DE1905362A1 - N-cyano-(thiono)phospor(on)amides-insecticides - and acaricides - Google Patents

Abstract

N-Cyano-(thiono)phospor(on)amides insecticides and acaricides. New cpds. of formula (where R1 is lower alkyl, lower alkoxy or pheny, R2 is lower alkyl and X is O or S), which have insecticidal and acaricidal activity and, in some cases, rodenticidal and post-emergence herbicidal activity, are prepd. by reacting the halide with H2HCN either in the presence of an acid-binding agent or in the form of an alkali(ne earth) or ammonium salt.

Description

Phosphorus, phosphonic or thionophosphorus (phosphonic) acid esters and Process for their preparation The present invention relates to new phosphorus, Phosphonic or. Thionophosphorus (phosphonic) acid esters, which are insecticidal and acaricidal Have properties and a process for the preparation of these compounds.

Substances of this structure have not yet been described in the literature been; only O, O-diethylthionophosphoric acid amide is known, but that has only a weak insecticidal effect (see Journ. Chem. Soc. 1961, p 5532).

It has now been found that phosphorus, phosphonic or thionophosphorus (- phosphonic) acid esters of the general formula (I) are characterized by excellent insecticidal and acaricidal properties.

In the above formula, R1 and R2 stand for the same or different, straight-chain or branched lower alkyl radicals, X1 also denotes a lower alkoxy or the phenyl group, while X is an oxygen or sulfur atom represents.

As was also found, phosphorus, phosphonic resp.

Thionophosphorus (phosphonic) acid esters of the above constitution (I) are obtained if phosphorus, phosphonic or thionophosphorus (pphosphonic) acid ester halides of the formula (II) with cyanamide in the form of its alkali, alkaline earth or monium salts or in the presence of acid binders.

In the latter formula, the symbols R1, R2 and X have the following meaning given above, while Hai stands for a halogen atom.

Surprisingly, the compounds according to the invention have im Compared to the known constitutional analog O, O-diethyl-thionophosphoric acid amide a significantly higher insecticidal and acaricidal effect; they thus represent a a real asset to technology.

The course of the reaction of the manufacturing process is shown by the following equation (III): where R1, R2, X and Hal have the aforementioned meaning.

However, R1 in the above formulas is preferably alkyl or Alkoxy radicals with 1 to 4 carbon atoms such as methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, iso-propyl, iso-propoxy, n-butyl, n-butoxy, iso-butyl, iso-butoxy, sec-butyl, sec-butoxy, tert-butyl, tert-butoxy or for phenyl; R2 is the same or different from R1 and preferably denotes C1 to C4 alkyl groups, for example ethyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl or tert. -Butyl, Hal is preferably a chlorine atom.

The starting materials required for the process, cyanamide or its alkali (preferably sodium or potassium), frdalkali (preferably calcium) or ammonium salts, and phosphorus, phosphonic or thionophosphorus (-phosphonic) acid ester halides of the formula (11) are known from the literature and also on an industrial scale Easily accessible The reaction is preferably carried out in the presence of solution or

Diluents carried out.

Practically all inert organic solvents can be used as such. These preferably include chlorinated hydrocarbons such as gasoline, Benzene, toluene, xylene, chlorobenzene and dichloromethane, dichloroethane, chloroform, Carbon tetrachloride, ethers, e.g. lithium and dibutyl ethers, dioxane and low boiling aliphatic ketones and nitriles, for example acetone, methyl ethyl ketone, methyl isopropyl ketone, Aceto and propionitrile.

As already mentioned above, one can use the salts of cyanamide as To use starting material, the e reaction also using the free cyanamide, However. Allow to run off in the presence of.? aur <binders. As such have Before all tertiary aliphatic, aromatic or heterocyclic amines such as Triethylamine and tributylamine, dimethylbenzylamine, diethylaniline and pyridine have proven their worth.

When the acid acceptor is liquid under the conditions of the reaction is, an excess of the same can be used as a solvent or diluent to serve.

The reaction temperatures can be within a relatively wide range can be varied. In general, between 10 and 6C, preferably at 20 to 500C.

Wienus equation (III) above is used for a quantitative Conversion per mole of ester halide theoretically 1 mole of cyanamide and optionally 1 another mole of acid binder is required.

