GB2225011A - Fungicidal acrylates - Google Patents

Fungicidal acrylates Download PDF

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Publication number
GB2225011A
GB2225011A GB8925683A GB8925683A GB2225011A GB 2225011 A GB2225011 A GB 2225011A GB 8925683 A GB8925683 A GB 8925683A GB 8925683 A GB8925683 A GB 8925683A GB 2225011 A GB2225011 A GB 2225011A
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Prior art keywords
compound
methyl
phenyl
optionally substituted
acrylate
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GB8925683A
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GB8925683D0 (en
Inventor
R Ian Christoper Richards
R Geoffrey Ross Cliff
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Bayer CropScience Ltd Great Britain
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Schering Agrochemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-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
    • A01N43/72—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
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/56—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • 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
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/16—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or 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
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    • 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
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/21—Radicals derived from sulfur analogues of carbonic acid

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
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  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Compounds of formula I <IMAGE> wherein R<3> is alkyl or cycloalkyl; R<4>is optionally substituted alkenyl; optionally substituted alkynyl; aryl or heterocyclyl; X is O, S, -CH=CH-, -C IDENTICAL C- or NH optionally substituted by alkyl or acyl; m and n are 0 to 3; p is 0 to 1; and the ring D is optionally further substituted and salts thereof; have activity against plant pathogenic fungi.

