EP0828713A2 - Microbicides a base de pyridine - Google Patents

Microbicides a base de pyridine

Info

Publication number
EP0828713A2
EP0828713A2 EP96916067A EP96916067A EP0828713A2 EP 0828713 A2 EP0828713 A2 EP 0828713A2 EP 96916067 A EP96916067 A EP 96916067A EP 96916067 A EP96916067 A EP 96916067A EP 0828713 A2 EP0828713 A2 EP 0828713A2
Authority
EP
European Patent Office
Prior art keywords
coch
alkyl
formula
compound
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96916067A
Other languages
German (de)
English (en)
Inventor
Thomas Maetzke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis Pharma GmbH
Novartis AG
Original Assignee
Novartis Erfindungen Verwaltungs GmbH
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novartis Erfindungen Verwaltungs GmbH, Ciba Geigy AG filed Critical Novartis Erfindungen Verwaltungs GmbH
Publication of EP0828713A2 publication Critical patent/EP0828713A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/18—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, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/83—Thioacids; Thioesters; Thioamides; Thioimides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/86—Hydrazides; Thio or imino analogues thereof

Definitions

  • the present invention relates to novel substituted pyridine derivatives of the formula I below.
  • the invention also relates to the preparation of these substances and to compositions which comprise a compound of the formula I as an active compound.
  • the invention furthermore relates to the preparation of the said compositions and to the use of the active compounds or the compositions for protecting plants against infestation with pernicious microorganisms, for example fungi, bacteria and viruses.
  • X j is halogen or hydrogen
  • X 2 is halogen
  • Rj is hydrogen; C r C 4 alkyl which can be unsubstituted or substituted by phenyl,
  • R 4 and R 5 form, together with the nitrogen atom, a cyclopentylamine, cyclohexylamine, morpholine or dimethylmorpholine ring;
  • R 6 , R 7 , R 8 , R 9 and R 10 are hydrogen, Cj-C ⁇ lkyl, phenyl or pyridyl, where the phenyl radical or pyridyl radical can be unsubstituted or substituted once to three times by halogen, Cj-C 4 alkyl, hydroxyl, C j -C 2 alkoxy, trifluoromethyl or trifluoromethoxy; n is 0 or 1; and R 15 and R 16 are hydrogen, C 1 -C 4 alkyl, phenyl or benzyl.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Alkyl on its own or as a constituent of another substituent, is to be understood as meaning straight-chain or branched-chain alkyls. Depending on the number of carbon atoms indicated, they constitute the following groups, for example: methyl, ethyl and the isomers of propyl, butyl, pentyl or hexyl, for example isopropyl, isobutyl, tert-butyl, sec-butyl or isopentyl.
  • Alkenyl is, for example, 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl.
  • Alkynyl is, for example, 1-propynyl or 1-butynyl.
  • Cycloalkyl is optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopropyl, cyclopentyl or cyclohexyl.
  • Examples of those 5- or 6-membered heterocycles having nitrogen, oxygen and/or sulfur as heteroatoms which are preferred are: thiophene, thiazole, furan and pyridine.
  • Both X j and X 2 are either chlorine or bromine;
  • A is hydrogen, OR 3 , SR 3 or NHR 4 ;
  • R j is hydrogen, acetyl or benzoyl
  • R 5 is hydrogen
  • X j and X 2 are chlorine; Z is COOH, COOCH 3 or COObenzyl; and R ⁇ is hydrogen or acetyl.
  • These acetals can be open acetals, which are derived from C alcohols which have only one OH group (e.g. methanol, ethanol, propanol, isopropanol, etc.), or ring acetals, which are formed from -C ⁇ diols (e.g. glycol, 1,2-propanediol or 1,3-propanediol) or from glycerol.
  • the compound of the formula III can be reacted with a N,N-dialkylchloroformamide, for example N,N-diethylchloroformamide, in a polar solvent, for example dimethylformamide (DMF) or acetonitrile, in the presence of a base, for example triethylamine, to yield a compound of the formula IV.
