solvent.
• a wettable powder is formed from: Active ingredient (Compound 1) 50% w/w Sodium dodecylbenzenesulphonate (Arylan SX85) 3% w/w
• a suspension concentrate is formed from: Active ingredient (Compound 1) 50% w/v Antifreeze (Propylene glycol) 5% w/v Ethoxylated tristyrylphenol phosphate(Soprophor FL) 0.5% w/v
• Antifoam (Rhodorsil AF426R) 0.003% w/v Water to 100 volumes by stirring the above ingredients together and milling in a bead mill.
• a water dispersible granule is formed from: Active ingredient (Compound 1) 50% w/w Sodium dodecylbenzenesulphonate (Arylan SX 85) 3% w/w
• Microfine silicon dioxide (Tixosil 38) 3% w/w by blending the above ingredients together, grinding the mixture in an air jet mill and granulating by addition of water in a suitable granulation plant (e.g. Fluid bed drier) and drying.
• a suitable granulation plant e.g. Fluid bed drier
• the active ingredient may be ground either on its own or admixed with some or all of the other ingredients.
• compositions may be prepared by replacing compound 1 in each of Examples Cl to C4 above with other compounds of formula (I) .
• a method for controlling the growth of weeds i.e. undesired vegetation
• a method for controlling the growth of weeds i.e. undesired vegetation
• the 1,3-oxazin-4-one derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions) , for example as hereinafter described.
• the compounds of formula (I) show herbicidal activity against dicotyledonous (i.e. broad- leafed) and monocotyledonous (e.g. grass) weeds by pre- and/or post-emergence application.
• pre-emergence application application to the soil in which the weed seeds or seedlings are present before emergence of the weeds above the surface of the soil.
• post-emergence application application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
• the compounds of formula (I) may be used to control the growth
• broad-leafed weeds for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album. Galium aparine. Ipomoea spp. e.g. Ipomoea purpurea, Sesbania exaltata, Sinapis arvensis, Solanum niqrum and Xanthium strumarium, and grass weeds, for example Alopecurus myosuroides, Avena fatua, Diqitaria sanquinalis, Echinochloa crus-galli, Eleusine indica and Setaria spp, e.g.
• the compound of formula (I) are particularly preferred as pre-emergence herbicides and for their control of grass species, in particular Echinochloa crus-qalli.
• the amounts of compounds of formula (I) applied vary with the nature of the weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature of the crops.
• the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop.
• application rates between 1 g and 1000 g of active material per hectare give good results. However, it is to be understood that higher or lower application rates may be used, depending upon the particular problem of weed control encountered.
• the compounds of formula (I) may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post- emergence application in a directional or non- directional fashion, e.g. by directional or non- directional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g.
• weeds at a locus of weed infestation which is an area used, or to be used, for growing of crops, e.g. the crops hereinbefore mentioned, application rates between 10 g and 500 g, and preferably between 25 g and 250 g, of active material per hectare are particularly suitable.
• the compounds of the invention are especially useful for controlling small seeded grass species, such as Alopecurus myosuroides, Poa annua, and Apera spica-venti.
• the compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, by pre- or post-emergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations.
• they may be applied in a directional or non- directional fashion (e.g. by directional or non- directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting of the trees or plantations at application rates between 50 g and 5000 g, and preferably between 50 g and 2000 g, most preferably between 100 g and 1000 g of active material per hectare.
• the compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable.
• non-crop-growing areas include airfields, industrial sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and fallow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks.
• the active compounds When used for such purposes in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought.
• the compounds of formula (I) When used to control the growth of weeds by pre-emergence application, the compounds of formula (I) may be incorporated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of formula I are used to control the growth of weeds by post-emergence application, i.e. by application to the aerial or exposed portions of emerged weeds, the compounds of formula I will also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germinating weeds in the soil.
• the compounds of the invention have been used in herbicidal applications according to the following procedures.
• the seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soil .
• the quantities of seed per pot were as follows:- Weed species Approx number of seeds/pot
• the compounds of the invention were applied to the soil surface, containing the seeds, as described in (a) .
• a single pot of each crop and each weed was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
• the compounds used to treat the plants were applied to the plants as described in (a) .
• a single pot of each crop and weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
• Paddy field soil was filled in 170 cm 2 plastic pots, a suitable amount of water and chemical fertilisers were added thereto and kneaded to convert it to a state of a paddy.
• Paddy rice plants variety; Koshihikari
• solutions were prepared in 100% acetone using compounds described in the Examples so that they contained active ingredients in an amount equivalent to 75, 300 and 1200 g/ha.
• the solutions were applied by dropping with a pipette. After 21 days from the application with the chemicals, herbicidal effects on each weed and phytotoxicity on paddy rice plants were visually assessed, and the results expressed as the percentage reduction in growth or damage to the crop or weeds in comparison with the plants in the control pots.
• Test Method A When applied pre- or post-emergence in Test Method A at lOOOg/ha or less compounds 1 to 8, 10, 11, 19, 20, 40-42, 48-50, 53, 54, 56 and

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• 1996
  • 1996-04-23 GB GBGB9608399.3A patent/GB9608399D0/en active Pending
• 1997
  • 1997-04-08 BR BR9708725A patent/BR9708725A/pt unknown
  • 1997-04-08 EP EP97916451A patent/EP0900216A1/en not_active Withdrawn
  • 1997-04-08 CN CN97194036A patent/CN1216542A/zh active Pending
  • 1997-04-08 HU HU9901754A patent/HUP9901754A3/hu unknown
  • 1997-04-08 JP JP53766497A patent/JP2001515465A/ja active Pending
  • 1997-04-08 AU AU25096/97A patent/AU2509697A/en not_active Abandoned
  • 1997-04-08 WO PCT/EP1997/001733 patent/WO1997040041A1/en not_active Application Discontinuation
  • 1997-04-08 EA EA199800942A patent/EA199800942A1/ru unknown
  • 1997-04-08 CA CA002250102A patent/CA2250102A1/en not_active Abandoned
  • 1997-04-08 KR KR1019980708421A patent/KR20000010565A/ko not_active Application Discontinuation
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  • 1997-04-21 AR ARP970101599A patent/AR006721A1/es unknown
  • 1997-04-21 ID IDP971325A patent/ID16813A/id unknown
  • 1997-04-22 CO CO97021281A patent/CO4761027A1/es unknown

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