Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/63—One oxygen atom
  • C07D213/64—One oxygen atom attached in position 2 or 6
• • 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
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • 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
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • 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
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • 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
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
• • 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
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
• • 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
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero 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
  • 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
  • A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
• • 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
  • A01N43/82—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 five-membered rings with three ring hetero 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/60—Three or more oxygen or sulfur atoms
  • C07D239/62—Barbituric acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
  • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
  • C07D241/18—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
  • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D257/04—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
  • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
  • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
  • C07D277/68—Benzothiazoles 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 in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
  • C07D285/13—Oxygen atoms

Definitions

• This invention relates to certain novel heteroarylyloxyacetic acid N- alkenylamides, the preparation of such compounds, herbicidal compositions 0 containing such compounds, and a method of combating undesired plant growth using such compounds.
• European patent application EP 0 005 501 discloses benzofused oxazol- 5 2-yl- and thiazol-2-yl-oxyacetamides, in which the amido nitrogen atom is substituted by hydrogen atoms and/or by optionally substituted alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl or aryl groups.
• alkenyl-substituted compounds in which the double bond is located in the 1- position with respect to the nitrogen atom, nor to cycloalkenyl compounds.
• EP 0 165 537 discloses a process for the preparation of benzofused oxazol-2-yl- and thiazol-2-yl-oxyacetamides, in which the amido nitrogen atom is substituted by one or two allyl groups, one cyclohex-
• the compounds of the present invention combine high herbicidal activity with the necessary selectivity and enhanced soil degradation.
• Het represents an optionally substituted, optionally benzofused nitrogen containing 5- or 6-membered heteroaromatic group
• R 1 represents an alkyl, alkoxyalkyl or cycloalkyl group
• R 2 represents a hydrogen atom
• R 3 represents an alkyl group, or R 2 and R 3 taken together form a single bond or a methylene group
• R 4 , R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom or a C.,-C 4 alkyl group with the provisos that a) at least two of R 4 , R 5 , R 6 , R 7 and R 8 must represent an alkyl group; and b) 2-(5-thfluoromethyl-1 ,3,4Jhiadiazol-2-yloxy)-N-methyl-N-(3,5,5- trimethylcyclohex-1-enyl)-acetamide is excluded; show excellent herbicidal activity at low dosages and possess higher selectivity in crops than those disclosed in the aforementioned patents. Accordingly, the present invention provides novel compounds of formula
• the compounds of formula I possess an excellent selective herbicidal activity in certain crops, such as rice, maize, cereals, soybeans, sugarbeets, canola, sunflowers or potatoes, as well as enhanced soil degradation.
• novel compounds of formula I show an excellent herbicidal activity against a broad range of weeds and exhibit a high degree of selectivity.
• benzofused nitrogen containing 5- or 6-membered heteroaromatic group includes azoles, such as pyrrole, pyrazole, and imidazole, oxazoles, thiazoles, thiadiazoles, azines such as pyridine, pyrimidine, pyrazine, pyridazine and triazines.
• benzofused azoles are preferred.
• Het preferably represents a thiadiazolyl, benzoxazolyl or benzthiazolyl group which may be substituted by one or more halogen atoms or alkyl, haloalkyl or phenyl groups.
• substituent groups which are optionally present may be any of those customarily employed in the modification and/or development of pesticidal compounds and are especially substituents that maintain or enhance the herbicidal activity associated with the compounds of the present invention, or influence persistence of action, soil or plant penetration, or any other desirable property of such herbicidal compounds.
• substituents there may be one or more of the same or different substituents present in each part of the molecules.
• optional substituents include halogen, especially fluorine, chlorine and bromine atoms, and nitro, cyano, amino, hydroxyl, C ⁇ - alkyl, C ⁇ -alkoxy, C ⁇ -haloalkyl, C ⁇ -haloalkenyl, C ⁇ -haloalkoxy, C - haloalkylthio and aryl groups such as phenyl.
