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WO1997003977A1 - Thiopyrannes microbicides - Google Patents

Thiopyrannes microbicides Download PDF

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Publication number
WO1997003977A1
WO1997003977A1 PCT/EP1996/002940 EP9602940W WO9703977A1 WO 1997003977 A1 WO1997003977 A1 WO 1997003977A1 EP 9602940 W EP9602940 W EP 9602940W WO 9703977 A1 WO9703977 A1 WO 9703977A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
plants
compounds
hydrogen
Prior art date
Application number
PCT/EP1996/002940
Other languages
English (en)
Inventor
Martin Zeller
Original Assignee
Novartis 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 Ag filed Critical Novartis Ag
Priority to AU65191/96A priority Critical patent/AU6519196A/en
Publication of WO1997003977A1 publication Critical patent/WO1997003977A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom

Definitions

  • the present invention relates to novel 2H-3,4-dihydrothiopyrans of formula I below, to the preparation of these substances and to agrochemical compositions comprising at least one of these compounds as active ingredient.
  • the invention also relates to the preparation of said compositions as well as to the use of the compounds or compositions for controlling or preventing the infestation of plants with phytopathogenic microorganisms, preferably fungi.
  • R has the following meaning:
  • alkyl, alkenyl and alkynyl radicals can be straight-chain or branched.
  • alkyl itself will be taken to mean, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl as well as their isomers, typically isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl, 2-methylhexyl, isooctyl.
  • Preferred compounds of formula I and their subgroups are also those, wherein the amino group and the COOR group are in cis position to one another (subgroup B).
  • a particularly preferred compound is cis-4-amino-2H-3,4-dihydrothiopyran-3-carboxylic acid.
  • Compounds of formula IV can be prepared by reacting a 2,3-dihydrothiopyran-4-one of formula II in an inert diluent such as a hydrocarbon, typically n-hexane, or in an ether, typically diethyl ether or tetrahydrofuran, or in a phosphoric triamide, typically hexamethylphosphoric triamide, or in mixtures of such inert diluents, first with a strong base such as alkali amide, typically lithium diisopropylamide or lithium tetramethyl- piperidide and then with a cyanoformate of formula III in the temperature range from -100° to +100°C, preferably from -80° to 0°C.
  • an inert diluent such as a hydrocarbon, typically n-hexane, or in an ether, typically diethyl ether or tetrahydrofuran, or in a phosphoric triamide, typically
  • Compounds of formula VI can be prepared by reacting a compound of formula IV with an oxime of formula V, wherein R j is hydrogen or C r C 6 alkyl, in an inert diluent such as an alcohol, typically methanol or ethanol, where appropriate in the presence of a base such as an organic base, typically triethylamine or pyridine, or an inorganic base, typically potassium carbonate or sodium carbonate, in the temperature range from -20°C to the reflux temperature of the reaction mixture, preferably from 0° to 50°C.
  • an inert diluent such as an alcohol, typically methanol or ethanol
  • a base such as an organic base, typically triethylamine or pyridine, or an inorganic base, typically potassium carbonate or sodium carbonate
  • Compounds of formula I can be prepared by reducing compounds of formula VI with metallic zinc in an inert organic or inorganic diluent such as an alcohol, typically methanol or ethanol, or in water or in a mixture of such inert diluents in the presence of an inorganic or organic acid such as a mineral acid, typically hydrochloric acid, or in a carboxylic acid, typically formic acid, in the temperature range from -70° to +100°C, preferably from -20° to +30°C.
  • an inert organic or inorganic diluent such as an alcohol, typically methanol or ethanol, or in water or in a mixture of such inert diluents
  • an inorganic or organic acid such as a mineral acid, typically hydrochloric acid, or in a carboxylic acid, typically formic acid, in the temperature range from -70° to +100°C, preferably from -20° to +30°C.
  • the compounds of formula I, wherein R is hydrogen, can be obtained by saponification of the esters on which they are based.
  • esters of formula I where appropriate in a diluent such as alcohol, typically methanol or ethanol, with optional addition of an inorganic or organic base such as an alkali metal hydroxide or alkaline earth metal hydroxide, typically sodium hydroxide, potassium hydroxide or barium hydroxide, with water in the temperature range from 0° to 150°C, preferably from 20° to 80°C.
  • a diluent such as alcohol, typically methanol or ethanol
