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
  • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero 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
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
  • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
• • 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
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-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
  • A01N43/72—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
  • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings

Definitions

• This invention relates to chemical compounds useful as herbicides, to processes for preparing them and to herbicidal compositions and processes utilising them.
• a number of derivatives of monic acid are known to have utility as biologically active compounds for use in human and veterinary medicine. Such compounds are described inter alia in GB 1587058.
• a herbicidal composition comprising a compound of the formula (I) or (IA) or (IB) in admixture with a herbicidally acceptable carrier or diluent, wherein Y
• R 3 is 0 or S and R is hydrogen or an agrochemically acceptable ester-forming radical; or R is a group -R wherein R is an optionally substituted aryl or heterocyclic group; or R is a group CO-NR R wherein R and R are the same or different and each represent an agrochemically acceptable amide-forming radical; stereoisomers of the compounds of formula (I), (IA)
• a process of severely damaging or killing unwanted plants which comprises applying to the plants, or to the growth medium of the plants, a herbicidally effective amount of a compound of the formula (I) or (IA) wherein Y represents (IC) or (ID) or (IE);
• R is a group CO-XR wherein X is 0 or S and R rs hydrogen or an agrochemically acceptable ester-forming radical; or
• R is a group -R wherein R is an optionally substituted heterocyclic
• R is a group -CO-NH-CI- -CO-W wherein W is hydrogen, optionally substituted phenyl, optionally substituted C- to C 20 alkyl, optionally substituted C 2 to C Community alkenyl, optionally substituted C 2 to C g alkynyl, optionally substituted heterocyclyl or C- to C 7 cycloalkyl; or
• R is a group -CO-NH-NH- or -C0-NH-NH-C0-Y wherein Y is optionally substituted C. to C 2Q alkyl, optionally substituted C 2 to C Force alkenyl, optionally substituted aryl, optionally substituted aralkyl or optionally substituted heterocyclyl; or
• R is a group CO-NR R wherein R and R are the same or different and each represent (a) hydrogen, or (b) C-_ 2Q alkyl, C 2 g alkenyl, either of which may be optionally substituted with C « 7 cycloalkyl, halogen, carboxy, C, 6 alkoxycarbonyl, carbamyl, aryl, heterocyclyl, hydroxy, C- , alkanoyloxy, amino, mono- or di-(C. ,)alkylamino; or (c) C, 7 cycloalkyl optionally substituted with C- 6 alkyl; or
• R and R together with the nitrogen atom to which they are attached represent an optionally substituted C R 7 heterocyclic ring;
• R is a group -CO-0-R wherein R is a C-_ 20 alkyl, C frustration cycloalkyl, C, 2Q alkenyl, aralkyl, cycloalkylalkyl, heterocyclyl or heterocyclylalkyl group which group is substituted with a ketonic oxo group; or R is a group
• aryl as used herein includes phenyl, and naphthyl optionally substituted with up to five substituents which may be independently selected from halogen, C-_ 6 alkyl, C. ,alkoxy, C- gthioalkyl, halo(C._ 6 )alkyl, hydroxy(C._ 6 )alkyl, halo(C,_ 6 )alkoxy, C 2 _ g alkenyl, C 2 _minister alkeneoxy, C 2 g thioalkenyl, C 2 _ g alkynyl, C 2 _ g alkyneoxy, C 2 _ g thioalkynyl, hydroxy, cyano, nitro, amino, mono- and di- C- 6 alkylamino, C. 6 alkanesulphinyl, C- g alkane sulphonyl, carboxy, C- galkoxycarbonyl, eind C. 6 alkoxycarbon
• aralkyl as used herein includes groups in which the aryl moiety is a phenyl group which may be optionally substituted as hereinbefore defined for aryl and in which the alkylene radical has from 1 to 4 carbon atoms.
• heterocyclyl as used herein includes aliphatic or aromatic single or fused rings comprising up to four hetero atoms in the ring selected from oxygen, nitrogen and sulphur and optionally substituted with aryl, with another heterocyclic ring or with one or more of those substituents mentioned above as optional substituents for aryl.
• X is preferably 0.
• Suitable ester-forming radicals, R include optionally substituted C- to C 2Q alkyl, optionally substituted C 2 to C 2Q , for example C 2 to C g alkenyl, optionally substituted C 2 to C 2Q , for example C 2 to C g alkynyl, optionally substituted C, to C 7 cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl.
