WO1993011118A1 - Azole derivative herbicides and fungicides - Google Patents

Azole derivative herbicides and fungicides Download PDF

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Publication number
WO1993011118A1
WO1993011118A1 PCT/EP1992/002723 EP9202723W WO9311118A1 WO 1993011118 A1 WO1993011118 A1 WO 1993011118A1 EP 9202723 W EP9202723 W EP 9202723W WO 9311118 A1 WO9311118 A1 WO 9311118A1
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Prior art keywords
group
compounds according
propyl
coor
optionally substituted
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PCT/EP1992/002723
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French (fr)
Inventor
Peter John West
Clive Leonard Cornell
Geoffrey Gower Briggs
Ulrich Bühmann
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Agrevo Uk Limited
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Application filed by Agrevo Uk Limited filed Critical Agrevo Uk Limited
Priority to BR9206862A priority Critical patent/BR9206862A/en
Priority to JP5509801A priority patent/JPH07501801A/en
Priority to EP92923799A priority patent/EP0619812A1/en
Publication of WO1993011118A1 publication Critical patent/WO1993011118A1/en
Priority to FI942596A priority patent/FI942596A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings

Definitions

  • This invention concerns new azole derivatives having herbicidal/fungicidal activity, processes for their preparation, and compositions containing them. Description
  • the invention provides the compounds of the formula:
  • Az is imidazol-1-yl or 1,2,4-triazol-1-yl
  • each X represents halogen, carboxy, nitro, cyano, a group COR 5 , COOR 5 or S(O) p R 5 , or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X together form a fused benzo group;
  • R 1 represents a group CN, COR 5 , COOR 5 or S(O) p R 5 ;
  • R 2 represents a group CN, COR 5 , COOR 5 , S(O) p R 5 ,
  • R 3 and R 4 which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group;
  • R 5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p is 0);
  • n 0 to 4.
  • p is 0 to 2. Any alkyl group present in the molecule is
  • the substituent groups may, for example, include halogen, alkoxy of 1 to 4 carbon atoms (eg methoxy or ethoxy), or aryl (eg phenyl).
  • Any alkenyl or alkynyl group present in the molecule is preferably of 2 to 6 carbon atoms, eg vinyl, allyl or propargyl.
  • Any cycloalkyl group present in the molecule is preferably of 3 to 7 carbon atoms, eg cyclopentyl or cyclohexyl.
  • substituent groups may, for example, include halogen, alkyl of 1 to 4 carbon atoms (eg
  • Any heteroaryl group present in the molecule is preferably thienyl, furyl or pyridyl.
  • R 1 is preferably a group -COOR 5a (particularly where R 5a is alkyl of 1 to 8 carbon atoms, allyl, phenyl or benzyl), and especially such a group where R 5a is methyl, ethyl, n-propyl, iso-propyl or n-butyl.
  • R 2 is preferably cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio,
  • R 5a is alkyl of 1 to 8 carbon atoms, methoxyethyl, cyclopentyl, allyl or benzyl, and especially methyl, ethyl, n-propyl, iso-propyl or
  • R 5b is alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl, especially phenyl).
  • R 1 and R 2 are identical and each represents -COOR 5 or phenylthio, or one represents -COOR 5 and the other represents phenylsulphonyl.
  • R 3 and R 4 are each preferably hydrogen.
  • Az is preferably 1,2,4-triazol-1-yl.
  • n is preferably 1 or 2.
  • X n preferably represents substitution in the 2- position, or disubstitution in the 2,4- or 2,5-positions on the phenyl ring.
  • Preferred substituent groups which X may represent include chloro, bromo, methoxy,
  • substitution patterns are 2-methoxy, 2-carboxymethyl, 2- chloro, 2,4-dichloro, 2 ,4-dimethoxy, 2-nitro-4-chloro, 2- methoxy-5-chloro and 2-methoxy-5-bromo.
  • the compounds of the invention may be prepared by a process in which a compound of the formula:
  • reaction represents a leaving group (especially chlorine), in the presence of a strong base (eg sodium hydride).
  • a strong base eg sodium hydride.
  • the reaction is preferably effected in a suitable inert solvent medium, eg dimethylformamide.
  • the compounds of formulae II and III are themselves either known compounds or may be made by processes analogous to those used for the preparation of similar known compounds.
  • the compounds of the invention have activity as herbicides where they exhibit activity against a number of weed species when applied both pre- and post- emergence.
  • the compounds are also comparatively safe to certain crop species, and may thus be of use as selective herbicides, particularly in the control of a range of weeds in cereals or other crops, eg wheat, barley, maize, soya beans, oilseed rape, cotton, sugar beet or,
  • the compounds of the invention also have activity as fungicides, where their activity is manifested
  • the invention also provides a method of combating weeds and/or fungi at a locus infested or liable to be infested therewith, which comprises applying thereto an effective amount of one or more compounds of formula I.
