DD146242A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to Schaedlingsbekaempfungsmittel for use in agriculture and forestry, in material and storage protection, in the hygiene sector and in veterinary medicine. The aim of the invention are pesticides with improved insecticidal, acaricidal and nematicidal activity. According to the invention, N-iso-propyl-S- (1,6-dihydro-6- (thi) oxopyridazine (1) yl-methyl) thiol-phosphoric acid ester amides of the formula I are used as active ingredients in the new pest control agents, in which R is alkyl of 1 to 6 carbon atoms and X is oxygen or sulfur.

Description

Berlin, 28.2.1980

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Pesticides Field of application of the invention

The invention relates to pesticides containing novel N-iso-Propyl-S ~ (l, 6-dihydro ~ 6- (thio) oxopyridazin (l) yl-methyl) -thiolphosphorsäureesteramiden, a process for their preparation and their use as pesticides , in particular as insecticides, acaricides and nematicides.

Characteristic of the known technical solutions

It is known that certain S- (I, 6-dihydro-6- (thio) -oxopyridazine (1) yl-methyl) - (thiono) thiol-phosphoric acid ester-. amides such as B. N-allyl-O-ethyl-S- (1,6-dihydro-3-methyl-6-oxopyridazine (1) yl-methyl) -thionothiol-phosphoric acid ester amide, N, N-dimethyl-O-ethyl- S- (1, O-dihydro-S-methyl-δ-oxopyridazine (1) yl-methyl) -thiol phosphoric acid ester amide and N-isopropyl-0-n-propyl-S- (1,6-dihydro-3-methyl 6-thioxopyridazine (I) yl-methyl) -thionothiol-phosphoric acid ester-amide, insecticidal, acaricidal and nematicidal properties (compare German Offenlegungsschriften Nos. 2,348,736 and 2,603,052). However, the effect of this compound, especially at low drug concentrations and application rates, is not always satisfactory.

Object of the invention

The aim of the invention is the provision of new pesticides with improved insecticidal, nematicidal and acaricidal activity, broad spectrum of treatment

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and favorable plant and warm-blooded toxicity. Explanation of the essence of the invention

The invention has for its object to find compounds which have the desired properties and which are suitable as active ingredient in pesticides.

There are now novel N-iso-propyl-S- (l, 6-dihydro-6- (thi) -oxo-pyridazine (l) yl-methyl) -thiolphosphorsäureesteramide the formula

0 OR N-CH-S-P (I)

NH-C ₃ H ₇ -ISO

found in which

R is alkyl of 1 to 6 carbon atoms and X is oxygen or sulfur.

Compounds of the formula (I) are obtained when 1,6-dihydro-1-chloromethyl-3-methyl-6- (thi) oxopyridazines of the formula

(II)

in which X has the meaning given above, with salts of N-iso-propyl-thiolphosphorsäure-esteramides of the formula

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⁰ Il y

M-S-P (III)

NH-C ₃ H ₇ .iso

in which R has the abovementioned meaning and M is an alkali metal, alkaline earth metal or ammonium equivalent,

optionally reacted using a diluent.

The new compounds (I) are distinguished by high activity as pesticides, in particular by excellent insecticidal, acaricidal and nematicidal properties.

Surprisingly, the M-iso-propyl · S- (l, 5-dihydro-6- (thi) oxopyridazine (l) -yl-methyl) -thiolphosphoric acid esteramides (I) according to the invention exhibit considerably higher insecticidal, acaricidal and nematicidal activity as known from the prior art compounds analogous constitution and the same direction of action.

The invention particularly relates to compounds of the formula (I) in which

R is straight-chain alkyl having 1 to 3 carbon atoms

and X is oxygen or sulfur.

