WO1996003879A1 - Insecticides - Google Patents

Abstract

Chloronicotinyl insecticides having the formula (I), in which the substituents X, A, Z and E have the meanings given in the description, are mixed with synergistic substances from the group of a) isochromane or benzodioxol compounds, b) propargyl derivatives, c) alkylphosphonic esters, d) phosphoric acid esters, e) azol derivatives, f) pinon esters, g) formamides, h) C12-21-carboxylic acid esters and amides, i) diarylamines, k) cyclic imides, and l) neem oil.

Description

Insecticidal agents

The present invention relates to insecticidal compositions based on chloromicinyl insecticides and synergists for insecticides.

Chloronicotinyl insecticides are known e.g. from EP-OS 192 060.

Synergists for insecticides are inhibitors for oxidases or cytochrome P 450 or increase the penetrability of cell membranes. You are known e.g. B. from chemistry of pesticides and pesticides Bnd. 7 K.

Naumann Chemistry of Synthetic Pyrethroid Insecticides Springer Verlag 1981 pages 3-5.

The present invention relates to mixtures of chloromotinyl insecticides of the formula (I)

in welcher

in which

A represents optionally substituted alkyl or a bifunctional group which is linked to the radical Z;

E represents an electron withdrawing group;

X stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom;

Z for a monofunctional group from the series alkyl, -OR, -SR, R

/

N stands

\

R

or represents a bifunctional group which is linked to radical A or radical X,

R represents hydrogen or alkyl,

with synergists from the group

Compounds of the formula (I) in which the radicals have the following meaning are preferred:

A stands for optionally substituted C -alkyl, or for a bifunctional group. Optionally substituted alkylene with 1-4, in particular 1-2, carbon atoms may be mentioned, it being possible for the alkylene groups to be interrupted by heteroatoms from the series N, O, S

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 atoms and / or hetero groups. Preferred heteroatoms are wise oxygen, sulfur or nitrogen and as hetero groups N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2 carbon atoms. As alkyl, methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned. The heterocych ring contains 5 to 7, preferably 5 or 6 ring members.

Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyl enimine, hexahydro-l, 3,5-triazine, morpholine, which may optionally be substituted by methyl.

E stands for an electron-withdrawing radical, with particular mention being made of NO ₂ or CN.

X stands for -CH = or -N =

Z represents optionally substituted radicals C _M -alkyl, -OR, -SR, -NRR, where R preferably represents hydrogen or C _M -alkyl,

In addition to the ring mentioned above, Z can be attached together with the atom

which it is bound and the rest

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

Examples of the heterocyclic ring are pyrrolidine, piperidine,

Piperazine, hexamethyleneimine, morpholine and N-methylpiperazine called. The following compounds may be mentioned as very particularly preferred compounds (I) according to the invention:

Preferred synergists are:

a) Isochroman derivatives of the formula

in which

R, R ¹ and R ^{2 may be the} same or different and represent hydrogen or alkyl.

Benzodioxole derivatives of the formula

R represents hydrogen, C alkyl, C ^ alkenyl, halogen or nitro,

R ^{1 represents} C _j _ ₄ - alkyl or hydrogen,

R ^{2 stands} for aralkyl, C _M alkyl, C ^ alkenyl, C _3.6 cycloalkyl or for hydrogen and also

R ¹ and R ² together for a C ₂ . ₅ -alkylene radical

for example

2- (3,4-methylenedioxyphenyl) propionitrile of the formula

Particular mention should be made of those listed in the following references

Compounds: BE-P 858 254; DE-OS 2 654 348; DE-OS 2 816 475; b) from the series of propargyl derivatives, the compounds of the formulas

wobei

in which

Alk is C _j _ ₄ alkyl and

Aryl represents phenyl.

Particular mention should be made of the compounds US Pat. No. 3,864,388; DE-OS 2 235 005; U.S. Patent 4,020,111; NE-OS 71 5782.

c) From the series of alkylphosphonic esters, the compounds mentioned in EP-OS 25 179 and US Pat. No. 3,338,783 are particularly mentioned;

d) from the series of phosphoric acid esters, the compounds of the formula

wobei

in which

n stands for the numbers 0 or 1

X and Y are independently O or S.

R represents optionally substituted alkyl, aryl or aralkyl. The compounds known from the following references US Pat. No. 4,035,490; JP-OS 54/147 927; as well as the connections of the formulas:

Kitazin

e) from the series of azole derivatives, the compounds of the formulas:

C "HH ₂ - ₅ -—NN ' ^{N ~} | Λ ^' / - ^" - ~ C CYHM ^M -— ^-

in which

Shark represents halogen,

Alk represents C alkyl,

and compounds of the formula

in welcher

in which

R represents alkenyl or alkynyl

and the leftovers

R ¹ , R ² , R ³ and R ⁴ , which may be the same or different, for

Hydrogen, cyano, nitro, halogen, carbamoyl, monoalkylamino- or dialkylamino-carbonyl, aminosulfonyl, minoalkylamino- or dialkylaminosulfonyl, for optionally by halogen, cyano,

Alkoxy or alkylthio substituted alkyl, or optionally halogen-substituted alkoxy, alkylthio or alkylsulfonyl, or in which two adjacent radicals R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ together represent alkylene or benzo.

