DD265550A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to novel O-methyl O-(3,5,6-trichloropyrid- 2-yl)thionophosphonic acid esters of the formula (I) <IMAGE> in which R represents methyl or ethyl, which esters can be used as pesticides.

Description

R is methyl or ethyl

in addition to extenders and / or surface-active agents

 2. Composition according to claim 1, characterized in that they are thionophosphonic esters of the formula

contain

 3. Composition according to claim 1, characterized in that they thionophosphonic acid ester of the formula

OCH.

contain.

4. Use of compounds of formula (I) according to claim 1, characterized gekonnzeichnet that they are used for controlling pests, preferably arthropods, in particular insects and for controlling dipterans, in particular compared to conventional pest control dipterans.

5. A method for controlling pests and / or Diptera, in particular compared to conventional pesticides resistant Dipteren, characterized in that compounds of the formula (I) according to claim 1 on pests, preferably arthropods, especially insects or their habitat and on Diptera or their habitat allow to act.

6. A process for the preparation of pesticides, characterized by mixing compounds of formula (I) according to claim 1 with extenders and / or surface-active agents.

Field of application of the invention

The invention relates to pesticides containing novel O-MethylO- (3,5,6-trichloro-pvtid-2-yl) -thionophosphonsäureestern, a process for their preparation and their use in pest control agents, in particular as insecticides, preferably in the control of resistant Dipteran species.

Characteristic of the known state of the art

It is known that certain O-ethyl-O- (3,5,6-trichloropyrid-2-yl) thio: iophosphonsäureester, such as. 8.0 Ethyl ü- (3,5,6-trichloropyrid-2-yl) -ethylthionophosphonsäureester, -melhylthionophosphonsäureestor and -phenylthionophosphonsäureester have insecticidal properties (see, for example, OE-OS 1670836).

Object of the invention

The aim of the invention is the Boreitstellung new pesticides with strong insecticidal activity, which are suitable for controlling animal pests, which occur in agriculture and forestry, in the protection of materials and materials and in the hygiene sector, are suitable, in particular for the control of Diptera, which are resistant to known pesticides.

Explanation of the essence of the invention

The invention has for its object to find new compounds that are suitable as active ingredient in pesticides with the desired properties.

New O-methyl-O- (3,5,6-trichloro-pyrid-2-yl) -thionophosphonic acid esters of the formula (I) have now been found,

/ OCH ₃

in which

R is methyl or ethyl.

It has furthermore been found that the novel O-methyl-O- (3,5,6-trichloropyrid-2-yl) thionophosphonic acid esters of the formula (I) are obtained if 2-hydroxy-3,5,6- trichloropyridine of the formula (II)

or the corresponding alkali metal, alkaline earth metal or ammonium salts with halides d ) r formula (III) S

11 / 0CH ₃ HbI-P ("I)

in which

R has the meanings given above and

Shark stands for halogen,

if appropriate in the presence of an acid acceptor, if appropriate in the equivalent of a bicylic organic amine and if appropriate in the presence of a diluent.

The O-methyl-O- (3,4,6-trichloropyrid-2-yl) -thionophosphonsäureester of formula (I) are outstanding in a superior manner by a high activity in the control of resistant Dipteren from.

If, for example, O-methyl-methylthionophosphonic acid ester chloride and 2-hydroxy-3,5,6-trichloropyridine are used as starting materials for the process according to the invention, the corresponding reaction can be outlined by the following formula scheme:

11 / -0CH ₃ ♦ Bas ·

HCl

DbS in the process according to the invention as starting material for the preparation of the novel compounds of formula (I) to be used 2-Hy <lroxy-3,5,6-trichloropyridine or the corresponding alkali metal, alkaline earth metal or ammonium salts are defined by the formula (II) , The alkali metal, alkaline earth metal or ammonium salts used are preferably the sodium-potassium, calcium or ammonium salts.

2-Hydroxy-3,5,6-trichloropyridine and the corresponding alkali metal, alkaline earth metal or ammonium salts are known and / or can be prepared by well-known methods and methods (see for example US-PS 3244586 and US-PS 4115557). ,

As examples of the compounds of the formula (II) may be mentioned:

2-H / droxy-3,5,6-trichloropyridine and the corresponding sodium, potassium, calcium and ammonium salts.