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If, for example, .alpha., .Alpha.-dihydro-1-chloromethyl-S-methyl-6-thioxopyridazine and the sodium salt of N-isopropyl-O-methylthiolphosphoric acid ester-amide are used as starting materials, the reaction of these compounds can be effected by the following Outlined formula scheme:

M ° ^CH 3

, , _NaC1

NH-C H ₇ -XSO

NH-C ₃ H ₇ -ISO

The starting materials to be used 1,6-dihydro-lchloromethyl ~ 3-methyl-5-öthi) oxo-pyridazines are defined by the formula (II) in which X is oxygen or sulfur.

The compounds of the formula (II) are already known (cf., DE-OSs 2,348,736 and 2,603,052).

Examples include:

l.e-dihydro-1-chloromethyl-S-methyl-6-oxopyridazine and 1, e-dihydro-1-chloromethyl-S-methyl-6-thioxo-pyridazine.

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The salts of N-iso-propyl-thiolphosphoric acid esteramides to be used as further starting materials are defined by the formula (III). Preferably stand in it

R is straight-chain alkyl having 1 to 3 carbon atoms

and M for sodium or potassium.

Examples include:

Sodium salt and potassium salt of O-methyl-N-isopropyl-thiophosphoric acid ester-amide, sodium salt and potassium salt of O-ethyl-N-isopropyl-thiophosphoric acid-esteramide and sodium salt and potassium salt of on-propyl-N-isopropyl-propylphosphoric acid ester-amide.

The starting compounds of the formula (III) are new. These compounds (III) are obtained when N-iso-Propylthionophosphorsäure-ester chlorides of the formula

H OR Cl-P- (IV)

^V NH-C ₃ H ₇ -XSO

in which R has the meaning given above (preferably straight-chain alkyl having 1 to 3 carbon atoms) with at least two equivalents of a hydroxy compound of the formula

M-OH; (V)

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in which M has the meaning indicated above (preferably sodium or potassium), optionally with the dilution of diluents such. As water and methanol, at temperatures between 0 and 100 C, preferably at 20 to 80 C, is reacted. The reaction products are then obtained, for example, by extraction with toluene and evaporation of the aqueous phase in vacuo. -

The precursors of the formula (IV) are known or can be prepared analogously to known processes (cf DE-OS 2 348 736).

Examples include: O-methyl, O-ethyl and O-n-propyl-N-iso-propyl-thionophosphorsäure ester chloride.

As examples of the hydroxy compounds of formula (V) may be mentioned sodium hydroxide and potassium hydroxide.

The process for preparing the N-iso-propyl-S- (1,6-dihydro-5- (thi) oxopyridazine (1) -yl) -thiol phosphoric acid ester-amides according to the invention is preferably carried out using suitable solvents or diluents , As such, virtually all inert organic solvents come into question. These include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzine, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, Methyl isopropyl and methyl isobutyl ketone and nitriles such as acetonitrile and propionitrile.

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The reaction temperature can be varied within a wider range. In general, one works between O and 100 ⁰ C, preferably at 20 to 80 ⁰ C.

The process of the invention is generally carried out at atmospheric pressure.

On 1 mol of l, 6-dihydro-l-chloro-methyl-3-methyl-6- (thi) oxo-pyridazines (II) is generally used between 1.0 and 1.2 mol, preferably between 1.05 and 1 15 of the salts of N-iso-propyl-thiol phosphoric ester amides (III).

The reaction is generally carried out in one of the above diluents, and the reaction mixture is stirred for several hours at the required temperature. Thereafter, with an organic solvent such. B. toluene and the organic phase worked up as usual by V.'aschen, drying and distilling off the solvent. The refractive index serves to characterize the products which are generally obtained in oily form.

The new N-iso-propyl-S- (1,6-dihydro-6- (thi) oxopyridazine- (1) -yl-methyl) -thol phosphoric acid ester amides (I) are characterized, as already mentioned, by excellent insecticidal agents , acaricidal and nematocidal activity. With low phytotoxicity, they have a good action against sucking and eating insects, as well as against spider mites and nematodes.

