DE2106300A1 - N-trihalomethanesulphenyl-n-methyl-carbamidoximes - with insecticidal, acaricidal and microbistatic activity - Google Patents

Abstract

Title cpds. of the formula : CH3S-C(CH3)2-CH=NOCON-(CH3)SCX3 (I) (where X is Cl and/or F) are insecticides with higher activity and lower toxicity towards warm-blooded animals than the known cpd. lacking the N-trihalomethanesulphenyl. (I) are prepd. by reacting X3CS-N-(CH3)-COF with CH3S-C(CH3)2-CH=NOH in a solvent or diluent in the presence of an acid acceptor.

Description

N-sulfenylated N-methylcarbamidoximes, process for their preparation The present invention relates to their use as insecticides and acaricides new N-sulfenylated N-methylcarbamidoximes, which have insecticidal and acaricidal properties own and a process for their preparation.

It is already known that N-trichloromethylthio compounds are a have insecticidal action (cf. German Patent 921 290). Farther it is known to use N-fluorodichloromethylthio compounds as acaricides (cf. Zeitschrift für Angewandte Chemie, Vol. 76, Page 807 (1964)). In the end are also N-methylcarbamidoximes, e.g. 3.

the 2-methyl- (2-methylthio) -propionaldehyde-0- (N-methylcarbamoyl) -oxime, have been described as insecticides (see U.S. Patent 3,217,037).

It has now been found that the new N-sulfenylated N-methylcarbamidoximes of the general formula (I) in which X stands for chlorine and / or fluorine atoms, have strong insecticidal and acaricidal properties.

It has also been found that the N-sulfenylated §-Xethylcarbamidoximes of the formula (I) are obtained if N-sulfenylated N-Methylcarbaiidsäurefluoride of the formula (II) in which X has the meaning given above, with 2-methylthio-2-methyl-propionaldehyde oxime of the formula (III) in the presence of a solution or diluent and an acid acceptor.

It is extremely surprising that the compounds according to the invention have a higher insecticidal and acaricidal effectiveness than known rim carbamates analogous constitution and the same direction of action. Also own the new Products are lower than the previously described N-methylcarbamidoximes Warm-blooded toxicity.

They thus represent an enrichment of the technology.

When using N- (fluorodichloromethylthio) -N-methylcarbamic acid fluoride, the course of the reaction can be represented by the following equation: CH | OH OH i3 CH3S-C-CH = NOH + FC-N-CH3> CH SC-CH = NO-N-SCFCl2 1 II 'acid binding 3 CH3 0 SCFCl2 medium CH3 The N-sulfenylated N-methylcarbamic acid fluorides required as starting materials are known (cf. Deutsche Auslegeschrift 1 297 095) and are clearly defined in general by formula (II).

The oxime (III) required as the second reaction component is also used already described in the literature (see Journal of Agricultural and Food Ghemistry Vol. 14, page 356 (1966)).

Practically all inert organic solvents can be used as diluents in question. These include ethers, such as diethyl ether, tetrahydrofuran and dioxane, Hydrocarbons such as benzene, chloroform and chlorobenzene.

To bind the hydrogen fluoride formed during the reaction the reaction mixture is preferably a tertiary organic acid acceptor Base, such as triethylamine, or inorganic bases, e.g. alkali hydroxides or -carbonate, too.

The reaction temperatures can vary within a wide range will; generally one works between -20 and + 100, preferably at 0 to 300C.

When carrying out the manufacturing process, the starting materials generally used in molar amounts, but there is a slight excess of oxime sometimes expedient.

The reaction mixture is worked up by customary methods.

As already mentioned above, the new compounds exhibit reduced Warm-blooded toxicity has excellent insecticidal and acaricidal properties; she are therefore suitable for combating sucking and biting insects, dipteras and mites, especially in crop protection.

In addition, the products also have a microbistatic effect.

