DE2455680A1 - SUBSTITUTED CARBOXYLMETHYL (DI) THIOL (THIONO) -PHOSPHORUS (PHOSPHONE) -ACID ESTERS OR -ESTERAMIDE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDE, ACARICIDE AND NEMATICIDE - Google Patents

Description

Hu / Hg "50Θ · Leverkusen, Bayerwerk

^Ia 23 Nov. 197 ¹ »

Substituted carboxylmethyl (di) thiol (thiono) phosphorus (phosphonic) acid esters or ester amides, processes for their preparation and their use as insecticides, acaricides and nematicides

The present invention relates to new substituted carboxy methyl (di) thiol (thiono) phosphorus (phosphonic) acid ester or -esteramide, a process for their preparation and their use as insecticides, acaricides and nematicides.

It is already known that substituted carboxymethyl or Carboxyethyl dithiophosphorus (phosphonic) acid ester, e.g. 0,0-dimethyl- or 0,0-diethyl-S- (l-ethylthio-l-carbäthoxymethyl) - or 0, O-diethyl-S- (l-carbmethoxy-2-ethylthio-ethyl) -thionothiolphosphoric acid ester, 0-Ethyl-S- (l-carbethoxy-2-ethylthioethyl) methane or phenylthionothiolphosphonic acid ester have insecticidal and acaricidal properties (compare German Auslegeschrift 1.068.699 and 1.212.777 or 1.188.859)

It has been found that the new substituted carboxylmethyl (di) thiol (thiono) phosphorus (phosphonic) acid esters or ester amides of the formula

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^X OR
RS-CH-SP _v ² (I)

I ^R 3

CO ₂ R ₁

in which

R for alkyl with Ibis 6, cycloalkyl with 5 to 7, alkenyl with 2 to 5 carbon atoms or for phenyl optionally substituted by halogen,

R ₁ for alkyl with 1 to 6 carbon atoms or nitrophenyl,

Rp for alkyl with 1 to 6 carbon atoms or optionally phenyl substituted by halogen,

R ^ for alkyl, alkylthio, alkylamino with, in each case 1 to 6 Carbon atoms or phenyl and

X stand for an oxygen or sulfur atom,

have strong insecticidal, acaricidal and nematicidal properties.

The compounds of the formula (I) are generally in the form of racemates.

It has also been found that the new substituted carboxy lmethyl (di) thiol (thiono) phosphorus (phosphonic) acid esters or -esteramides of the formula (i) can be obtained if one (thiono) - (di) thiolphosphorus (phosphonic) acid ester or ester amide derivatives of the formula

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^{R? 0} ) ch (id

in which Rp, FU and X have the meaning given above and

M stands for hydrogen, an alkali, alkaline earth or ammonium equivalent,

with haloacetic ester derivatives of the formula

RS-CH-HaI (III)

in which R and R _{1 have} the meaning given above and

Hai stands for halogen, in particular chlorine or bromine,

optionally in the presence of an acid acceptor and optionally reacted in the presence of a solvent or diluent.

Surprisingly, the substituted carboxylmethyl (di) thl oil according to the invention have (thiono)) pho sphor (pho sphonic) acid esters or esteramides have a better insecticidal, acaricidal and nematicidal effect than the closest from the state

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compounds of analogous constitution and known in the art same direction of action. The substances according to the invention are not only effective against plant-damaging insects and mites and nematodes, but also in the veterinary sector against animal ectoparasites such as parasitic ones Fly larvae.

If, for example, the potassium salt of O-ethyl-N-methyl-thiolthionophosphoric acid ester amide is used and 1-chloro-1-secbutylthio-acetic acid n-butyl ester as starting materials, the course of the reaction can be represented by the following equation be reproduced:

S COpCi Hq-η

PS ^w K * CHSCHCl

Q © ι

PS ^w K * + SeC-C ₇ H ₀ S-CH-Cl

CH ₃ -NH '^ y - KCl

^ ^Ό / PS-CH-SC / H _Q -sec.
CH ₃ -NH ' 7 ^y

The starting materials to be used are clearly and generally defined by the formulas (II) and (III). Preferably stand in it however

R for straight-chain or branched alkyl with 1 to 5, in particular 1 to 4, straight-chain or branched Alkenyl, with 2 to 4, in particular 3, carbon atoms, cyclohexyl, phenyl or monosubstituted or polysubstituted Halophenyl, especially chlorophenyl,

R _1. , For straight-chain or branched alkyl having 1 to 4, in particular -1 to 3, carbon atoms or phenyl substituted one or more times by nitro, Le A 16 o87-4 -

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R ₂ for straight-chain or branched alkyl having 1 to 4, in particular 1 to 3, carbon atoms, phenyl bsrw. phenyl substituted one or more times by halogen, in particular chlorophenyl,

R, for straight-chain or branched alkyl with 1 to 3, especially 1 or 2, straight-chain or branched alkylthio with 1 to 4, especially 1 to 3, monoalkylamino with 1 to 5, in particular 1 to 4 carbon atoms or phenyl and

X for sulfur.

The (thiono) (di) thiolphosphorus (phosphonic) acid esters or. Esteramide derivatives (II) are known from the literature and according to generally customary processes manufacturable (compare e.g. German Auslegeschrift 1.141.634 and I.l64.4o8), as well as the haloacetic acid ester derivatives (III), which e.g. by converting acetic acid derivatives (see reports of the German Chemical Society 64 (1931), p. 545 and 69 (1936) p. 2oo4; Journal of Chemical Society Japan 5jo (1929) p. 687 and Journal of American Chemical Society 7 £ (1948) pp. 2849-2853) with common halogenating agents, such as sulfuryl chloride or N-bromosuccinimide can be obtained.

As examples of the (thiono) (di) thiolphosphorus (phosphoric acid ester- or ester amide derivatives (II) are mentioned in detail:

O-methyl, O-ethyl, O-n-propyl, 0-iso-propyl, O-n-butyl, O-iso-butyl, 0-sec-butyl, otert-butyl, O-phenyl, 0-2-chlorophenyl, 0-2,5-dichlorophenyl, 0-2,6-dichlorophenyl, O-4-chlorophenyl, 0-4,6-Di chlorophenyl, O-pentachlorophenyl methane or " -ethane-, -n-propane, -iso-propane or -phenylthiolphosphonic acid ester, the corresponding thiono compounds and the corresponding alkali, alkaline earth and ammonium salts, respectively

