CH593614A5 - Organo (thio) phosphorus cpds - insecticides, acaricides - Google Patents

Abstract

Title cpds. have the formua:- (where R1 is lower alkyl; R2 is lower alkyl or alkoxy or Ph; R3 is Ph opt. substd. (e.g. by halogen, alkyl or alkoxy), phenalkyl opt. substd., alkyl, haloalkyl, cyanoalkyl, alkenyl, alkynyl or Alkyl interrupted by one or more O or S atoms; X is O or or S; R2 is alkyl or Ph when R2 is alkyl). A prefd. cpd. has R1 and R2 = Et, X = S and R3 = benzyl. Prepn. is by reacting an appropriate phosphorus halide with MO-CH=CMe.COOR3 where M is an alkali metal.

Description

  

  
 



   The present invention relates to a pest control agent which, as the active component, is a compound of the formula
EMI1.1
 where Rl is a lower alkyl radical, R2 is a lower alkyl, alkoxy or phenyl radical, R3 is a lower cyanoalkyl or an alkyl radical interrupted by one or more sulfur atoms and X is oxygen or sulfur.



   The lower alkyl radicals mentioned for R1 and R2 are branched or unbranched and have 1 to 5, preferably 1 to 4, carbon atoms. Examples of such residues are u. a. Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, seki butyl, tert-butyl, n-pentyl. The lower alkoxy radicals mentioned under R2 correspond in the alkyl part to the lower alkyl radicals defined by R and R2.



   The phenyl radical mentioned for R2 is substituted or unsubstituted. Halogen, such as fluorine, chlorine or bromine or lower alkyl and alkoxy radicals, as defined above, are suitable as substituents. The phenyl nucleus can be substituted one or more times, the substituents not having to correspond in the case of multiple substitution.



   The lower cyanoalkyl radicals which are suitable for R3 have 1 to 4 carbon atoms and are branched or unbranched. Suitable alkyl radicals are u. a. Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl. The alkyl radicals which are interrupted one or more times by sulfur and which can also stand for R3 have 2 to 8 carbon atoms. They are also branched, but preferably unbranched, and interrupted once to three times, preferably once or twice, by sulfur.



   The compounds of the formula I are prepared by processes known per se. For example, one can proceed in such a way that an alkali metal salt of a formylpropionic acid ester of the formula
EMI1.2
 wherein R3 has the meaning given above and Me is an alkali metal, such as. B. sodium or potassium, with an ester halide of the formula
EMI1.3
 where Rl, R2 and X have the meaning given and Hal represents halogen, in particular chlorine or bromine, is converted. The reaction takes place at temperatures between 0 and 150 "C, preferably between 10 and 80" C, in the presence or absence of a solvent. Suitable solvents are preferably inert organic solvents such as. B.



  Benzene, toluene, xylenes, mono- or polychlorobenzenes, acetonitrile or ketones (acetone, methyl ethyl ketone).



   The compounds of the formula I have a pesticidal effect and can be used to combat a wide variety of pests in the animal and plant kingdom.



  Their insecticidal and acaricidal properties deserve special mention.



   They act, for example, against sucking and biting insects such as Diptera and representatives of the order Acarina, such as. B. ticks and mites. The sucking insects mainly include aphids (Aphidae) z. B. Myzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolli, Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis, Myzus cerasi; then further shield and lice (Coccina) z. B. Aspidiotus hederae, Lecanium hesperidum, Pseudococcus maritimus; Thrips species (Thysanoptera) z. B. Hercinothrips femoralis; Bugs z. B.



  Piesma quadrata, Rhodnius prolixus, Triatoma infestans; Cicadas z. B. Euscelis bilobratus Nephotettix bipunctatus.



   Examples of biting insects include: Plutella maculipennis, Lymantria dispar, beetles such as Sitophilus granarius, Colorado potato beetle (Leptinotarsa decemlineata), leaf beetles (Aulacophora femoralis), soil species such as wireworms (Agriotes sp.). Grubs, e.g. B. Melolontha melolontha, Orthopter z. B. Acheta domesticus, termites e.g. B. Leucotermes reticulitermes sp .; Hymenoptera etc., then Eastern species such as Prodenia litura, the flour moth (Ephestia kühniella), the large wax moth (Galleria mellonella), then pests of storage (Dermestes frischii); Trogoderma granarius, Tribolium castaneum, Calandra and Sitophilus zea mais etc., Stegobium paniceum, Tenebrio molitor, Aryzaephilus surinamensis, Agriotes, Blattella germanica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fus domesticus, Gryllus domesticus.



   The dipteras mainly include flies (Drosophila melanogaster, Ceratitis capitata, Musca domestica), mosquitoes z. B. mosquitoes (Aedes aegypti, Culex pipiens, Anopheles), blowflies such as Lucilia sericata etc.



   Among the mites, the spider mites (Tetranychidae) should be emphasized as major pests z. B. Tetranychus telarius, T. althaeae, T. urticae, Paratetranychus pilosus, Panonychus ulmi, then gall mites (Eriophyes ribis), tarsonemids z. B. Hemitarsonemus latus, Tarsonemus pallidus.