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Therefore, the compounds (I) of the present invention can be successfully used in crop protection as a pesticide.

The active compounds are suitable for good plant tolerance and favorable toxicity to warm-blooded animals for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products 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 above mentioned pests include:

From the order of Isopoda z. B. Oniscue asellus, Armadillidium vulgaris, Porcellio scaber.

From the order of Diplopoda z. B. Blaniulus guttulatus.

From the order of Chilopoda z. Geophilus carpophagus, Scutigera spec.

From the order of Symphyla z. B. Scutigerella immaculata.

From the order of Thysanura z. B. Lepisma saccharina.

From the order of Collembola z. B. Onychiurus armatus.

From the order of Orthoptera z. Blatta orientalis, Periplaneta americana, Leucophaca maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of Dermaptera z. B. Forficula auricularia.

From the order of Isoptera z. B. Reticulitermes epp.

From the order of Anoplura z. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of Mallophaga z. B. Trichodectes spp.

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Damalinea spp. '

From the order of Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

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

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorura, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae "Laodelphax striatellus, Nilaparvat'a lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of Lepidoptera z, B. 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 spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo epp., Pyrausta nubilalis, Ephöstia kuehniella, Galleria mellonella , Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. «From the order of Coleoptera 2. B. Anobium puncta'tum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaodon cochlearla.e, Diabrotica spp.,

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Psylliodes chrysocephala, 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., Meligethos aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica. From the order of Hymenoptera ζ. B. Diprion spp., Hoplocampa spp., Lasius spp., Monornorium pharaonis, Vespa spp. From the order of Diptera z. 8. Aedes spp .; Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp. Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of Siphonaptera z. Xenopsylla cheopis, Ceratophyllus spp. , ,

From the order of Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhlpicephalus 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

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semipenotrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

Dio active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substances impregnated natural and synthetic substances, ultrafine encapsulations in polymeric substances and in seed coatings, also in Formulations with Brennerineri, such as smoke cartridges, doses, spirals u. Ä., And ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner, for. Example , by mixing the active compounds with extenders, ie liquid solvents, pressurized verr liquid gases and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, ¹ such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. 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; with liquefied gaseous extenders or

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Carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are: z. 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 are: z. Crushed 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 shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylarylpolyglykol ether, alkyl sulfonates, alkyl sulfates, aryl sulfates and protein hydrosysates; as dispersants in question: z. As lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate may be used in the formulations.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, ferrocyan blue, and organic dyes such as alizarin, azole metal phthalocyanine dyes, and trace nutrient salts such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc are used.

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

The application of the active compounds according to the invention takes place in the form of their commercially available formulations and / or the use forms prepared from these formulations.

The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active compound concentration of the application name can be from 0.0000001 to 100% Gevu- active ingredient by weight, preferably between 0.01 and 10 -. Lie%.

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

When used against hygiene and storage pests, the active ingredients are characterized by an excellent residual effect on wood and clay and by a good alkali stability on limed substrates.

Example of embodiment

The invention will be explained in more detail below on some Ausführungsboispielen.

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Example A ·

Limit concentration test / nematodes

Test nematode: Meloidogyne incognita Solvent: 3 parts by weight of acetone 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, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The preparation of active compound is intimately mixed with soil that is heavily contaminated with the test nematodes. In this case, the concentration of the active ingredient in the preparation plays virtually no role, the only decisive factor is the amount of active substance per unit volume of soil, which is stated in ppm. Pour the treated soil into pots, sow lettuce and keep the pots at a greenhouse temperature of 27 ^° C.

After four weeks, the roots of the roots are examined for nematode infestation (root galls) and the efficiency of the active ingredient is determined in % . The efficiency is 100 %, if the infestation is completely avoided, it is 0 %, if the infestation is just as high as in the control plants in untreated, but equally contaminated soil.

In this test, z. For example, the following compounds of Preparation Examples have superior efficacy over the prior art: 1, 2, 3, and 4.