• halogen especially fluorine, chlorine and bromine atoms
• nitro cyano, amino, hydroxyl, C ⁇ - alkyl, C ⁇ -alkoxy, C ⁇ -haloalkyl, C ⁇ -haloalkenyl, C ⁇ -haloalkoxy, C - haloalkylthio and aryl groups such as phenyl.
• One to five substituents may be employed, with one to two substituents being preferred, and one substituent being most preferred.
• Het in particular represents a group selected from the formulae (1) and (2)
• R 9 represents a hydrogen or halogen atom or a haloalkyl group
• X represents O or S
• Y represents independently of each other, a halogen atom or an optionally substituted alkyl group; and n is an integer from 0 to 4.
• Y preferably is a fluoro or chloro atom or a C alkyl, C, .4 fluoroalkyl, C ⁇ alkoxy or C, ⁇ fluoroalkoxy group, and particularly, a chloro atom.
• n is preferably 0, 1 or 2, and is most preferably 0 or 1.
• thiadiazole derivatives (1 ) and the benzoxazole (2) derivatives of formula I wherein X is an oxygen atom are particularly preferred.
• any of the above mentioned moieties comprises an alkyl group
• such groups may be linear or branched and may contain 1 to 6, preferably 1 to 4, carbon atoms.
• Examples of such groups are methyl, ethyl, propyl, butyl, isobutyl and tertiary-butyl groups.
• the alkyl portion of a haloalkyl, haloalkoxy, haloalkylthio, alkylthio or alkoxy group preferably has from 1 to 4 carbon atoms, and more preferably, 1 or 2 carbon atoms.
• any of the above mentioned moieties comprises a alkoxyalkyl group
• such groups may be linear or branched and may contain 2 to 6, and preferably 3 to 5, carbon atoms.
• Examples of such groups are methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxy-1 - methylethyl and methoxybutyl.
• Halogen means a fluorine, chlorine, bromine or iodine atom, and preferably is fluorine, chlorine or bromine.
• any of the above mentioned moieties comprises a haloalkyl group
• such groups may be linear or branched and may contain 1 to 6, preferably 1 to 4, carbon atoms.
• Examples of such groups are halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl and halotertiary-butyl groups.
• Haloalkyl moieties of any groups within the definitions used herein can contain one or more halogen atoms, preferably fluorine, chlorine or bromine.
• Haloalkyl preferably is a mono-, di-, tri- or perfluoroalkyl group, especially trifluoromethyl, pentafluoroethyl, 2,2,2-thfluoroethyl or 1 , 1 , 1 - trifluoroprop-2-yl groups, with trifluoromethyl being most preferred.
• R 1 preferably is a C- ⁇ alkyl, a C 2 . 6 alkoxyalkyl or C 3 . 7 cycloalkyl group, with ethyl, propyl, isopropyl, cyclopropyl and 2-methoxyethyl groups being most preferred.
• R 2 and R 3 together form a single bond, the resulting ring system is a substituted cyclopent-1-enyl group.
• the resulting ring system is a substituted cyclohex-1-enyl group, e.g., a 3,3,5-trimethylcyclohex-1-enyl or a 3,5,5-trimethylcyclohex-1-enyl group.
• R 2 represents a hydrogen atom and R 3 represents an alkyl group, in particular, a methyl group
• the resulting branched alkenyl group is of the formula
• R 4 through R 8 independently represent preferably a hydrogen or a C, ⁇ alkyl group, in particular, a hydrogen atom or a methyl group, provided that at least at least two of these substituents are C M alkyl groups. Most preferred are those compounds of formula I, in which R 4 represents a hydrogen atom; R 5 and R 7 are methyl groups, and one of R 6 and R 8 is a methyl group and the other a hydrogen atom.
