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WO1993024463A1 - Pyrazolines substituees et leur utilisation comme pesticides - Google Patents

Pyrazolines substituees et leur utilisation comme pesticides Download PDF

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Publication number
WO1993024463A1
WO1993024463A1 PCT/EP1993/001229 EP9301229W WO9324463A1 WO 1993024463 A1 WO1993024463 A1 WO 1993024463A1 EP 9301229 W EP9301229 W EP 9301229W WO 9324463 A1 WO9324463 A1 WO 9324463A1
Authority
WO
WIPO (PCT)
Prior art keywords
spp
formula
pyrazolines
substituted
triethylamine
Prior art date
Application number
PCT/EP1993/001229
Other languages
German (de)
English (en)
Inventor
Johannes Kanellakopulos
Rainer Fuchs
Christoph Erdelen
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Publication of WO1993024463A1 publication Critical patent/WO1993024463A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • the invention relates to new, substituted pyrazolines, several processes for their preparation and their use as pesticides.
  • R 1 , R 2 and R 3 have the meaning given above, either
  • R 4 has the meaning given above
  • R 4 has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.
  • reaction sequence of process (b) according to the invention can be represented by the following formula:
  • Formula (II) provides a general definition of (a) and (b) pyrazolines which are unsubstituted in the 1-position as starting materials.
  • R 1 , R 2 and R 3 represent those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention.
  • pyrazolines of the formula (II) which are unsubstituted in the 1-position are not yet known. They are obtained, for example, if phenacylamine derivatives of the formula (V)
  • R 1 , R 2 and R 3 have the meaning given above, with dimethylmethyleneimmonium chloride of the formula (VI)
  • R 1 , R 2 and R 3 have the meaning given above, optionally with hydrazine hydrate in the presence of a diluent such as acetonitrile at temperatures between 30 ° C and 80 ° C.
  • Phenacylamine derivatives of the formulas (V) or (Va) are known or can be obtained in analogy to known processes (cf., for example, Chem. Ber, 122, 295-300 [1989]; J. Med. Chem, 29, 333-341 [1986 ]; J. Amer. Chem. Soc. 98, 3621-3627
  • Phenacyldiamine derivatives of the formula (VII) are known in some cases (see, for example, US 2980674 [1957] and CA 56: 3419 [1962]).
  • Phenacyl enamine derivatives of the formula (VIII) are known or can be obtained by analogy with known processes (cf., for example, Chem. Ber. 93, 387-391 [1960]; Sankyo Kenkyusho Nempo 15, 36 [1963] or Chem. Abstr. 60: 11876d
  • Formula (III) provides a general definition of the isocyanates required as starting materials for carrying out process (a) according to the invention.
  • R 4 preferably represents those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention.
  • the isocyanates of the formula (III) are generally known compounds of organic chemistry.
  • Formula (IV) provides a general definition of the carbamic acid chlorides required as starting materials for carrying out process (b) according to the invention.
  • R 4 represents those radicals which have already been mentioned for these substituents in connection with the description of the substances of the formula (I) according to the invention.
  • the carbamic acid chlorides of the formula (IV) are generally known or can be obtained using known processes (cf., for example, JP 57-108057 or Chem. Abstr, 98: 53440y; JP-A 50-089344 or Chem. Abstr. 83: 205987n; DE-A
  • Inert organic solvents are suitable as diluents for carrying out processes (a) and (b) according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, if appropriate halogenated hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone or butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl
  • Processes (a) and (b) according to the invention can be carried out without reaction auxiliaries.
  • All customary inorganic or organic bases can be used as reaction aids. These include, for example, alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide or also ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate or ammonium amine triethylamine amine, such as triethylamine amine, as well as triethylamine amine, as well as triethylamine, amine triethylamine amine, such as triethylamine, as well as triethylamine, amine triethylamine, as well as triethylamine, amine triethylamine
  • Processes (a) and (b) according to the invention are usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • reaction products are worked up, worked up and isolated using generally customary methods (cf. the preparation examples).
  • 1.0 to 2.5 mol, preferably 1.0 to 1.5 mol, of carbamic acid chloride of the formula (IV) are generally employed per mol of pyrazoline of the formula (II) which is unsubstituted in the 1-position ) and optionally 0.01 to 2.0 mol, preferably 0.1 to 1.2 mol, of base used as reaction auxiliary.
  • the reaction is carried out, worked up and isolated according to generally customary methods.
  • the active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Diplopoda e.g. Blaniulus guttulatus
  • Chilopoda e.g. Geophilus carpophagus, Scutigera spec
  • Symphyla e.g. Scutigerella Immaculata
  • Thysanura e.g. Lepisma saccharina
  • Collembola e.g. Onychiurus armatus
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis,
  • Dermaptera e.g. Auricular forficula
  • Pemphigus spp. Pediculus humanus corporis, Haematopinus spp ,, Linognathus spp;
  • Damalinea spp from the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci;
  • Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp;
  • Homoptera from the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum humenae, Phyophorosumum, Phyophorosumum, Myzus sononum, Myzus sononum.
  • Homoptera for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum humenae, Phy
  • Lepidoptera from the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp;
  • Scorpio maurus for example Scorpio maurus, Latrodectus mactans
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp ,, Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes, Psoroptes Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae,
  • Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
  • the active compounds according to the invention can be used particularly successfully to control insects which damage plants, for example against the larvae of horseradish leaf beetles (Phaedon cochleariae) or against the caterpillars of the cockroach (Plutella maculipennis).
  • the active substances can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., and ULV cold and warm mist formulations.
  • customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., and ULV cold and warm mist formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalene, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide;
  • Solid carrier materials are suitable: for example natural stone powder, such as ka
  • Solid carrier substances for granules are: eg broken and fractionated natural Ge stones such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks;
  • suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • the following may be used as dispersants: for example
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g.
  • Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others.
  • the active compounds can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active substances When used against hygiene pests and pests of stored products, the active substances are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
  • the preparation and use of the active compounds according to the invention can be seen from the examples below:
  • reaction mixture is cooled, precipitated solid is filtered off with suction and dried.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed) 0% means that no beetle larvae have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cabbage cockroach (Plutella maculipennis) while the leaves are still moist.
  • the death rate is determined in%. 100% means that all caterpillars have been killed) 0% means that no caterpillars have been killed.