  • the invention provides a herbicidal and/or fungicidal composition which comprises one or more compounds of formula I in association with a suitable carrier and/or surface active agent.
  • compositions of the invention usually contain from 0.01 to 99% by weight of the present compounds, and are normally produced initially as concentrates
  • ingredient comprises from 0.01 to 5% by weight of the formulation applied.
  • the carrier may be water, in which case an organic solvent may also be present, though this is not usually employed.
  • a flowable suspension concentrate may be formed by grinding the compound with water, a wetting agent and a suspending agent, eg xanthan gum.
  • the carrier may alternatively be a water immiscible organic solvent, eg a hydrocarbon which boils within the range 130-270C, eg xylene, in which the compound is dissolved or suspended.
  • An emulsifiable concentrate containing a water immiscible solvent may be formed with a surface active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water.
  • the carrier may alternatively be a water-miscible organic solvent eg 2-methoxy ethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or dimethylformamide.
  • a water-miscible organic solvent eg 2-methoxy ethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or dimethylformamide.
  • the carrier may alternatively be a solid, which may be finely divided or granular.
  • suitable solids are limestone, clays, sand, mica, chalk,
  • the carrier can be of natural or synthetic origin or can be modified natural material.
  • Wettable powders soluble or dispersible in water may be formed by admixing the compound in particulate form with a particulate carrier or spraying molten compound on to the carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture.
  • An aerosol composition may be formed by admixing the compound with a propellant, eg a polyhalogenated alkane such as dichlorofluoromethane, and suitably also with a solvent.
  • 'surface active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.
  • the surface active agents used may comprise anionic surface active agents, for example mono- or di-esters of phosphoric acid with a fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulfates such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignin sulfates, petroleum sulfonates, alkylaryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, or more complex sulfonates such as the amide sulfonates, eg the sulfonated condensation product of oleic acid and N-methyl taurine or
  • sulfosuccinates eg the sodium sulfonate of dioctyl
  • the surface active agents may also comprise
  • non-ionic agents for example condensation products or fatty aeid esters, fatty alcohols, fatty acid amides or alkyl-substitutedphenols with ethylene oxide, fatty esters of polyhydric alcohol ethers eg sorbitan fatty acid esters, condensation products of such esters with ethylene oxide eg polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5- decyn-4,7-diol, or ethoxylated acetylenic glycols.
  • condensation products or fatty aeid esters for example condensation products or fatty aeid esters, fatty alcohols, fatty acid amides or alkyl-substitutedphenols with ethylene oxide, fatty esters of polyhydric alcohol ethers eg sorbitan fatty acid esters, condensation products of such est
  • the surface active agents may also comprise cationic agents, for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl
  • Preferred surface active agents include ethoxylated fatty alcohol sulfates, lignin sulfonates, alkyl-aryl sulfonates, salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, sodium oleoyl N-methyltauride, dialkyl sulfosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.
  • the present active compounds may be admixed with another pesticide, eg a herbicide, fungicide or
  • herbicide or a plant growth regulator, particularly another herbicide.
  • Suitable further herbicides include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metolachlor, fluometuron, oxyfluorfen, fomesafen, bentazone, prometryne, norflurazon,
  • chlomazone EPTC, imazaquin, and especially isoproturon, methabenzthiazuron, trifluralin, ioxynil, bromoxynil, benazolin, mecoprop, fluroxypyr, alachlor, acifluorfen, lactofen, metribuzin, pendimethalin, ethofumesate, benfuresate, phenmedipham, benzophenap, butachlor, chlomethoxyfen, dimepiperate, mefenacet, molinate, naproanilide, oxadiazon, piperophos, prometryne,
  • simetryne simetryne, pyrazolate, pretilachlor, thiobencarb and pyributicarb.
  • Suitable further fungicides include fenpropimorph, propiconazole, triadimefon, triadimenol, diclobutrazol, prochloraz (and metal complexes of this eg the manganese chloride complex), and guazatine.
  • the present compound may be applied to plants, the soil, land or aquatic areas, and particularly to a locus at which a crop is growing. Examples
  • Benzenethiol (3.86g) was added to a solution of potassium hydroxide (1.9g) in ethanol (100ml) and the mixture was stirred for 30 minutes.