• R 1 represents an alkyl or alkoxyalkyl group, in particular, a C 2 . 3 alkyl or 2- methoxyethyl group,
• Het represents a group selected from the formulae (1) and (2)
• Y represents a halogen atom, in particular, a chlorine atom, or a methyl group, n is 0 or 1 , and
• R 9 represents a C1-4 fluoroalkyl group, in particular, a trifluoromethyl group.
• R 1 represents a C
• Het represents a group selected from the formulae (1) and (2)
• Y represents a halogen atom, in particular, a chlorine atom, or a methyl group, n is 0 or 1 ;
• R 9 represents a C ⁇ fluoroalkyl group, in particular, a trifluoromethyl group; and the dashed line indicates the presence of a double bond in one or the other position, provided that R 1 represents a C 2.5 alkyl or C 3 . 5 alkoxyalkyl group, in the event that Het represents a group of formula (1 ).
• Particularly preferred are the compounds of formulae IB1 to IB4
• R 1 represents an ethyl or isopropyl group.
• R 1 represents a C,. 5 alkyl group, or a methoxy-C, ⁇ alkyl group, in particular, a methyl, ethyl, isopropyl, methoxymethyl, 2-methoxyethyl or 2- methoxy-1-methylethyl group, and n is 0 or 1.
• the compounds of formula I are obtained and used as an isomeric mixture of compounds of formula I which differ only in the location of the double bond.
• the present invention preferably relates to a mixture of isomeric compounds of formula I which differ only in the location of the double bond, in particular a mixture of the compounds of formula IB.
• the invention is exemplified by the following representative compounds:
• the compounds of formula I are oils, gums, or, predominantly, crystalline solid materials. They are superior by virtue of their valuable herbicidal properties. For example, they can be used in agriculture or related fields for the control of undesired plants.
• the compounds of general formula I possess a high herbicidal activity within a wide concentration range and at low dosages, and may be used in agriculture without any difficulties, in particular, for the selective control of undesired plants such as Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Galium aparine, Stellaria media, Veronica persica, Digitaria sanguinalis, Lolium perenne, Lamium purpureum, Viola arvensis, Abutilon theophrasti, Ipomoea purpurea and Amaranthus retroflexus by pre- and post-emergence application, and particularly in certain crops, such as maize and rice.
• the compounds of formula I can be prepared by conventional methods.
• a particularly suitable process for the preparation of the compounds of general formula I comprises the reaction of a compound of formula II:
• the reactions may be carried out in the absence or presence of a solvent which promotes the reaction or at least does not interfere with it.
• a solvent which promotes the reaction or at least does not interfere with it.
• Preferred are polar, aprotic or protic solvents, suitable solvents being N,N- dimethylformamide, dimethylsulfoxide, sulfolane, acetone, acetonitrile, methyl ethyl ketone, or an ether, such as tetrahydrofuran or dioxane, or alcohols, or water, or mixtures thereof.
• the reaction is carried out at a temperature between ambient temperature and the reflux temperature of the reaction mixture, preferably at elevated temperature, especially at reflux temperature. Substantially equimolar amounts of reactants are typically used.
• the reaction may be carried out in the presence of a basic compound such as an alkali hydroxide, bicarbonate or carbonate, e.g. sodium or potassium hydroxide, bicarbonate or carbonate, an alkali alkoxide, e.g. sodium ethoxide, or an organic base such as triethylamine.
• a phase transfer catalyst preferably a tetraalkyl-ammonium halide, and most preferably, tetraethyl-ammonium bromide.
• Suitable leaving groups L 1 or L 2 are, for instance, alkyl- and arylsulfonyl, in particular, methylsulfonyl, alkyl- and arylsulfonyloxy or perfluoroalkylsulfonyloxy groups, and halogen atoms, particularly fluorine, chlorine and bromine.
