CS264146B2 - Insecticide and process for preparing active component - Google Patents

Description

The present invention relates to an insecticidal composition which comprises as active ingredient the novel O-methyl-O- (3,5,6-trichloropyrid-2-yl) thionophosphonic acid esters. The invention further relates to a process for the preparation of these novel compounds and to their use in insecticidal. compositions, preferably for combating resistant Diptera species.

3e already known that certain O-ethyl-O- (3,5,6-trichloropyrid-2-yl) thionophosphonic acid esters such as o-ethyl-O- (3,5 / 6-trichloropyrid-2-yl) the ethanethionic phosphonic acid ester, methanthionophosphonic acid and phenylthiophosphonic acid have insecticidal properties (cf., for example, DE-OS 16 70 836).

We have now found new O-methyl-O- (3,5,6-trichloropyrid-2-yl) thionophosphonic acid esters of the general formula i

(I) in which

R is methyl or ethyl.

At the same time, it has been found that these new active compounds of the formula I are suitable for combating insects.

Accordingly, it is an object of the present invention to provide an insecticidal composition, characterized in that it contains at least one compound of the formula I as defined above as an active ingredient.

The present invention also relates to a process for the preparation of the novel O-methyl-O- (3,5,6-trichloropyrid-2-yl) thionophosphonic acid esters of the general formula (I) by reacting 2-hydroxy-3,5 6-trichloropyridine of formula II

Cl OH or alkali metal salts of this compound, or alkaline earth metal salts of this compound, or the corresponding ammonium salts of the halides of the formula III

OCH ₃

R

(III) wherein r has the above meanings and

Hal represents a halogen atom, optionally in the presence of an acid-binding agent, optionally in the presence of a bicyclic organic amine, and optionally in the presence of a diluent.

The thionophosphonic acid o-methyl-O- (3,4,6-trichloropyrid-2-yl) esters of formula (I) are surprisingly highly effective in combating resistant diptera species (Diptera).

If, for example, methanthionophosphonic acid o-methyl ester chloride and 2-hydroxy-3,5,6-trichloropyridine o-methyl ester are used as starting materials in the process of the invention, the corresponding reaction can be illustrated by the following reaction scheme:

The 2-hydroxy-3,5,6-trichloropyridine or corresponding alkali metal, alkaline earth metal or corresponding ammonium salts of this compound which are used in the process of the invention as starting materials for the preparation of the novel compounds of formula I are defined by the formula II. The alkali metal salts, alkaline earth metal salts or ammonium salts of said compound are preferably sodium, potassium, calcium or ammonium salts.

The 2-hydroxy-3,5,5-trichloropyridine and the corresponding alkali metal, 8 alkaline earth metal or ammonium salts of this compound are known and / or can be prepared according to generally known methods and methods (cf., for example, U.S. Pat. No. 3,244,586 and U.S. Pat. No. 4,115,577).

□ Examples of compounds of formula II include:

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

The halides which are additionally used as starting materials in the process according to the invention are generally defined by formula III. In this formula III, R is methyl or ethyl and Hal is halogen, preferably chlorine or bromine.

The compounds of formula (III) are known compounds.

□ Examples of halides of formula III are:

CS 264146 82

O-methyl-ethanethionophosphonic acid O-methyl ether chloride / O-methyl-ethanethionophosphonic acid / O-methyl ethanethionophosphonic acid o-methyl ethanethionophosphonic acid o-methyl ester bromide process for the preparation of the new thionophosphonic acid O-methyl-O- (3,5,6-trichloropyrid-2-yl) esters The solvents according to the invention are preferably carried out using diluents. Virtually all inert organic solvents are suitable as diluents. These preferably include aliphatic and aromatic / optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, petrol, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether and dibutyl ether, glycol dimethyl ethers and diglycol dimethyl ethers, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone, onitrile and propionitrile ·

Suitable acid-binding agents are all customary acid-binding agents. In particular, alkali metal carbonates and alkali metal alkoxides such as sodium carbonate and potassium carbonate, potassium tert-butoxide, aliphatic, aromatic or heterocyclic amines such as e.g. triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine · If a compound of formula II is used in the form of a salt, the addition of an acid binding agent may be omitted.

The process according to the invention can be carried out in the presence of a bicyclic organic amine such as quinclidine and 1,4-diazabicyclo (2,2,2) octane, preferably 1,4-diazabicyclo (2,2,2) octane as catalyst. can be used simultaneously as an acid-binding agent · In this case, at least molar amounts of bicyclic organic amine are used, in particular 1,4-diazabicyclo (2,2,2) octane ·

In an advantageous embodiment of the process according to the invention, alkali metal carbonates, in particular sodium carbonate and / or potassium carbonate, are used as acid-binding agents and a catalytic amount of 1,4-diazabicyclo (2,2,2) octane is used as catalyst.