  • a N,N-dialkylchloroformamide for example N,N-diethylchloroformamide
  • a polar solvent for example dimethylformamide (DMF) or acetonitrile
  • a base for example triethylamine
  • a compound of the formula IV with a lithium base, for example lithium 2,2,6,6-tetramethylpiperidide (LTMP), lithium diisopropylamide (LDA) or lithium hexamethyldisilazide (LHMDS), in an aprotic solvent, for example te rahydrofuran (THF), diethyl ether or hexane, at -20 to -80°C, and reaction with an electrophile, for example an alkyl chloroformate, a N,N-dialkylchloroformamide or C0 2 , yields, after aqueous working-up, a compound of the formula la or Ig, which, by means of acidic hydrolysis, for example in a mixture of concentrated hydrochloric acid and acetic acid, react to form a compound of the formula lb, which, by means of subsequent acid-catalysed esterification in an alcohol, for example methanol, yields a compound of the formula Ic, which,
  • a lithium base for example lithium 2,2,6,6-tetramethylpiperidide, lithium diisopropylamide or lithium hexamethyldisilazide
  • the compounds of the formula I in which X l is hydrogen or halogen, X 2 is halogen and Z is -CH(OR 2 ) 2 , and R is an alkyl radical (Cmpd. If), can be prepared by reacting a compound of formula le with an alcohol, for example methanol or ethanol, or with a glycol, for example ethylene glycol, in a solvent, for example toluene, which can be used as an entraining agent, under acidic catalysis using, for example, p-toluenesulfonic acid, and azeotropic removal of the water of reaction.
  • an alcohol for example methanol or ethanol
  • a glycol for example ethylene glycol
  • solvent for example toluene
  • the 2-fluoro-3-pyridinol (lllb) which is produced here is novel and can be prepared in high yield by diazotizing 2-amino-3-hydroxypyridine with sodium nitrite in a mixture of pyridine and hydrogen fluoride at temperatures of less than 25°C.
  • N,N-diethyl-2,6-dichloro-3-(N-diethylcarbamoyloxy)isonicotinamide which can be hydrolysed in a mixture of acetic acid and concentrated hydrochloric acid to give 2,6-dichloro-3-hydroxyisonicotinic acid, esterified in sulfuric methanol to give methyl 2,6-dichloro-3-hydroxyisonicotinate and finally reacted with acetyl chloride in a suitable solvent, for example acetonitrile, in the presence of a base such as pyridine or triethylamine to give methyl 2,6-dichloro-3-acetyloxyisonicotinate.
  • a suitable solvent for example acetonitrile
  • the 2,6-dichloro-3-hydroxyisonicotinoyl chloride can be obtained by reaction of the corresponding carboxylic acid with thionyl chloride or oxalyl chloride and be reacted with nucleophiles, for example benzyl alcohol or methylamine, to give benzyl 2,6-dichloro-3-hydroxyisonicotinate or N-methyl-2,6-dichloro-3-hydroxyisonicotinamide.
  • nucleophiles for example benzyl alcohol or methylamine
  • the corresponding thiocarboxylates or thiocarboxamides can be obtained by reaction with a thionating agent, for example phosphorus pentasulfide or
  • Suitable reaction-inert solvents and diluents are used as reaction media in process schemes 1 to 3, in conformity with the relevant reaction conditions.
  • Examples which may be mentioned are: aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes and petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; ethers and ether-like compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether), tert-butyl methyl ether, etc.), anisole, dioxane and tetrahydrofuran; nitriles, such as acetonitrile and propionitrile; N,N-dialkylated amides, such as dimethylformamide; dimethyl sulfoxide; ketones, such as acetone, diethyl
  • the compounds of the formula I according to the invention display a spectrum of activity which is very favourable in practice for protecting plants against diseases which are caused both by fungi and by bacteria and viruses.
  • the underlying mode of action of the compounds according to the invention is directed, in particular, towards effecting a general increase in the resistance of the treated plants, resulting in the achievement of a general antimicrobial resistance to a broad spectrum of harmful microorganisms.