The sucking insects mainly include aphids (Aphidae) such as the common peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato lice (Macrosiphum solanifolil), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black Cherry aphid (Myzus cerasi), also scale and mealybugs (Coccina), e.g. the ivy shield (Aspidiotus hederae) and cup scale (Lecanium hesperidum) as well the mealybug (Pseudococcus maritimus); Cystic tubercles (Thysanoptera) such as Hercinothrips femoralis and bedbugs, for example beetroot (Piesma quadrata), cotton (Dysdercus intermedius), bed bug (Cimex leqtularius), predatory bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars should be mentioned above all (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden after (Euproctis chrysorrhosa) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frostworm (Cheimatobia brumata), Oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large wax moth (Galleria mellonella), Farther The permanent insects include beetles (Coleoptera) e.g. corn (Sitophilus granarius = Calandra granaria), potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), Raspberry (Byturus tomentosus), table bean (Bruchidius = Acanthoscelides obtectus), Bacon (Dermestes frischi), Khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegoblum paniceum), common meal beetle (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. B. Wire worms (Agriotes spec.) and white grubs (Melolontha melolontha); Cockroaches like the Germans (Ehattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae); Oriental (Blatta orientalis), giant (Blaberus giganteus) and giant black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also orthopteres e.g. the House crickets (Acheta domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small house fly (Fannia canicularis), gloss fly (Phormia aegina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcitrans); further back, e.g. Mosquitoes such as the yellow fever (Aedes aegypti), house (Culex pipiens) and malaria gaps (Anopheles stephensi).

The mites (Acari) include the spider mites (Tetranychidae) like the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), gall mites, e.g. the currant mite (Eriophyes ribis) and tarsonemids for example the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

When used against hygiene and storage pests, especially Flying and nodding, the process products are also characterized by excellent quality Residual effect on wood and clay as well as good alkali stability on limed Documents from.

Depending on their intended use, the new active ingredients can be converted into the usual ones Formulations such as solutions, emulsions, suspensions, powders, Pastes and granulates. These are prepared in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers optionally with the use of surface-active agents, ie emulsifying and / or Dispersants, e.g. in the case of using water as an extender organic solvents can optionally be used as auxiliary solvents can. The main liquid solvents that can be used are: aromatics (e.g. Xylene, benzene). Chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), Alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; as solid carriers: natural rock flour (e.g. kaolins, clays, talc, chalk) and synthetic rock flour (e.g. highly dispersed Silicic acid, silicates); as emulsifier: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, Alkyl sulfonates and aryl sulfonates; as a dispersant: e.g. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients.

The formulations generally contain between (), 1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90, The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, Pastes, soluble powders, dusts and granules can be applied. The application happens in the usual way, e.g. by spraying, atomizing, atomizing, dusting, Scattering, smoking, gassing, pouring, pickling or encrusting.

The ingredient concentrations in the ready-to-use preparations can be varied in larger areas. 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 method (ULV) should be used where it is possible to formulations up to 95% or even to apply the 100% active ingredient alone.

EXAMPLE A Drosophila Test Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent that contains the specified amount of emulsifier and dilutes the Concentrate with water to the desired concentration.

1 cm³ of the active ingredient preparation is on a pilter paper disc with 7 cm diameter pipetted on. They are placed wet on a glass in which 50 are lying on top (Drosophila melanogaster) and covers it with a glass plate.

After the specified times, the destruction in% is determined.

100% means that all flies have been killed, 0% means that no fly was killed.

Active ingredients, active ingredient concentrations, evaluation times and degree of destruction are shown in Table 1 below: Table 1 (Drosophila test) Active ingredient active ingredient concentration degree of destruction tration in ffi in% 1 day OB RAW 3 XC-CH = NOCN 0.2 100 OH 1 NH 0.02 100 3 0 0.002 40 SCH3 (known) CHD / CH C-CH = NOCN 0.02 100 0.002 100 Example B Phaedon-Larven-est solvent: 3 parts by weight of dimethylforamide 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 containing the specified amount of emulsifier, and the concentrate is diluted with water to the desired concentration .

Cabbage leaves (Brassica oleracea) are sprayed with the active ingredient preparation dripping wet and populated with mustard beetle larvae (Phaedon cochleariae).

After the specified times, the degree of destruction is determined in s. 100 P means that all of the beetle larvae have been killed. 0% means that none Beetle larvae were killed.