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O, S-dimethyl-, O, S-diethyl-, O ^ -Di-n-propyl-, 0, S-di-isopropyl-, O, S-di-n-butyl-, 0, S ~ di-iso-butyl-, 0, S-di-SeC.-butyl-, O, S-di-tert-butyl-, 0-ethyl-S-n-propyl-, O-ethyl-S-n-butyl-, O-ethyl-S-sec.-butyl-, O-n-propyl-S-ethyl-, O-n-propyl-S-isopropyl-, O-phenyl-S-methyl-, O-phenyl-S-ethyl-, O-phenyl-S-npropyl-, O-phenyl-S-iso-propyl-, O-phenyl-S-n-butyl-, 0-phenyl-S-sec.-butyl-, O-phenyl-S-iso-butyl-, O-phenyl-S-tert-butyl-, O-4-chlorophenyl-S-methyl-, O-4-chlorophenyl-S-ethyl-, O-4-chlorophenyl-S-n-propyl-, 0-4-chlorophenyl-S-n-butyl-, 0-2,4-dichlorophenyl-S-methyl-, 0-2, A-dichlorophenyl-S-ethyl-, 0-2,4-dichlorophenyl-S-n-propyl-, 0-2,4-dichlorophenyl-S-iso-propyl-, 0- ^ 2,4-dichlorophenyl-S-n-butyl-, 0-2,4-dichlorophenyl-S-sec.-butyl-, O-pentachlorophenyl-S-ethyl-, O-pentachlorophenyl-S-n-propyl-, O-pentachlorophenyl-S-iso-propyl-, O-pentachlorophenyl-S-n-butyl-, O-pentachlorophenyl-S-sec.-butyl-, 0-2,4,6-trichlorophenyl-S-ethyl-, 0-2,4,6-trichlorophenyl-S-n-propyl-, 0-2,4,6-trichlorophenyl-S-iso-propyl-, 0-2,4,6-trichlorophenyl-S-n-butyl-, 0-2,4,6-trichlorophenyl-S-sec.-butyl-, 0-2,4,6-trichlorophenyl-S-tert. ~ Butyl- dithiophosphoric acid ester, the corresponding thiono compounds and the corresponding alkali, alkaline earth or ammonium salts, furthermore

O-methyl-N-methyl-, 0-ethyl-N-äthy1-, O-n-propyl-N-n-propyl-, O-iso-propyl-N-iso-propyl-, O-n-butyl-N-n-butyl-, 0-iso-butyl-N-iso-butyl-, 0-sec-butyl-N-sec-butyl-, O-tert-butyl-N-tert-butyl-, O-methyl-N-n-pentyl-, O-ethyl-N-n-pentyl-, O-n-propyl-N-n-pentyl-, O-iso-propyl-N-n-pentyl-, 0-n-butyl-N-n-pentyl-, O-iso-butyl-N-n-pentyl-, O-sec-butyl-N-n-pentyl-, 0-tert-butyl-N-n-pentyl-, O-phenyl-N-methyl-, O-phenyl-N-ethyl-, O-phenyl-N-n-propyl-, O-phenyl-N-iso-propyl-, 0-phenyl-N-n-butyl-, O-phenyl-N-iso-butyl-, O-phenyl-N-sec.butyl-, 0-phenyl-N-tert-butyl-, O-phenyl-N-n-pentyl-, 0-2,4-dichlorophenyl-N-methyl-, 0-2,4-dichlorophenyl-N-ethyl-, 0-2,4-dichlorophenyl-N-n-propyl-, 0-2,4-dichlorophenyl-N-iso-propyl-, 0-2,4-dichlorophenyl-N-n-butyl-, 0-2,4-dichlorophenyl-N-iso-butyl-,

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0-2,4-dichlorophylene-N-tert. -butyl-, 0-2,4,6-trichlorophenyl-N-ethyl-, 0-2,4,6-trichlorophenyl-Nn-propyl-, 0-2,4,6-tri-chlorophenyl-N-iso- propyl-, 0-2.4 _f 6-trichlorophenyl-Nn-butyl-, 0-2,4,6-trichlorophenyl-N-sec-butyl-, 0-2,4,6-trichlorophenyl-N-tert. -butyl-, 0-2,4,6-trichlorophenyl-Nn-pentyl-, O-pentachlorophenyl-N-ethyl-, O-pentachlorophenyl-Nn-propyl-, 0-penta- 'chlorophenyl-N-iso-propyl- , Q-pentachlorophenyl-Nn-butyl-, O-pentachlorophenyl-N-sec-butyl-, 0-pentachlorophenyl-N-tert-butyl- or O-pentachlorophenyl-Fn-pentyl-thiolphosphoric acid ester amide, the corresponding thiono compounds and the corresponding alkali, alkaline earth or ammonium salts.

As examples of haloacetic ester derivatives to be reacted according to the process (III) are mentioned in detail:

Methylthio, ethylthio-jn-propylthio, iso-propylthio, n-butylthio, sec-butylthio-, iso-butylthio-, tert.; - butylthio-, n-pentylthio-, Vinylthio-, allylthio-, bututeri (2) ylthio-, butene (3) -ylthio-, Cyclohexylthio, phenylthio, 4-chlorophenylthio, 2,4-dichlorophenylthio-, 2,4,6-trichlorophenylthio-, pentachlorophenylthio-chloro or -bromoacetic acid methyl or -ethyl-, -n-propyl-, -iso-propyl-, -η-butyl-, -iso-butyl-, -tert-butyl- or -4-nitrophenyl ester.

The process for making the compounds of the invention is preferred with the use of suitable solutions or thinner. Practically all inert organic solvents can be used as such include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, Gasoline, methylene chloride, chloroform, carbon tetrachloride, Chlorobenzene., Or ethers, e.g. diethyl and dibutyl ethers, dioxane, also ketones, for example acetone / methylethyl, methyl · isopropyl and Methyiisobutyiketon, also nitriles, such as Aceto- and propiohitrile.

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All customary acid binders can be used as acid acceptors Alkali carbonates and alcoholates, such as sodium and potassium carbonate, methylate, ethylate or potassium tert-butylate, also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyrldine.

The reaction temperature can be varied within a relatively wide range. Generally one works between 0 and 12o ° C, preferably at 2o to 5o ° C.

The reaction is generally allowed to proceed under normal pressure.

To carry out the process, the starting materials are generally employed in equimolar proportions. An excess one or the other component is generally of no use

substantial advantages. The salt-like phosphoric acid component is preferably added to that in one of the above Solvent or diluent dissolved haloacetic acid ester derivative and stir for one to several hours at the stated temperatures. After the reaction has ended, pour the reaction mixture in an organic solvent, e.g. toluene, washed twice with water, dried over sodium sulfate and the solvent was distilled off.

The new compounds are often in the form of oils, which usually not allowed to distill undecomposed, but by so-called "Incipient distillation", i.e. by prolonged heating under freed from the last volatile constituents under reduced pressure to moderately elevated temperatures and purified in this way will. The refractive index is used to characterize them.