  • the great advantage of the compounds according to the invention is that, when they are used for treating plants, they do not act directly on the phytopathogenic microorganisms but, instead, activate and stimulate the plant's own biological defence system prior to infestation, thereby providing the possibility of ensuring that the treated plants maintain their health by themselves, frequently without additional microbicidal substances being used during the vegetative period. Consequently, it is characteristic of the active compounds of the formula I that they do not exert any direct effect on the microorganisms but, instead, have the effect of immunizing healthy plants against plant diseases.
  • the resulting immunization against plant diseases can be employed to protect a large number of crop plants so that the appearance of harmful organisms on the plants or plant parts (fruits, blossoms, foliage, stalks, tubers and roots) of different economically useful crops is efficaciously prevented, with subsequently accruing plant parts also remaining free of phytopathogenic microorganisms.
  • the active compounds of the formula I exhibit their activity both by way of foliage application and systemically.
  • They may also be employed as dressing agents for treating seed (fruit, tubers and grains) and plant cuttings in order to protect them against fungal infections, for example against Fusarium nivale, Helminthosporium gramineum and Ustilago nuda, and also against phytopathogenic microorganisms which occur in the soil.
  • the spectrum of activity of the compounds of the formula I extends, for example, to phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Colletotrichum, Helminthosporium, Fusarium, Septoria, Cercospora and - 9 -
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Colletotrichum, Helminthosporium, Fusarium, Septoria, Cercospora and - 9 -
  • Basidiomycetens e.g. the genera Hemileia, Rhizocotonia and Puccinia
  • Ascomycetes e.g. Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula
  • the Oomycetes which belong to the Phycomycetes (e.g. Phytophthora, Plasmopara, Pythium, Bremia etc.).
  • the compounds according to the invention are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp., Pseudomonas spp. and Erwinia amylovora, and also against tobacco mosaic virus).
  • the invention also relates to compositions which comprise the compounds of the formula I as an active compound component, in particular plant-protecting compositions, and also to their use in the agricultural sector or related areas.
  • the present invention also includes the preparation of these compositions, wherein the active substance is intimately mixed with one or more of the herein-described excipients and surfactants.
  • the invention also includes a process for treating plants, wherein the novel compounds of the formula I, or the novel compositions containing these compounds, are applied.
  • Active compounds of the formula I are customarily used in the form of compositions and may be added, simultaneously or successively, to the surface or plant to be treated together with additional active compounds.
  • additional active compounds may be either fertilizers, trace element-supplying agents or other preparations which influence plant growth.
  • selective herbicides such as insecticides, fungicides, bactericides, nematicides or moUuscicides, or mixtures of several of these preparations, additionally, where appropriate, together with excipients, surfactants or other administration-promoting additives which are customary in formulation technology.
  • Suitable excipients and additives may be solid or liquid and are those substances which are appropriate in formulation technology, for example natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickening agents, binding agents or fertilizers.
  • a preferred method for applying an active compound of the formula I or an agrochemical composition which comprises at least one of these active compounds is application to the foliage (foliage application).
  • the frequency and rate of application depend on the infestation pressure of the pathogen concerned.
  • the active compounds of the formula I can also gain entry into the plant (systemic effect) by way of the soil and through the roots, by means of the plant site being drenched with a liquid preparation or the substances being introduced into the soil in solid form, for example in the form of granules (soil application).
  • the compounds of the formula I can also be applied (coating) to seed grains by either drenching the grains with a liquid preparation of the active compound or coating them with a solid preparation.
  • further modes of application are possible in particular cases, for example specific treatment of the plant stems or the buds, and the treatment of rice plants by means of the so-called "into water application” or "seedling box application”.
  • the compounds of the formula I are employed in unaltered form or, preferably, together with the adjuvants which are customary in formulation technology.
  • they are expediently processed, in a known manner, for example into emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusting compositions or granules, or by encapsulations in, for example, polymeric substances.
  • the methods of application such as spraying, nebulizing, dusting, scattering, coating or pouring, are, like the type of composition, selected in accordance with the sought-after aims and the given conditions.
  • Advantageous rates of application are in general from 0.5 g to 5 kg of active substance (AS) per ha; preferably from 1 g to 2 kg of AS ha, in particular from 1 g to 600 g of AS/ha and particularly preferably from 1 g to 500 g of AS/ha.