• alkyl, alkenyl or alkynyl groups, such as those represented by R include
• R such as those represented by R
• R include C. ⁇ alkyl halo-C. 6 alkyl and those substituents listed above in relation to alkyl, alkenyl and alkynyl groups.
• R When R is alkyl, optionally substituted by aryl it may be regarded as an aralkyl group as defined above.
• Suitable ester-forming radicals R also include C. to C, 0 alkyl optionally substituted by hydroxy, halogen, cyano. Suitable ester-forming
• radicals R also include C 2 to C- 0 , for example C 2 to C, alkenyl, for example vinyl, prop-2-ene-l-yl, and but-l-ene-4-yl which may be unsubstituted or optionally substituted by hydroxy (except in the case of vinyl), by halogen or by cyano.
• alkenyl for example vinyl, prop-2-ene-l-yl, and but-l-ene-4-yl which may be unsubstituted or optionally substituted by hydroxy (except in the case of vinyl), by halogen or by cyano.
• a further preferred group R is a C. . « alkyl group, and preferably a
• C- Q and preferably optionally substituted C. 6 , for example C. to C, alkyl group, an optionally substituted C 2 to C g , and preferably optionally substitued C
• C for example C 2 to C, alkenyl group, an optionally substitued C ⁇ to C g , and preferably optionally substitued C
• C for example
• n' is an integer from 1 to 4 and R is hydrogen or a C ⁇ to C, alkyl group.
• A is preferably oxygen.
• substituents may be those indicated above for alkyl, alkenyl, alkynyl and aryl respectively. Unless otherwise specified, alkyl, alkenyl and alkynyl groups,
• X is 0 and R is hydrogen
• metal salts e.g. aluminium, alkali metal salts, such as sodium or potassium, alkaline earth metal salts, such as calcium or magnesium, and ammonium or substituted ammonium salts for example those with lower alkyl-amino such as triethylamine, hydroxy-lower alkylamines such as
• 2-hydroxyethylamine bis(2-hydroxyethyl)-amine, or tri-(2-hydroxyethyl)-amine, cycloalkylamines such as bicyclohexyl-amine, or with procaine, dibenzylamine, N,N-dibenzyl-ethylenediamine,
• N-ethylpiperidine N-benzyl- ⁇ -phenethyl-amine, dehydroabietylamine
• N,N'-bis-dehydroabietylethylenediamine or bases of the pyridine type (such as pyridine, collidine, or quinoline) or trimethylsulphonium.
• R is an optionally substituted heterocyclic group -R , preferred
• R is an optionally substituted heterocyclic ring of
• R may be a group of formula (IV) wherein R is itself an optionally substituted heterocyclic group, for example a group of the formula (IVa), (IVb) or (IVc) in which formulae R 16 , R 17 , and R 18 may be the same or different each is selected from hydrogen, halogen, optionally substituted (C- g)alkyl, aryl, aralkyl, heterocyclyl, (C» g)alkoxy, hydroxy, carboxy and salts thereof, (C «_g)alkoxycarbonyl, carbamoyl, mono- or di-(C 1 _g)alkylcarbamoyl, sulphamoyl, mono- and di-(C- g)alkylsulphamoyl, cyano, nitro, amino, mono-and di-(C.,_g)alkylamino, acylamino, ureido,
• R is a group of formula (IVc) and R , R and R are preferably hydrogen.
• a further suitable ester-forming radical R is a group R wherein R represents an optionally substituted C,_ 2Q alkyl, for example C, . Q alkyl,
• one sub class of the group R when it is a group -CO-OR is a group of formula (V) wherein Z is an optionally substituted C. to C. 2 alkylene group (-(CH 2 ) , ,- wherein n" is from 1 to 12) and R represents a
• Optional substituents may be those specified above for the groups alkyl, cycloalkyl, alkenyl, aryl and heterocyclyl respectively.