• R ⁇ R , R 5 , R 6 , R 7 and R 8 are as hereinbefore defined
• R 2 represents a hydrogen atom
• R 3 represents an alkyl group
• L 1 represents a hydroxy group or a leaving group selected from alkyl- and arylsulfonyl, alkyl- and arylsulfonyloxy or perfluoroalkylsulfonyloxy groups and halogen atoms.
• R 2 represents a hydrogen atom
• R 3 represents an alkyl group
• L 1 represents a hydroxy group or a leaving group selected from alkyl- and arylsulfonyl, alkyl- and arylsulfonyloxy or perfluoroalkylsulfonyloxy groups and halogen atoms.
• Most preferred are the compounds of formula IIA wherein
• R 1 represents an alkyl or alkoxyalkyl group
• L 1 represents a hydroxy group or a halogen atom.
• R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for the compounds of formula I, by reaction with 2-chloroacetyl chloride and subsequent reaction with alkali acetate and deacylation with aqueous -alcoholic alkali hydroxide solution.
• the imines of formula IV can be prepared by condensation of a primary amine and the corresponding ketone.
• reaction product contains a mixture of isomeric compounds of formulae I and II which differ only in the location of the double bond.
• Ketones which are readily commercially available, such as 3,5,5- trimethylcyclohexanone, 2,2,4-trimethylcyclopentanone, 2,4,4- trimethylcyclopentanone and di-(2-methylpropyl)-ketone or the like, are preferred.
• the condensation reaction between the ketone and the amine can be carried out by known procedures, as by removing the product water by azeotropic distillation.
• the elimination of the water may be accelerated by addition of acid or acid catalysts, such as hydrochloric acid, p-toluenesulfonic acid or ammonium sulfate, or basic compounds such as sodium or potassium hydroxide, and alkali carbonates, or by dehydrating agents such as TiCI 4 or molsieves.
• the present invention also concerns the methods of using the compounds of formula I as herbicides.
• this invention provides a method of combating undesired plant growth at a locus by treating the locus with herbicidally effective amount of a compound of formula I, typically incorporated into a herbicidal composition.
• the locus is most suitably the plants in a crop area, with typical crops being cereals, maize, soybeans, sunflower or cotton.
• application may also be to the soil for those compounds having pre-emergence herbicidal action, or to the water, e.g., for crops such as paddy rice.
• the invention also provides a method of combating undesired plant growth at a locus, comprising application of such a compound or composition.
• Particularly interesting activity has been found against grasses and broad leaf weeds, both pre- and post-emergence. Selectivity in important crop species such as wheat, barley, maize, rice and soybeans has also been found.
• the effective amount of the active ingredient, a compound of the invention may be, for example, from 0.05 to 10 kg/ha, preferably 0.01 to 4 kg/ha, in particular, 0.05 -3 kg/ha, and most preferably, 0J to 1 kg/ha.
• the locus may be an agricultural or horticultural locus, comprising, for example, a plant or soil. In a preferred method the locus contains undesired plant growth and treatment is by foliar spray application.
• the compounds of general formula I exhibit herbicidal activity.
• the invention further provides a herbicidal composition which comprises an active ingredient, which is at least one compound of formula I as defined above, and one or more carriers.
• a method of making such a composition is also provided which comprises bringing a compound of formula I as defined above into association with the carrier(s).
• Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers in order to broaden the scope of herbicidal activity of the composition.
• a composition according to the invention preferably contains from 0.5% to
• An agronomically acceptable carrier in a composition according to the invention is any material with which the active ingredient can be formulated to facilitate application to the locus to be treated, which may, for example, be a plant, seed or soil, or to facilitate storage, transport or handling.
• the carrier may be solid or liquid, and includes material which is normally a gas but which has been compressed to form a liquid.
• compositions may be manufactured into, e.g. emulsions, emulsifiable concentrates, solutions, oil-in-water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, microcapsules, gels, aerosols and other formulation types by well-established procedures. These procedures include intensive mixing and/or milling of the active ingredients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally, solid and/or liquid auxiliaries and/or adjuvants.