  • AS active substance
  • compositions, preparations or combinations which comprise the active compound of the formula I and, where appropriate, a solid or liquid additive are prepared in a known manner, for example by intimately mixing and/or grinding the active compounds with extenders, for example with solvents, solid excipients and, where appropriate, surface-active compounds (surfactants).
  • Suitable solvents are: aromatic hydrocarbons, preferably the C 8 to C 12 fractions, for example xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, and also their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and also, where appropriate, epoxidized plant oils such as epoxidized coconut oil or soyabean oil; or water.
  • aromatic hydrocarbons preferably the C 8 to C 12 fractions, for example xylene mixtures or substituted naphthalenes
  • natural crushed rocks such as calcite, talc, kaolin, montmorillonite or attapulgite
  • solid excipients for example for dusting compositions and dispersible powders.
  • Highly disperse silicic acid or highly disperse, absorbent polymers can also be added in order to improve the physical properties.
  • Porous types for example pumice stone, crushed brick, sepiolite or bentonite, are suitable for use as granulated, adsorptive granular excipients, while calcite or sand, for example, are suitable for use as non-sorptive excipient materials.
  • a large number of pregranulated materials of inorganic or organic nature can be used, such as, in particular, dolomite or comminuted plant residues.
  • Natural (animal or vegetable) or synthetic phospholipids from the cephalins and lecithins series which can, for example, be obtained from soyabeans, are also particularly advantageous application-promoting additives which can lead to a marked reduction in the rate of application.
  • nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties are suitable for use as surface-active compounds.
  • surfactants are also understood to mean surfactant mixtures.
  • Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble, synthetic surface-active compounds.
  • Soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (CJO-C 22 ), for example the sodium salts or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can, for example, be obtained from coconut oil or tallow oil.
  • CJO-C 22 substituted or unsubstituted ammonium salts of higher fatty acids
  • the sodium salts or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can, for example, be obtained from coconut oil or tallow oil.
  • the fatty acid methyllaurine salts may also be mentioned.
  • phosphates for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct, also come into consideration.
  • nonionic surfactants which may be mentioned are nonylphenol polyethoxy ethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethylene ethanol, polyethylene glycol and octylphenoxypolyethoxy ethanol.
  • fatty acid esters of polyoxyethylenesorbitan such as polyoxyethylene- sorbitan trioleate, also come into consideration.
  • the cationic surfactants are, in particular, quaternary ammonium salts which contain, as N substituents, at least one alkyl radical having from 8 to 22 C atoms, and, as additional substituents, have lower, halogenated or non-halogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • These salts are preferably present as halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the agrochemical preparations comprise from 0.1 to 99 %, in particular from 0.1 to 95 %, of the active compound of the formula I, from 99.9 to 1 %, in particular from 99.8 to 5 %, of a solid or fluid additive, and from 0 to 25 %, in particular from 0.1 to 25 %, of a surfactant.
  • concentrated compositions are more likely to be preferred as a commercial product, the consumer uses diluted compositions as a rule.
  • compositions may also comprise further additives, such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers, or other active compounds for achieving special effects.
  • additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers, or other active compounds for achieving special effects.
  • Agrochemical compositions which comprise compounds of the formula I as the active component likewise constitute a constituent of the present invention.
  • THF tetrahydrofuran
  • TMP tetramethylpiperidine
  • N,N-diethyl-2,6-dichloro-3-(N-diethylcarbamoyloxy)isonicotinamide are boiled at reflux for 72 hr in a mixture of 50 ml of acetic acid and 100 ml of concentrated hydrochloric acid. After that, most of the acetic acid is distilled off and the remaining suspension is diluted with 200 ml of water and cooled down to 0°C; the solid is then filtered off with suction. 2.2 g of beige crystals are obtained having an m.p. of 213-215°C (decomposition).
  • Emulsion concentrates a) b) c) Active compound from Tables 1 to 6 25 % 40 % 50 % Calcium dodecylbenzenesulfonate 5 % 8 % 6 % Castor oil polyethylene glycol ether 5 % - - (36 mol of ethylene oxide) Tributylphenoyl polyethylene glycol - 12 % 4 % ether (30 mol of ethylene oxide Cyclohexanone . 15 % 20 % Xylene mixture 65 % 25 % 20 %
  • Emulsions of any desired concentration may be prepared from these concentrates by diluting with water.