  • Ethyl bromo(2,4- dichlorophenyl) acetate (9.4g) was added dropwise and the mixture was then heated at reflux for 4 hours. After cooling, the mixture was concentrated in vacuo and the residue partitioned between dichloromethane (100ml) and water (100ml). The organic layer was separated and the aqueous solution extracted further with dichloromethane (2 x 100ml). The organic extracts were combined, dried with magnesium sulfate and concentrated in vacuo. The resulting liquid was distilled to give 8.5g of the desired compound, bp 128-45°C at 0.1 mmHg.
  • Seeds of the test species listed below were each sown in 8.5cm square pots filled to within 2cm of the top with sterile loam, and were covered with a 2-5mm layer of loam. The pots were watered, and then treated by

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

Herbicidal compounds of formula (I) where: Az is imidazol-1-yl or 1,2,4-triazol-1-yl; each X represents halogen, carboxy, nitro, cyano, a group COR?5, COOR5¿ or S(O)¿pR?5, or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X together form a fused benzo group; R1 represents a group CN, COR?5, COOR5¿, or S(O)¿pR?5; R2 represents a group CN, COR?5, COOR5¿, S(O)¿pR?5, SO2N(R5)2, P(O)(OR5)2, nitro, aryl, heteroaryl or aralkyl; R?3 and R4¿, which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group; R5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p=0); n is 0 to 4; and p is 0 to 2.

Description

Title: Azole Derivative Herbicides and Fungicides Field of the invention
This invention concerns new azole derivatives having herbicidal/fungicidal activity, processes for their preparation, and compositions containing them. Description
In one aspect, the invention provides the compounds of the formula:
Figure imgf000003_0001
where:
Az is imidazol-1-yl or 1,2,4-triazol-1-yl;
each X represents halogen, carboxy, nitro, cyano, a group COR5, COOR5 or S(O)pR5, or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X together form a fused benzo group;
R1 represents a group CN, COR5, COOR5 or S(O)pR5;
R2 represents a group CN, COR5, COOR5, S(O)pR5,
SO2N(R5)2, P(O) (OR5) 2, nitro, aryl, heteroaryl or aralkyl;
R3 and R4, which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group;
R5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p is 0);
n is 0 to 4; and
p is 0 to 2. Any alkyl group present in the molecule is
preferably of 1 to 8, especially of 1 to 4, carbon atoms, eg methyl, ethyl, n-propyl, isopropyl or t-butyl. Where such a group is substituted, the substituent groups may, for example, include halogen, alkoxy of 1 to 4 carbon atoms (eg methoxy or ethoxy), or aryl (eg phenyl).
Any alkenyl or alkynyl group present in the molecule is preferably of 2 to 6 carbon atoms, eg vinyl, allyl or propargyl.
Any cycloalkyl group present in the molecule is preferably of 3 to 7 carbon atoms, eg cyclopentyl or cyclohexyl.
Any aryl moiety present in the molecule is
preferably a phenyl moiety. Where such a group is substituted, the substituent groups may, for example, include halogen, alkyl of 1 to 4 carbon atoms (eg
methyl), alkoxy of 1 to 4 carbon atoms (eg methoxy or ethoxy), nitro, or a further phenyl group.
Any heteroaryl group present in the molecule is preferably thienyl, furyl or pyridyl.
R1 is preferably a group -COOR5a (particularly where R5a is alkyl of 1 to 8 carbon atoms, allyl, phenyl or benzyl), and especially such a group where R5a is methyl, ethyl, n-propyl, iso-propyl or n-butyl.
R2 is preferably cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio,
-COOR5a (particularly where R5a is alkyl of 1 to 8 carbon atoms, methoxyethyl, cyclopentyl, allyl or benzyl, and especially methyl, ethyl, n-propyl, iso-propyl or
n-butyl), or -SO2R5b (where R5b is alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl, especially phenyl).
In a particularly preferred group of compounds of formula I, R1 and R2 are identical and each represents -COOR5 or phenylthio, or one represents -COOR5 and the other represents phenylsulphonyl. R3 and R4 are each preferably hydrogen.
Az is preferably 1,2,4-triazol-1-yl.
n is preferably 1 or 2.
Xn preferably represents substitution in the 2- position, or disubstitution in the 2,4- or 2,5-positions on the phenyl ring. Preferred substituent groups which X may represent include chloro, bromo, methoxy,
methoxycarbonyl and nitro. Specific preferred
substitution patterns are 2-methoxy, 2-carboxymethyl, 2- chloro, 2,4-dichloro, 2 ,4-dimethoxy, 2-nitro-4-chloro, 2- methoxy-5-chloro and 2-methoxy-5-bromo.