• the form of the application such as spraying, atomizing, dispersing or pouring, can be chosen in accordance with the desired objectives and the given circumstances of application.
• the solvents utilized may be aromatic hydrocarbons, e.g. Solvesso® 200, substituted naphthalenes, phthalic acid esters, e.g., dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g., cyclohexane or paraffins, alcohols and glycols, as well as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N- methyl-2-pyrrolidone, ⁇ -butyrolactone, higher alkyl pyrrolidones, e.g.
• n- octylpyrrolidone or cyclohexylpyrrolidone epoxidized plant oil esters, e.g. methylated coconut or soybean oil ester and water. Mixtures of different solvents are often suitable as carriers.
• Solid carriers which may be used for dusts, wettable powders, water dispersible granules, or granules, can be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties may be improved by addition of highly dispersed silica gel or polymers.
• Carriers for granules can be porous material, e.g., pumice, kaolin, sepiolite, bentonite or non-sorptive carriers such as calcite or sand. Additionally, a multitude of pre-granulated inorganic or organic materials can be used, such as dolomite or crushed plant residues.
• compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application.
• a carrier which is a surfactant facilitates this process of dilution.
• at least one carrier in a composition according to the invention is a surfactant.
• the composition may contain two or more carriers, at least one of which is a surfactant.
• the surfactants utilized can be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties depending on the nature of the particular compound of formula I to be formulated.
• surfactant is also intended to encompass mixtures of two or more surfactants.
• Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain, in addition to a solid inert carrier, 3 to10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer(s) and/or other additives such as penetrants or retention enhancers (stickers). Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with a further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient.
• Water dispersible granules and granules are usually prepared so as to have a size between 0J5 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents. The so-called "dry flowables" consist of relatively small granules having a relatively high concentration of active ingredient.
• Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives, such as stabilizers, penetrants and corrosion inhibitors.
• Suspension concentrates are usually milled so as to obtain a stable, non-sedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0J to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and retention enhancers (stickers), and water or an organic liquid in which the active ingredient is substantially insoluble. Certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystallization, or as antifreeze agents, in the case of water. Aqueous dispersions and emulsions, for example, compositions obtained by diluting the formulated product according to the invention with water, also lie within the scope of the invention.
• the biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution.
• An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active.
• the adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient.
• compositions are preferably in a concentrated form whereas the end user generally utilizes diluted compositions.
• the compositions may be diluted to a concentration down to 0.001% of active ingredient.
• the application rates usually are in the range from 0.01 to 10 kg a.i./ha. Examples of formulations according to the invention are:
• Active Ingredient Compound of Example 2 30 % (w/v) Emulsifier(s) Atlox ® 4856 B / Atlox ® 4858 B ) 5 % (w/v) (mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics / mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics)
• Solvent Shellsol ® A 2 to 1000 ml (mixture of C 9 - C 10 aromatic hydrocarbons)
• Active Ingredient Compound of Example 3 50 % (w/v) Dispersing agent Soprophor ® FL 3) 3 % (w/v) (polyoxyethylene polyaryl phenyl ether phosphate amine salt) Antifoaming agent Rhodorsil ® 422 3) 0.2 % (w/v)
• Active Ingredient Compound of Example 17 60 % (w/w) Wetting agent Atlox ® 4995 1) 2 % (w/w) (polyoxyethylene alkyl ether)
• SUBSTITUTE SHEET (RUL ⁇ 26) Dispersing agent Witcosperse ® D-60 6) 3 % (w/w) (mixture of sodium salts of condensed naphthalene sulfonic acid and alkylarylpolyoxy acetates
• Carrier / Filler Kaolin 35 % (w/w)
• Active Ingredient Compound of Example 19 50 % (w/w) Dispersing / Witcosperse ® D-450 6) 8 % (w/w) Binding agent (mixture of sodium salts of condensed naphthalene sulfonic acid and alkyl sulfonates)
• Disintegrant Ag rimer ® ATF 7 2 % (w/w)
• Carrier / Filler Kaolin 35 % (w/w)
• compositions of this invention can also comprise other compounds having biological activity, e.g., compounds having similar or complementary pesticidal activity or compounds having plant growth regulating, fungicidal or insecticidal activity. These mixtures typically have a broader spectrum of activity than the compound of general formula I alone. Furthermore, the other components can be selected so as to exert a synergistic effect on the pesticidal activity of the compound of general formula I.
