WO1997016971A1

WO1997016971A1 - Insecticides

Info

Publication number: WO1997016971A1
Application number: PCT/EP1996/004574
Authority: WO
Inventors: Wolfgang Wirth; Uwe Priesnitz; Gerhard Baron
Original assignee: Bayer Aktiengesellschaft
Priority date: 1995-11-03
Filing date: 1996-10-22
Publication date: 1997-05-15
Also published as: DE19540948A1; AU7296996A; ZA969209B

Abstract

The invention concerns insecticides containing agonists or antagonists of the nicotinergenic acetyl choline receptors of insects, urea or urea derivatives and surface-active compounds.

Description

Insecticidal agents

The present invention relates to insecticidal compositions containing agonists or antagonists of the nicotinergic acetylcholine receptors of insects, urea or its derivatives and surface-active substances

Agonists or antagonists of the nicotinergic acetylcholine receptors of insects are known, for example from the following publications

European Patent Application Nos. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600,

192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389, German Offenlegungsschriften Nr. 3 639 877, 3 712 307, Japanese Offenlegungsschriften Nr 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072, U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686 ,

5,034,404, PCT applications No. WO 91/17 659, 91/4965, French application No. 2 611 1 14, Brazilian application No. 88 03 621

Reference is hereby expressly made to the methods, processes, formulas and definitions described in these publications, as well as to the individual preparations and compounds described

Mixtures of insecticides with ammonium salts are known from EP-A 664 081. The compatibility and the action of these mixtures are not satisfactory in every case

The subject of the present invention are

1 insecticidal agent, characterized by a content of a mixture of

Agonists or antagonists of the nicotinergic acetylcholine receptors of insects, urea or its derivatives, as well as surfactants and

other fillers

Use of mixtures of agonists or antagonists of the nicotinergic acetone receptors in insects, urea or its Derivatives as well as surface-active substances and possibly other fillers for controlling insects

Process for controlling insects, characterized in that agonists or antagonists of the nicotinergic acetylcholine receptors in insects, urea or its derivatives and surface-active substances and, if appropriate, further fillers are allowed to act on insects and / or their habitat

Process for the preparation of insecticidal agents, characterized in that agonists or antagonists of the nicotinergic acetylcholine receptors of insects with urea or its derivatives,

Extenders and / or diluents and surface-active substances mixed

The action and plant tolerance of the mixtures according to the invention are outstanding

Agonists or antagonists of the nicotinergic acetylcholine receptors of insects are sometimes summarized under the term nitromethylenes and related compounds

These compounds can preferably be represented by the general formula (I)

(A)

/

NI (Z) \ (I) ^,

X E

in which

R represents hydrogen, optionally substituted radicals from the group acyl, alkyl,

Aryl, aralkyl, heteroaryl or heteroarylalkyl, A for a monofunctional group from the series hydrogen, acyl, alkyl,

Aryl or a bifunctional group which is linked to the radical Z,

E represents an electron-withdrawing residue,

X stands for the radicals -CH = or = N-, the radical -CH = instead of

H atom can be linked to the radical Z;

Z for a monofunctional group from the series alkyl, -O-R, -S-R,

R N stands for a bifunctional group that is associated with the

R

Radical A or the radical X is linked.

Compounds of the formula I in which the radicals have the following meaning are particularly preferred

R represents hydrogen and also optionally substituted radicals from the

Series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroarylalkyl.

Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl-) - (aryl-) - phosphoryl, which in turn can be substituted, may be mentioned as acyl radicals.

_{Examples of} alkyl which may be mentioned are C _μl0 -alkyl, in particular C, _.4- alkyl, in particular methyl, ethyl, i-propyl, see- or t-butyl, which in turn can be substituted

Phenyl, naphthyl, in particular phenyl, may be mentioned as aryl

Phenylmethyl and phenethyl may be mentioned as aralkyl

Heteroaryl with up to 10 ring atoms and N, O, S in particular N as heteroatoms may be mentioned as heteroaryl. Thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl and benzothiazolyl may be mentioned in particular Heteroaryl alkyl which may be mentioned are heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms

Examples of substituents are, preferably, alkyl with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, l- and t-butyl, alkoxy with preferably 1 to 4 , in particular 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy, alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio , n- and i-propylthio and n-, i- and t-butylthio, haloalkyl preferably having 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to 5, in particular 1 to 3, halogen atoms, the halogen atoms being identical or different and as halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, hydroxy, halogen, preferably fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine, cyano, nitro, amino, monoalkyl and Dialkylamino with preferably 1 to 4, in particular 1 or 2 Koh len¬ atoms per alkyl group, such as methylamino, methyl-ethyl-amino, n- and l-propylamino and methyl-n-butylamino, carboxyl, carbalkoxy with preferably 2 to 4, in particular 2 or 3 carbon atoms, such as carbomethoxy and Carboethoxy, sulfo (-SO ₃ H), alkylsulfonyl with preferably

1 to 4, in particular 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl, arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl, and also heteroarylamino and heteroarylalkylamino such as chloropyidylamino and chloropyridylmethylamino

A particularly preferably represents hydrogen and also optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have the meanings given for R. Furthermore, stands for a bifunctional group. Optionally substituted alkylene with 1-4, in particular, may be mentioned 1-2 carbon atoms, where the substituents listed above are mentioned and where the alkylene groups are

Heteroatoms from the series N, O, S can be interrupted

A and Z together with the atoms to which they are attached can form a saturated or unsaturated heterocyclic ring. The heterocyclic ring can contain a further 1 or 2 identical or different hetero- contain atoms and / or hetero groups The hetero atoms are preferably oxygen, sulfur or nitrogen and the hetero groups N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. The alkyls are methyl, ethyl, n- and i- Propyl and n-, I- and t-butyl called The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members

Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, hexahydro-l, 3,5-tπazιn, morpholine, which may optionally be preferably substituted by methyl

E stands for an electron-withdrawing radical, in particular NO ₇ , CN,

Haloalkylcarbonyl such as 1,5-halogen-C _M -carbonyl, in particular COCF ₃ may be mentioned

X stands for -CH = or -N =

Z stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where R and the substituents preferably have the meaning given above

In addition to the ring mentioned above, Z can also join the atom

which it is bound and the rest ^

form a saturated or unsaturated heterocyclic ring in the place of X. The heterocyclic ring may contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and as hetero groups N-alkyl, the alkyl or N-alkyl group, preferably 1 to 4, in particular 1 or 2 carbon atoms, and alkyl may be methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ring contains 5 to 7 , preferably 5 or 6 ring links

Examples of the heterocyclic ring include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine Compounds of the general formulas (II) and (III) may be mentioned as very particularly preferred compounds which can be used according to the invention

Subst.

in which

n represents 1 or 2,

Subst. Stands for one of the substituents listed above, in particular for halogen, very particularly for chlorine,

A, Z, X and E have the meanings given above,

The following compounds may be mentioned in detail

CH,

Urea derivatives may be mentioned

Urea-formaldehyde condensates, crotonylidene urea

Urea is particularly preferably used

Surfactants are mentioned

Fatty alcohol ethoxylates, fatty amine ethoxylates, silicone surfactants

It is particularly preferably used

Isotridecyl alcohol 6-glycol ether (Renex) 36, tri (dimethylsiloxane) polyglycol ether (Silwet L 77, Tegopren 5840)

The mixtures according to the invention 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 products and materials and in the hygiene sector. They are resistant to normally sensitive and resistant species and effective against all or individual stages of development The pests mentioned above include

From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porecellio scaber From the order of the Diplopoda, for example, Blaniulus guttulatus

From the order of the Chilopoda, for example Geophilus carpophagus, Scutigera spec

From the order of the Thysanura, for example Lepisma saccharina

From the order of the Collembola, for example Onychiurus armatus

From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differential is, Schistocerca gregaria

From the order of the Dermaptera eg Forficula auriculaπa

From the order of the Isoptera e.g. Reticulitermes spp

From the order of the Anoplura, for example Pedculus humanus corpoπs, Haematopinus spp, Linognathus spp

From the order of the Mallophaga, for example Trichodectes spp, Damalinea spp

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thπps tabaci

From the order of Heteroptera, for example Eurygaster spp, Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp

From the order of the Homoptera, for example Phylloxera vastatrix, Pemphigus spp, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterusiphonis, Hyalopterusiphonsis, Hyalopterusiphonsis humuh, Rhopalosiphum padi, Empoasca spp, Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stnatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp, Psyl

From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniaπus,

Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, malacosoma neustπa. Euproctis chrysorrhoea, Lymantπa spp, Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp, Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp, Trichoplusia ni, Carpocapsa pomonella, Pieris spp, Chilo spp, Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella , Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana

From the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodariaisppa, Psylliodaria syp.