  • an inorganic or organic base such as an alkali metal hydroxide or alkaline earth metal hydroxide, typically sodium hydroxide, potassium hydroxide or barium hydroxide, with water in the temperature range from 0° to 150°C, preferably from 20° to 80°C.
  • the acid addition salts of the compounds of formula I can be prepared by reacting the compounds of formula I with the corresponding acid, where appropriate in an inert diluent.
  • the basic salts of the compounds of formula I, wherein R is hydrogen can be prepared by reacting the compounds of formula I, wherein R is hydrogen, with the corresponding base, where appropriate in an inert diluent.
  • the basic salts of the compounds of formula I, wherein R is hydrogen, are obtained as products in reaction step c). They can be isolated by foregoing the separation of the alkali metal ion or alkaline earth metal ion.
  • the compounds of formula I are oils or solids which are stable at room temperature and which are distinguished by valuable microbicidal properties. They can be used in the agricultural sector or related fields preventively and curatively for controlling plant-injuring microorganisms.
  • the novel compounds of formula I are not only distinguished by excellent microbicidal and, in particular, fungicidal, action at low rates of concentration, but also by being particularly well tolerated by plants.
  • compounds of formula I have, for practical purposes, a very advantageous biocidal spectrum for controlling phytopathogenic microorganisms, in particular fungi. They have very useful curative and preventive properties and are used for protecting numerous cultivated plants.
  • the compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phyto- pathogenic fungi.
  • novel compounds of formula I are particularly effective against special species of the fungal classes Fungi imperfecti (e.g. Cercospora, Botrytis, Helminthosporium, Fusarium Septoria, Pyricularia and Alternaria), Basidiomycetes (e.g. Hemileia, Rhizoctonia, Puccinia) and also Ascomycetes (e.g. Podosphaera, Monilinia, Uncinula, Cercosporella, Erysiphe and Venturia), Deuteromycetes (e.g.. Rhynchosporium) and, in particular, against Oomycetes (e.g.
  • Fungi imperfecti e.g. Cercospora, Botrytis, Helminthosporium, Fusarium Septoria, Pyricularia and Alternaria
  • Basidiomycetes e.g. Hemileia, Rhizoctonia, Puccinia
  • Ascomycetes e.g. Podo
  • Plasmopara, Peronospora, Pythium, Bremia and Phytophthora themselves constitute an important enrichment of the compositions for controlling phytopathogenic fungi.
  • the compounds of formula I can also be used as dressing agents for the treatment of seeds (fruit, tubers, grains) and plant cuttings for the protection against fungus infections as well as against phytopathogenic fungi which occur in the soil.
  • the invention also relates to compositions which contain compounds of formula I as active components, in particular plant-protecting compositions, as well as to their use in the agricultural sector or related fields.
  • this invention also embraces the preparation of said compositions, which comprises intimately mixing the active substance with one or more than one substance or substance group described herein.
  • the process for the treatment of plants is also included, which process is distinguished by the application of the novel compounds of formula I or the novel compositions.
  • target crops to be protected as disclosed above typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum, spelt, triticale and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, straw ⁇ berries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinache, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado,
  • the compounds of formula 1 are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • These further compounds can be both fertilisers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
  • a preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula I may also be applied to propagation material (grains, fruit, tubers, shoots, seedlings, roots etc.) (dressing) either by drenching, for example, cereal grains (seeds) or potato tubers or freshly cut shoots with a liquid formulation of the compound or by coating them with a solid formulation.
  • the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation and are usefully formulated in known manner to, for example, emulsifiable concentrates, coatables pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha and, most preferably, from 20 g to 600 g a.i./ha.
  • compositions containing the compound of formula I and, if desired, a solid or liquid adjuvant are prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and, optionally, surfacte active compounds (surfactants).
  • extenders e.g. solvents, solid carriers and, optionally, surfacte active compounds (surfactants).