• Combinations of at least two herbicides can be included in a single formulation or later added in a suitable form during the preparation of the tank mix.
• Exemplary herbicides which can be used in such mixtures include the following: amethydione, bilanafos, metabenzthiazuron, metamitron, metribuzin, 2,4-D, 2,4-DB, 2,4-DP, alachlor, alloxydim, asulam, atrazine, bensulfuron, bentazon, bifenox, bromoxynil, butachlor, carfentratone, chloridazon, chlorimuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, clopyralid, cyanazine, cycloate, cyclosulfamuron, cycloxydim, dichlobenil, diclofop, dimethenamid, EPTC, ethiozin, fenoxaprop, flamprop, fluaz
• a typical formulation containing a compound according to the invention may consist of 100-500 g of active ingredient (compound of formula I), 30 g of dispersing agent, 2 g of antifoaming agent, 2 g of structure agent, 50 g of anti- freezing agent, 0.5 g of a biocidal agent and water ad 1000 ml. Prior to use it is diluted with water to give the desired concentration of active ingredient.
• a total quantity of 140 g (ca. 3J mol) of gaseous ethylamine is bubbled into a stirred mixture of 3,3,5-trimethylcyclohexanone (42 g, 0.3 mol), p-toluene sulfonic acid (0.5 g) and toluene (150 ml) at room temperature over a period of ca. 2 days.
• the progress of the reaction is monitored periodically by the removal of small samples of the reaction mixture for mass spectrometric analysis.
• anhydrous sodium sulfate ca.
• a solution of 2-chloroacetyl chloride (22.3 g, 0J9 mol) in toluene (100 ml) is added dropwise over 30 minutes to a stirred mixture of 1A (40.0 g, ca. 0.18 mol) in toluene (400 ml) at 0 °C. During the addition, a light-coloured precipitate is formed. The mixture is allowed to warm gradually to room temperature and stirred for a further 16 hours. The mixture is then cooled again to ca. 0 °C and a solution of triethylamine (21.0 g, 0.205 mol) in toluene (100 ml) is added dropwise.
• the compounds of the invention are tested pre- and post-emergence using the species in the table below.
• HORVW Hordeum vulgare winter barley
• ECHCG Echinochloa crus-galli barnyardgrass
• the pre-emergence herbicidal activity of the compounds of the present invention is exemplified by the following test in which the seeds of a variety of monocotyledonous and dicotyledonous plants are separately mixed with potting soil and planted on top of approximately one inch of soil in separate pots. After planting, the pots are sprayed with the selected aqueous acetone solution containing test compound in sufficient quantity to provide the equivalent of about 0.8 to 0J kg per hectare of test compound per pot. The treated pots are then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse procedures. The results are set out in Tables 4, 6 and 8 below.
• the post-emergence herbicidal activity of the compounds of the present invention is demonstrated by the following test, wherein a variety of monocotyledonous and dicotyledonous plants are treated with formulations prepared from solutions of the test compounds in acetone containing 0.4 % by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-155. These acetone solutions are diluted with water and the resulting formulations applied at dosage levels equivalent to about 0.4 to 0.2 kg per hectare of test compound per pot. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices. The results of the test are set out in Tables 5, 7 and 9 below.