• a further sub-class of the group R is a group CO-OR and R is a
• R and R together with the nitrogen atom to which they are attached represent an optionally substituted C-_ 7 heterocyclic ring or
• R is hydrogen and R is a group -NR -N R wherein R is
• R 23 24 hydrogen or C- , alkyl are R and R , which may be the same or different, may independently take any of the meanings given for R and R under (a), (b), (c), (d), (e) and (f) above or (h)
• RR 5 iiss hhyyddrrooggeenn aanndd
• RR 6 iiss aa ggrroouupp -CR 25 R 26 -C0-W or - NR 27 -C0-W
• W is optionally subjssttiittuutteedd pphheennyyll or optionally ssuubbssttiittuutteedd hheetteerrooccyyccllyyll,
• R and R are those wherein R is hydrogen or a C, , alkyl group and R is a C. , alkyl group, each of which alkyl groups may independently be optionally substituted by C-_ 7 cycloalkyl, C- , alkoxy, halogen, carboxy, C. g alkoxycarbonyl, carbamyl, optionally substituted aryl, optionally substituted heterocyclyl, hydroxy, C. fi alkanoyloxy, amino, mono- or
• R and R together with the nitrogen atom to which they are attached represent an optionally substituted Cc_ 6 aliphatic heterocyclic ring.
• suitable groups wherein R and R together with the nitrogen atom to which they are attached form an optionally substituted Ce heterocyclic ring there may be mentioned morpholinyl, piperidyl, piperazinyl, or pyrollidinyl, each of which may be optionally substituted by halogen or C- , alkyl.
• R 5 is hydrogen and R 6 is a group -CR 25 R 26 -C0-W or - NR 27 -C0-W,
• R , R and R are preferably hydrogen and W is preferably optionally substituted phenyl or an optionally substituted 5 or 6-membered heterocyclic ring containing from 1 to 3 heteroato s selected from oxygen, nitrogen and sulphur, for instance thienyl or furanyl.
• Suitable substituents for W when it is a phenyl or heterocyclyl group include those mentioned previously and especially halogen, C. to C, alkyl, C « to Cg alkoxy, hydroxy, carboxy, C--Cg alkoxycarbonyl, carbamoyl, mono- or di- (C. to Cg) alkyl carbamoyl, sulphamoyl, mono- and di-(C. to Cg) sulphamoyl, cyano, for example m- or p- cyano, nitro, amino, mono- and di- (C. to Cg) alkylamino, C- to C ⁇ acylamino, ureido, C.
• CO-XR X is 0 or S and R is a C- ⁇ n alkyl group substituted by a 11 J.-J-U -. group -A-R wherein A is 0 or a group S(0) wherein x is 0, 1 or 2 and R is an optionally substituted C. to C.
• Q akyl group, an optionally substituted C 2 to C g alkenyl group, an optionally substitued C 2 to C g alkynyl group, an optionally substituted phenyl group, an optionally substituted C-_ 6 alkyl carbonyl group, optionally substituted C, 7 cycloalkyl group or an optionally substituted C, 7 heterocyclic group
• R is not a group -(CH 2 ) 2 - when R is ethyl.
• Optional substituents may be those indicated previously as suitable for alkyl, alkenyl, alkynyl, phenyl, cycloalkyl or heterocyclyl retrospectively.
• R is a C. , alkyl group substituted by a group -A-R
• A is 0 or a group S(0) wherein x is 0, 1 or 2 and R is an optionally substituted C- to Cg akyl group, an optionally substituted C 2 to
• R is not a group -(CH 2 ) 2 - when R is ethyl.
• R is the group
• n' is an integer from 1 to 4 A is 0 or a
• Such compounds having the tri-substituted double bond in the E-configuration are referred to as monic acid C, monic acid A and monic acid B respectively.
• the compounds of the present invention are derivatives of Monic acid A.
• the compounds of the present invention may exist in the E (natural) and Z (or iso) geometrical forms in respect of the tri-substituted double bond.
• the stereochemistry of the compound of formula (I) is thus preferably defined such that the moiety (VT) is that moiety having the trivial name "normonyl"
• Table 2 lists examples of compounds for use in the composition of the present invention wherein the compound is of formula (IB), being derivatives of pseudomonic acid.
• Table 3 lists examples of compound for use in the composition of the present invention wherein the compound is of formula (I) and Y is of formula (IC), being derivatives of monic acid C.
• the compounds may be regarded as derivatives of monic acid which may be prepared by the selective hydrolysis of pseudomonic acid.
• a further useful starting material is the ketone which may be obtained from pseudomonic acid by ozonolysis at -50 to -80°C as described for example in GB 1587 060.
• Derivatives of pseudomonic acid may of course be prepared directly for pseudomonic acid as starting material.
• hydroxy groups In general it is desirable to protect the hydroxy groups during reactions of the the starting material such as monic acid or derivatives thereof or the corresponding ketone.
• suitable protecting groups are silyl groups since these are readily removed under mild conditions. Such groups are introduced by conventional silylating agents, including halosilanes and silazanes.