The halides also to be used as starting materials in the process according to the invention are represented by the formula (III)

in general, the ~ ^! ert. In this formula (III) R is methyl or ethyl, and Hal represents halogen, preferably chlorine ode ι ^r Bror.

The compounds of formol (III) are known. Examples of the halides of the formula (III) include: O-Methyl-methylthionophosphonsäureostor- and O-'dethylethylthionophosphonsäureestorchlorid or bromide. The inventive method zw preparation aer new O-methyl-O- (3,5,6-trichloropyrid-2-yl) -thionophosphonsäureester

of formula (I) is preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halide hydrocarbons, such as pentane. Hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, onzole.

Toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers Diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, Methyl ethyl, methyl isopropyl and methyl isobutyl ketone and nitriles such. For example, acetonitrile and propionitrile. Acid acceptors which can be used are all customary acid dyes. Alkali carbonates have proven particularly useful

and -alcoholates such as sodium and potassium carbonate, potassium tert-butyl.!, Further aliphatic, aromatic or heterocyclic

Amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzyldimine and pyridine. If the connection of the

General Fornel (II) is used as a salt, the addition of the acid acceptor is dispensable.

The process according to the invention can be carried out in the presence of an acyclic organic amine, such as quinuclidine and 1,4- Diazabicyclo (2,2,2) octane (DABCO), preferably DABCO be carried out as a catalyst. The bicyclic organic Amine can also be used as an acid acceptor at the same time. In this case, at least molar amounts of

bicyclic organic amine, in particular used by DABCO.

In a preferred embodiment, alkali metal carbonates in particular sodium carbonate and / or acid acceptors Potassium carbonate and used as a catalyst catalytic amounts DABCO. The inventive method is generally carried out at temperatures between ^{0 0} C and 120 ⁰ C. Is preferred

the temperature range between 2O ⁰ C and 100 ⁰ C. The reactions are generally durjngeführt under atmospheric pressure

For carrying out the process according to the invention, to 1.0 mole of the compound of the formula (II) or the salt of 1.0 to

1,3MoI, preferably between 1,0 and 1, MoI halide of formula (III) and in case of use oinos bicyclic

Amines as catalyst 0.01 to 0.08 moles, preferably between 0.02 to 0.06 moles of bi-organic amine (preferably DABCO). The reaction is generally carried out in a diluent as well as in the presence of an acid acceptor

carried out. The acid acceptor is added in amounts suitable to bind the appropriate hydrogen halide. Preferably, 0.8 to 2.5, in particular 0.9 to 1.8, mol of acid acceptors are used per mole of the compound of the formula (II). After the reaction is filtered and the solvent is distilled off in vacuo.

The compounds of formula (!) Are obtained in the form of oils, which can be distilled partly not undecomposed, but by

so-called "distilling off", that is, by prolonged heating under reduced pressure to moderately elevated temperatures, freed from the last volatiles and purified in this way

Refractive index. The active compounds are suitable for controlling animal Schadlinrjen, preferably Arthiopoden, in particular insects, the

in agriculture, forestry, voestalpine and material protection as well as in the hygiene sector. They are preferably used in the household and hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The aforementioned pests include:

From the order of Isopoda z. B. Oniscus asellus, Armadillidium vulgaris, Porcellio scaber, From the order of Diplopoda z. B. Blaniulus guttulatus. From the order of Chilopoda z. Geophilus carpopliagus, Scutigera spec. From the order of Symphyla z. B. Scutigerolla immaculate. Aui. the order dor Thysanura z. B. Lepisma saccharina. Out of order, Collembola z. ß. Onychiurus armatus. From the order of Orthoptera z. B. orientalis oriental, Periplaneta americana, Leucophaea maderao, Blattella germanica, Acheta

domesticus, Gryllotalpa spp., Locusta mipratorla migratorioidos, Molanoplus differentialis, Schistocerca gregaria.