Specific preferred compounds are those of the
Examples provided hereinafter. Particular mention may be made, however, of di-n-propyl (2,4-dichlorophenyl)[(1H- 1,2,4-triazol-1-yl)methyl]malonate, ethyl 2-(2,4- dichlorophenyl)-2-(phenylsulfonyl)-3-(1H-1,2,4-triazol-1- yl)propionate and n-propyl 2-(2,4-dichlorophenyl)-2- (phenylsulfonyl)-3-(1H-1,2,4-triazol-1-yl)propionate.
The compounds of the invention may be prepared by a process in which a compound of the formula:
Figure imgf000005_0001
where R1, R2, X and n are as defined hereinbefore is reacted with a compound of the formula:
R3
|
Z - C - Az (III) |
R4 where R3and R4 are as defined hereinbefore, and Z
represents a leaving group (especially chlorine), in the presence of a strong base (eg sodium hydride). The reaction is preferably effected in a suitable inert solvent medium, eg dimethylformamide.
The compounds of formulae II and III are themselves either known compounds or may be made by processes analogous to those used for the preparation of similar known compounds.
The compounds of the invention have activity as herbicides where they exhibit activity against a number of weed species when applied both pre- and post- emergence. The compounds are also comparatively safe to certain crop species, and may thus be of use as selective herbicides, particularly in the control of a range of weeds in cereals or other crops, eg wheat, barley, maize, soya beans, oilseed rape, cotton, sugar beet or,
especially, rice, where their control of barnyardgrass is particularly useful.
The compounds of the invention also have activity as fungicides, where their activity is manifested
particularly against fungal diseases of plants, eg barley powdery mildew (Erysiphe graminis). They are also active against vine downy mildew (Plasmopara viticola) as well as being active against diseases such as rice blast
(Pyricularia oryzae), wheat brown rust (Puccinia
recondita) and potato blight (Phytophthora infestans).
Accordingly, the invention also provides a method of combating weeds and/or fungi at a locus infested or liable to be infested therewith, which comprises applying thereto an effective amount of one or more compounds of formula I.
In addition, the invention provides a herbicidal and/or fungicidal composition which comprises one or more compounds of formula I in association with a suitable carrier and/or surface active agent.
The compositions of the invention usually contain from 0.01 to 99% by weight of the present compounds, and are normally produced initially as concentrates
containing from 0.5 to 99%, preferably from 0.5 to 85%, and especially from 10 to 50% by weight thereof. Such concentrates are diluted if necessary before application to the locus to be treated such that the active
ingredient comprises from 0.01 to 5% by weight of the formulation applied.
The carrier may be water, in which case an organic solvent may also be present, though this is not usually employed. A flowable suspension concentrate may be formed by grinding the compound with water, a wetting agent and a suspending agent, eg xanthan gum.
The carrier may alternatively be a water immiscible organic solvent, eg a hydrocarbon which boils within the range 130-270C, eg xylene, in which the compound is dissolved or suspended. An emulsifiable concentrate containing a water immiscible solvent may be formed with a surface active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water.
The carrier may alternatively be a water-miscible organic solvent eg 2-methoxy ethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or dimethylformamide.
The carrier may alternatively be a solid, which may be finely divided or granular. Examples of suitable solids are limestone, clays, sand, mica, chalk,
attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulfonates and solid fertilizers. The carrier can be of natural or synthetic origin or can be modified natural material.
Wettable powders soluble or dispersible in water may be formed by admixing the compound in particulate form with a particulate carrier or spraying molten compound on to the carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture. An aerosol composition may be formed by admixing the compound with a propellant, eg a polyhalogenated alkane such as dichlorofluoromethane, and suitably also with a solvent.
The term 'surface active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.
The surface active agents used may comprise anionic surface active agents, for example mono- or di-esters of phosphoric acid with a fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulfates such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignin sulfates, petroleum sulfonates, alkylaryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, or more complex sulfonates such as the amide sulfonates, eg the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl
sulfosuccinates eg the sodium sulfonate of dioctyl
succinate.
The surface active agents may also comprise
non-ionic agents, for example condensation products or fatty aeid esters, fatty alcohols, fatty acid amides or alkyl-substitutedphenols with ethylene oxide, fatty esters of polyhydric alcohol ethers eg sorbitan fatty acid esters, condensation products of such esters with ethylene oxide eg polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5- decyn-4,7-diol, or ethoxylated acetylenic glycols.
The surface active agents may also comprise cationic agents, for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl
trimethylammonium bromide, or ethoxylated tertiary fatty amines.
Preferred surface active agents include ethoxylated fatty alcohol sulfates, lignin sulfonates, alkyl-aryl sulfonates, salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, sodium oleoyl N-methyltauride, dialkyl sulfosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.