• the hydroxyl-protecting groups may subsequently be removed by methods known in the art, including enzymatic methods.
• silyl protecting groups may generally be removed by mild acid hydrolysis followed by alkaline hydrolysis as described for example by J P Clayton, K Luk and N H Rogers in
• the compound No 1 of Table 1 is a known compound and may be prepared for example as described above. A more detailed preparation is given in
• Table 1 may also be prepared from monic acid by routine methods as described for example in GB 1,587,058. Typical processes include the reaction of monic acid with a base, for example a hydroxide, carbonate or bicarbonate of the desired cation followed by the removal of water; ion exchange with an appropriate resin; and reaction with amines.
• a base for example a hydroxide, carbonate or bicarbonate of the desired cation followed by the removal of water; ion exchange with an appropriate resin; and reaction with amines.
• R is a group -C0XR and X is 0 and R is an agrochemically acceptable ester-forming radical are also disclosed in GB 1,587,059.
• Compound No 3 of Table 1 is a known compound and may be prepared for example using the general methods described in GB 1,587,059 or as more specifically described in J Antibiot. 198841(5).
• Compound No 4 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0002 371 as more specifically
• Compound Nos 6 and 7 of Table 1 are known compounds and may be prepared for example as described in EP 0025 288 and as more specifically
• R in the compound of formula (I) is a group of formula -C0-0-R and R is a C, 2 n alkyl, C, g cycloalkyl, C. 2Q alkenyl, aralkyl, cycloalkylalkyl, heterocyclyl or heterocyclylalkyl group which group is substituted with a ketonic oxo group, may be prepared using the general methods described in
• Compound No 8 of Table 1 is a known compound and may be prepared for example using the methods disclosed in Japanese patent No 54-151132.
• Compound No 10 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0052437, and as more specifically described in Example 2 thereof.
• Compounds of formula (I) are known compounds and may be prepared for example using the methods disclosed in EP 0052437, and as more specifically described in Example 2 thereof.
• R is a group -CO-OR
• Patent No 54-12376 or EP 0052437 are examples of EP 0052437.
• Compound No 14 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0087 953, and as more specifically described in Example 21 thereof.
• Compounds of formula (I) are known compounds and may be prepared for example using the methods disclosed in EP 0087 953, and as more specifically described in Example 21 thereof.
• R is a group -C0-NH-CH 2 -C0-W as hereinbefore defined
• EP 0087 953 where it is an
• Compound No 19 may be prepared using an analogous method to that described in Example 14 of EP 0087 953 (5-methyl-2-(l-normon-2-yl)oxazole or as more specifically described in J Chem Soc, Perkin Trans. I 1989 (11) 2059-63. Similarly,
• Compound No 22 of Table 1 may be prepared as described in Example 10 of
• Compound No 15 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0123378, and as more specifically disclosed in Example 8 thereof.
• R is a group -C0-NH-NH 2 or -C0-NH-NH-C0-W as hereinbefore defined
• R is a group -C0-NH-NH 2 or -C0-NH-NH-C0-W as hereinbefore defined
• R is a group -R .
• Compound No 18 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0399 645, and as more specifically disclosed in Example 16 thereof.
• -C0NR R may be prepared using the general methods described in
• reaction for example an alkali metal salt, with a compound R -L wherein L is a leaving group such as halogen or mesolate to form an ester.
• the reaction suitably takes place in a solvent such as dimethylformamide or dimethylsulphoxide at a temperature in the range 10°C to 100°C and optionally in the presence of a co-solvent such as hexamethylenephosphonamide or N,N-dimethylpropyleneurea and optionally in the presence of a catalyst, such as an iodide catatlyst.
• a catalyst such as an iodide catatlyst.
• the salt of monic acid or pseudomonic acid may be prepared in situ, for example by treatment of the acid with the appropriate base such as the carbonate.
• compounds of formula (I), (IA) or (IB) wherein R is 5 6 the group -COXR or -CONR R may be prepared by the action of a compound
• R XH or R R NH on a monic or pseudomonic acid or a simple activated derivative thereof is preferably 3 5 6 R XH or R R NH on a monic or pseudomonic acid or a simple activated derivative thereof.
• the raction takes place in a solvent such as tetrahydrofuran, diethyl ether, dichloromethane or chloroform and at a temperature in the range from -10°C to 70°C.