As already mentioned several times, the substituted carboxylmethyl (di) thiöl (thiono) phosphorus according to the invention

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(Phosphonic) acid esters or ester amides are characterized by their excellent insecticidal, acaricidal and nematicidal effectiveness. They are not only effective against plant, hygiene and stored product pests, but also in the veterinary and medical sector against animal parasites (ectoparasites) such as parasitic fly larvae. They have a good effect against sucking as well as eating insects and mites with low phytotoxicity . T. ¹ "also has a fungicidal activity.

For this reason, the compounds according to the invention can be used successfully as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors can be used.

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Those according to the invention / which can be produced according to the invention / according to the invention Usable active ingredients are suitable "with good plant tolerance and favorable when flowering rtoxiz it at to combat all or individual including the pre-embryonic normally sensitive and resistant developmental stages of arthropods / nematodes / phytopathogenic fungi, as far as they are considered pests or pathogens of plant diseases in agriculture, in forests, in storage and Material protection and hygiene are known.

Among the economically important agricultural and forestry as well as storage, material and hygiene pests include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgar, porcellio scaber

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

From the order of the Symphyla e.g. Scutigerella immaculata From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans

From the order of the Acarina e.g. Acarus siro, Argäs reflexus, Ornithodoros moubata, Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus microplus, Rhipicephalus evertsi, Sarcoptes scabiei, Tarsonemus spec. Bryobia praetiosa, Panonychus citri, Panonychus ulmi, Tetranychus telarius, Tetranychus tumidus, Tetranychus urticae From the order of the Thysanura e.g. Lepisma saccharina From the order of the Collembola e.g. Onychiurus armatus From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta doinesticus, Gryllotalpa spec., Locusta migrotoria migratorioides, Melanoplus differentialis, Schistocerca gregaria

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-AA-

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

From the order of the Isoptera, e.g. Reticulitermes spec.

Vastatrix from the order of the Anoplura, for example _Phylloxera;

Pemphigus spec., Pediculus humanus corporis

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

Thrips tabaci

From the order of the Heteroptera e.g. Eurygaster spec,

Dysdercus intermedius, Piesma quadrata, Cimex lectularius,

Rhodnius prolixus, Triatoma spec.

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 arundinis, Macrosiphum avenae, Myzus cerasi, Myzus persicae, Phorodon humuli, Rhopalosiphum padi, Empoasca spec. Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii,

Aspidiotus hederae, Pseudococcus spec., Psylla spec.

From the order of the Lepidoptera, e.g. Pectinophora gossypiella,

Bupalus piniarius, Cheimatobia brumata, Lithocolletis

blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spec, Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spec, Euxoa spec, Feltia 'spec, Earias insulana, Heliothis spec,

Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spec., Trichoplusia ni,

Carpocapsa pomohella, Pieris spec., Chilo spec., Pyrausta

nubilalis, Ephestia kühniella, Galleria mellonella,

Cacoecia podaha, Capua reticulana, Choristoneura fumiferana,

Clysia ambiguella, Homona magnanima, Tortrix viridana From the order of the Coleoptera, e.g. Anobium punctatum,

Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa

decemlineata, Phaedon cochleariae, Diabrotica spec,

Psylliodes chrysocephala, Epilachna varivestis, Atomaria spec,

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Oryzaephilus surinamensis, Anthonomus spec, Sitophilus spec, Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spec, Trogoderma spec, Anthrenus spec, Attagenus spec, Lyctus spec, Meligethes aeneus, Ptinus spec, Niptus hololeucus, Gibbium psylloides, Tribolium spec, Tenebr-io molitor, Agriotes spec, Conoderus

spec., Melolontha melolontha, Amphimallus solstitialis, Costelytra zealandica

From the order of the Hymenoptera e.g. Diprion spec, Hoplocampa spec., Lasius spec., Monomorium pharaonis, Vespa spec

From the order of the Diptera e.g. Aedes spec, Anopheles spec,

Culex spec., Drosophila melanogaster, Musca domestica, Fannia spec, Stomoxys calcitrans, Hypoderma spec, Bibio

hortulanus, Oscinella frit, Phorbia spec, Pegomyia hyoscyami, Calliphora erythrocephala, Lucilia spec., Chrysomyia spec

Ceratitis capitata, Dacus oleae, Tipula paludosa From the order of the Siphonaptera, e.g. Xenopsylla cheopis

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The active ingredients can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, Granules, aerosols, suspension emulsion concentrates, seed powder, Active ingredient-impregnated natural and synthetic materials, Finest encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and tub mist formulations.

These formulations are produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents, for example, can also be used as auxiliary solvents will. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or Methylene chloride,

aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. 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, as well as water; Liquefied gaseous extenders or carriers are liquids that are which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons; as solid carrier materials: natural rock flour, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and synthetic

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see rock flour, such as highly dispersed silica, aluminum oxide and silicates; as emulsifiers and / or foam-producing agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolysates; as a dispersant: e.g. lignin, sulphite waste liquors and methyl cellulose. The active compounds according to the invention can be used in the formulations present in a mixture with other known active ingredients.

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

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom. The application happens in the usual way, z. B. by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10 %, preferably between 0.01 and 1 %.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations of up to 95% or even the 100% active ingredient alone. ■

When used against hygiene and stored product pests, the active ingredients are characterized by an excellent residual effect on wood and clay as well as good alkali stability on whitewashed documents. -

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Example A.

Limit concentration test / soil insects I

Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the production of an appropriate preparation of the active substance if 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation plays a role here practically no role, the only decisive factor is the amount of active substance by weight per unit volume of soil, which is given in ppm (= mg / 1). The bottom is filled into pots and these are left to stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after a further 2 to 7 days the degree of effectiveness of the active ingredient is determined in % by counting the dead and living test insects. The efficiency is 100 % if all test insects have been killed, it is 0 % if just as many test insects are still alive as in the case of the untreated control.

Active ingredients, application rates and results are based on the following Table 1 shows:

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-Xt-

Table 1

Tenebrio molitor larvae in the soil.

Active ingredient

Degree of destruction in % at an active ingredient concentration of 10 ppm

,, CO-OC ₂ H ₅

C ₂ H ₅ S-CH

S-P

(known)

• CO-OC ₂ H ₅

jS-CH ο ⁵ \ 3 OCH SP.