The present active compounds may be admixed with another pesticide, eg a herbicide, fungicide or
insecticide, or a plant growth regulator, particularly another herbicide. Suitable further herbicides include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metolachlor, fluometuron, oxyfluorfen, fomesafen, bentazone, prometryne, norflurazon,
chlomazone, EPTC, imazaquin, and especially isoproturon, methabenzthiazuron, trifluralin, ioxynil, bromoxynil, benazolin, mecoprop, fluroxypyr, alachlor, acifluorfen, lactofen, metribuzin, pendimethalin, ethofumesate, benfuresate, phenmedipham, benzophenap, butachlor, chlomethoxyfen, dimepiperate, mefenacet, molinate, naproanilide, oxadiazon, piperophos, prometryne,
pyrazoxyfen, pyrazosulfuron-ethyl , bensulfuron ,
simetryne, pyrazolate, pretilachlor, thiobencarb and pyributicarb.
Suitable further fungicides include fenpropimorph, propiconazole, triadimefon, triadimenol, diclobutrazol, prochloraz (and metal complexes of this eg the manganese chloride complex), and guazatine.
The present compound may be applied to plants, the soil, land or aquatic areas, and particularly to a locus at which a crop is growing. Examples
The invention is illustrated by the following
Examples, in which Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Ph = phenyl, Cypent = cyclopentyl, Bz = benzyl, Im = imidazol-1-yl, Py = pyrimidin-2-yl, and Tr = 1,2,4-triazol-1-yl:
Example 1
Dipropyl (2 ,4-dichlorophenyl)[(1H-1,2,4-triazol-1- yl)methyl]malonate
(a) Propyl (2 ,4-dichlorophenyl)acetate
A solution of (2,4-dichlorophenyl) acetic acid (50g), propanol (300ml) and concentrated sulfuric acid (20 drops) was heated at reflux for 7 hrs. After cooling, the solution was concentrated in.vacuo and ethyl acetate (500ml) and aqueous sodium bicarbonate (200ml) were added to the residue. The organic layer was separated, dried with magnesium sulfate and evaporated. The resulting liquid was distilled to give 47.7 g of propyl (2,4- dichlorophenyl) acetate, bp 112°C at 0.1 mmHg.
(b) Dipropyl (2 ,4-dichlorophenyl)malonate
Propyl (2,4-dichlorophenyl) acetate (24.7g) was added to a stirred solution of lithium di-iso-propylamide (0.1 M) in dry tetrahydrofuran (250ml) at -78°C. After 90 minutes propyl chloroformate (12.3g) was added dropwise and the resulting solution was stirred for a further
60 minutes and finally for 16 hours at room temperature. 5% Hydrochloric acid (30ml) was added and the mixture was partially evaporated in vacuo to remove most of the tetrahydrofuran. The residual liquid was extracted with ether (3 x 100ml), dried with magnesium sulfate and concentrated in vacuo. Fractional distillation of the residual liquid afforded 10.4 g of dipropyl (2,4- dichlorophenyl)malonate as a colourless liquid, bp 142°C at 0.4 mmHg. (c) Dipropyl (2,4-dichlorophenyl)[(1H-1,2,4-triazol-1- yl)methyl]malonate
Sodium hydride (0.9 g, 80% in mineral oil) was added portionwise and with stirring to a solution of dipropyl (2, 4-dichlorophenyl) malonate (9.9g) in 1,2- dimethoxyethane (120ml). The mixture was stirred for 30 minutes at room temperature and sodium iodide (0.4g) and 1-chloromethyl-1H-1,2,4-triazole (3.6g) were added. The mixture was heated at reflux for 30 minutes, cooled with ice, and water (100ml) added. The solvent was removed by concentration in vacuo and dichloromethane (100ml) was added to the residue. The organic. layer was separated and the aqueous layer was further extracted with
dichloromethane (2 x 100ml). The organic extracts were combined, washed with water (50ml) and dried with
magnesium sulfate. Concentration of the organic extracts in vacuo gave an oil which solidified on standing. This was recrystallised from a hexane/diisopropyl ether mixture to give 3.7 g of the desired compound as a white solid, mp 62-4°C.
Example 2
Ethyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)-3-(1H- 1,2,4-triazol-1-yl)propionate
(a) Ethyl ( 2,4-dichlorophenyl) (phenylthio) acetate
Benzenethiol (3.86g) was added to a solution of potassium hydroxide (1.9g) in ethanol (100ml) and the mixture was stirred for 30 minutes. Ethyl bromo(2,4- dichlorophenyl) acetate (9.4g) was added dropwise and the mixture was then heated at reflux for 4 hours. After cooling, the mixture was concentrated in vacuo and the residue partitioned between dichloromethane (100ml) and water (100ml). The organic layer was separated and the aqueous solution extracted further with dichloromethane (2 x 100ml). The organic extracts were combined, dried with magnesium sulfate and concentrated in vacuo. The resulting liquid was distilled to give 8.5g of the desired compound, bp 128-45°C at 0.1 mmHg.