• the compounds for use in the compositions of the present invention are active against a broad range of weed species including monocotyledonous and dicotyledonous species. Many compounds show good selectivity in crops, particularly wheat, barley, maize, oil seed rape, sugar beet and rice.
• the compounds for use in compositions of the present invention are preferably applied directly to unwanted plants (post-emergence application) but they may also be applied to the soil before the unwanted plants emerge (pre-emergence application).
• a process of severely damaging or killing unwanted plants which comprises applying to the plants or the the growth medium of the plants a herbicidally effective amount of a compound of the formula (I) or (IA) or
• Novel compounds of the present invention are preferably used in the form of a composition
• a composition comprising a compound of formula (I) in admixture with a carrier comprising a solid or liquid diluent.
• compositions of the present invention include both dilute compositions, which are ready for immediate use, and concentrated compositions, which require to be diluted before use, usually with water.
• the compositions Preferably contain from 0.01% to 90 by weight of the active ingredient.
• Dilute compositions ready for use preferably contain from 0.01 to 2% of active ingredient, while concentrated compositions may contain from 20 to 90% of active ingredient, although from 20 to 70% is usually preferred.
• the solid compositions may be in the form of granules, or dusting powders wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.
• a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum.
• a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite
• Liquid compositions may comprise a solution or dispersion of an active ingredient in water optionally containing a surface-active agent, or may comprise a solution or dispersion of an active ingredient in a water-immiscible organic solvent which is dispersed as droplets in water.
• Surface-active agents may be of the cationic, anionic, or non-ionic type or mixtures thereof.
• the cationic agents are, for example, quaternary ammonium compounds (e.g. cetyltrimethylammonium bromide).
• Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium,calcium, and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid.
• Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alk lphenols such as octyl- or nonyl- phenol (e.g. Agral 90) or octyl-cresol.
• Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbita ⁇ monolaurate; the condensation products of the partial ester with ethylene oxide; the lecithins; and silicone surface active agents (water soluble surface active agents having a skeleton which comprises a siloxane chain e.g. Silwet L77).
• a suitable mixture in mineral oil is Atplus 411F.
• aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent(s).
• organic solvents include, for example, ethylene di-chloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.
• compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use.
• the concentrates are usually required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
• Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active ingredient(s).
• Dilute preparations ready for use may contain varying amounts of the active ingredient(s) depending upon the intended purpose; amounts of 0.01% to 10.0% and preferably 0.1% to 2%, by weight of active ingredient(s) are normally used.
• a preferred form of concentrated composition comprises the active ingredient which has been finely divided and which has been dispersed in water in the presence of a surface-active agent and a suspending agent.
• Suitable suspending agents are hydrophilic colloids and include, for example, polyvinylpyrrolidone and sodium carboxymethy1cellulose, and the vegetable gums, for example gum acacia and gum tragacanth.
• Preferred suspending agents are those which impart thixotropic properties to, and increase the viscosity of the concentrate. Examples of preferred suspending agents include hydrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorite, saponite, and saucorite. Bentonite is especially preferred.
• Other suspending agents include cellulose derivatives and polyvinyl alcohol.
• the rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an application rate of from 0.0001 to 20 kilograms per hectare is suitable while from 0.001 to 10, for example 0.001 to 2 kilograms per hectare may be preferred.
• compositions of the invention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activity. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula (I) (IA) or (IB) as hereinbefore defined with at least one other herbicide.
• the other herbicide may be any herbicide not having the formula (I) (IA) or (IB). It will generally be a herbicide having a complementary action in the particular application.