• the compounds of the invention i.e., the compounds of E.XAMPLE 3 and EXAMPLE 2 when compared to a mixture of 2-(5-thfiuoromethyl-1 ,3,4- thiadiazol-2-yloxy)-N-(3,5,5-trimethylcyclohexen-1-yl)-N-methylacetamide and 2-(5-trifluoromethyl-1 ,3,4-thiadiazol-2-yloxy)-N-(3,3,5-trimethylcyclohexen-1-yl)- N-methylacetamide (COMPOUND B), the state of the art (US Patent No. 4,585,471) display clearly better crop tolerance in wheat, maize, soybeans and rice than COMPOUND B, as shown in Table 4 below.
• Example 2 200 20 0 0 15 90 100 100 100
• Example 3 200 0 0 0 0 0 75 100 97 100
• Example 3 200 0 0 70 80 60
• Example 8 the compounds of the invention of Example 8 are tested pre- and post-emergence and compared with 2-(5-trifluoromethyl-1 ,3,4-thiadiazol-2- yloxy)-N-(2,4-dimethylhept-2-en-3-yl)-N-(2-methoxyethyl)acetamide COMPOUND C, the state of the art (International Patent Application WO 97/08160). Each pot is examined three weeks after treatment and phytotoxicity is assessed according to the rating system set forth below.
• Example 8 displays clearly better crop tolerance in wheat, maize, soybeans and rice than COMPOUND C as shown in the following Tables 6 and 7:
• the compound of EXAMPLE 8 showed clearly better selectivity in both wheat and rice than COMPOUND C, of PCT WO 97/08160.
• the compound of the invention was sufficiently selective in wheat at 400 g/ha and showed good selectivity in rice even at the highest dose of 800 g/ha, while Compound C was tolerated in both crops at the reduced dose of 200 g/ha only.
• the compound of the invention was considerably more active on monocotyledonous weeds (Alopecurus, Setaria, Echinochloa) and dicotyledonous weeds (Amaranthus, Galium).
• the Compound of EXAMPLE 8 was sufficiently selective in wheat and barley at the highest dose of 400 g/ha and in maize at 200 g/ha.
• COMPOUND C was clearly less selective in these crops than the compound of the invention.
• the compound of the invention was markedly more active on Alopecurus myosuroides and Apera spica-venti, both of which are important grass weeds in European cereals. Both grasses were well controlled by the compound of the invention at the wheat and barley selective dose of 400 g/ha.
• COMPOUND C did not display sufficient levels of activity on Apera at any rate and Alopecurus control was not achieved at barley or wheat selective doses.
• the compounds of the present invention of Examples 17 and 19 demonstrate good selectivity in wheat, barley, soybeans and rice. Furthermore high levels of activity on Alopecurus, Digitaria, Echinochloa, Setaria faben and S. viridis are recorded at crop selective doses.
• the compound of the invention was clearly more tolerant in barley and more active on Alopecurus, Loiium and Apera, which are key grasses in grain cereals, than the compound of the state of the art.
• the compound of the invention was sufficiently tolerant in barley up to 400 g/ha, while the highest rate tolerated by the compound of the state of the art was 200 g/ha.
• the crop selective dose of 400 g/ha the compound of the invention showed good control of Alopecurus and Apera (98 and 95 %, respectively), while the compound of the state of the art displayed clearly less control of these grasses at the doses tolerated by barley.

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• 1998
  • 1998-11-05 CN CN98811197A patent/CN1122665C/zh not_active Expired - Fee Related
  • 1998-11-05 KR KR1020007005347A patent/KR20010032160A/ko not_active Application Discontinuation
  • 1998-11-05 EP EP98956614A patent/EP1047679A1/en not_active Withdrawn
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  • 1998-11-05 JP JP2000521085A patent/JP2001523672A/ja active Pending
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  • 1998-11-05 AU AU13098/99A patent/AU1309899A/en not_active Abandoned
  • 1998-11-05 WO PCT/US1998/023587 patent/WO1999025702A1/en not_active Application Discontinuation
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