  • Suitable solvents may typically be: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms such as xylene mixtures or substituted naphthalenes; phthalates such as dibutyl or dioctyl phthalate; aliphatic hydrocarbons such as cyclohexane or paraffins; alcohols and glycols and their ethers and esters such as ethanol, diethylene glycol, 2-methoxyethanol or 2-ethoxyethanol; ketones such as cyclohexanone; strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide; as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
  • aromatic hydrocarbons preferably the fractions containing 8 to 12 carbon atoms such as xylene mixtures or substituted naphthalenes
  • phthalates such as dibutyl or dioctyl phthalate
  • the solid carriers typically used for dusts and dispersible powders are usually natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • highly dispersed silicic acid or highly dispersed absorbent polymers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, including pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand.
  • innumerable pregranulated materials of inorganic or organic origin may be used, especially dolomite or pulverised plant residues.
  • suitable surfactants are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be understood to include surfactant mixtures.
  • Suitable anionic surfactants may be so-called water-soluble soaps as well as water-soluble synthetic surface-active compounds.
  • nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ether, polyadducts of polypropylene and polyethylene oxide, tributyl- phenoxy polyethoxyethanol, polyethylene glycol and octylphenoxy polyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan are also suitable nonionic surfactants, typically polyoxyethylene sorbitan trioleate.
  • Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, at least one C 8 -C 2 alkyl radical and, as further substituents, unsubstituted or halogenated alkyl, benzyl or hydroxy-lower alkyl radicals.
  • Further surfactants customarily employed in the art of formulation are known to the expert or can be found in the relevant literature.
  • the agrochemical formulations will usually contain from 0.1 to 99 % by weight, preferably from 0.1 to 95 % by weight, of the compound of formula I, from 99.9 to 1 % by weight, preferably from 99.8 to 5 % by weight, of a solid or liquid adjuvant, and from 0 to 25 % by weight, preferably from 0.1 to 25 % by weight, of a surfactant.
  • compositions may also contain further adjuvants such as stabilisers, antifoams, viscosity regulators, binders or tackifiers as well as fertilisers, micronutrient donors or other formulations which influence plant growth for obtaining special effects.
  • adjuvants such as stabilisers, antifoams, viscosity regulators, binders or tackifiers as well as fertilisers, micronutrient donors or other formulations which influence plant growth for obtaining special effects.
  • R j H or lower alkyl, preferably methyl
  • the aqueous phase is adjusted to pH > 9 with 2 n of sodium hydroxide solution and extracted twice with 500 ml each of ethyl acetate.
  • the organic phases are washed once with 200 ml of a saturated solution of sodium chloride, dried over potassium carbonate and concentrated under vacuum, giving 2H-4-amino-3,4-dihydrothiopyran-3- carboxylic acid methyl ester (cis/trans-diastereoisomeric mixture) in the form of an oil (compound 3.1).
  • the product obtained (mixture of diastereoisomers) is chromatographed over silica gel with ethyl acetate/n-hexane.
  • the first component to elute is cis-2H-4-amino-3,4- dihydrothiopyran-3-carboxylic acid methyl ester (compound 3.2) in the form of an oil;
  • the second component to elute is trans-2H-4-amino-3,4-dihydrothiopyran-3-carboxylic acid methyl ester (compound 3.3) in the form of an oil.
  • Wettable powders a) b) c) compound of Table 3 or 4 25 % 50 % 75 % sodium ligninsulfonate 5 % 5 % - sodium laurylsulfate 3 % - 5 % sodium siisobutylnaphthalenesulfonate - 6 % 10 % octylphenol polyethylene glycol ether - 2 % - (7-8 mol ethylene oxide) highly disperse silica 5 % 10 % 10 % kaolin 62 % 27 % -
  • the compound is thoroughly mixed with the adjuvants and the mixture is well ground in a suitable mill to give wettable powders which can be diluted with water to suspensions of any desired concentration.
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • the compound is mixed with the adjuvants, ground and moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground compound mixture is uniformly applied in a mixer to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
  • the finely ground compound is intimately mixed with the adjuvants to give a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Vine seedlings in the 4-5 leaf stage are sprayed with a spray mixture prepared from a wettable powder formulation of the compound (0.02 % active ingredient). After 24 hours, the treated plants are infected with a spore suspension of the fungus. Evaluation of the fungus attack is made after a 6-day incubation at 95-100 % relative humidity and at 20°C.