The compounds mentioned in the following references are particularly mentioned: DE-OS 2833 193; JP-OS 53/81 625;

f) from the group of the Pinonester the compounds of the formula

Alk stands for C - alkyl

and the compounds mentioned in JP-OS 673 514;

g) dimethylformamide from the group of formamides;

h) from the group of Carbonsäureester and amides may be mentioned: Capryldiethylamid, _{C] 2} .ι ₈ -Carbonsäureisopropylester.

In particular, the compounds listed in the following references are mentioned: JP-OS 74/21 068; JP-OS 73/99 337; i) from the group of diarylamides, the compounds mentioned in EP-OS 926 should be mentioned. In particular it should be mentioned:

k) the following compounds may be mentioned for the cyclic imides:

und

and

The active substance mixtures can be converted into the 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., as well as ULV cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or

Dispersing agents and / or foaming agents. In the case of the use of water as an extender, organic solvents can also be used as Auxiliary solvents can be used. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, 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 dimethyl formamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers are possible: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for

Granules are possible: 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 from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifiers and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor 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, for example 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 mixture, preferably between 0.5 and 90%.

The active substance mixtures are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids and nematodes, 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:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare,

Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus. From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus aπnatus.

From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp.,

Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera e.g. Forficula auricularia.

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

From the order of the anoplura e.g. Pediculus humanus co oris, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

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

From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,

Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci,

Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arυndinis,

Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,

Phylloxera vastatrix, Pemphigus spp., Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

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. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera sppi, Trichoplapsia s., Trichoplusia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidana. From the order of the Coleoptera. t. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelic ^{■ •} -, obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaeαυn cochleariae, Diabroticauspppp spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodeπna spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus sppium, sides., Nipt ., Tenebrio molitor, Agriotes 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 Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp. From the order of the Arachnida, for example Scorpio maurus and Latrodectus mactans. From the order of the Acarina, for example Acarus siro, Argas spp., O ithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

Plant-parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidoms spp., Xiphinema spp., Trichodorus spp.

The active compound mixtures according to the invention 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, etc.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active ingredient concentration of the use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms.

The following examples use imidacloprid of the following formula as an insecticidal active ingredient from the group of chloronicotinyl insecticides:

Beispiel A

Example A

Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of 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.

After the desired time, the plants are populated with horseradish leaf beetle larvae (Phaedon cochleariae). After each 7 days, the death rate is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

0.02% of the synergist of the respective test concentration of the imidaclopride was admixed. The following mixtures, for example, showed synergistic effects in this test:

T belle A

(plant-damaging insects) Phaedon larva test

Example B

Plutella test (BLT resistance)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of 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 dipping into the active ingredient preparation of the desired concentration and with caterpillars of the cabbage cockroach

(Plutella maculipennis, BLT resistance) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

0.02% of the synergist of the respective test concentration of the imidaclopride was admixed. The following mixtures, for example, showed synergistic effects in this test:

Table B

(plant-damaging insects) plutella test (resistant)

Example C

Spodoptera test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of 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 caterpillars of the owl butterfly (Spodoptera frugiperda) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

0.02% of the synergist of the respective test concentration of the imidaclopride was admixed. The following mixtures, for example, showed synergistic effects in this test:

T belle C

(plant-damaging insects) Spodoptera fmgiperda test

Example D

Nephotettix test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of 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.

Rice seedlings (Oryzae sativa) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the green leafhopper (Nephotettix cincticeps) while the seedlings are still moist.

After the desired time, the kill is determined in%. 100% means that all cicadas have been killed; 0% means that no cicadas have been killed.

0.02% of the synergist of the respective test concentration of the imidaclopride was admixed. The following mixtures, for example, showed synergistic effects in this test:

Table D

(plant-damaging insects) Nephotettix test

Example E

Myzus test

Solvent: 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of 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), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration.

After the desired time, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

Table E

(plant-damaging insects) Myzus test

Claims

Claim 1. Mixtures of chloromotinyl insecticides of the formula (I)

in which A represents optionally substituted alkyl or a bifunctional group which is linked to the radical Z; E represents an electron withdrawing group; X stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom; Z for a monofunctional group from the series alkyl, -O-R, -S-R, R N stands R stands for a bifunctional group which is linked to the radical A or the radical X, R represents hydrogen or alkyl, with synergists from the Gmppe a) Isochroman or benzodioxole compounds b) propargyl derivatives c) alkylphosphonic acid esters d) phosphoric acid esters e) azole derivatives