To carry out the process, it is expedient to add to the solution or suspension of the cyanamide in one of the above-mentioned diluting agents Stir the relevant ester halide at the stated temperatures. After completion after the addition, the mixture is left for some time (2 to 6 hours) if necessary Stirred while heating, then cooled, acidified and the excreted salty Filtered off precipitate. The filtrate is mixed with suitable indifferent Solvents, preferably one of the aromatic hydrocarbons mentioned above such as benzene, the organic phase is optionally separated off, dried and the solvent is distilled off. That which remains as a residue, usually in oily form In most cases, the reaction product cannot be distilled without decomposition; it can however, by briefly heating under reduced pressure to weak to moderate elevated temperatures (50 to 800C) freed from the last volatile components and be cleaned in this way. In addition to the values, the Elemental analysis especially the refractive index.

As already mentioned several times, the new products stand out excellent insecticidal and acaricidal properties. They also own partly also a rodenticidal effect.

werner is in higher concentrations during a post emergence application determine a certain, often desired, inhibition of plant growth.

For this reason, the compounds of the present invention can be used with success in plant and stored product protection as well as in the hygiene sector to combat harmful sucking and biting insects and dipteras as well as against mites (acarina) will.

The sucking insects mainly include aphids (Aphidae) like the green peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi.), pea macrosiphum pisi) and potato mouse (Macrosiphum solanifolii), 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 as the mealybug (Eseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and bedbugs, for example the beet (Piesma quadrata), cotton (Dysdercus intermedius), bed bug (Cimex lectularius), predatory bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Naphotettix bipunctatus.

Among the biting insects there are mainly nine caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden after (Euproctis chrysorrhoea) and ring moth (Malacosoma neustria) furthermore the cabbage (kamestra brassicae) and the seed owl (grotiæ segetum), the large cabbage whitefish (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).

The biting insects also include beetles (Coleoptera) e.g. Corn (Sitophilus granarius = Calandra granaria), potato (Leptin6tarsa decemlineata), Dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), Raspberry (Byturus tomentosus), table bean (Bruchidius = Acanthoscelides obtectus), Bacon (Dermestes friachi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), maize- tCalandra or Sitophilus zeamais), bread- (Stegobium paniceum), common flour (Tenebrio molitor) and grain beetle (Oxyzaepfiinus surinamensis), but also species living in the soil, e.g. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like the Germans (Blatells germanica), American (Periplaneta americana), Wiadeira- (Laucophaea or Rhyparobia madeirae), oriental (Blatta orientalis), giant (Blaberus giganteus) and giant black cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Acheta domesticus); Termites like the earth termites (Reticulltermes flavipes) and Hymenoptera ie ants, for example the meadow ant (asius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Geratitis capitata), room (Musca domestica), small Shben fly (Fannia canicularis), gloss fly (Phormia aegina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcitrans); also mosquitoes, z. B. Mosquitoes such as the yellow fever (Aedes aegypti), house (Culex pipiens) and malaria mosquito (Anopheles stephensi).

The mites (Acari) particularly include the spider mites (Tetranychidae) like the bean (Tetranchus 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); and finally ticks such as the leather tick (Ornithodorus moubata).

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 granules.

These are prepared in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers, possibly with the use of surface-active agents, i.e. 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 wic @ olyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulfonAtes and arylsulfonates; as dispersant: ZsB. Lignin, sulphite waste liquors and methyl cellulose.

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

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

The concentrations of the active ingredient can be varied within a wide range will. In general, concentrations of from 0.00001% to 20% are used, preferably from 0.01 2 to 5%.

Lie active ingredients can be used as such, in the form of their formulations or the forms of use prepared from it, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and granules can be used. It is used in the usual way, e.g. by pouring, spraying, atomizing, gasifying, smoking, scattering, veriEub etc..

The excellent effect of the products is evident from the following test results emerged Example A Plutella test solvent: 3 parts by weight acetone 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.

The active ingredient preparation is sprayed on Kohi leaves (Brassica oleracea) They become dewy and populate with caterpillars of the cabbage moth (Plutella maculipennis).

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

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 1 below Table 1 (Plutella test) Active ingredient active ingredient concentration degree of killing (Consistency) tration in% in 9 after 3 days S. (C2H50) 2P-NH2 0.1 0 (known) S. II (C2H50) 2P-NH-CN 0.1 100 0.01 100 0 (C2H50) 2P "-NH-CN 9.1 100 C 2B, S II iP-NH-CN 0, i 100 C2H50 0.01 20 Example B Phaedon larvae test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight altylaryl polyglycolite 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 .

The active ingredient preparation is sprayed with cabbage leaves (Brassica oleracea) dripping wet and populated with horseradish leaf beetle larvae (Phaedon cochleariae).