(b) Ethyl (2,4-dichlorophenyl) (phenylsulfonyl) acetate A mixture of ethyl (2,4-dichlorophenyl)- (phenylthio) acetate (3.4g) and m-chloroperbenzoic acid (4.97 g, 90%) in chloroform (30ml) was heated at reflux for 16 hours. After cooling, dichloromethane (30ml) was added and the mixture was filtered. The filtrate was washed with sodium bicarbonate solution (25ml), dried with magnesium sulfate and concentrated in vacuo. The resulting solid was recrystallised from diisopropylether to give 1.8 g of the desired compound as a white solid, mp 86-8°C.
(c) Ethyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)-3- (1H-1,2,4-triazol-1-yl)propionate
Sodium hydride (0.81 g; 80% in mineral oil) was added portionwise and with stirring to a solution of ethyl (2,4-dichlorophenyl) (phenylsulfonyl) acetate (10g) in 1,2-dimethoxyethane (80ml) and dimethylformamide (20ml). The mixture was stirred at room temperature for 30 minutes before adding sodium iodide (0.1g) followed by 1-chloromethyl-1H-1,2,4-triazole (3.15g). This mixture was heated at reflux for 1 hour, cooled with ice, and water (100ml) was added. The solvent was removed in vacuo, and ethyl acetate (100ml) and water (100ml) were added. The organic layer was separated and the aqueous solution was extracted with ethyl acetate (2 x 100ml). The combined organic extracts were dried with magnesium sulfate and concentrated in vacuo. The resulting oil was flash chromatographed on silica using 3% methanol indichloromethane at eluent to obtain 2.3 g of the desired compound as a yellow solid, mp 74°C.
Examples 3-116
The following compounds of formula I where R3 and R4 are both hydrogen, and Az is 1,2,4-triazol-1-yl except where otherwise ind icated, were prepared by methods analogous to those described in Examples 1 and 2:
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
The following compound of formula I in which Az is
1,2,4-triazol-1-yl, R4 is hydrogen, and R3 is methyl, was prepared by methods analogous to those described in Examples 1 and 2:
116 2,4-diCl COOEt COOEt Oil
HERBICIDAL EXAMPLE A (Pre-Emergence)
Seeds of the test species listed below were each sown in 8.5cm square pots filled to within 2cm of the top with sterile loam, and were covered with a 2-5mm layer of loam. The pots were watered, and then treated by
application to the soil surface in a spray cabinet with the compounds of the Examples listed below formulated as a solution/suspension in 3:1 by volume of acetone and the wetting agent polyoxyethylene (20 moIs) monolaurate solution (10 g per litre). The concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 200 litres per hectare.
After 3 to 4 weeks growth in a glasshouse (minimum temperature 16°C for temperate species, 21°C for non- temperate species, 16 hours per day photoperiod) the plants were visually assessed for any herbicidal
response. All differences from an untreated control were scored accordingly to an index where 0 = no effect, 1 =
1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below, the following letters are used to denote the plant species:
a - Triticum aestivum (wheat)
b - Hordeum vulgare (barley)
c - Beta vulgaris (sugar beet)
d - Brassica napus (rape)
e - Alopecurus myosuroides (blackgrass)
f - Avena fatua (wild oat)
g - Elymus repens (couch)
h - Bromus sterilis (barren brome)
i - Viola arvensis (field pansy)
j - Stellaria media (chickweed)
k - Galium aparine (cleavers)
l - Matricaria inodora (scentless mayweed)
m - Polygonum lapathifolium (Pale persicaria)
n - Veronica persicae (Buxbaum's speedwell).
The results obtained were as follows:
Figure imgf000017_0001
Figure imgf000018_0001
HERBICIDAL EXAMPLE B (Post-Emercrence)
The plant species listed below were grown in 8 . 5cm square pots containing sterile loam in a glasshouse (minimum temperature 16 °C for temperate species , 21°C for non-temperate species , 16 hours per day photoperiod) , and were treated in a spray cabinet at the 2-3 leaf stage with the compounds of the Examples listed below
formulated as a solution/ suspension in 3 : 1 by volume of acetone and the wetting agent polyoxyethylene (20 mols) monolaurate solution (10 g per litre) . The concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 200 litres per hectare.
After 3-4 weeks, the plants were visually assessed for any herbicidal response. All differences from an untreated control were scored according to an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect.