(known)

(CH,), C-S

^ CH-S-

C ₂ H ₅ -OC

-CH, I00

(CH ₃ ) ₃ CS

| / ^0C 2 ^H 5

-C ₂ H ₅ 100

CO-OC ₂ H ₅

C ₂ H ₅ S-CH

\ s-

IOO

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Table 1 (continued) Tenebrio molitor larvae in the soil

Active substance kill rate in %

an active ingredient concentration of 10 ppm

CO-OC ₂ H ₅
C ₂ H S-CH _sc ο I00

^{2 5} \ n ^cH

CO-OC ₂ H ₅
H I00

JO-OC ₂ H ₅

iso-C, H_S-CH "I00

CO-OC ₂ H ₅

H> S-CH 100

\ \\ / 3
SP

^ C ₂ H ₅

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Table 1 (continued) Tenebrio molitor larvae in the soil

Active ingredient

Degree of destruction in % . an active ingredient concentration of 1 ο ppm

CO-OC ₃ H ₇ -ISO

iso-C, H ₇ S-CH S _nu ³⁷ \ li ^ ^C 2 ^H 5

• OCH. I00

CO-OC _O H _K

NS

H _c I00

iso-C

CO-OC ₅ H ₇ -IsO

S-P

OC ₃ H ₇ -

iso I00

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Example B.

Limit concentration test / soil insects II

Test insect: Fhorbia antiqua maggots in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only thing that matters is the amount of active substance by weight per unit volume of soil, which is given in ppm (= mg / l). One fills the bottom in Pots and lets stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after a further 2 to 7 days the degree of effectiveness of the active ingredient is determined in % by counting the dead and living test insects. The degree of effectiveness is 100 % t when all test insects have been killed, it is 0 % t when just as many test insects are still alive as in the case of the untreated control.

Active ingredients, application rates and results are based on the following Table 2 shows:

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Act 2

Phorbia anti qua maggots in the soil

Active ingredient

Degree of death in % at an active ingredient concentration of 5 ppm

CO-OC ₂ H ₅

C ₂ H ₅ S-CH

\ S-P

wCpHj- (known)

CO-OC ₂ H ₅

H σ ptl <3

* ⁵ \ \\ / ^0CE 3

S-P

OCH,

(known)

"CH-S-P"

C ₂ H ₅ -O-CO

I00

-j

CH-S-P

C ₂ H ₅ -O-CO

1oo

C0-0C _o H _c / 2 5

s-p

^ OC ₃ H ₇ -Ii 100

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Table 2 (continued) Phorbia antiqua maggots in the soil

Active substance kill rate in %

an active ingredient concentration of 5 ppm

CO-OC ₂ H ₅
CH

ISO-C ^ E ₇ S-CH q nmj 1OO

3 7 \ O ₁ DCH,

CH _s q

CO-OC ₂ H ₅
ISO-C ₃ H ₇ S-CH _{? I} ^ I00

C ₂ H ₅

CO-OC ₂ H ₅
S-CH ο rtrtit I00

f
SP

^C 2 ^H 5

C ^ E ₇
³⁷

CO-OC ₃ H ₇ -ISO

3-CH

ISO-C ^ E ₇ S-CH q _n ττ Ι00

³⁷ 3 ^CH

'OC ₂ H ₅

CO-OC ₃ H ₇ -ISO

iso-C ^ H ^ S-CH C ₅ r. υ Ι00

CH C ₅ r. υ

\ j / ° ²⁵

'OCH ₃

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• Table 2 (continuation) Phorbia antiqua maggots in the soil

Active ingredient

Degree of destruction in % at an active ingredient concentration of 5 ppm

CO-OC ₂ H ₅

Vp

C ₂ H ₅ too

CO-OC ₂ H

-SC 1oo

co-oc, a, - ± so

₃ H ₇

IsO-Ca ₇ -S-CH

100

IsO-C

^ H ₇

CO-OC ₃ H ₇ -ISO

-S-CH ο

loo

Le A 16 o87

- 23 -

609822/1081

Table 2 (continued)

Fhorbia antiqua maggots in the ground

Active ingredient

Degree of destruction in % at an active ingredient concentration of 5 ppm

CO-OC ₂ H ₅

H \

^N s

. too

CO-OC ₀ H, - / 25

Cl-fVs-CH _{q nrH} \ _s J- N ^ S ^ / OCH ^ too

CO-OC ₂ H ₅

OCHr ₇ -ISO

1oo

C ₀ HcSCHC-O

NO,

Γ ^OG 2 ^H 5

1oo

Le A 16 o87

- 24 -

6098 22/108 1

Example C
Tetranychus test (resistant)

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which are approximately 10 to 30 cm in height, sprayed to runoff. These bean plants are strong with everyone Stages of development of the common spider mite or bean spider mite (Tetranychus urticae).

After the specified times, the destruction is determined in % . 100 % means that all spider mites have been killed; 0 % means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below:

Le A 16 o87 - 25 -

609822/1081

Table 3

Tetranychus test

Active ingredient

Active ingredient kill concentration in % after in % 2 days

C ₂ H ₅ S-CH

(known) o, o1

7o 0

CO-OC ₂ H ₅

C ₂ H ₅ S-CH

-P (OC ₂ H ₅ (known) o, o1

7o 0

CO-OC ₂ H ₅ o, o1

I00 45

ISO-Ca ₇ S-CH

CH q _qr> υ \ Π / ^SC 3 ^H 7 ⁿ

\ sp ^x

OC ₂ H ₅ o, o1

I00

CO-OC ₂ H ₅

(CHz) -zC — S — CH ο nvt

\ gJ / o, o1

I00 4o

Le A 16 o87 - 26 -

809822/1081

Example D
Plutella test

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount Solvent and the specified amount of emulsifier and ver · ^ thin the concentrate with water to the desired one Concentration.

Cabbage leaves are sprayed with the active compound preparation (Brassica oleracea) becomes dewy and populates them with caterpillars of the cabbage moth (Plutella maculipennis).

After the specified times, the destruction is determined in % . 100 % means that all the caterpillars have been killed; 0 % means that none of the caterpillars have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in Table 4 below:

Le A 16 o87 - 27 -

609 822/1 08 1

Table 4

2 «-

Plutella test active ingredient

Active substance kill concentration in % after in % 3 days

CO-OC ₂ H ₅ C ₂ H ₅ S-CH ₂ -CH 3 OC ₂ H ₅

(known)