  • the solutions are suitable for use in the form of very small drops.
  • Ready-to-use dusting compositions are obtained by intimately mixing the excipients with the active compound.
  • the active compound is mixed with the additives and ground homogeneously in a suitable mill. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
  • Xylene mixture 50 % Emulsions of any desired concentration may be prepared from this concentrate by diluting with water.
  • Ready-to-use dusting compositions are obtained by mixing the active compound with the excipients and grinding on a suitable mill.
  • the active compound is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a current of air.
  • the finely ground active compound is applied uniformly, in a mixer, to the kaolin which has been moistened with polyethylene glycol. Dust-free coating granules are obtained in this manner.
  • the finely ground active compound is mixed intimately with the additives.
  • a suspension concentrate is obtained from which suspensions of any desired concentration may be prepared by diluting with water.
  • Example 3.1 Effect against Colletotrichum lagenarium on Cucumis sativus L. a) Residual protective effect
  • cucumber plants After having been cultivated for 10 days, cucumber plants are sprayed with a spray liquor (concentration: 200 ppm) which has been prepared from a wettable powder of the active compound.
  • a spray liquor concentration: 200 ppm
  • the plants are infected with a spore suspension (approximately 1.5xl0 5 spores/ml) of the fungus and incubated at a temperature of 23°C for 30 hours at high atmospheric humidity. The incubation is then continued at normal atmospheric humidity and at from 22°C to 23°C.
  • a spore suspension approximately 1.5xl0 5 spores/ml
  • cucumber plants After having been cultivated for 10 days, cucumber plants are treated, by means of application to the soil, with a spray liquor which has been prepared from a wettable powder of the active compound (concentration: 60 or 20 ppm based on the soil volume).
  • the plants are infected with a spore suspension (approximately 1.5xl0 5 spores/ml) of the fungus and incubated at a temperature of 23°C for 30 hours at high atmospheric humidity. The incubation is then continued at normal atmospheric humidity and at 22°C. 10 days after the infection, the protective effect is assessed on the basis of the fungal infestation.
  • a spore suspension approximately 1.5xl0 5 spores/ml
  • Example 3.2 Effect against Puccinia graminis on wheat a) Residual protective effect
  • wheat plants are sprayed with a spray liquor (0.02 % active substance) which has been prepared from a wettable powder of the active compound. After 24 hours, the treated plants are infected with an uredo spore suspension of the fungus. After a 48-hour incubation at 95-100 % relative atmospheric humidity and at approximately 20°C, the infected plants are placed in a greenhouse at approximately 22°C. The development of rust pustules is assessed at 12 days after the infection.
  • a spray liquor 0.02 % active substance
  • a spray liquor (0.006 % active substance based on the soil volume) which has been prepared from a wettable powder of the active compound is supplied by pouring to wheat plants 5 days after they have been planted. After 48-72 hours, the treated plants are infected with an urediospore suspension of the fungus. After a 48-hour incubation at 95-100 % relative atmospheric humidity and at approximately 20°C, the infected plants are placed in a greenhouse at approximately 22°C. The development of rust pustules is assessed at 12 days after the infection.
  • Example 3.3 Effect against Phytophthora infestans on tomato plants a) Residual protective effect
  • tomato plants After having been cultivated for 3 weeks, tomato plants are sprayed with a spray liquor
  • a spray liquor (0.002 % active substance based on the soil volume) which has been prepared from a wettable powder of the active compound is supplied by pouring to tomato plants after they have been cultivated for 3 weeks. Care is taken, in this context, to ensure that the spray liquor does not come into contact with the parts of the plants which are above the soil. After 48-72 hours, the treated plants are infected with a spore suspension of the fungus. The fungal infestation is assessed after incubating the infected plants for 24-96 hours at 90-100 % relative atmospheric humidity and at 20°C.