In the table below, the letters used denote the same plant species as in Herbicidal Example A:
The results obtained were as follows :
Figure imgf000019_0001

Claims

1. The compounds of the formula:
Figure imgf000020_0001
where:
Az is imidazol-1-yl or 1,2,4-triazol-1-yl;
each X represents halogen, carboxy, nitro, cyano, a group COR5, COOR5 or S(O)pR5, or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X together form a fused benzo group;
R1 represents a group CN, COR5, COOR5 or S(O)pR5;
R2 represents a group CN, COR5, COOR5, S(O)pR5, SO2N(R5) 2, P(O) (OR5)2, nitro, aryl, heteroaryl or aralkyl;
R3 and R4, which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group;
R5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p=O);
n is 0 to 4; and
p is 0 to 2.
2. The compounds according to claim 1 where R1 is COOR5a (where R5a is alkyl of 1 to 8 carbon atoms, allyl, phenyl, phenylthio, benzyl or cyano).
3. The compounds according to claim 2 where R5a is
methyl, ethyl, n-propyl, iso-propyl or n-butyl.
4. The compounds according to any of claims 1 to 3 where R2 is cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio, COOR5a (where R5a is alkyl of 1 to 8 carbon atoms, methoxyethyl, cyclopentyl, allyl or benzyl), or SO2R5b (where R5b is alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl).
5. The compounds according to claim 4 where R2 is COOR5a (where R5a is methyl, ethyl, n-propyl, iso-propyl or n-butyl) or SO2R5b (where R5b is phenyl).
6. The compounds according to any of claims 1 to 5 where R3 and R4 are each hydrogen.
7. The compounds according to any of claims 1 to 6 where each group X represents chloro, bromo, methoxy, metnoxycarbonyl or nitro.
8. The compounds according to any of claims 1 to 7 where X. represents mono-substitution in the 2-position, or disubstitution in the 2,4- or 2,5-positions on the phenyl ring.
9. A compound selected from:
di-n-propyl (2,4-dichlorophenyl)[(1H-1,2,4-triazol-1- yl)methyl]malonate;
ethyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)-3- (1H-1,2,4-triazol-1-yl)propionate; and
n-propyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)-3- (1H-1,2,4-triazol-1-yl)propionate.
10. A herbicidal and/or fungicidal composition which
comprises one or more compounds according to any of claims 1 to 9, in association with a suitable carrier and/or surface active agent.
AMENDED CLAIMS
[received by the International Bureau on 14 April 1993 (14.04.93) ;
original claim 1 amended ; other claims unchanged (2 pages) ]
1. The compounds of the formula:
Figure imgf000022_0001
where:
Az is imidazol-1-yl or 1,2,4-triazol-1-yl;
each X represents halogen, carboxy, nitro, cyano, a group COR5, COOR5 or S(O)pR5, or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group;
R1 represents a group COR5, COOR5, SH or S(O)pR5; R2 represents a group CN, COR5, COOR5, SH,
S(O)pR5, SO2N(R5)2, P(O) (OR5)2, nitro, aryl, heteroaryl or aralkyl;
R3 and R4, which may be the same or different, each represent hydrogen, or an optionally
substituted alkyl, aryl or heteroaryl group;
R5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group;
n is 0 to 4; and
p is 0 to 2;
with the proviso that R1 and R2 do not
simultaneously represent groups of formula S(O)pR5 where R5 is in each case alkyl or alkenyl.
2. The compounds according to claim 1 where R1 is COOR5a (where R5a is alkyl of 1 to 8 carbon atoms, allyl, phenyl, phenylthio, benzyl or cyano).
3. The compounds according to claim 2 where R5a is
methyl, ethyl, n-propyl, iso-propyl or n-butyl.
4. The compounds according to any of claims 1 to 3
where R2 is cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio, COOR5a (where R5a is alkyl of 1 to 8 carbon atoms,
methoxyethyl, cyclopentyl, allyl or benzyl), or SO2R5b (where R5b is alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl).
5. The compounds according to claim 4 where R2 is COOR5a (where R5a is methyl, ethyl, n-propyl, iso-propyl or n-butyl) or SO2R5b (where R5b is phenyl).
6. The compounds according to any of claims 1 to 5
where R3 and R4 are each hydrogen.
7. The compounds according to any of claims 1 to 6
where each group X represents chloro, bromo,
methoxy, methoxycarbonyl or nitro.
8. The compounds according to any of claims 1 to 7
where Xn represents mono-substitution in the 2- position, or disubstitution in the 2,4- or 2,5- positions on the phenyl ring.
9. A compound selected from:
di-n-propyl (2,4-dichlorophenyl) [(1H-1,2,4-triazol- 1-yl)methyl] malonate;
ethyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)-3- (1H-1,2,4-triazol-l-yl)propionate; and
n-propyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)- 3-(1H-1,2,4-triazol-1-yl) propionate.