   The order Acarina also includes ticks, i. H.



  Ectoparasites such as Boophilus microplus, Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylviarum, Rhipicephalus bursa, Pneumonyssus caninum, Lealaps nutalli, Acarapis woodi, Psorergates ovis etc.



   Mention should also be made of the good action of the compounds of the formula I against rice stem burrs, such as Chilo suppres salis, Chilo plejadellus Zinck, Chilolotraea polychrysa, Diatraea saccharalis, Niphadoses palleucus Common, Tryporyza incertulas, Tryporyza, innotata, Elignos fasmellina nubilola, Busse lignosuscausinia nubilola. Sesamia calamistics, Sesamia inferens, etc.



   The above list of pests does not claim to be complete.



   The active ingredients of the formula I can be used alone or together with suitable carriers and / or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology, such as. B. natural or re generated substances, solvents, dispersants, network; Adhesives, thickeners, binders and / or fertilizers.



   Further known insecticidally and / or acaricidally active compounds can be added to the active ingredients of the formula I.



   In many cases, this measure spreads the spectrum of activity of the active substances of the formula I, in other cases real synergistic effects can be achieved.



   For example, phosphoric acid derivatives, carbamates, chlorinated hydrocarbons, nitrophenols and derivatives or formamidines can be added.



   For application, the compounds of the formula (I) can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in a customary formulation which is part of general knowledge in application technology. Furthermore, cattle dips, i. H. Cattle baths, and spray races, d. H. Mention should be made of spray courses in which aqueous preparations are used.



   The agents according to the invention are produced in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can be present and used in the following working-up forms: Solid working-up forms:
Dusts, grit, granules, coated granules, impregnation granules and homogeneous granules Liquid processing forms: a) Active ingredient concentrates dispersible in water:
Wettable powder, pastes, emulsions: b) Solutions
The active ingredients are mixed with solid carriers for the production of solid forms (dusts, grit). As carriers come z. B.

  Kaolin, talc, bolus, loess, chalk, limestone, lime grit, ataclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, fertilizers, such as Ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as grain flour, tree bark meal, wood flour, nut shell meal, cellulose powder, residues from plant extractions, activated carbon, etc., each individually or as mixtures with one another.



   Granules can be produced very easily by dissolving an active ingredient of the formula I in an organic solvent and applying the resulting solution to a granulated mineral, e.g. B. Attapulgite, SiO2, Granicalcium, Bentonite etc.



  applies and then the organic solvent evaporates again.



   Polymer granules can also be produced by mixing the active ingredients of the formula I with polymerizable compounds (urea / formaldehyde; dicyandiamide / formaldehyde; melamine / formaldehyde or others), whereupon a gentle polymerization is carried out, which does not affect the active substances, and which still granulation is carried out during gel formation. It is cheaper to use finished, porous polymer granules (urea / formaldehyde, polyacrylonitrile, polyester and others) with a certain surface and favorable, predeterminable adsorption / desorption ratios with the active ingredients, for. B. in the form of their solutions (to be impregnated in a low-boiling solvent3 and that
Remove solvent.

  Such polymer granules can also be applied in the form of micro-granules with a bulk density of preferably 300 liters to 600 liters with the aid of atomizers. The atomization can be used over large areas of crops
Help can be carried out by airplanes.



   Granules are also made by compacting the carrier material with the active ingredients and additives and then
Chop available.



   These mixtures can also be added to the active ingredient stabilizing additives and / or nonionic, anionic and cationic substances, such as the
Improve the adhesive strength of the active ingredients on plants and plant parts (adhesives and adhesives) and / or better
Ensure wettability (wetting agents) and dispersibility (dispersants).



   For example, the following substances come into question: Olein
Lime mixture, cellulose derivatives (methyl cellulose, carboxy methyl cellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols with 5 to 15 ethylene oxide residues per molecule and 8 to 9 carbon atoms in the alkyl group, ligninsulphonic acid, its alkali and alkaline earth metal salts, polyethylene glycol with polyglycol ethers (carbowax) 5 to 20 ethylene oxide residues per molecule and 8 to 18 carbon atoms in fatty alcohol, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea-formaldehyde and latex products.



   Active ingredient concentrates dispersible in water, d. H.



  Wettable powders, pastes and emulsion concentrates are agents that can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives stabilizing the active ingredient, surface-active substances and anti-foaming agents and optionally solvents.



   The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and pulverulent carriers in suitable devices until homogeneous and grinding. Suitable carriers are, for example, those mentioned above for the solid processing forms. In some cases it is advantageous to use mixtures of different carriers.

  The following can be used, for example, as dispersants: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, and alkali, ammonium and alkaline earth salts of ligninsulfonic acid, further alkylarylsulfonates, alkali metal sulfates, alkali metal sulfates, alkali metal sulfates, alkali metal sulfates, alkali metal sulfates such as salts of sulfated hexadecanols, heptaecanols, octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary acetylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

 

   As antifoam agents such. B. Silicones in question.