From the order of Dermaptera z. B. Forficula auricularia. From the order of the Iac ptera z. B. Reticulitermes spp .. From the order of the Anoplura t. Phylloxera vastatrix, Pemphigus spp., Pedicius humanus corporis, Haematopinus spp., Linognathusspp. From the order of Mallophage z. R. Trichodectes spp., Damalinea spp. From the order of Thysanoptera z. B. Horcinothrips femoralis, Thrips tabaci. From the order of Heteroptera z. B. Eurygaeter spp., Dysdercus intermedius, Piesma squares, Cimex lectularius, Rhodnius

prolixus, Trlatomn spp.

From the order of Homoptera z. Aleurodos brassiere, Bomisia tabaci, Trialourodos · aporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribia, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum

"Venae, Myzusspp., Phoro Jon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticep-.

Lecanium corni, Saissetia olease, Laodolphax striatellus, Nilaparvata lugene, Aonidia ma aurantii, Asidiotus hedorae, Peeudococcus op. Psylla spp. From the order of Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Li'.hocolletis

blancardella, Hypenomeuta padella, Plutoila maculipennis, Malacosoma noustria, Euproctis chrysorrhoea, Lymantria spp.

Bucculatrix thurbnrtolla, Phylloc ¹ StIs citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera

exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalls, Ephestia kuehniella, Galleria mellrnella, Tineola bisselliella, Tinea pellionella,

Hofmnnnophila pseudospretella, Cauoecia podana, Capua relicdlana, Choristoneura fumiferana, Clysia ambiguella, Homona

magnanima, Tortrix viridana.

From the order of Coleoptera ζ. B. Anobium punctatun., Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides

obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.

Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptuu hololeucus, Gibbium psylloides, Tribolium

spp., Tenebrio molitor, Agrlotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialls, Costelytrazealandica.

From the order of H / menoptora z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of Diptere e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp. Colliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuteobra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannin spp., Bibio hortulanus, Oscinella sp., Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa. From the order of Siphcnaptera z. Xenopsylla cheopis, Ceratophyllus spp. From the order of Arachnida z. B. Scorpio maurus, Latrodectus mactans. From the order of Acarinn z. Acarus siro, Argas spp., Ornithodoros 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. The active compounds according to the invention are distinguished by an outstanding insecticidal activity, in particular in the case of Combating resistant Diptera, such as Musca domestica. They continue to show a good action against aphids like

z. Myzus porsicae and other plant-damaging mites such as Tetranychus urticae, and may also be useful in the control of soil insects such as e.g. B. Phorbia antiqua maggots are used. However, the compounds of the formula (I) according to the invention which are used in the hay and hygiene sector are also particularly preferred for the

Bokämpfung the (compared to the usual pesticides, especially compared to the usual Phosphoric acid esters) resistant Dipteren species, preferably Musca domestica or Aedes spp., In particular Musca

domestica.

The active compounds can be converted into conventional, depending on their respective physical and / or chemical properties Formulations are converted, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols Active substance-impregnated natural and synthetic substances, ultra-fine encapsulations in poly me; substances and in enveloping measurements for Seeds, further in formulations with fuel packs, such as smoke cartridges, doses, spirals, etc., as well as ULV KaIt- and Warm Nobel formulations. These formulations are herges'allt in a known manner, for. B. by mixing the active ingredients with extenders, ie

liquid solvents, pressurized liquefied gases and / or solid carriers, optionally under

Use of surface-active agents, that is to say emulsifiers and / or dispersants and / or foaming agents Means. In the case of using water as an extender z. As well as organic solvents as Hilfslösungsir.ittel

be used. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or

Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or Methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. As 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; By liquefied gaseous diluents or carriers is meant those liquids which are gaseous at normal temperature and under normal pressure,

z. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: z. B. '. Natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or

Diatomaceous earth and ground synthetic minerals, such as fumed silica, alumina and silicates; as solid Carriers for granules come in Krage: z. Broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic Material such as sawdust, coconut shell, corncobs and tobacco stalks; as emulsifier and foaming agent

are suitable: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene

Fatty alcohol ethers, e.g. B. Alkylarylpolyglykol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; when Dispersants are suitable: e.g. Lignin-sulphite liquors and methylcellulose. It may contain in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or

latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural

Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and

be vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic Fart substances, such as Alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, 3or, copper, cobalt, Molybdenum and zinc are used: The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%. The active ingredients can be prepared in their commercial formulations as well as in those from these formulations Forms of use mixed with other active substances, such as insecticides, attractants, sterilants, acaricides, nematicides, Fungicides, growth regulators or herbicides. Examples of insecticides include Phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by microorganisms

Fabrics u.a.