• Examples of useful complementary herbicides include:
• B. hormone herbicides particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, clopyralid, and their derivatives (eg. salts, esters and amides);
• D Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, dinoseb and its ester, dinoseb acetate;
• dinitroaniline herbicides such as dinitramine, trifluralin, ethalflurolin, pendimethalin, oryzalin;
• arylurea herbicides such as diuron , flumeturon, metoxuron, neburon, irk " -k isoproturon , chlorotoluron , chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, methabenzthiazuron;
• phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
• H 2-phenylpyridazin-3-ones such as chloridazon and norflurazon;
• I uracil herbicides such as lenacil , bromacil and terbacil;
• J. triazine herbicides such as atrazine , simazine, aziprotryne, cyanazine, pro etryn, dimetha etryn, simetryne, and terbutryn;
• K phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
• L thiocarbamate herbicides such as cycloate, vernolate, olinate,
• M. l,2,4-triazin-5-one herbicides such as metamitron and metribuzin;
• N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
• anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor , and dimethachlor; ddiihhaalloobbeeinzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil; Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof;
• diphenylether herbicides such as lactofen, fluroglycofen or salts or ester thereof, nitrofen, bifenox, aciflurofen and salts and esters thereof, oxyfluorfen, fomesafen, chlornitrofen and chlomethoxyfen;
• S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
• U. sulfonyl urea herbicides such as chlorsulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as DPX-M6313, chlorimuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof, 2-[3-(4-methoxy-6-methyl-l,3,5- triazin-zyl)-3-methylureidosulphonyl) benzoic acid esters such as the methyl ester thereof (DPX-LS300) and pyrazosulfuron;
• V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
• arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican ;
• X amino acid herbicides such as glyphosate and glufosinate and their kk kk salts and esters , sulphosate (glyphosate trimesium) and bialaphos;
• Y organoarsenical herbicides such as monosodium methanearsonate (MSMA);
• Z herbicidal amide derivative such as napropamide, propyzamide, carbeta ide, tebutam, bromobutide, isoxaben, naproanilide and naptalam; AA triketones such as sulcotrione; BB.
• miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac and mefanacet; CC.
• useful contact herbicides include: bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat;
• This Example illustrates the preparation of cyanomethyl monate A (Compound No 9 of Table 1).
• This Example illustrates the preparation of 3-bromobenzyl monate A (Compound No 11 of Table 1).
• This Example illustrates the preparation of 3-methylbenzyl monate A (Compound No 12 of Table 1).
• This Example illustrates the preparation of 4-hydroxymethylbenzyl monate A (Compound No 13 of Table 1).
• This Example illustrates the preparation of 4-dimethylaminobenzoyl- monhydrazide A (Compound No 16 of Table 1).
• This Example illustates the preparation of l-bromo-8-octyl monate A (Compound No 17 of Table 1).
• the Example illustrates the preparation of cetyl monate A (Compound No 20 of Table 1).
• Decyl monate A (Compound No 73 of Table I)
• Pent-4-ynyl monate A (Compound No 31 of Table I) NMR ⁇ (CDCl 3 ) 5.78 (1H, s), 4.20 (2H, t), 2.21 (3H, s), 1.22 (3H, d),
• Ethyl propion-2-yl monate A (Compound No 45 of Table I), obtained as a mixture of diastereoisomers.
• Monic acid A 200mg, 0.58mM was dissolved in tetrahydrofuran (5ml) and cooled to -10°C under nitrogen. Triethylamine (59mg, 0.58mM) and isobutylchloroformate (80mg, 0.58mM) were added and stirred for 30 minutes. A solution of diethylamine (47mg, 0.58mM) in tetrahydrofuran (0.5 ml) was added an the reaction mixture stirred for 1 hour and then at room temperature for 2 hours. The reaction mixture was filtered and evaporated in vacuo.
• N-(2,4-Dichlorophenyl)-N-methylmonic amide A (Compound No 60 of Table 1) hi NMR ⁇ (CDCl 3 ) 7.50-7.15 (3H, m), 5.49 (1H, s), 3.20 (3H, s), 2.18 (3H, s), 1.22 (3H, d), 0.95 (3H, d).
• N-(2-Ethoxyethyl)monicamide A (Compound No 78 of Table 1).
• N-(Ethoxycarbonylmethyl)monicamide A (Compound No 66 of Table 1) X H NMR ⁇ (CDCl 3 ) 6.24 (1H, t), 5.73 (1H, s), 4.23 (2H, q), 4.0 ⁇ 2.19 (3H, s), 1.30 (3H, t), 1.22 (3H, d), 0.92 (3H, d).
• N,N-Dimethylmonichydrazide A (Compound No 82 of Table 1).
• N-(2,5-Dichlorophenyl)monicamide A (Compound No 59 of Table 1) hi NMR ⁇ (dg-DMSO) 9.42 (IH, s), 7.86 (IH, d), 7.46 (IH, d), 7.18 (IH, dd),
• N-Allylmonicamide A (Compound No 86 of Table 1).