  • Grapevine seedlings are sprayed, at the 4-5 leaf stage, with a spray liquor (0.02 % active substance) which has been prepared from a wettable powder of the active compound.
  • the treated plants are infected with a sporangial suspension of the fungus.
  • the fungal infestation is assessed after incubating for 6 days at 95-100 % relative atmospheric humidity and at 20°C.
  • Example 3.5 Effect against Piricularia oryzae on rice plants a) Residual protective effect
  • rice plants After having been cultivated for 2 weeks, rice plants are sprayed with a spray liquor (0.02 % active substance) which has been prepared from a wettable powder of the active compound. After 48 hours, the treated plants are infected with a conidial suspension of the fungus. The fungal infestation is assessed after incubating for 5 days at 95-100 % relative atmospheric humidity and at 24°C.
  • a spray liquor 0.2 % active substance
  • a spray liquor (0.006% active substance based on the soil volume) which has been prepared from a wettable powder of the active compound is supplied by pouring to 18 day-old rice plants. After that, the pots are filled with water to such an extent that the lowest parts of the rice plant stems are standing in the water. After 96-120 hours, the treated rice plants are infected with a conidial suspension of the fungus. The fungal infestation is assessed after the infected plants have been incubated for 5 days at 100 % relative atmospheric humidity and at approximately 24°C.
  • Example 3.6 Effect against Pseudomonas lachrymans on Cucumis sativus L. a) Residual protective effect
  • cucumber plants After having been cultivated for 10 days, cucumber plants are sprayed with a spray liquor (concentration: 200 ppm) which has been prepared from a wettable powder of the active compound.
  • a spray liquor concentration: 200 ppm
  • cucumber plants After having been cultivated for 10 days, cucumber plants are treated, by means of application to the soil, with a spray liquor which has been prepared from a wettable powder of the active compound (concentration: 60 or 20 ppm based on the soil volume).
  • Example 3.7 Immunizing effect against tobacco mosaic virus on tobacco 8 week-old tobacco plants are sprayed (concentration: 200 ppm) or injected (concentration: 200 ppm) with a formulated solution of the active compound. After 4 days, the plants are inoculated mechanically with a suspension of tobacco mosaic virus (0.5 ⁇ g/ml + carborundum) and incubated at a temperature of 20°-22°C.
  • the protective effect is assessed on the basis of the number and size of the local lesions.
  • Example 3.8 Effect against Xanthomonas oryzae on rice (Oryza sativa) a) Residual protective effect
  • rice plants After having been cultivated for 3 weeks in a greenhouse, rice plants are sprayed with the test substance in the form of a spray liquor (0.02 % active substance). After this spray coating has dried on for one day, the plants are placed in a climate chamber at 24 °C and 75-85 % relative atmospheric humidity, and infected. The infection is achieved by cutting off the leaf tips with a pair of scissors which has previously been immersed in a suspension of Xanthomonas oryzae. After having been incubated for 10 days, the cut leaves, if infested, wilt, roll up and become necrotic. The extent of these disease symptoms is used to assess the residual activity of the test substance. b) Systemic effect
  • a suspension of the test substance is supplied to rice plants by pouring such that the rice plant itself is not wetted (0.006 % active substance based on the soil volume).
  • the plants are placed in a climate chamber at 24°C and 75-85 % relative atmospheric humidity, and infected.
  • the infection is achieved by cutting off the leaf tips with a pair of scissors which has previously been immersed in a suspension of Xanthomonas oryzae. After having been incubated for 10 days, the cut leaves, if infested, wilt, roll up and become necrotic. The extent of these disease symptoms is used to assess the systemic activity of the test substance.
  • Example 3.9 Effect against Xanthomonas vesicatoria on pepper (Capsicum annuum) a) Residual protective effect
  • pepper plants of the "California Wonder" variety are sprayed with the test substance in the form of a spray liquor (0.02 % active substance). After this spray coating has dried on for one day, the plants are placed in a climate chamber at 26°C and 95-100 % relative atmospheric humidity and infected by spraying the undersides of the leaves with a standardized suspension of Xanthomonas vesicatoria. After 6 days of incubation, round, initially watery, subsequently necrotic, bright spots are formed on the leaves, if they arc infested. The extent of these spots is used to assess the residual activity of the test substance.