o, o1

I00 0

CH, S-CH _q

³ \ JS-> o, o1

I00 I00

CO-OC ₀ IL ^{2 5}

ν S OCH ₃ ^X SP ^X o, o1

I00 I00

NS
\

CO-OC ₂ H ₅

s-p

Xc ₂ H ₅ o, o1

I00 I00

C ₀ Hp-S-CH S, CH-

CO-OC ₂ H ₅ S , CH,

p

OC ₃ H ₇ -IsO

₃ H ₇ 0, o1

I00 I00

Le A 16 o87

- 28 - 609822/1081

24S5680

Table 4 (continued) Plutella test

Active ingredient active ingredient kill rate

concentration in % after in% 3 days

CO-OC ₂ H ₅

C ₀ Hp-S-CH ο nnu °> ^{1 1o} °

■ ■> \ \\ / ^ÖLti 1 ■

\ ο 'ρ / o, o1 1oo

CO-OC ₂ H ₅

' o, 1 I00

2 5 o, o1 I00

C ₂ H ₅

CO-OC ₂ H ₅

C ₀ Hp-S-CH _ς ηπ TT O, 1 IOO

\ _q U / o, o1 I00

CO-OC ₂ H ₅

C ₀ Hp-S-CH ο ςπ rr "0.1 IOO

S-P o, o1 I00

OC ₂ H ₅

Le A 16 o87 - 29 -

609822/1081

2465680

Table 4 (continued)
Plutella test

Active ingredient active ingredient kill rate

concentration in % after

in 3 days

^ CO-Of V- NOo
/ X = / ^d . o, 1 1oo

S XH, o, o1 1oo

\ J /

CO-O - / N \ _ NO
/ \ = J ^ά o, 1 1oo

2 "5 °"< ^x S / CoH. ο _f o1 1oo

CO-OC ₂ H ₅

CHo = CH-CH ₀ -S-CH _{Q nnu} o, 11oo

^ * ■ \ ο y UUH ₃

o, o1 1oo

.CO-OC ₂ H ₅

ISO-C ₃ H ₇ S-CH s _0CH ^{0> 1 1o} ° \ Ii y 3 o, o1 loo

^ CO-OC ₂ H ₅

1SO-C ₃ H ₇ S-CH s CH - ° ' ^{1 10} °

\ Κ y 2 5 o, o1 I00

Le A 16 o87 - 3o -

809822/1081

T abe 1 1 e 4 (continued)
Plutella test

Active ingredient .. --.-... Degree of killing of active ingredient

. . concentration in % after . [. '[' 'in % 3 days

^J o, 1 1oo

ISO-C ₃ H ₇ S-CH _s se "-η o.o1 1oo

H ς on ο. ν. I SC ₃ H ₇ -Xi

^X SP ^X

■ / ■■■■ -, - ^ ■? '- . - ... o, 1 1oo

^ ₃ CS-CH _& ^ - _{Ofp1 1oo}

o, 1 1oo

(CH ₃ ) ₃ CS-CH _{s CH}

\ H / 2 5 o, o1 1oo

CO-OC ₂ H ₅

H} S-CH _σ nrw '■

^ÜOH 3 o, o1 1oo

CO-OC ₀ H ,.

^{2 5} o, 1 too

H > - S-CH ς no w λ α

^X S-P '

Le A 16 o87 - 31 -

609822/1081

Table 4 (continued)

Plutella test

Active ingredient Active ingredient kill concentration in % after in % 3 days

NS \

CO-OC ₂ H

₂ H ₅

o · ™

OC ₂ H

₂ H ₅ o, o1

I00 I00

CO-OC ₀ H, -

o, o1

I00 I00

—Ν

8 ^SC 3 ^H 7- ⁿ

\ 8 / ^SC 3 ^H 7 ö, o1

I00 I00

ISO-CHr ₇ p

, H _v ³

-CH \

CO-OC ₃ H ₇ -ISO

₃ H ₇

OC ₃ H ₇ -ISO

₃ H ₇ -o, o1

I00 I00

Le A 16 o87 - 32 -

6098 22/108 1

Table 4 (continued) Plutella test

Active ingredient active ingredient kill rate

concentration in % after in% 3 days

CO-OC ₃ H ₇ -ISO 0 1 loo ISO-C ₅ H ₇ o, o1 loo C ₂ H ₅ ISO-C ₅ H ₇ CO-OC ₅ H ₇ -XSO
NS
\ S: 0C _o H _K
VK ²⁵ o, 1
o, o1 loo
too

Le A 16 087 - 33 -

609822/1081

Example E Drosophila test

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

1 cm of the active compound preparation is placed on a filter paper disk pipetted on with a diameter of 7 cm. This is placed wet on the opening of a glass vessel in which there are fifty fruit flies (Drosophila melanogaster) and covers it with a glass plate.

After the specified times, the destruction in % is determined. 100 % means that all the flies have been killed; 0 % means that no flies have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 5 below:

Le A 16 o87 - 34 -

$ 098-22 / 1081

Drοs ophila-Te st

T a b e 1 1 e

Active ingredient active ingredient concentration
in %

Degree of destruction in % after 1 day

₁ -S-CHp "* CH

(known) o, o1
o, oo1

loo

4o

"C0-0C _o H ²

CpHf-o-CHp-CH Q

(known)

CH o, oo1

1oo. loo O

C ₀ H ^ S-CH ₀ -CH 2 5 ^

CO-OC ₂ H ₅

(known) 0.1

CO-OC ₂ H ₅

CS ₅ SC

S-P

OC-zHxT-iso

₃ H ₇ -I ο, 0-1
ο, 00I

loo loo

/ Le A 16 087

- 35 ■ 609822/1081

T a t> e 11 e 5 (continued) Drosophila test

Active ingredient active ingredient kill degree;

concentration in % after in % 1 day

CH, S-CH
³ \

^J o, o1 1oo

\ (I γ 3 o, oo1 1oo

S-F

^X 2 ^H 5
CO-OC ₂ H ₅

CH, S-CH _n o, o1 loo

\ _s _ ^ / ^ ⁵ o, oo 1 I00

C ₂ H ₅
CO-OC ₂ H ₅

Λ JT (J «ζ Ο, θ1 IOO

\ M / 3 O.OOI IOO

CO-OC ₀ Hp.
/ 2 5

■ i _H q ptl O, O1 1OÖ

'2 ⁿ 5 \ S OCH, o, oo1 I00

CO-OC ₂ H ₅

3-dH _{s oc H} o, o1 I00

\ g_jp / O _# OO1 IOO

C ₂ H ₅

Le A 16 o87 - 36 -

609822/10 81

Table 5 (continued)

Drosophila test

Active ingredient

Active ingredient concentration
in %

Degree of destruction in % by day

CO-OC ₂ H ₅ C ₂ H ₅ S-CH g ^ ₀ C ₃ H _7-11

S-P

C ₂ H ₅ o, o1
o, oo1

Ί00 I00

CO-O H (C ₂ H ₅ S-dH S ^N SP

'.CH

OC ₀ H, o, o1
o, oo1

I00 I00.