Active ingredients, active ingredient concentrations, times of evaluation and results are shown in Table 2 below: Table 2 (Phaedon larvae test) Active ingredient active ingredient concentration degree of destruction tration in% in% 3 days CH / CHg CH / T t CH3 0.2 100 0.02 100 3 0.002 20 (known) CH3 CH 0.2 100 C-CH = NOiN 3 0.02 100 OH3i \ SCFC12 0.002 SOH3 Example Myzus test (contact effect) Solvent: 3 parts by weight of disethylformaside emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate active ingredient preparation, 1 part by weight of active ingredient is mixed with the specified amount of solvent containing the specified narrow emulsifier and the concentrate is diluted with water to the desired level Concentration.

Cabbage plants (Brassica oleracea), which are heavily infested by the plum aphid (Myzus persicae), dripping wet sprayed.

After the specified times, the degree of destruction is determined in% 100% means that all aphids have been killed, 0% means that none Aphids were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below: Table 3 (Myzus test) Active ingredient active ingredient concentration degree of abatement tration in% in% 1 day CK, -CH = mOCN / CH, 1 . 0.2 100 CH / | h H 0.02 100 3 SCH3 ° 0.002 80 0.0002 0 (known) OH3 CH3 0.2 100 3 \ C ~ cg = ff ~ o ~ C ~ N 0.02 100 ni 0 SOFOl2 0.002 100 SOH3 0.0002 50 3 0.0002 50 Example D Toxicity test / peroral test animal: Evaluation according to: albino rat (Rattus norvegicus) 7 days To produce a suitable active ingredient preparation, 3 parts by weight of active ingredient are mixed with 2.8 parts by weight of highly disperse silica and 4.2 parts by weight of talc.

With the addition of a little powdered vegetable gum, one exhibits this active ingredient concentrate by rubbing with water suspensions, which are listed in 1 ml of liquid contain the amount of active ingredient to be applied per 100 g of animal weight. Dosing takes place volumetrically after weighing the test animals.

It is applied by means of a steel button probe per 06.

The evaluation is carried out after the above specified period of time has elapsed, calculated from the application of the active ingredient.

The determination of the LD50 values (active ingredient dose with which 50% of the treated Animals are killed) is carried out from the cortality values in geometric progression varied doses in the usual way.

Active ingredients and LD50 values are shown in Table 4 below. The indexed value is taken from the literature: 1) FREAR, D.E.H.

Pesticide Index, Fourth Edition, 1969 Table 4 Toxicity test (albino rat / peroral) LD50 values Active ingredient (in mg / kg body weight) 3 \ C ~ CH = NoC-Ns 5 CH ACH) Õ H 3 (known) CH3N C-CH = NO ~ p ~ N / CH3 35 C-.CH = NO-Fd-N SCPC1, 3 CH3 \ wCH CH3 / i i0 \ S1CH3 3 Manufacturing examples A solution of 26.6 g (2/10 mol) of 2-methylthio-2-methyl-propionaldehyde oxime and 42 g (2/10 mol) of N-methyl-N- (fluorodichloromethylthio) carbamic acid fluoride in 200 ml of ether is mixed with 22 g (2/10 mol) of triethylamine added. The temperature of the mixture is allowed to rise to 350C, the solution is shaken out with water after the reaction has subsided, the ethereal solution is dried over sodium sulfate, concentrated under reduced pressure and 50 g of 77% of the theory of the above sulfenylated N-methylcarbamidoxime are obtained in the form of a yellow oil with the refractive index n ° 1.5178.

In an analogous way, the connection becomes the following constitution with the refractive index nD20 1.5210.

Claims (6)

Claims N-sulfenylated N-methylcarbamidoximes of the formula in which X stands for chlorine and / or fluorine atoms. 2. Process for the preparation of N-sulfenylated N-methylcarbamidoximes, characterized in that N-sulfenylated N-methylcarbamic acid fluorides of the formula in which X has the meaning given in claim 1, with 2-methylthio-2-methyl-propionaldehyde oxime of the formula in the presence of a solvent or diluent and an acid acceptor. 3. Insecticidal and acaricidal agents characterized by a content of compounds according to claim 1. 4. A method for combating insects and mites, characterized in that that one compounds according to claim 1 on the said pests or their habitat can act. 5. Use of compounds according to Claim 1 for combating Insects and mites. 6. Process for the production of insecticidal and acaricidal agents, characterized in that compounds according to Claim 1 are mixed with extenders and / or mixes surfactants.