  • pepper plants of the "California Wonder" variety are watered with a suspension of the test substance (0.006 % active substance based on the soil volume).
  • the plants are placed in a climate chamber at 26°C and 95-100 % relative atmospheric humidity and infected by spraying the undersides of the leaves with a standardized suspension of Xanthomonas vesicatoria. After incubating for 6 days, round, initially watery, subsequently necrotic, bright spots are formed on the leaves, if they are infested. The extent of these spots is used to assess the systemic activity of the test substance.
  • Example 3.10 Dressing effect against Fusarium nivale on rye
  • Rye of the Tetrahell variety which has been naturally infected with Fusarium nivale, is dressed with the test substance on a mixing roller, with the following concentrations being used: 600, 200 or 60 ppm of active substance (based on the weight of the seed).
  • the experimental plantation is cultivated under normal field conditions (preferably in a region where there is a complete covering of snow during the winter months).
  • the percentage proportion of plants which are infested with Fusarium is determined in the spring immediately after the snow has melted.
  • Example 3.11 Dressing effect against Helminthosporium gramineum on barley Winter barley of the "Cl" variety, which has been naturally infected with Helminthosporium gramineum, is dressed with the test substance on a mixing roller, with the following concentrations being used: 600, 200 or 60 ppm of active substance (based on the weight of the seed).
  • the percentage proportion of stems which are infested with Helminthospora is determined at the time of earing up.
  • Example 3.13 Dressing effect against Colletotrichum lagenarium on Cucumis sativus L.
  • Cucumber seeds are dressed with a solution of the active compound (concentration: 180 g/100 kg of seed). These seeds are sown.
  • the plants are infected with a spore suspension (approximately 1.5xl0 5 spores/ml) of the fungus and incubated for 36 hours at a high atmospheric humidity and at a temperature of 23°C. The incubation is then continued at normal atmospheric humidity and at from 22° to 23°C.
  • the protective effect is assessed on the basis of the fungal infestation.
  • Example 3.14 Residual protective effect against Venturia inaequalis on apple shoots
  • Apple cuttings having fresh shoots of 10-20 cm in length are sprayed with a spray liquor (0.02 % active substance) which has been prepared from a wettable powder of the active compound.
  • a spray liquor 0.2 % active substance
  • the treated plants are infected with a conidial suspension of the fungus.
  • the plants are then incubated for 5 days at 90-100 % relative atmospheric humidity and placed in a greenhouse at 20-24°C for a further 10 days. Scab infestation is assessed 15 days after the infection.
  • Example 3.15 Effect against Cercospora nicotianae on tobacco

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention se rapporte à de nouveaux dérivés de pyridine substitués de la formule générale (I) dans laquelle X1 représente halogène ou hydrogène, X2 représente halogène; Z représente -C(=O)A, -C(=S)A ou -CH(OR2)2, et dans laquelle A représente hydrogène, OR3, SR3, NR4R5, NHOR6, -ON=CR7R8 ou NH-N(=C)n(R9)R10; R1 est tel que défini dans le descriptif. Les nouveaux composés actifs possèdent des propriétés protégeant les plantes et sont notamment appropriés pour protéger les plantes contre les infestations de micro-organismes phytopathogènes tels que les champignons, les bactéries et les virus.