The process according to the invention is generally carried out at temperatures between 0 ° C and 120 ° C. Preferably, the reaction is carried out at a temperature of between 20 ° C and 100 ° C · The reactions are generally carried out at atmospheric pressure · 1.0 to 1.3 mol, preferably 1.0 to 1.3 mol, preferably 1 mol of the compound of formula II or salt thereof between 1.0 to 1.2 mol of a halide of formula III and in the presence of using a bicyclic amine as a catalyst 0.01 to 0.08 mol, preferably between 0.02 to 0.06 mol, of a bicyclic organic amine, preferably 1,4-diazabicyclo ( 2,2,2) octane ·

The reaction is generally carried out in a diluent and in the presence of an acid binding agent. The acid binding agent is used in an amount suitable to bind the corresponding hydrogen halide. 5, in particular 0.9 to 1.8 moles of acid binding agent · After the reaction, the reaction mixture is filtered and the solvent is distilled off in vacuo ·

The compounds of the formula I are obtained in the form of oils which in part cannot be distilled without decomposition, but by so-called distillation, i.e. by longer heating under reduced pressure to slightly elevated temperatures, the last volatiles are freed and thus purified. quarry ·

The active substances are suitable for controlling insects occurring in agriculture, forestry, for the protection of stocks and materials as well as in the field of hygiene · the active substances are preferably used in households and in the field of hygiene. as well as resistant species, as well as against all or only individual developmental stages of insects:

from the order of the isopods, for example Oniscus asellus, Armadillidium vulgare, Porcellio ecaber * from the Dipopoda class, such as the Blaniulus guttulatus;

from the class of the Chilopoda, for example Geophilus carpophagus, Scutigera spec ·;

from the centipede class (Symphyla) ,. for example

Scutigerella immaculata;

from the order of the Thysanura, such as the small fish (Lípísma saccharina);

from the order of the Collembola, for example Onychiurus armatus;

from the order of the Orthoptera, for example

Cockroach (Blatta oriente lis) /

American cockroach (Periplaneta americana) /

Leucophaea maderae, Domestic Russian (Blattella germanica) / House Cricket (Acheta domestícus), Gryllotalpa spec · / Locusta migratoria migratorioides _t Melanoplus differentialis, Schistocerca gregaria;

from the order of the Dermaptera / e.g.

Common earwig (Forficula auricularia);

from the order of the Isoptera / for example, the Rhetulitermes spec;

from the order of the lice (Anoplura) / for example, the aphid (Phylloxera vastatrix), the louse (Pemphigus spec ·) / the louse (Pediculus humanus corporis), Haematopinus spec · /

Linognathus spec.

from the order of the Mallophaga, for example, the Trichodectee spec. / Damalinea spec;

from the order of the Thysanoptera / e.g., Hercinothrips femoralis / Thrips tabaci;

from the order Heteroptera / e.g. Eurygaster spec. / Dysdercus intermediud / Piesma quadrata, Cimex lectularius _t

Rhodniua prolixua,.

Triatorna spec · * from the order of the Homoptera, for example Aleurodee brassicae, Bemloia tabaci, Trialeurodes vaparariorum, Aphis gosaypli, Brevicoryne brassicae, currant apricot Poppy Aphid (Doralis fabae), Apple Aphid (Doralis pomi), Eriosoma lanigerum, Hyalopterus arundinia, Macrosiphum avanae, Myzua spec ·, Phorodon humuli, Rhopaloa Empoaeca spec.), Euacelia bilobatua, Nephotettix cincticepa, Lecanium corni, Saiaaetia oleae, Laodelphax atriatellus, Nilaparvata lugens, Aonidella aurantii, Aapidiocua specerala spec. ·) *

From the order of the butterflies (Lepidoptera), for example, pectlnophora gossypiella, Bupalus piniariua, Cheimatobia brumata, Lithocolletie blancardella, Hyponemeuta padella, Plutella maculipennia musk (Euprostis chryaorrhoea), moth (Lymantria apec ·), Bucculatrix thurberiella, hazel tree (Phyllocnistia citrella), osseed (Agrotia spec ·), oatifolia (Euxoa spec ·), Feltia spec ·, Eariae insulana, blister beetle Laphygma exigua, Cabbage moth (Mameatra brassicae), Eosnoid moth (Panolia flammea), Prodenia litura, Spodoptera spec, Trichoplusia ni, Carpocapaa pomonella, Pierie spec ·