Anthonomus pp, Sitophilus spp, Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp, Trogoderma spp, Anthrenus spp, Attagenus spp, Lyctus spp, Meligethes aeneus, Ptinus holium sppno, Pt , Agπotes spp, Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica

From the order of the Hymenoptera, for example Diprion spp, Hoplocampa spp, Lasius spp, Monomorium pharaonis, Vespa spp ..

From the order of the Diptera e.g. Aedes spp, Anopheles spp, Culex spp, Drosophila melanogaster, Musca spp, Fannia spp, Calliphora erythrocephala,

Lucilia spp, Chrysomyia spp, Cuterebra spp, Gastrophilus spp, Hyppobosca spp, Stomoxys spp., Oestrus spp, Hypoderma spp, Tanaus spp, Tannia spp, Bibio hortulanus, Oscinella frit, Phorbia spp, Pegomyia hyoscyata, Dacitis capitus, Ceratitis capit paludosa

From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp

From the order of the Arachnida, for example Scorpio maurus, Lactrodectus mactans

Chewing biting insects, for example from the orders Coleoptera or Lepidoptera, may be mentioned

The respective physical and / or chemical properties of the mixtures according to the invention can be converted into customary formulations. those 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, furthermore in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm fog formulations

These 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 Foaming agents If water is used as an extender, organic solvents can also be used as auxiliary solvents. Liquid solvents are essentially aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes. Chlorethylene 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 dimethyl formamide and dimethyl sulfoxide, and also water Liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellant, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; solid carrier materials are possible, e.g. natural rock powders such as kaolins , Clays, talc, chalk, quartz, attapulgite, montmoπllonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates, as solid carrier materials for granules come into question e.g. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, as emulsifiers and / or foam-generating agents are possible, for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Examples of suitable dispersants include lignin sulfite waste liquors and methyl cellulose Adhesives such as carboxymethylcellulose, 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 lphthalocyanin dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The mixtures according to the invention can also contain other active ingredients, such as

Insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas and others.

The mixtures according to the invention can also be used in their commercially available

Formulations and in the use forms prepared from these formulations are present 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 mixtures according to the invention contain agonists and antagonists of the nicotinergic acetylcholine receptors of insects in concentrations of 0.1 to 50% by weight, preferably 0.1 to 25% by weight, very particularly preferably 0.1 to 10% by weight.

The mixtures according to the invention contain urea or its derivatives in concentrations of 99 to 45% by weight, preferably 95 to 35% by weight.

The mixtures according to the invention contain surface-active substances in concentrations of 0.1 to 10% by weight, preferably 0.2 to 5% by weight.

The active substance content of those prepared from the commercially available formulations

Application forms can vary widely. The active ingredient concentration of the agonsites or antagonists of the nicotinergic acetylcholine receptors of Insects in the use forms can be from 0.0001 to 1% by weight of active compound, preferably between 0.0016 and 0.1% by weight.

The application takes place in a customary manner adapted to the application forms by spraying, atomizing, dusting, spraying, pouring.

When used against hygiene and storage pests, they stand out

Active substances characterized by an excellent residual effect on wood and clay as well as a good alkali stability on limed substrates.

In the following examples, the compound with the common name imidacloprid (1- (2-chloro-5-pyridinyl-methyl) -2-nitroiminoimidazoline) is used as a representative of an agonist or antagonist of the nicotinergic acetylcholine receptors of insects.

Claims

claims

1 insecticidal agent, characterized by a content of a mixture of

Agonists or antagonists of the nicotinergic acetylcholine receptors of insects, urea or its derivatives as well as surface-active substances and optionally other fillers

2. Use of mixtures of agonists or antagonists of the nicotinergic acetylcholine receptors in insects, urea or its derivatives as well as surface-active substances and optionally other fillers for controlling insects.

3 method for controlling insects, characterized in that

Agonists or antagonists of the nicotinergic acetylcholine receptors in insects, urea or its derivatives, as well as surface-active substances and optionally other fillers, can act on insects and / or their habitat.

4 Process for the preparation of insecticidal agents, characterized in that agonists or antagonists of the nicotinic acetylcholine receptors of insects are mixed with urea or its derivatives, extenders and / or diluents and surface-active substances