EP96916067A 1995-05-24 1996-05-14 Microbicides a base de pyridine Withdrawn EP0828713A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH154695 1995-05-24
CH1546/95 1995-05-24
PCT/EP1996/002060 WO1996037472A2 (fr) 1995-05-24 1996-05-14 Microbicides a base de pyridine

Publications (1)

Publication Number Publication Date
EP0828713A2 true EP0828713A2 (fr) 1998-03-18

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EP96916067A Withdrawn EP0828713A2 (fr) 1995-05-24 1996-05-14 Microbicides a base de pyridine

Country Status (6)

Country Link
EP (1) EP0828713A2 (fr)
JP (1) JPH11510788A (fr)
AU (1) AU5896396A (fr)
IL (1) IL118380A0 (fr)
WO (1) WO1996037472A2 (fr)
ZA (1) ZA964127B (fr)

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US6133447A (en) * 1998-02-27 2000-10-17 Novartis Crop Protection, Inc. Process for the preparation of substituted pyridines
AU6049199A (en) 1998-09-16 2000-04-03 Dow Agrosciences Llc 2-methoxyimino-2-(pyridinyloxymethyl)phenyl acetamides with (derivatised) hydroxyalkyl derivatives on the pyridine ring
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US6355660B1 (en) 1999-07-20 2002-03-12 Dow Agrosciences Llc Fungicidal heterocyclic aromatic amides and their compositions, methods of use and preparation
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CZ2002487A3 (cs) * 1999-08-20 2002-06-12 Dow Agrosciences Llc Fungicidní heterocyklické aromatické amidy, prostředky na jejich bázi, způsoby jejich pouľití a přípravy
EP1234827A3 (fr) * 1999-08-20 2003-06-18 Dow AgroSciences LLC Amides aromatiques, hétérocycliques fongicides et leurs compositions ainsi que mode d'emploi et préparation
KR100720766B1 (ko) * 1999-08-20 2007-05-22 다우 아그로사이언시즈 엘엘씨 살균성 헤테로사이클릭 방향족 아미드 및 그 조성물, 이용및 제조방법
US8138191B2 (en) 2007-01-11 2012-03-20 Critical Outcome Technologies Inc. Inhibitor compounds and cancer treatment methods
WO2009079797A1 (fr) 2007-12-26 2009-07-02 Critical Outcome Technologies, Inc. Composés et procédé pour le traitement du cancer
CA2999435A1 (fr) 2010-04-01 2011-10-06 Critical Outcome Technologies Inc. Composes et methodes pour le traitement du vih
CN102321016B (zh) * 2011-07-29 2013-04-10 山东轻工业学院 5-溴-2-羟基异烟酸甲酯的合成方法
AU2013370491B2 (en) 2012-12-28 2016-10-06 Corteva Agriscience Llc Synergistic fungicidal mixtures for fungal control in cereals
CN113173838A (zh) 2014-12-30 2021-07-27 美国陶氏益农公司 具有杀真菌活性的吡啶酰胺化合物
BR112017013105A2 (pt) 2014-12-30 2017-12-26 Dow Agrosciences Llc picolinamidas com atividade fungicida
KR20170100550A (ko) 2014-12-30 2017-09-04 다우 아그로사이언시즈 엘엘씨 살진균 활성을 갖는 피콜린아미드 화합물
JP6777637B2 (ja) 2014-12-30 2020-10-28 ダウ アグロサイエンシィズ エルエルシー 殺真菌剤としてのピコリンアミド
BR112017013645A2 (pt) 2014-12-30 2018-03-06 Dow Agrosciences Llc uso de compostos de picolinamida com atividade fungicida
US10214490B2 (en) 2016-08-30 2019-02-26 Dow Agrosciences Llc Picolinamides as fungicides
US10334852B2 (en) 2016-08-30 2019-07-02 Dow Agrosciences Llc Pyrido-1,3-oxazine-2,4-dione compounds with fungicidal activity
WO2018044991A1 (fr) 2016-08-30 2018-03-08 Dow Agrosciences Llc Composés de thiopicolinamide à activité fongicide
WO2018045006A1 (fr) 2016-08-30 2018-03-08 Dow Agrosciences Llc Composés de n-oxyde de picolinamide à activité fongicide
BR102018000183B1 (pt) 2017-01-05 2023-04-25 Dow Agrosciences Llc Picolinamidas, composição para controle de um patógeno fúngico, e método para controle e prevenção de um ataque por fungos em uma planta
TW201842851A (zh) 2017-05-02 2018-12-16 美商陶氏農業科學公司 用於穀類中的真菌防治之協同性混合物
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Publication number Publication date
WO1996037472A3 (fr) 1997-01-09
ZA964127B (en) 1996-11-25
IL118380A0 (en) 1996-09-12
WO1996037472A2 (fr) 1996-11-28
AU5896396A (en) 1996-12-11
JPH11510788A (ja) 1999-09-21

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