CO-0

C ₂ H ₅ S-CH

^C 2 ^H 5

OC ₂ H ₅ o, o1
o, oo1

I00 I00

CO-OC ₂ H ₅ IsO-CJH ₇ S-CH ο

S-P

■ C ₂ H ₅ J-

o, o1
o, oo1

I00 too

CO-OC ₂ H ₅

1 SO-C ₃ H ₇ S-CH

₃ H ₇

\ ti

^N SP o, o1
o, oo1

I00 I00

C ₂ H ₅

Le A 16 o87 - 37 -

609822/1081

Table 5 (continued)

Drosophila test

Active ingredient CO-OC ₂ H ₅ . C ₂ H ₅ Active ingredient o, o1 Degree of destruction (CH,), CS-CH _{s CH}
\ Ii / ³
S-P ^ C0-0C, H ₇ -iso concentration o, oo1 in % after ^0C 2 ^H 5 / ^{3 7} in % 1 day , 'CO-OCpHc ISO-C ^ a ₇ S-CH α ρ υ
^{3 7} \ g / ^C 2 ^H 5
SP I00 o, o1 I00 (CH,), CS-CH ο _n "
\ n / ^C 2 ^H 5
^X SP o, oo1 ^ OC ₂ H ₅ CO-OC ₃ H ₇ -ISO o, o1 I00 ISO-C ^ H ₇ S-CH 0 _nnu
\ \\ / 3 o, oo1 I00 S-P I00 I00 o, o1 o, oo1 I00 I00

Le A 16 o87

- 38 -

809822/1081

Example F

Test with parasitic fly larvae

Solvent: 35 parts by weight of ethylene polyglycol monomethyl ether _;

35 parts by weight of nonylphen oil polyglycol ether

Mixed to produce an appropriate active ingredient preparation one 3o. parts by weight of the active substance concerned with the specified amount of solvent that corresponds to the above Contains portion of emulsifier, and dilute the concentrate obtained in this way with water to the desired concentration.

About 20 fly larvae (Luciliä cuprina) are placed in a test tube which contains approx. 2 cm of the horse muscle. 0.5 ml of the active compound preparation are placed on this horse meat. After 24 hours the degree of destruction is determined in % . Babel means 100% that all larvae and 0% that none of the larvae have been killed. ·

Investigated active ingredients, applied active ingredient concentrations and the test results obtained are shown in Table 6:

Le A 16 o87 - 39 -

609822/108 1

Day 6

Test with parasitic fly larvae

Active ingredient active ingredient degree of depletion

concentration in % (Lucilia in ppm cuprIna res.)

C ₂ H ₅ O jj

PS-CH-CO ₀ C ₀ H, -S 2 2 5

f ^C 2 ^H 5

1oo Ioo Io Ioo 1 1oo

π w η $, ^s -C /, H _Q -tert. too 1oo

2 ^M 5 \ II I ■ ^y 1o 1oo

^ P-S-CH-CO ^ -C ^ H ^ -iso 1 too

1oo 10O

to 1 oo

1 Ioo o, 1

loo too

C ₀ Hp- S SC ₀ Hp- 3o Ioo

^{2 5} ^ - ^^ Il I ²⁵ Io 1oo

^ PS-CH-CO ₀ C ₀ H ₁ , 3 1 oo

iso-C, H ₇ -HN o, 3

CH ^ O I f ^C 2 ^H 5 ¹ °° ^ ⁰⁰

3 ■ —1 | I 3o 1oo

PS-CH-COC ₀ H. 1o too

P υ '* * ■ ^D 3 1oo

^C 2 ^H 5 1

_H 1oo 1oo

2 ^rt 5 3o 1oo

PS-CH-CO ₂ C ₂ H ₅ ' ^1o

Le A 16 o87 - 4o -

609822/1081

-W-

Table 6 (continued) Parasitic Fly Larvae Test

Active ingredient

Active substance kill concentration in % (Lucilia in ppm cuprina res.)

C ₂ H ₅ O,

SC ₂ H ₅ 100

30th

10

100 100 100

C ₂ H ₅

'-S-CH-CO ₂ C ₂ H ₅ 100
3o

1o

I00 I00 I00 I00

C ₂ H ₅

'PS-CH-CO ₀ C ₀ H ₁ . 2 2 100

1o

1
0.1

loo 100 Too

-iso

PS-CH-CO ₀ C ₀ H.

'2 "5

I00
3o
1o

o, 3

I00 I00 I00 I00 > 5o

C ₂ H ₅ -

SCjHy-iso '-S-CH-CO ₂ C ₂ H ₅ 100
1o
1
0.1

I00 I00 > 5o

Le A 16 o87

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609822/108 1

Tabel

; to -

6 (continued)

Test with parasitic fly larvae

Active ingredient

Active ingredient concentration
in ppm

^CH

° \ fl P

C ₂ H ₅

PS-CH-CO ₀ C ₀ Hc-2 2 5

I00

1o

Degree of destruction in % (Lucilia cuprina res.)

iso-C H ₇ OS SC ₂ H ₅
PS-CH-CO ₂ C ₂ H
CH ₃ loo
1o
1 too
loo ^C 2 ^H 5 ° \ f | 1 ^{3 7}
TS-CH-CO ₂ C ₂ H ₅
C ₆ H ₅ loo
30th
1o
3
1 loo
too
loo
> 5o _r π _n ς SC, H _v -iso
C ₂ H ₅ O ^^^ S [37
^ ^s ^ PS-CH-CO ₂ C ₂ H ₅
1SO-C ₃ H ₇ -HN 100
30th
1o
3
1
0.3 loo
loo
loo
loo
> 5o _s s - / ^ h \
PS-CH-CO ₂ C ₂ H ₅
C ₂ H ₅ ^ I00
1o
1 I00
I00

100
I00

Le A 16 o87

- 42 -

609822/108 1

Tab. 6 (continued) Test with parasitic fly larvae

Active ingredient active ingredient concentration
in ppm

Degree of destruction in % (Lucilia cuprina res.)

PS-CH-CO ₂ C ₂ H ₅ 1 OO

3o

1o

1oo 1oo 1oo

P-S-CH-CO, 100

1o

1oo 1oo 1oo

1oo

1o

1oo 1oo 1oo

PS-CH-CO ₂ C ^ Hr ₇ -IsO

Ψ? ' 100

30th
1o

loo

loo

loo

C ₂ H ₅ OC ₂ H ₅

PS-CH-CO ₂ C ₂ H ₅ 100
1o
1
0.1

I00 I00 <5o

1oo

3o

1o

I00 I00 I00

Le A 16

- 43 609 8 22/108 1

7 4 S 5 6 8

Table 6 (continued)
Test with parasitic fly larvae

Active ingredient active ingredient kill rate

concentration in % (Lucilia ■ in ppm cuprina res.)

S SV / \\ ■ too 1oo

H TA = / 3o. 1oo

PS-CH-CO ₀ C ₀ H, - 1o - loo

2 2 5,

run ^ Γ 3 7 3ο 1οο

3 1οο.

