Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles

Definitions

• the present invention relates to fungicidal compositions based on nicotinic derivatives, novel nicotinic derivatives and the use of nicotinic derivatives for the control of fungal plant diseases, and in particular against rice blast.
• a more particular subject of the invention is fungicidal compositions characterized in that they contain, as active material, at least one compound of formula:
• A is a thiazolyl radical of one of the formulas
• R 1 and R 2 which are identical or different, are:
• a linear or branched alkyl or alkenyl radical of 1 to 18 carbon atoms unsubstituted or substituted by a phenyl or phenoxy the phenyl ring of which can be substituted with one to five substituents chosen from the group comprising a halogen atom, an alkyl or alkoxy radical of 1 to 4 carbon atoms, . or a phenyl radical unsubstituted or substituted by one to five substituents chosen from the group comprising a halogen atom, an alkyl or alkoxy radical of 1 to 4 carbon atoms. either a pyridyl or thiofenyl radical
• - Z is an optionally substituted methylene radical
• - m is an integer from 1 to 4, preferably 1 or 2.
• - Y is a halogen atom or an alkyl or alkoxy radical of 1 to 4 carbon atoms
• - n is an integer from 0 to 3.
• Preferred compounds have the formula I, in which A has the formula II, more particularly those in the formula in which R 2 is an alkyl radical of 1 to 4 carbon atoms or a phenyl unsubstituted or substituted by 1 to 3 substituents chosen from the group comprising a chlorine atom, a methyl or ethyl radical, or methoxy or ethoxy.
• the derivatives of formula I can be obtained according to several methods: first, the reaction of a compound of formula V with a suitable thiazoloalkyl halide can be carried out according to the scheme (Method A):
• M is an alkali metal atom
• X is a halogen atom and the other substituents have the same meaning as above.
• the reaction is carried out in an aliphatic or aromatic solvent medium, for example optionally halogenated hydrocarbons (for example toluene), or amides, ketones, or nitriles (for example acetonitrile).
• a catalyst of the phase transfer catalyst type such as, for example, tris (dioxa-3,6 heptyl) amine (TDA-1) or crown ether 18-6.
• the reaction is carried out in an aromatic solvent such as for example toluene, in the presence of a catalytic amount of a base such as sodium methylate with distillation of the methanol-solvent azeotrope as the methanol is formed.
• aromatic solvent such as for example toluene
• Example 3 By operating according to the procedures of Examples 1 or 2, the following compounds are obtained, the formula and the physico-chemical characteristics of which are given in the following table:
• Example 4 The procedure of Example 2 is followed by replacing chloromethyl-4-methyl-2-thiazole with an equimolar amount of (chloro) -2-ethyl-5 methyl 4-thiazole. 5.5 g of a compound with a melting point of 88 ° C. are obtained, corresponding to 2-cyano-nicotinate of (methyl-4) 5-thiazolyl-2 ethyl.
• Example 5 Greenhouse test, on Piricularia o ryzae Potted rice plants (Marcheti rosa variety) 10 cm high, are treated by watering the soil, with an aqueous suspension containing:
• This suspension applied to 7 cm square pots, corresponds to a dose of approximately 60 kg / ha of active ingredient.
• the product is left to absorb by the soil.
• Part of the rice plants were not treated to serve as controls.
• all the rice plants are contaminated with a suspension of Pyricularia oryzae spores obtained by scraping off an in vitro culture, by spraying the leaves at the rate of 5 ml of suspension per pot.
• the pots are incubated for 48 h at 25 ° C under 100 ° relative humidity. The plants are then placed in a greenhouse observation cell
• the products according to the invention can be used alone, dispersed or dissolved in water or in the form of compositions which can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, of thixotropic agents, penetration agents, stabilizers, sequestrants, etc. as well as other known active materials with pesticide properties (notably insecticides or fungicides) or with properties promoting plant growth (especially fertilizers) or with properties regulators of plant growth. More generally, the compounds according to the invention can be combined with all the solid or liquid additives corresponding to the usual techniques of formulation.
• 0.5 to 5000 ppm of active substance are suitable; these values are indicated for the compositions ready for application.
• Ppm means "part per million”.
• the zone from 0.5 to 5000 ppm corresponds to a zone from 5x10 -5 to 0.5% (percentages by weight).
• compositions suitable for storage and transport they more advantageously contain from 0.5 to 95% (by weight) of active substance.
• the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 5.10 -5 % to 95% (by weight).
• the compounds according to the invention are generally associated with s uppo r t s and even t u l emen t s s agen t s tens i oac t i f s.
• support in the present description, is meant an organic or mineral, natural or synthetic material, with which the active material is associated to facilitate its application to the plant, to seeds or to the soil.
• This support is therefore generally inert and it must be acceptable in agriculture, especially on the treated plant.
• the support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.).
• the surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines , substituted phenols (especially alkylphenols or arylphenols), ester salts of sulfosuccinic acids, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols.
• the presence of at least one surfactant is generally essential when the active material and / or the inert support are not soluble in water and the vector agent for the application is water.
• compositions used in the invention can be in fairly diverse forms, solid or liquid.
• forms of solid compositions mention may be made of dusting powders (with an active ingredient content of up to 100%).
• liquid compositions or intended to constitute liquid compositions during application mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, powders wettable (or spraying powder), granules, pastes.
• Emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, emulsions or solutions ready for application containing, for their part, 0.001 to 20% of active material.
• the emulsifiable concentrates can contain, when necessary, a suitable co-solvent and from 2 to 20% of suitable additives, such as stabilizers, surfactants, in particular emulsifiers, penetrating agents, corrosion inhibitors, dyes, adhesives.
• suitable additives such as stabilizers, surfactants, in particular emulsifiers, penetrating agents, corrosion inhibitors, dyes, adhesives.
• emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to grading.
• the concentrated suspensions are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0 , 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is little or not soluble: certain organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreezes for water .
• Example SP 1 is the composition of several aqueous suspensions according to the invention:
• An aqueous suspension comprising: - active material (compound No. 1) briefly-2018. 500 g / l
• Example SP 2 - Aqueous suspension A concentrated fluid suspension is thus obtained.
• Example SP 2 - Aqueous suspension A concentrated fluid suspension is thus obtained.
• An aqueous suspension comprising: -active material (compound 2) ...2016-2018 7-8 100 g / l
• Example SP 3 - Aqueous suspension An aqueous suspension is prepared comprising:
• Wettable powders are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0 to 5% of a wetting agent, 3 to 10% of a dispersing agent, and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents , etc.
• Example PM 1 wettable powder - active material (compound 1 according to the invention) 50%
• Example PM 2 10% wettable powder - active ingredient (compound 4) briefly a wettable powder - active ingredient (compound 4) convenientlyanna a .
• Example PM 3 75% wettable powder containing the same ingredients as in the example above, in the following proportions: - active ingredient (compound n ° 2) briefly-2018 ................. 75%
• Example PM 4 90% wettable powder
• Example PM 5 50% wettable powder
• the active material is intimately mixed in appropriate mixers with the additional substances and ground with mills or other suitable grinders.
• the compounds according to the invention can advantageously be formulated in the form of water-dispersible granules also included within the scope of the invention.
• These dispersible granules of apparent density generally comprised between approximately 0.3 and 0.6, have a particle size generally comprised between approximately 150 and 2000 and preferably between 300 and 1500 microns.
• the content of active material (compound No. 4) of these granules is generally between approximately 1% and 90%, and preferably between 25% and 90%.
• the rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water.
• These granules can be essentially of two distinct types depending on whether the charge selected is soluble or not in water.
• the filler When the filler is water-soluble, it can be mineral and preferably organic. Excellent results have been obtained with urea.
• an insoluble filler it is preferably mineral, such as kao lin or bentonite.
• surfactant adjuvants of which more than half is constituted by at least one dispersing agent, essentially anionic, such as a poly (alkaline or alkaline earth naphthalene sulfonate) or an alkaline or alkaline earth lignosulfonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali or alkaline earth alkyl naphthalene sulfonate.
• dispersing agent essentially anionic, such as a poly (alkaline or alkaline earth naphthalene sulfonate) or an alkaline or alkaline earth lignosulfonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali or alkaline earth alkyl naphthalene sulfonate.
• anionic such as a poly (alkaline or alkaline earth naphthalene sulfonate) or an alkaline or alkaline earth
• the granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above. Preferably, it is obtained by extrusion, operating as indicated in the examples below.
• Example GD I Dispersible granules containing 90% active material
• Example GD 2 Dispersible granules with 75% active ingredient
• This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between 0.16 and 0.40 mm.
• These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions.
• aqueous dispersions and emulsions for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the compositions which can be used in the present invention.
• the emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".
• This process is characterized in that it consists in applying to these plants an effective amount of a composition containing as active material a compound according to formula (I).
• effective amount means an amount sufficient to allow the control and destruction of the fungi present on these plants.
• the doses of use can however vary within wide limits according to the fungus to fight, the type of culture, climatic conditions, and depending on the compound used.
• doses ranging from 1 g / hl to 500 g / hl corresponding substantially to doses of active material per hectare from 10 g / ha to approximately 5000 g / ha generally give good results.