• Monic acid A (80mg, 0.23mM) was dissolved in tetrahydrofuran (3ml) and cooled to -10°C under nitrogen. Triethylamine (24mg, 0.23mM) and a solution of isobutylchloroformate (32mg, 0.23mM) in tetrahydrofuran (0.7ml) were added and stirred for 20 minutes. A solution of methylthioglycolate (25mg, 0.23mM) in tetrahydrofuran (0.5 ml) was added an the reaction mixture stirred for 1 hour and then at room temperature for 3 hours. The reaction mixture was evaporated in vacuo and the resulting residue stored at room temperature for 7 days.
• Phenyl monate A (Compound No 50 of Table 1)
• Neopentyl monate A (Compound No 38 of Table 1) NMR ⁇ (CDCl 3 ) 5.78 (IH, s), 3.79 (2H, s), 2.21 (3H, s), 1.21 (3H, d),
• Trimethylsulphonium iodide (59mg, 0.29mM) was dissolved in water (5ml) and treated with Dowex 1X2 (H0 ⁇ ) resin for 10 minutes. The solution was filtered into a solution of monic acid A (lOOmg, 0.29 mM) in water (10ml). The solution was freeze-dried to give the desired product.
• Pseudomonic acid A 200mg, 0.40mM was dissolved in acetone (2ml) and stirred with l-chloro-2vinyloxyethane (85mg, 0.60mM) and sodium iodide (132mg, 88mM). Potassium carbonate (83mg, 0.60mM) was added and the mixture stirred at room temperature for 2 hours and at reflux overnight. Volatile components were removed by evaporation in vacuo. The residue was taken up in dimethylformamide (1ml) and N,N-dimethylpropyleneurea (0.5ml) and heated at 80°C for 4 hours.
• Pseudomonic acid A 200mg, 0.40mM was dissolved in tetrahydrofuran (4ml) and cooled to -10°C under nitrogen. Triethylamine (41mg, 0.40mM) and isobutylchloroformate (55mg, 0.40mM) were added and stirred for 30 minutes. A solution of diethylamine (32mg, 0.40mM) in tetrahydrofuran (2ml) was added an the reaction mixture stirred for 30 minutes and then stood at room temperature overnight. The reaction mixture was filtered and evaporated in vacuo. The residue was taken up in water (10ml) and extracted with chloroform (3x10ml).
• Monic acid A 50mg, 0.15mM was dissolved in tetrahydrofuran (2ml) and was treated with isopropylamine (8.6mg, 0.15mM). After 20 minutes at room temperature, a precipitate formed which was collected by filtration to give the desired product.
• Pseudomonic acid A triethylamine salt (Compound No 98 of Table 2)
• Monic acid C (1.62g, 0.49mM) was taken up in a mixture of dimethylformamide (1ml) and N,N-dimethylpropyleneurea (0.43ml). Potassium carbonate (0.102g, 0.74mM) was added and the reaction mixture stirred for 1 hour at 80-90°C. After cooling to room temperature, a solution of 2-chloroethylethylether (0.107g, 0.99mM) in dimethylformamide (0.5ml) was added and the mixture stirred at room temperature for 19 hours, at 90°C for 6 hours and then left to stand at room temperature overnight.
• N-Methoxymonicamide A (Compound No 106 of Table 1)
• This Example illustrates the herbicidal properties of compounds according to the invention.
• the herbicidal activity of the compounds was tested as follows: Each chemical was formulated by dissolving it in an appropriate amount, dependent on the final spray volume, of a solvent/surfactant blend which comprised 78.2 gm/litre of Tween 20 and 21.8 gm/litre of Span 80 adjusted to 1 litre using methylcyclohexanone.
• Tween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan laurate.
• Span 80 is a Trade Mark for a surface-active agent comprising sorbitan mono-laurate. If the chemical did
• the sprayed aqueous emulsion contained 4% of the initial solvent/surfactant mix and the test chemical at an appropriate concentration.
• the spray compositions so prepared were sprayed onto young pot plants (post-emergence test) at a spray volume equivalent to 1000 litres per hectare for Compound Numbers 1 to 22 and 400 litres per hectare for Compound Numbers 23 to 94. Damage to plants was assessed 13 days after spraying by comparison with untreated plants, on a scale of 0 to 9 where 0 is 0% damage, 1 is 1-5% damage, 2 is 6-15% damage, 3 is 16-25% damage, 4 is 26-35% damage, 5 is 36-59% damage, 6 is 60-69% damage, 7 is 70-79% damage, 8 is 80-89% damage and 9 is 90-100% damage.

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• 1993
  • 1993-03-15 GB GB939305238A patent/GB9305238D0/en active Pending
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