Chilo spec · / Corn moth (Pyrausta nubilalis), Meal moth (Ephestia kuehniella), Wax moth (Galleria mellonella), Tineola biaselliella, Tinea pellionella, Hofmannophila pseudospretella, both butch (Cacoecia podana), Homona magnanima, Tortrix viridana * from the order of the beetles (Coleoptera), for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoecelides obtectus, Hylotrupes besulus Agelastica alni), Colorado potato beetle (Leptinotersa decemlineata), cress leaf beetle (phaedon cochleariae), Diabrotica spec ·, Psylliodes chrysocephala, Epilachna varivestis, Atomaria specus, Surza · (Sitophilus spec ·), Grooved Lobe (otiorrhynchua sulcatua), Cosmopo lites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermeates spec ·, Trogoderma spec ·, Anthrenus spec ·, Attagenus spec ·, Lyctus spec · ), helicopter (Ptinus spec ·), felt helicopter (Niptus hololeucus), Gibbium psylloides, darkling beetle (Tribolium spec ·), darkling beetle (Tenebrio molitor), click beetle (Agtiotes spec ·), Conoderus spec ·, cockchafer (Melolontha melolontha) , Summer Chafer (Amphimallon solstitialis), Coatelytra zealandica *.

from the order of the Hymenoptera, for example Diprion spec ·, Hoplocampa spec, Lasius spec ·

Monomorium pharaonls, vespa spec.

of the order Dlpera, for example, the mosquito (Aedes spec.), anofeles (Anopheles spec ·), mosquito (Culex spec ·), fruit fly (Drosophlla melanogaster), fly (Musea spec ·) · sunshine (Fannia spec ·) , Calliphora erythrocephala, Lucilia spec., Chrysomyia spec., Cuterebra spec., Gastrophilus spec., Hyppobosca spec., Stomoxys spec., Oestrus spec. Hypoderma spec ·), Horsefly (Tabanus spec ·), Tannia spec ·, Blush hortulanus, Oscinella frlt, Phorbia spec, Pegomyia hyoscyaml, Ceratitie capitata, Dacus oleae , Tipula paludosa?

from the order of the siphonaptera, for example, Xenopsylla cheopis, ceratophyllus spec;

from the order of Arachnida, for example

Scorpio maurus, Latrodectus mactans;

from the order of the mites (Acarina), for example Acarus sulfur, Arga8 spec, Ornithodoros spec, Dermanyssus gallinae, Eriophyes ribie Phyllocoptruta oleivora, Boophilus spec. Rhlplcephalus spec ·, Amblyomma spec ·, Hyalomma spec ·, ixodes spec ·, Psoroptes spec, Chorloptes spec, Sarcoptee spec, Tareonemus spec · Bryobia praetoosa), (Panonychus spec ·) · Tetranychus spec · о

The active compounds according to the invention are distinguished by excellent insecticidal activity, in particular in combating resistant diptera species, such as house flies (Musea domestica). Furthermore, these active compounds have a good effect against aphids such as peach aphids (Myzus persicae) and mites damaging plants such as spider mite (Tetranyohus urticae) and can also be used in the control of soil insects such as larvae of Phorbia antiqua ). However, the compounds of the formula I according to the invention are particularly advantageously used in the household and in the field of hygiene in combating resistant Diptera species (i.e. species which are resistant to conventional pest control agents, in particular conventional phosphoric esters), preferably against housefly (Musea domestaca) or mosquitoes (Aedes spp.), in particular against housefly (Musea domestica).

The active substances can, depending on their physical and / or chemical properties, be converted into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active substances, finely encapsulated compositions in polymeric substances , seed coatings, flame retardants such as smoke cartridges, smoke towers, smoke spirals and the like, as well as formulations of active substance concentrates for cold or hot mist dispersion.

These compositions are prepared in known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, with liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or reinforcing agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: 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 as well as 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 fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed, naturally agglomerated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, as well as granules of organic material such as sawdust, coconut shells. nuts, corn sticks and tobacco stems. Suitable emulsifiers and / or reinforcing agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin and synthetic phospholipids. Other additives may be mineral and vegetable oils.

In addition, these compositions may contain coloring agents such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active ingredient.

_п CS 264146 82

The active compounds according to the invention can be present in the form of commercial preparations as well as in the form of application preparations which have been prepared from these concentrates in admixture with other active substances such as insecticides, baits, sterilizing agents, acaricides, nematicides, fungicides, substances regulating plant growth or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others.

Further, the active compounds according to the invention can be present in the form of commercially available formulations as well as in the form of application preparations which have been prepared from these concentrates in admixture with synergistically active substances. Synergically active substances are represented by compounds which increase the effect of the active substances without the added synergistic active substance having to be itself active.