IsO-C ₃ H ₇ -HN ¹ . . ... "

00 I 00

S 9 ^ ₃ " ₇ -iso 3ο. 1οο

Il 'Ί η Ί r \ / ->

_r " _n S SCH,

P-S-CH-C

CO ₀ C ₃ H.

d. eL O

1οο 1οο - ' 1οο 1ο 1οο 1οο 1 1οο 1οο 0.1 ■ · 1οο 1οο 1οο 1ο 1 σο 1 1οο 1οο 3ο 1ο 3

SCH ₃ '-S-CH-CO ₂ C ₂ H ₅

eO S SCH, 5 \ κ T 3

PSCHC

PS-CH-CO ₀ C ₉ H 6 ^H 5

Le A 16 o87 - 44 -

609822/1081

24B5680

Tabel

(Continuation)

Test with parasitic fly larvae

Active ingredient C ₂ H ₅ -HN S- \ y- Cl ^C 2 ^H 5 Active ingredient Degree of destruction C ₂ H ₅ O _x §
PS- ( concentration in% (Lucilia _{; H} -co ₂ c ₂ h ₅ in ppm cuprina res.) loo loo 3o loo C ₀ Hr-O S? ^CH 3 UJO loo
loo 2 5 \ Ii ι
PS-CH-CO ₂ C ₂ H ₅ 1 <5o iso-C, H ₇ -HN ' o, 3 - loo I00 S SCH, 1o
A. I00 IsO-C ₃ H ₇ Oj | j 3 \ PS-CH-CO ₀ C ₀ H ₁ -
• 2. 2. O
H/ IOO I00 ö S-CH ₀ -CH = CH ₀ 3O
1O
3 I00
I00
I00 CH ₃ OJ ₁ I.
PS-CH-CO ₂ C ₂ H 1 - ^C 2 < I00 I00 C ₀ Hr-O S S _0-CH -CH = CH ₀ 3o I00 2 5 \. | _f j 2 2 1o
3 I00
I00 PS-CH-CO ₂ C ₂ H ₅ 1 ' I00 I00 3o I00 1o
3
1 I00
I00
> 5o o, 3

Le A 16 o87

- 45 -

609822/1081

Table 6 (continued) Parasitic Fly Larvae Test

Active ingredient Active ingredient kill concentration in % (Lucilia in ppm cuprina res.)

CH, O

3 ° \ Ι |

Cl

PS-CH-CO ₂ C ₂ H ₅

1oo loo 3o 1 00 1o loo 3 loo 1 <5o o, 3 loo loo 1o loo 1 loo

> M

P-S-CH-CO,

Le A- 16 o87 - 46 -

609822/1081

HJ-

' Production examples ι

Example 1 (CH ₃ J ₃ CS. Η (

■ TH-S-P

17.8 g (0.1 mol) of the sodium salt of methanthionothiolphosphonic acid O-ethyl ester are added to a solution of 21.0 g (0.1 mol) of ethyl chloro-tert-butylthioacetate in 2oo ml of acetonitrile, and the mixture is stirred for one hour 40 ° C. and then poured into 300 ml of toluene. The organic phase is washed twice with 2oo ml of water each time and dried over sodium sulfate. After the solvent has been distilled off, the residue is distilled off at 50 ° C. under reduced pressure. 25 g ( 75 % of theory) O-ethyl-S- (1-tert-butyl-, thio-1-carbethoxymethyl) .-. Methane - thionothiolphosphonic acid ester in the form of a yellow oil with a refractive index n _D : 1.522o.

Analogously to Example 1), the following compounds of

formula

? R

^R 3

getting produced:

'-S-CH-CO ₂ R ₁ (I)

Le A 16 o87 - 47 -

609822/1081

f at

<° game

> No. XR

Yield refractive (% of index:
Theory)

ο 2 S (CH,), C-

DD

<3

C ₂ H ₅ -

S (CH ₃ ) ₃ C- -C ₃ H ₇ -ISO C ₂ H ₅ - C ₂ H ₅ -

n ^ ⁶ : 1.5227

81

: 1.5117

C ₂ H ₅ -

82

: 1,500

S - (

S - (

S -C ₀ H ₁ :

S -. (

S - (

0 -C ₂ H ₅

JS ... -C

-C ₂ H ₅

C ₂ H ₅

C ₂ H ₅

C ₂ H ₅

C ₂ H ₅

C ₂ H ₅ -

C ₂ H ₅ -

CH ₃ -

C ₂ H ₅ -

C ₂ H ₅ -

C ₂ H ₅ -C ₂ H ₅ -

95

: 1,531o

.2o.

3SJH-C ₃ H ₇ -IsO 51 njp 1.5282

C ₂ H ₅ -

85 n _D : l, 54lo 63 n ²⁰ 1.5612 71 n ^: 1.5392 9o nf: I, 54o6 76 _n 23. 1.5286

C ₂ H ₅ - NH-C ₄ H ₉ -SeC. ^x 85:; n ^ ^D : Γ, 4968

JS?

tr *
φ

ι σ -P- CD OO PO ΪΌ
- **. ■ __ »
ο

Example
No. XR

yield

{% of the refraction theory) index:

13th

14th

S -

-C ₃ H ₇ -IsO

15 S -C ₃ H ₇ -ISO

16 S -

17 S -

18 S -C ₃ H ₇ -ISO

19 S -C, H ₇ -iso

2o S -C ₃ H ₇ -ISO

21

22 · ■ p

23 ·. S.

-C ₂ H ₅

-C ₂ H ₅

-C ₂ H ₅

-C ₂ H ₅

-C ^ H _C

-C ₂ H ₅

- ^C 2 ^H 5

-C ₂ H ₅

_7- η NH-C ₃ H ₇ -IsO •, C ₂ H ₅ - ·.,.;. ■

C ₃ H ₇ -ISb CH ₃ -

C ₂ H ₅ - NH-C ₂ H ₅

C ₂ H ₅ -

C ₂ H ₅ -

NH-C ₃ H ₇ -IsO

₃ H ₇

C ₂ H ₅ -

CH ₃ -

NH-C ₂ H ₅ -

79
82
84
44
72
71
85
87
86
'86

': 1.5221

η ²³ : 1.5323 η ²³ : 1.5247 η ²³ : 1.5273 η ²³ : 1.5332 η ²² : 1.5538 η ²³ : 1.53ο8 η ²³ : 1.5186 η ²³ : 1.5372

η | ² : 1.5432

η ²² : 1.5357

UO

OS

O I

Example no. Z R

24 S -C ₃ H ₇ -ISO

29 3d ^31: 32

-C ₃ H ₇ -ISO C ₂ H ₅ -

25 S -C ₃ H ₇ -IsO -C ₃ H ₇ -ISo -CH

₃ H ₇

26 S -C

₃ H ₇ -I

ISO

27 S - // VS 28 p

S S S S

₃ H ₇

C ₃ H ₇ -IsO -C ₂ H ₅

-CoH -C ₂ H ₅

₂ H ₅

C ₂ H ₅

C ₂ H ₅

C ₂ H ₅ -C ₂ H ₅ - ^C 2 ^H 5 -C ₂ H ₅ -C ₂ H ₅

C ₂ H ₃ -

C ₂ H ₅ -

-C ₂ H ₅

, H ^

yield

(% of the refraction theory) index:

84 η ^22
n D * 1.5183 85 η ^22
n D * 1.52ο8 79 ■ 1.5445 91 η ²² : 1.57ο3 84 n ^: .1,5962 η 83 η ^21
n D * 1.5743 ^ -iso 74 η ^21
n D ' 1.5651 84 η ²¹ 1,559S

84

n ²¹ : 1.5432

33 S -C ₃ H ₇ -ISO

-C ₃ H ₇ -ISd -C ₂ H

'-ZLirj— J.OVJ - \ jniXf- - NH- C ^ Hr ^ - ISO OH-

-24.