Description

FS;GICIDES This invention relates to compounds having pesticidal and especially fungicidal activity.
According to the invention there is provided a compound of formula I
wherein R3 is alkyl or cycloalkyl; R' is optionally substituted alkyl; optionally substituted alkenyl; optionally substituted alkynyl; aryl or heterocyclyl; X is O, S, -CH=CH-, -CC- or NH optionally substituted by alkyl or acyl; m and n are 0 to 3; p is 0 or 1; and the ring D is optionally further substituted; and acid addition salts of any compounds which are basic and basic addition salts of any compounds which are acidic.
Compounds of the invention can exist as structural isomers and the invention includes individual isomers as well as mixtures of these.
Alkyl groups are preferably of 1 to 8 carbon atoms.
Alkenyl and alkynyl groups are generally of three to eight carbon atoms. Substituents, when present on any alkyl, alkenyl or alkynyl group, include halogen, alkoxy (e.g. of 1 to 4 carbon atoms), haloalkoxy (e.g. difluoromethoxy) hydroxy, alkylthio, nitro, optionally substituted amino, carboxy, alkoxycarbonyl, cyano, acyloxy and aryl. Aryl groups are usually phenyl, optionally substituted, e.g. by halogen, aryl, aryloxy, nitro, cyano or optionally substituted alkyl, alkoxy, alkylthio, alkylsulphonyl, alkylsulphinyl, optionally substituted amino, alkoxycarbonyl or acyloxy.The term heterocyclyl includes groups such as thienyl, furyl, pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, thiazolinyl, thiazolidinyl, oxazolyl, oxazolinyl, benzimidazolyl, tetrazolyl, benzoxazolyl, thiadiazolyl, dioxolanyl, imidazopyridinyl, 1, 3-benzoxazinyl, 1, 3-benzothiazinyl, oxazolopyridinyl, triazolyl, triazinyl, imidazolyl, morpholino, benzofuranyl, pyrazolinyl, quinolinyl, quinazolinyl, dihydroquinazolinyl or benzothiazolyl, which themselves may be substituted, e.g. as for phenyl. The ring D can be substituted in a similar manner as described for phenyl.
The term 'acyl' includes the residue of sulphonic and phosphorus containing acids as well as carboxylic acids.
Acyl groups are preferably alkanoyl e.g. of 1 to 4 carbon atoms. Amino groups may be substituted, e.g. by one or two alkyl groups or two substituents can form a ring, e.g. to form a morpholino or piperidino ring.
R3 is preferably methyl.
The compounds of the invention are particularly valuable as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe graminis), vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides), rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), damping off (Rhizoctonia solani), wheat brown rust (Puccinia recondita), potato blight (Phytophthora infestans) and apple scab (Venturia inaequalis). Other fungi against which the compounds may be active include other powdery mildews, other rusts, and general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidiomycete origin.
The compounds of the invention also have insecticidal activity.
The invention thus also provides a method of combating pests (i.e. fungi and insects) at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.
The invention also provides an agricultural composition comprising a compound of formula I in admixture with an agriculturaily acceptable diluent or carrier.
The composition of the invention may of course include more than one compound of the invention.
In addition the composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties. Alternatively the compounds of the invention can be used in sequence with the other active ingredient.
The diluent or carrier in the composition of the invention can be solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, elsifying agent or wetting agent. Suitable surface-active agents include anicnic compounds such as é carboxylate, for example a metal carboxylate of a log chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulphates such as sodium dodecyl sulphate, sodium octadecyl sulphate or sodium cetyl sulphate; ethoxylated fatty alcohol sulphates; ethoxylated alkylphenol sulphates; lignin sulphonates; petroleum sulphonates; alkyl-aryl sulphonates such as alkyl-benzene sulphonates or lower alkylnaphthalene sulphonates, e.g. butyl-naphthalene sulphonate; salts of sulphonated naphthalene-formaldehyde condensates; salts of sulphonated phenol-formaldehyde condensates; or more complex sulphonates such as the amide sulphonates, e.g.
the sulphonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulphosuccinates, e.g. the sodium sulphonate of dioctyl succinate. Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5decyn-4,7-diol, or ethoxylated acetylenic glycols.
Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder; a seed dressing, a fumigant, a smoke, a bait, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
A granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.
Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.
The concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.001 to 3.0 per cent by weight, especially 0.01 to 1.0 per cent by weight. In a primary composition the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
In the method of the invention the compound is generally applied to seeds, plants or their habitat. Thus the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds. When the soil is treated directly the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds. A suitable application rate is within the range of from 0.05 to 20 kg per hectare, more preferably from 0.1 to 10 kg per hectare.
Alternatively the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition.When the active compound is applied directly to the plant a suitable rate of application is from 0.01 to 10 kg. per hectare, preferably from 0.05 to 5 kg per hectare.
The compounds of the invention may be prepared in a variety of ways.
When p is 1 and X is O, S or optionally substituted NH a compound of formula II
wherein Z is a leaving group, such as halogen, can be reacted with a compound of formula III R (CH2) Xp H (III) In another process, a compound of formula IV