  • the compounds of Tables 3 and 4 inhibit the fungus infestation completely (residual infestation 0 to 10 %), whereas Plasmopara infestation of untreated but infected control plants is 100 %.
  • tomato plants are sprayed with a spray mixture prepared from a wetttable powder formulation of the compound (0.02 % active ingredient). After 48 hours, the treated plants are infected with a spore suspension of the fungus. Evaluation of the fungus attack is made after a 4-day incubation of the infected plants at 90-100 % relative humidity and at 18°C.
  • tomato plants are treated with a spray mixture prepared from a wettable powder formulation of the compound (0.002 % active ingredient, based on the volume of soil), taking care that the spray mixture does not come into contact with the parts of the plant above the ground.
  • the treated plants are infected with a spore suspension of the fungus. Evaluation of the fungus attack is made after a 4-day incubation of the infected plants at 90-100 % relative humidity and at 18°C.
  • Wheat plants are sprayed 6 days after sowing with an aqueous spray mixture (0.02% active ingredient) to drip point and infected with a uredospore suspension of the fungus 48 hours later. After a 48-hour incubation (conditions: : 95-100% relative humidity at 20°C), the plants are stood in a greenhouse at 22°C. Evaluation of the rust pustule development is made 10 days after infection.
  • Wheat plants are watered 4 days after sowing with an aqueous spray mixture (0.002% active ingredient, based on the volume of the soil), taking care that the spray mixture does not come into contact with parts of the plant above the ground. 96 hours later, the plants are infected with a uredospore suspension of the fungus. After a 48-hour incubation (conditions: 95 to 100% relative humidity at 20°C), the plants are stood in a greenhouse at 22°C. Evaluation of rust pustule development is made 10 days after infection.
  • potato plants (Bintje) are treated with a spray mixture prepared from a wettable powder formulation of the compound (0.002 % active ingredient, based on the volume of soil), taking care that the spray mixture does not come into contact with parts of the plants above the ground.
  • the treated plants are infected with a spore suspension of the fungus. Evaluation of the fungus attack is made after a 5-day incubation of the infected plants at 90-100% relative humidity and at 20°C.
  • Compounds of foramula I are generally able to reduce the infestation to less than 20%, in some cases even completely, in particular the compounds 3.2 and 4.2.
  • Wheat plants (7 days old) are sprayed with spray mixture prepared from a formulated test substance (0.02% a.i.) and are infected with a conidia suspension of the fungus 48 hours later. After a 48-hour incubation time (95-100 % relative humidity and at 20°C), the plants are stood in a greenhouse at 21°C. Evaluation of the infestation is made 11 days after infection.
  • the compounds of formula I reduce the infestion to less than 20 % compared with the untreated control.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention se rapporte à de nouveaux 2H-3,4-dihydrothiopyrannes de la formule générale suivante (I) et à ses sels. Dans cette formule, R représente hydrogène, C1-C8 alkyle, C3-C8 alcényle ou C3-C8 alcynyle et n vaut 0, 1 ou 2. Ces substances sont de précieux microbicides que l'on peut utiliser dans la protection phytosanitaire sous forme de compositions adéquates, et qui servent généralement à venir à bout des maladies fongiques.
PCT/EP1996/002940 1995-07-14 1996-07-04 Thiopyrannes microbicides WO1997003977A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU65191/96A AU6519196A (en) 1995-07-14 1996-07-04 Thiopyrans microbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH208495 1995-07-14
CH2084/95 1995-07-14

Publications (1)

Publication Number Publication Date
WO1997003977A1 true WO1997003977A1 (fr) 1997-02-06

Family

ID=4225532

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002940 WO1997003977A1 (fr) 1995-07-14 1996-07-04 Thiopyrannes microbicides

Country Status (4)

Country Link
AR (1) AR002809A1 (fr)
AU (1) AU6519196A (fr)
WO (1) WO1997003977A1 (fr)
ZA (1) ZA965937B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6225270B1 (en) 1996-12-02 2001-05-01 Henkel Kommanditgesellschaft Auf Aktien Shaped soap products containing alkyl oligaglycasides and talcum

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 86, no. 27, 1977, Columbus, Ohio, US; abstract no. 189719f, page 591; column 1; XP002015358 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6225270B1 (en) 1996-12-02 2001-05-01 Henkel Kommanditgesellschaft Auf Aktien Shaped soap products containing alkyl oligaglycasides and talcum

Also Published As

Publication number Publication date
ZA965937B (en) 1997-01-07
AU6519196A (en) 1997-02-18
AR002809A1 (es) 1998-04-29

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