The active ingredients may further prepared in their commercial formulations as much as one of these formulations Application forms in mixture with synergists are present. Synergists are compounds through which the effect of Active ingredients is increased without the added synergist itself must be active. The active substance content of the formulations prepared from the commercial formulations can be widely used

vary. The active ingredient concentration of the use forms may be from 0.00001 to 95% by weight of active ingredient, preferably between 0.001 and 10% by weight.

The application is done in a custom forms adapted to Anwondungsformen.

When used against hygiene and storage pests, the active ingredients are characterized by an excellent Re Odualwirkung on wood and clay and by a guti alkali stability on limed documents.

"~ Embodiment

The invention is explained in more detail below with reference to some examples.

The biological activity of the compounds according to the invention will be explained with reference to the examples of use.

Production Work Example 1

A mixture of 5 g (0.025 mole) of 2-hydroxy-3,5,6-trichloropyridine, 5.2 g (0.038 mole) of potassium carbonate, 3.6 g (0.025 mole) of O-methylmethylthionophosphonic acid ester chloride and 80 ml of acetonitrile is stirred at 20 ° C. for 2 hours 400 ml of toluene are then added and the mixture is shaken twice with 200 ml of water each time, the organic phase is separated off, dried over sodium sulfate and then concentrated under reduced pressure in vacuo.

This gives 4.8 g (63% of theory) of O-methyl-O- (3,5,6-trichloro-2-pyridyl) -methylthionophosphonsäureester in the form of colorless crystals with the melting point 66 ° C.

Example 2

C)

A mixture of 15 g (0.075 mol) of 2- "droxy-SSe-trichloropyridine, 15.5 g (0.11 mol) of potassium carbonate, 0.5 g of 1,4-diazabicyclo- (2,2,2) -octane, 11, 8 g (0.075 mol) OMc: thionophosphonsfiureesterchlorid and 150 ml of toluene is stirred at 50 ° C for 3 hours. Then it is cooled to 2O ⁰ C, sucked from the anc mixing salt and eingeenqt the filtrate in vacuo. The residue is undistilled at 60 ° C in a high vacuum.

This gives 22 g (92% of theory) of 0-Vb! Hyl-O- (3,5,6-trichloropyrid-2-yl) -ethylphosphonsäureester as a yellow oil of refractive index n§ ^? : 1.5500.

use Examples

In the following example of use, the compounds listed below are used as comparative compounds:

(A) C

(B)

HVOC ₂ H ₅ S

from DEOS1670836

Example A

LTioo test for Diptera

Test animals: Musca domestica (resistant)

Solvent: acetone

2 parts by weight of active compound are taken up in 1000 parts by volume of solvent. The solution thus obtained is with

diluted further solvent to the desired lower concentrations.

2.5 ml of active ingredient solution are pipetted into a Petri dish. There is a filter paper on the bottom of the Petri dish

a diameter of about 9.5cm. The Petri dish remains open until the solvent has completely evaporated. Depending on the concentration of Wirkstofflosung the amount of active ingredient per m ² filter paper is different levels. Next, add about 25 test animals to the Petri dish and cover with a glass lid.

The state of the test is constantly monitored. It determines the time that is necessary for a 100% knock-down effect.

In this test, z. B. the compounds of Preparation Examples (1) and (2) has a 100% action in one

Example active compound concentration of 0.002% after 75 and 120 minutes, while the comparative compounds (A) and (B) showed a 100% effect at the same concentration only after 4 hours. The comparative compound (C 1) showed no effect (0%) even after 4 hours at an active compound concentration of 0 2%.

Claims (1)

claims: 1. Pesticides, characterized by a content of at least one
O-methyl-O-ß.FS-trichloropyrid ^ -yD-thionophosphonsäureester of formula (I), OCH. (D in v'icher