can be reacted with the ylide obtained under basic conditions from a phosphonium compound of formula V
where Q is an anion, especially halogen, such as bromine.
The compounds of formula II and IV are either known or can be obtained by methods well known in the art.
The invention is illustrated in the following examples.
Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses. Temperatures are in C.
Example 1 Methyl 2-(2-methylphenyl)acrylate (0.75 g) was dissolved in carbon tetrachloride (10 ml). N-bromosuccinimide (0.2 g) was added and the mixture heated under reflux. The reaction was illuminated by a 300 watt lamp. Benzoyl peroxide was added at a rate of about 0.5 mg every 10 minutes for about 2 hours. The mixture was cooled, filtered and evaporated to give methyl 2-[2-(bromomethyl)phenyl]acrylate. 5-Chloro2-mercaptobenzothiazole (1.03 g) in tetrahydrofuran (5 ml) was added dropwise to sodium hydride (0.140 g of 80% dispersion in oil) in tetrahydrofuran (5 ml) and the mixture stirred for 45 minutes at room temperature. A solution of methyl 2-[2-(bromomethyl)phenyl]acrylate (0.00426 mol) in tetrahydrofuran (5 ml) was added dropwise and the mixture stirred for 18 hours at room temperature.
It was evaporated and the residue partitioned between ethyl acetate and water. The organic phase was dried and evaporated and the residue purified by silica-gel chromatography to give methyl 2-[2-(5-chlorobenzothiazol-2-ylthiomethyl)phenyl]acrylate, m.p. 76-77".
(Compound 1) The starting material was prepared as follows: Dimethyl sulphoxide (10 ml) was added to sodium hydride (0.185 g of 80% dispersion in oil) and the mixture heated under nitrogen at 80" for 45 minutes. It was then cooled in ice and methyltriphenylphosphonium bromide (2.2 g) added over 5 minutes. The mixture was stirred at room temperature for 15 minutes and methyl 2-methyl Z-oxobenzeneacetate (1 g) in dimethyl sulphoxide (2 ml) was added. The mixture was stirred at room temperature for 1 hours and extracted with ether. The extract was washed with water and then brine, evaporated to reduced volume, filtered and the filtrate evaporated under reduced pressure. The residue was purified by silica-gel chromatography to give methyl 2-(2-methylphenyl)acrylate.
An alternative method of preparing this starting material is as follows: Dimethyl oxalate (54 g) in tetrahydrofuran (300 ml) was added to sodium hydride (10.1 g of 80% dispersion in oil) in tetrahydrofuran (200 ml) under nitrogen at room temperature. Methyl 2-methylbenzeneacetate (50 g) was added dropwise and a few drops of methanol added and the mixture warmed slightly. It was stirred overnight and poured into ice-water containing acetic acid (21 ml), extracted with ether and the extract worked up to give dimethyl 2-(2-methylphenyl)-3-oxosuccinate. A mixture of this product (69 g), potassium carbonate (37.4 g) formaldehyde (21.9 ml) and water (300 ml) was stirred overnight at room temperature. The mixture was extracted with dichloromethane and the extract worked up to give the desired starting material.
Example 2 A mixture of methyl 2-[2-(bromomethyl)phenyl]acrylate (3 g) in tetrahydrofuran (40 ml) and phenylimino (methylthio)methanethiol (2.37 g) was stirred for 5 hours at room temperature. Triethylamine (1.80 ml was added and the mixture stirred overnight and evaporated. The residue was extracted with ether and the extract worked up to give methyl 2-{2-[(phenylimino)(methylthio)methylthiomethyl]phenyl}acrylate, obtained as an oil, nD20 1.6817.
(Compound 2) Example 3 In a similar manner the following were obtained: a) Methyl 2-[2-(5-phenylpyrimidin-2-ylthiomethyl)phenyl] acrylate, m.p. 190-191". (Compound 3) b) Methyl 2-[2-(benzothiazol-2-ylthiomethyl)phenyl]- acrylate, oil (Compound 4) c) Methyl 2-[2-(benzoxazol-2-ylthiomethyl)phenyl]- acrylate, oil (Compound 5) d) Methyl 2-[2-(4-methylphenylthiomethyl)phenyl] acrylate, oil (Compound 6) e) Methyl 2-[(dodecylthiomethyl)phenyl]acrylate, oil (Compound 7) f) Methyl 2-[2-(4,4-dimethyl-5-methylene-2-thiazclin 2-ylthiomethyl)phenyl]acrylate, nD20 1.5861 (Compound 8) g) Methyl 2-{2-[(dodecylimino) (methylthio)methylthio methyl]phenyl]acrylato, nD20 1.6919 (Compound 9) h) Methyl 2-[2-(4-phenyl-2-thiazolin-2-ylthiomethyl) pher.yl]acrylate, nD2 1.6446 (Compound 10) 1) Methyl 2-[2-[(hexylimino) (methylthio)methylthio methyl]phenyl]acrylate, nD20 1.6873 (Compound 11) j) Methyl 2-[2-[1-(phenylimino)ethylthiomethyl]phenyl] acrylate, nD20 1.6886. (Compound 12) k) Methyl 2-[2-(pyrrolidinothiocarbonylthiomethyl)phenyl] acrylate, mp 62-63 (Compound 13) l) Methyl 2-[2-(5-phenyl-2-oxazolin-2-ylthiomethyl) phenyl]acrylate, m.p. 90-93 . (Compound 14) m) Methyl 2-C2-[(N-methylbenzylamino)thiocarbonyl- thiomethyl]phenyl)acrylate, nD20 1.6259.
(Compound 15) n) Methyl 2-[2-(benzoylthiomethyl)phenyl]acrylate, nD20 1.6082. (Compound 16) o)Methyl 2-{2-[(N-methylbenzylamino)methyl]phenyl] acrylate, oil (Compound 17) p) Methyl 2-[2-(4,4-diethyl-5-methylene-2-thiazolin- 2-ylthiomethyl)phenyl]acrylate, nD20 1.6859.
(Compound 18) q) Methyl 2-[2-(4,5-dimethylthiazol-2-ylthiomethyl) phenyl]acrylate, nD20 1.5959. (Compound 19) Test Example A Compounds are assessed for activity against one or more of the following: Phytophthora infestans: late tomato blight (PI) Plasmopara viticola: vine downy mildew (PV) Erysiphe graminis: barley powdery mildew (EG) Pyricularia oryzae: rice blast (PO) Pellicularia sasakii: rice sheath blight (PS) Botrytis cinerea: grey mould of tomato (BC) Venturia inaegualis: apple scab (VI) Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants. These plants were then inoculated with appropriate test pathogens and kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the leaf surface was visually estimated.
Compounds were considered active if they gave greater than 50% control of the disease at a concentration of 125 ppm (w/v) or less.
Activities were demonstrated as follows (+ = active).
Compound PI PV EG PO PS BC VI No 1 + 2 + + 3 + + + + 4 + + + 5 + + + + 8 + + + + 10 + + 11 + + + 12 + + + 13 + + + 15 + + 16 + 17 + 18 + + + 19 + +