The active ingredient content of the application formulations prepared from the formulations currently on the market may be within wide limits. The concentration of active ingredient in the dosage forms may be from 0.00001 to 95% by weight of active ingredient, and is preferably between 0.001 and 10% by weight of active ingredient.

Administration is carried out in a manner customary for a particular dosage form.

When used against hygiene pests and against storage pests, the active compounds are distinguished by an excellent residual effect on wood and clay as well as good stability to alkalis on lime substrates.

The following examples illustrate the biological activity of the compounds of the formula I according to the invention.

Examples illustrating a process for the preparation of active substances

Example 1

A mixture of 5 g (0.025 mol) of 2-hydroxy-3,5,6-trichloropyridine, 5.2 g (0.038 mol) of potassium carbonate, 3.6 g (0.025 mol) of methantionophosphonic acid O-methyl ester and 80 ml of acetonitrile is stirred for 2 hours at 20 ° C. Toluene (400 ml) was added and the reaction mixture was extracted with water (2 x 200 ml). The organic phase was then separated, dried over sodium sulphate and evaporated under reduced pressure.

4.8 g (63% of theory) of methanthionophosphonic acid O-methyl-O- (3 / 5,6-trichloro-2-pyridyl) ester are obtained in the form of colorless crystals, m.p.

CS 254146 B2

A mixture of 15 g (0.075 mol) of 2-hydroxy-3,5,6-trichloropyridine, 15.5 g (0.11 mol) of potassium carbonate, 0.5 g of 1,4-diazabicyclo (2.2.2; octane, Ethylthionophosphonic acid O-methyl ester chloride (11.8 g, 0.075 mol) and toluene (150 ml) were stirred at 50 ° C for 3 hours. The reaction mixture was cooled to 20 ° C, the inorganic salt was filtered off and the filtrate evaporated under reduced pressure. is distilled at 60 ° C under high vacuum ·

22 g (92% of theory) of ethanephosphonic acid o-methyl-o- (3,5,6-trichloropyrid-2-yl) ester are obtained in the form of a yellow oil having a refractive index .alpha .: 1.5500.

Examples illustrating biological activity:

In the following example, which illustrates the insecticidal activity of the compounds of the invention, the following compounds were used as comparative agents:

(A) (B)

(These compounds are known from DH-OS 16 70 836)

Example A ^LT 100 ^{test for} double-winged insects: housefly (Musea domestica) (resistant strain)

Solvent Acetone parts by weight of active substance are dissolved in 1000 parts by volume of solvent. The solution thus obtained is diluted with additional solvent to the desired lower concentration.

Pipette 2.5 ml of drug solution 86 into a petri dish. On the bottom of a Petri dish there is a filter paper about 9.5 cm in diameter. The Petri dish is left open until the solvent had completely evaporated, the concentration of the active compound solution is an amount of active ingredient per .mu.m @ ² of filter paper varied, then placed in the Petri dish is placed about 25 test insects and the Petri dish was covered with a glass lid .

The condition of the test insects is continuously monitored. The time required to reach a condition where 100% of the specimens are in the knock down * (effect) is determined.

In this test, for example, the compounds of Examples 1 and 2 show a 100% effect, for example at an active agent concentration of 0.002% after 75 and 120 minutes, while the comparative compounds A and V show a 100% effect at the same active compound concentration only after 4 hours. Comparative Compound c exhibits a 0% effect at an active compound concentration of 0.2% even after 4 hours.

Claims (4)

SUBJECT OF THE INVENTION Insecticidal composition, characterized in that it contains at least one thionophosphonic acid O-methyl-O- (3,5,6-trichloropyrid-2-yl) ester of the general formula I (I) as an active ingredient. where R is methyl or ethyl. 2. A composition according to claim 1, wherein the active ingredient is a methanthionophosphonic acid o-methyl-O- (3,5,6-trichloropyrid-2-yl) ester of the formula: II 3. A composition according to claim 1, wherein the active ingredient is an o-methyl-O- (3,5,6-trichloropyrid-2-yl) ethanethionophosphonic acid ester of the formula: 4. A process for the preparation of thionophosphonic acid O-methyl-O- (3,5,6-trichloropyrid-2-yl) esters of the general formula I OCH ₃ R (D. in which R represents a methyl group or an ethyl group, characterized by reacting 2-hydroxy-3,5,6-trichloropyridine of formula II (II) or its corresponding alkali metal salt, alkaline earth metal salt or ammonium salt with halides of formula III WITH I » ^0CH 3 Hal ~ P (III) in which R is as defined above and Hal represents a halogen atom, optionally in the presence of an acid-binding agent, optionally in the presence of a bicyclic organic amine, and optionally in the presence of a diluent.