10. A herbicidal and/or fungicidal composition which
comprises one or more compounds according to any off claims 1 to 9, in association with a suitable
carrier and/or surface active agent. STATEMENT UNDER ARTICLE 19
Claim 1 of the above application has been amended (a) to exclude the possibility that R1 can be CN, (b) to add a proviso that R1 and R2 do not simultaneously represent groups of formula S(O)pR5 where R5 is in each case alkyl or alkenyl, (c) to exclude the possibility that two adjacent groups X may together form a fused benzo group, and (d) to insert SH as an explicit designation for R1 and R2, and remove the equivalent designation of hydrogen for the group R5.
Amendment (a) is made to overcome citations EP 61840, EP 251775, US 4073921 , and US 4167576.
Amendment (b) is made to overcome citation EP 61794.
Amendment (c) is made to overcome citation EP 1 6587.
PCT/EP1992/002723 1991-12-04 1992-11-25 Azole derivative herbicides and fungicides WO1993011118A1 (en)

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EP92923799A EP0619812A1 (en) 1991-12-04 1992-11-25 Azole derivative herbicides and fungicides
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EP0576199A2 (en) * 1992-06-25 1993-12-29 Rohm And Haas Company Fungicidal and herbicidal triazoles
EP0606748A1 (en) * 1993-01-15 1994-07-20 Rohm And Haas Company Cyanosulfonylethyltriazoles and their use as fungicides
EP1088827A1 (en) * 1999-09-29 2001-04-04 SSP Co., Ltd. Azole derivatives or salts thereof
US7595338B2 (en) 2005-04-29 2009-09-29 Wyeth Process for preparing 3,3-disubstituted oxindoles and thio-oxindoles
WO2019093522A1 (en) * 2017-11-13 2019-05-16 株式会社クレハ Azole derivative, intermediate compound, method for producing azole derivative, agent for agricultural and horticultural use, and material protection agent for industrial use
WO2020213739A1 (en) * 2019-04-19 2020-10-22 株式会社クレハ Bactericidal agent for agricultural or horticultural use, plant disease control method, and product for plant disease control use

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EP0575122A2 (en) * 1992-06-17 1993-12-22 Rohm And Haas Company Fungicidal (2-aryl-2-substituted) ethyl-1,2,4-triazoles
EP0575122A3 (en) * 1992-06-17 1994-05-25 Rohm & Haas Fungicidal (2-aryl-2-substituted) ethyl-1,2,4-triazoles
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EP0576199A2 (en) * 1992-06-25 1993-12-29 Rohm And Haas Company Fungicidal and herbicidal triazoles
EP0576199A3 (en) * 1992-06-25 1994-05-18 Rohm & Haas Fungicidal and herbicidal triazoles
EP0606748A1 (en) * 1993-01-15 1994-07-20 Rohm And Haas Company Cyanosulfonylethyltriazoles and their use as fungicides
EP1088827A1 (en) * 1999-09-29 2001-04-04 SSP Co., Ltd. Azole derivatives or salts thereof
US6528500B1 (en) 1999-09-29 2003-03-04 Ssp Co., Ltd. Azole derivatives or salts thereof
US7595338B2 (en) 2005-04-29 2009-09-29 Wyeth Process for preparing 3,3-disubstituted oxindoles and thio-oxindoles
WO2019093522A1 (en) * 2017-11-13 2019-05-16 株式会社クレハ Azole derivative, intermediate compound, method for producing azole derivative, agent for agricultural and horticultural use, and material protection agent for industrial use
AU2018365928B2 (en) * 2017-11-13 2020-02-27 Kureha Corporation Azole derivative, intermediate compound, method for producing azole derivative, agent for agricultural and horticultural use, and material protection agent for industrial use
JPWO2019093522A1 (en) * 2017-11-13 2020-04-02 株式会社クレハ Azole derivative, intermediate compound, method for producing azole derivative, agricultural and horticultural drug and industrial material protective agent
US10945434B2 (en) 2017-11-13 2021-03-16 Kureha Corporation Azole derivative, intermediate compound, method for producing azole derivative, agricultural or horticultural chemical agent, and protective agent for industrial material
WO2020213739A1 (en) * 2019-04-19 2020-10-22 株式会社クレハ Bactericidal agent for agricultural or horticultural use, plant disease control method, and product for plant disease control use
KR20210141781A (en) * 2019-04-19 2021-11-23 가부시끼가이샤 구레하 Agro-horticultural fungicide, plant disease control method and plant disease control product
KR102404296B1 (en) 2019-04-19 2022-05-31 가부시끼가이샤 구레하 Agricultural and horticultural fungicides, methods for controlling plant diseases and products for controlling plant diseases

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