   The active ingredients are mixed, ground, sieved and passed with the additives listed above in such a way that the solid content of the wettable powders does not exceed a particle size of 0.02 to 0.04 and of the pastes 0.03 mm. To produce emulsion concentrates and pastes, dispersants such as those listed in the previous sections, organic solvents and water are used. Examples of suitable solvents are alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and mineral oil fractions boiling in the range from 120 to 350 ° C. The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.



   The agents according to the invention can also be used in the form of solutions. For this purpose, the active ingredient or several active ingredients of the general formula I are dissolved in suitable organic solvents, solvent mixtures or water. The organic solvents used can be aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils, alone or as a mixture with one another.



   The content of active ingredient in the agents described above is between 0.1 and 95/0, it should be mentioned that concentrations of up to 99.5% are used for application from an airplane or other suitable application devices.



   The active ingredients of the formula I can be formulated as follows, for example:
Dusts: The following substances are used to produce a) 50 / above and b) 2% proprietary dust: a) 5 parts of active ingredient
95 parts of talc; b) 2 parts of active ingredient
1 part of highly dispersed silica
97 parts of talc
The active ingredients are mixed and ground with the carrier substances.



   Granules: The following substances are used to produce 5% granules: 5 parts of active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (grain size 0.3-0.8 mm) .



   The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and then the acetone is evaporated in vacuo. Spray powder: The following ingredients are used to produce a) 40% proprietary, b) and c) 25% proprietary spray powder:

   a) 40 parts of active ingredient
5 parts of lignin sulfonic acid sodium salt,
1 part dibutylnaphthalenesulfonic acid sodium salt,
54 parts of silica; b) 25 parts of active ingredient
4.5 parts calcium lignosulfonate,
1.9 parts of champagne chalk hydroxyethyl cellulose
Mixture (1: 1),
1.5 parts of sodium dibutyl naphthalene sulfonate,
19.5 parts of silica,
19.5 parts of champagne chalk,
28.1 parts of kaolin; c) 25 parts of active ingredient
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts of champagne-chalk-hydroxyethyl cellulose
Mixture (1: 1),
8.3 parts sodium aluminum silicate,
16.5 parts kieselguhr,
46 parts of kaolin; d) 10 parts of active ingredient
3 parts mixture of the sodium salts of saturated
Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid-formaldehyde condensate,
82 parts of kaolin.



   The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of any desired concentration.



   Emulsifiable concentrates: The following substances are used to produce a) 10% and b) 250,000 emulsifiable concentrate.



  a) 10 parts of active ingredient
3.4 parts epoxidized vegetable oil,
3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylaryl sulfonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene; b) 25 parts of active ingredient acid ester,
2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate fatty alcohol poly glycol ether mixture,
5 parts of dimethylformamide,
57.5 parts of xylene.



   Emulsions of any desired concentration can be prepared from these concentrates by diluting them with water.



   Spray: The following ingredients are used to produce a) 5% spray: a) 5 parts of active ingredient
1 part epichlorohydrin,
94 parts of gasoline (boiling points 160-190 C); example
A) 42.5 g of the sodium salt of formylpropionic acid ethyl mercapto ethyl ester, the preparation of which is described under B), were heated to 40 to 50 ° C. in 200 ml of acetonitrile.



  32 g of dimethylthiochlorophosphate were added dropwise in about 15 minutes and the temperature was kept at 40 to 50 ° C. for a further 4 hours. The salts were then suction filtered, the solvent was removed in vacuo and the residue was taken up in 100 ml of methylene chloride Methylene chloride solution twice with 30 ml of normal sodium hydroxide solution each time and the methylene chloride was removed in vacuo at a bath temperature of 50 ° C. The residue obtained was 38.2 g of a yellow oil (n26 1.4922) of the formula
EMI3.1
 The following connections were established in an analogous manner: Verb. R1 R2 R3 X Physical no.

  Data (2) C2H5 C2H5O C2H4S C2H5 S n26 1.4770 (3) C2H5 C2H5O C2H4CN S n9D6 1.4612 B) Sodium salt of formylpropionic acid ethyl mercaptoethyl ester
23 g of sodium were dissolved in 400 ml of alcohol and the solution was heated to 60 ° C. in a pressure vessel. Carbon monoxide was injected with 10 atmospheres and the temperature was allowed to drop to room temperature. After the uptake of carbon monoxide was complete, 172 g of ethyl mercapto propionate (pro / 80 " C) too. At room temperature, carbon monoxide was injected with 40 atmospheres until the pressure remained constant.

  The semi-solid mass, consisting mainly of the sodium salt of Formylpropionsäureäthylmer captoäthylesters was washed out with ether and dried under vacuum. Yield: 206 g of crude product.



   The sodium salt of formyl propionic acid cyanoethyl ester can be prepared in an analogous manner.

 

Claims (1)

PATENT CLAIM Pesticide which, as an active component, is a compound of the formula I. EMI4.1 where Rt is a lower alkyl radical, R2 is a lower alkyl or alkoxy radical or the phenyl radical, R3 is a lower cyanoalkyl or an alkyl radical interrupted by one or more sulfur atoms and X is oxygen or sulfur.