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Example B Phaedon larval test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound 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 are populated with horseradish beetle larvae (Phaedon cfeochleariae) while the leaves are still moist.

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

In this test, z. For example, the following compounds of Preparation Examples have superior efficacy over the prior art: 1, 2, 3, and 4.

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Example C

Tetranychus test (resistant) ·

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris) that are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) 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 spider mites have been killed; 0 % means' that no spider mites have been killed.

In this test, z. For example, the following compounds of Preparation Examples have superior efficacy over the prior art: 1, 2, 3, and 4.

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Producible ungsbei games, Example 1:

(D

NH-C ₃ H ₇ -ISO

A mixture of 15.8 g (0.1 mol) of 1,6-dihydro-1-chloromethyl-3-methyl-5-oxopyridazine and 24.3 g (0.11 mol) of the potassium salt of the O-ethyl N-iso-propyl-thiolphosphoric acid ester amide is heated to 50 ° C. in 200 ml of acetonitrile for 13 hours. Then, the reaction mixture is cooled to 20 C and poured into 500 ml of toluene. The toluene solution is washed with 50 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and then evaporated. This gives 25 g (82 % of theory) of O-ethyl-N-isopropyl-S- (l, 6 ~ dihydro-3-methyl-6-oxo-pyridazin (l) yl-methyl) - thiolphosphorsäureesteramid as a yellow oil with the ßrechungs-

00 index n ^: 1.5396.

Analogously, the following compounds were prepared:

Yield: O _oc υ 74 % of theory;

Refractive index: ₍₂₎ ⁿ D ^:

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CH.

0 Il

-CH ₂ -SP

OC ₃ H ₇ -η

Yield: 82 % of theory; Refractive index:: 1.5280

(3)

OCH

NH-C ₃ H ₇ -ISO

Yield:

89 % of theory; Refractive index:

nf: 1.5495

(4)

The alkali metal salts of the Thiolphosphorsäureesteramide to be used as starting materials can, for. B. be prepared as follows:

Example a:

KS-P

0C ₃ H ₇ -n

NH-C ₃ H ₇ -ISO

(5)

A mixture of 150 ml of water, 100 ml of methanol, 61.6 g (1.1 mol) of potassium hydroxide and 107.8 g (0.5 mol) of thionophosphoric acid 0-propyl ester N-iso-propy1amidchlorid is refluxed for 1 hour and then cooled to room temperature. The solution is shaken with 200 ml of toluene, the aqueous phase is separated off and evaporated to dryness in vacuo. The residue is triturated with acetone, filtered from undissolved and the solvent is distilled off in vacuo. 59 g (53 % of theory) of potassium remain behind

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salt of the On-propyl-N-iso-propyl-thiolphosphorsäureesteramids with the melting point of 144 ⁰ C.

Analog can be produced:

KS-P 06)

NH-C ₃ H ₇ -IsO

KS-P ^ (7)

NH-C ₃ H ₇ -XSO

Claims (5)

Erfindunqsanspruch 1. Pesticides, characterized by a content of N-iso-propyl-S ~ (l, 6-dihydro-6 ~ (thi) oxopyridazin (l) yl-mQthyl) -thiolphosphorsäure-esteramides of the formula OR
-CH-SP ^ (I) NH-C ₃ H ₇ -ISO found in which R is alkyl of 1 to 6 carbon atoms and X is oxygen or sulfur, Quaking diluents and / or surface-active agents. 2. Insecticidal, acaricidal or nematicidal agents according to item 1, characterized by a content of compounds according to item 1. 3. A method for controlling pests, characterized in that one lets compounds act according to point 1 on said pests or their praise habitat, 4. Use of compounds according to item 1, characterized in that they are used for controlling pests. 28.2.1980 · AP C.07 F / 216 - 21 - 56 229/12 5. A process for the preparation of pesticides, characterized by mixing compounds according to item 1 with extenders and / or surface-active agents.