D '

1.5132

34 S -C ₃ H ₇ -IO

-C ₃ H ₇ -ISO -C; , -iso -CH-

85 n ²⁴ i I, 5o97

σν ο co

Le A 1 at
game
No. X R. σι ο
CD
■ * ^ , 35 S. -CH ₃ 36 S. -CH, 37 S. -CH ₃ 38 S ' -CH,

4o S -CH,

41 S YH

R-: yield

( % eier refractive \,

Theory) index:

42 43

45; '■

S. S.

- ^C A. -CH ^
■ '■. D ■ ■ -C ₂ H -C ₂ H ₅ -C ₂ H ₅ -C ₂ H - ^C 2 ^H 5, -C ₂ H ₅ ■ Ö -C ₂ H ₅ ^ -C ₃ H ₇ -ISO -NH- - ^C 2 ^H 5, -C ₃ H ₇ -ISO -CH ₃ -C ₂ H ₅ -. -CH ₃

^C 2 ^H 5

CHo = CH-CHp- -CpHc

95 88 79 88

87 87 -NH-CH ₇ -iso 71

-CH,

-NH-C ₂ H ₅

.... C ₂ H ₅ . -CH,

.-C ₂ H -C ₀ H,

83 9o 92 ■ 9 $ "

ng ^ · '1.5368 n ^ ³ : 1.5448; n | ³ : 1.5686 n ²² : 1.5296

n ² ^ ³ : 1.5312 η ²² : 1.5392 n ²³ : 1.5314 n ² ) ² : 1.5469 n ^ ¹ : 1.5415 ........ π | ³ ϊ 1.5772

tr «

cn αϊ co

tr »

(D

ο οο

Example No. X R

yield
(% of
Theory)

46 S C1- / 7

47 S -

cn ί I 48 • S ' —Γ PT ^;
ζ ,? '· ο
co VJI OD 49 S. - ^C 2 ^H 5 ' NJ. ' O 03 - - »" ■. ■>

-C ₃ H ₇ -iso -

Cl.

'-CH,

-C ₂ H ₅

Refractive in, dex:

86 · ■ τι ^: 1.5750

77 ■■ ■■ "■ crack: 1.5635

48 ■ '■■ · η ²² : 1.576ο

63 '..' ■ n ^ ² : 1/5673

cn cn 'cn

The haloacetic acid ester derivatives used as starting materials (III) can ζ. B. be manufactured as described below:

SC, eds-tert. Cl-CH-CO ₂ C ₂ H ₅

To a solution of 19 g (0.1 mol) of tert-butylthioacetic acid ethyl ester 15.4 g (0.11 mol) of sulfuryl chloride are added dropwise to 50 ml of carbon tetrachloride. Then 2 hours will take Heated to reflux. The reaction mixture is then washed twice with water and once with saturated sodium bicarbonate solution washed, dried over sodium sulfate and concentrated. The crude ethyl chloro-tert-butylthioacetate is used directly further processed. :

Analogously, the following compounds of the general

formula

SR

Hal-CH-CO ₂ R ₁

(III)

getting produced:

Physical,
_Hal data (refractive index, melting point

-Tert. -

- ^C 2 ^H 5 -C ₂ H ₅

-iso Cl Cl Cl

ii | ¹ liter 1.4589

98-10I

Io2-lo5

Le A 16 o87

- 53 "-

6 0 9822/1081

Physically. Data (Bre-IT-, chung index, melting point ⁸ )

-C ^ Hy-iso - ^C 6 ^H 5
-CH,

CH ₂ -CH = CH ₂

-C ₂ H ₅ -C ₂ H ₅

Cl "ng ¹ : 1.4979 Cl "G ¹ " 1.4637 Cl n ^22
n D * 1.5457 Cl ⁿ D ^2; 1.4791 Cl n ^23
n D * 1.4989 Cl 1.5591

With N-bromosuccinimide the following compound of the formula

SC ^ H, -Br-CH-CO-O- ^ ^x V

with the refractive index n ² / *: 1.5927.

Le A 16 o87

-54 -

609822/10 8 1

Claims (1)

Claims in which - _,; - ' ,,:, ~ "~ r -.". ".,; - .: *" ... ■ R for alkyl with 1 to 6, cycloalkyl with 5 to 7,, alkenyl with 2 to 5 carbon atoms or for....' optionally substituted by halogen Phenyl, R ₁ for alkyl with 1 to 6 carbon atoms or:. ■ '' Nitrophehyl, ■ "" ■ ■ "· -"" ^: '. R ₂ for alkyl with Λ to 6 carbon atoms or phenyl optionally substituted by halogen, R, for alkyl, alkylthio, .Alkyläminb with in each case 1 to 6 carbon atoms · 'or, "Phenyl and' X stand for an oxygen or sulfur atom " Process "for" the preparation of substituted carboxylmethyl (di) thiol (thiono) phosphorus (phosphonic) acid esters or ester amides, characterized in that (Thiono) - (Di) ■ Thiolphosphorus (phosphonic) acid esters or ester amide derivatives of the formula R ₂ '-SM (II) in which R ₂ , R- and X have the meaning given in claim 1 and "* ^{>: <} "" Le A 16 o87 ■ '■' - 55 - M for hydrogen, an alkali, alkaline earth or ammonium equivalent stent, with haloacetic ester derivatives of the formula RS-CH-HaI (III) in which R and R ^ have the meaning given in claim 1 and Hai stands for halogen, in particular chlorine or bromine, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a solvent or diluent implements. 3. Insecticidal, acaricidal and nematicidal agents, marked by a content of compounds according to claim 1. 4. A method of combating insects, mites and nematodes, characterized in that one compounds according to claim 1 can act on the said pests or their habitat. 5. Use of compounds according to Claim 1 for combating insects, mites and nematodes. 6. Process for the preparation of insecticides, acaricidal and nematicidal agents, characterized in that compounds according to claim 1 are mixed with extenders and / or surface-active agents. Le A 16 o87 - 56 - 609822/108 1