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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)

Abstract

L'invention concerne de nouvelles pyrazolines substituées qui ont la notation donnée dans le descriptif, ainsi que plusieurs procédés de fabrication les concernant et leur utilisation comme pesticides.
PCT/EP1993/001229 1992-05-29 1993-05-17 Pyrazolines substituees et leur utilisation comme pesticides WO1993024463A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4217864.9 1992-05-29
DE19924217864 DE4217864A1 (de) 1992-05-29 1992-05-29 Substituierte Pyrazoline

Publications (1)

Publication Number Publication Date
WO1993024463A1 true WO1993024463A1 (fr) 1993-12-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/001229 WO1993024463A1 (fr) 1992-05-29 1993-05-17 Pyrazolines substituees et leur utilisation comme pesticides

Country Status (3)

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AU (1) AU4313193A (fr)
DE (1) DE4217864A1 (fr)
WO (1) WO1993024463A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005007157A1 (fr) * 2003-07-15 2005-01-27 Bayer Healthcare Ag Pyrazolines utilisees comme antagonistes par-1 pour traiter des maladies cardio-vasculaires
US8669053B2 (en) 1999-08-18 2014-03-11 Illumina, Inc. Compositions and methods for preparing oligonucleotide solutions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0226536A2 (fr) * 1985-12-02 1987-06-24 Ciba-Geigy Ag Dérivés de la (di)alcoxycarbonylamino-s-triazine avec activité contre les insectes parasites des animaux et des plantes
EP0466408A1 (fr) * 1990-07-13 1992-01-15 Rohm And Haas Company Carboxamides de N-aryl-3-aryl-4,5-dihydro-1H-pyrazoles-1 substitués en position 4 et leurs procédés de préparation
EP0529451A1 (fr) * 1991-08-28 1993-03-03 Bayer Ag Pyrazolines substitués comme pesticides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0226536A2 (fr) * 1985-12-02 1987-06-24 Ciba-Geigy Ag Dérivés de la (di)alcoxycarbonylamino-s-triazine avec activité contre les insectes parasites des animaux et des plantes
EP0466408A1 (fr) * 1990-07-13 1992-01-15 Rohm And Haas Company Carboxamides de N-aryl-3-aryl-4,5-dihydro-1H-pyrazoles-1 substitués en position 4 et leurs procédés de préparation
EP0529451A1 (fr) * 1991-08-28 1993-03-03 Bayer Ag Pyrazolines substitués comme pesticides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8669053B2 (en) 1999-08-18 2014-03-11 Illumina, Inc. Compositions and methods for preparing oligonucleotide solutions
WO2005007157A1 (fr) * 2003-07-15 2005-01-27 Bayer Healthcare Ag Pyrazolines utilisees comme antagonistes par-1 pour traiter des maladies cardio-vasculaires

Also Published As

Publication number Publication date
AU4313193A (en) 1993-12-30
DE4217864A1 (de) 1993-12-02

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