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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)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Plural Heterocyclic Compounds (AREA)
• Pyridine Compounds (AREA)

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• 1987
  • 1987-07-10 FR FR8710175A patent/FR2617844B1/fr not_active Expired - Lifetime
• 1988
  • 1988-06-28 IL IL86894A patent/IL86894A0/xx unknown
  • 1988-06-30 AU AU20717/88A patent/AU2071788A/en not_active Abandoned
  • 1988-06-30 JP JP63505878A patent/JPH02504031A/ja active Pending
  • 1988-06-30 KR KR1019890700446A patent/KR890701583A/ko not_active Application Discontinuation
  • 1988-06-30 HU HU884185A patent/HUT54466A/hu unknown
  • 1988-06-30 BR BR888807610A patent/BR8807610A/pt unknown
  • 1988-06-30 WO PCT/FR1988/000347 patent/WO1989000568A1/fr not_active Application Discontinuation
  • 1988-06-30 EP EP88905894A patent/EP0371045A1/fr not_active Withdrawn
  • 1988-07-08 GR GR880100452A patent/GR880100452A/el unknown
  • 1988-07-08 ES ES8802148A patent/ES2010764A6/es not_active Expired
  • 1988-07-08 DD DD88317744A patent/DD285278A5/de unknown
  • 1988-07-08 ZA ZA884943A patent/ZA884943B/xx unknown
  • 1988-07-09 CN CN88104340A patent/CN1030585A/zh active Pending
  • 1988-07-11 US US07/217,327 patent/US4908375A/en not_active Expired - Fee Related

Non-Patent Citations (1)

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