Claims (2)

  1. CLAIMS 1. A compound of formula I
    wherein R3 is alkyl or cycloalkyl; R4 is optionally substituted alkyl; optionally substituted alkenyl; optionally substituted alkynyl; aryl or heterocyclyl; X is O, S, -CH=CH-, -C-C- or NH optionally substituted by alkyl or acyl; m and n are 0 to 3; p is 0 or 1; and the ring D is optionally-further substituted; and acid addition salts of any compounds which are basic and basic addition salts of any compounds which are acidic.
  2. 2. An agricultural composition which comprises a compound claimed in claim 1 in admixture with an agriculturally acceptable diluent or carrier.
GB8925683A 1988-11-19 1989-11-14 Fungicidal acrylates Withdrawn GB2225011A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5416110A (en) * 1992-08-08 1995-05-16 Basf Aktiengesellschaft Benzyl derivatives and pesticides containing them
US11970489B1 (en) 2023-10-23 2024-04-30 King Faisal University 4-[(substituted 1H-benzimidazol-2-ylsulfanyl)methyl]-6-substituted-2H-chromen-2-ones as larvicidal agents

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4151179A (en) * 1975-03-12 1979-04-24 Fisons Limited 2-(4H-1-Benzopyran-6-yl)propionic acids

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US4151179A (en) * 1975-03-12 1979-04-24 Fisons Limited 2-(4H-1-Benzopyran-6-yl)propionic acids

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Title
CA 82 (13) : 85829 T *
CA 85 (21) : 159105 Q *
CA 86 (5) : 26219 D *
CA 91 (11) : 83017 p *
CA 97 (3) : 23989 w *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5416110A (en) * 1992-08-08 1995-05-16 Basf Aktiengesellschaft Benzyl derivatives and pesticides containing them
AU661181B2 (en) * 1992-08-08 1995-07-13 Basf Aktiengesellschaft Benzyl derivatives and pesticides containing them
US11970489B1 (en) 2023-10-23 2024-04-30 King Faisal University 4-[(substituted 1H-benzimidazol-2-ylsulfanyl)methyl]-6-substituted-2H-chromen-2-ones as larvicidal agents

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