After the specified times, the degree of destruction is determined in%. 100 means that. all 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. Degree of destruction 63 itution3 tration in 5 'in-after 3 days 4P-aJH2 0.1 0 s 0.1 p ~ s Q, 1 100 2 0.01 30 0 1 0.1 o) P-SH-aN 100 0.01 30 5 0.1 100 t2S50 Example C Myzus test (contact effect) Solvent: 3 parts by weight 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 which contains the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

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

After the specified times, the degree of destruction is determined in%. 100.0 means that all aphids have been killed, 0% means that no 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 destruction (Constitution) tration in 5 'in 5' after 24 hours S. II (C2Hs0) 22-NH2 0.1 0 (known) S. (C2H5 °) 22-NH-N 0.1 100 0 (C2H50) 2P "-NH-CN 0.1 100 0.01 85 Example D Tetranychus-est solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable 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.

Bean plants (Phaseolus vulgaris), which have a height of about 10 - 30 cm, sprayed dripping wet. These bean plants are strong with all stages of development of the common spine mite (Tetranychus urticae) infested.

After the specified times, the effectiveness of the active ingredients will be prepared determined by counting the dead animals. The degree of destruction thus obtained becomes given in ffi. 100 5 'means that all spider mites have been killed, 0 5' means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 4 below: Table 4 (Tetranychus test) Active ingredient active ingredient concentration degree of killing (Constitution) tration in s in% 48 hours S. (021150) 22-NH2 0 n (e2H50) 2P-NH-CE 0.1 100 S. C2H5 - P-NH-CN 0.1 98 C2H50 Example 1: 0.5 molar batch 45 g of sodium cyanamide are suspended in 500 cc of acetone.

87 g of O, O-diethylphosphoric acid ester chloride are added to this suspension at 30 to 40 ° C. with stirring, Stir the mixture for a further 4 hours, then cool it down to 100C and acidify she with 50 cc conc. Hydrochloric acid. The precipitated common salt is filtered off and 400 com benzene were added to the filtrate. When distilling off the volatile Acetone, benzene and water pass over. The residue is at bath temperature of 6û ° C held under a pressure of 1 Torr for a short time.

This gives 87 g (98% of theory) of the cyanamido-phosphoric acid de-O, O-diethyl ester as a water-soluble oil with the refractive index nD24 = 1.4643.

Calculated for a molecular weight of 178: P 17.4%; N 15.7%; Found: P 91%; N 15.3%.

The mean toxicity of the compound is per os in the rat 10 mg / kg.

Example 2: 0.5 molar batch Dissolve 42 g of cyanamide in 100 ccm of anhydrous pyridine, add 95 g of O, O-diethylthionophosphoric acid ester chloride dropwise to this solution at 30 to 400C while stirring, stir the mixture for 4 hours and then pour the reaction mixture into 30G ccm 20% ige hydrochloric acid. The separated oil is taken up in 200 cc of benzene, the benzene layer is separated off, dried over sodium sulfate, the solvent is distilled off and the residue is then kept at a bath temperature of 600C for a short time under a pressure of 1 torr. In this way, 80 g (73% of theory) of cyanamido-thionophosphoric acid O, O-diethyl ester are obtained as a water-insoluble, pale yellow oil with a refractive index nD24 = 1.5389.

Calculated for a molecular weight of 194: P 15.9%; S 16.4%; N 14.4% Found: P 15.9; S 16.3%; N 14.0 ß In the rat per os, the compound possesses a mean toxicity of 100 mg / kg.

Example 3: 0.5 molar batch. 86 g of ethylthionophosphonic acid-0-ethyl ester chloride are added to a suspension of 42 g of sodium cyanamide in 500 cc of acetone with stirring at 30 to 4000 . The water-insoluble oil is taken up in 200 cc of benzene, the benzene solution is separated off, dried over sodium sulfate and then the solvent is distilled off. The residue is kept at a bath temperature of 65 ° C. for a short time under a pressure of 1 torr and in this way 72 g (81% of theory) of the cyanamido-ethylthionophosphonic acid O-ethyl ester are obtained in the form of a pale yellow, water-insoluble oil the refractive index 11D = 1.5532.

- 18 - P S N Calculated for a molecular weight of 178: 17.4%; 17.9%; 15.7% Found: 17.1%; 18.0%; 15.0% The mean toxicity (DL50) of the compound in the rat per os is 10 mg / kg.

Claims (6)

P a t e n t a n s p r ü c h e: 1) Phosphorus, phosphonic or thionophosphoric (phosphonic) acid esters of the formula in which R1 and R2 are identical or different, straight-chain or branched lower alkyl radicals, R1 also denotes a lower alkoxy or the phenyl group, while X represents an oxygen or sulfur atom. 2) Process for the production of phosphorus, phosphonic or Thionophosphoric (-phosphonic) acid esters, characterized in that phosphorus, phosphonic or thionophosphoric (-phosphonic) acid ester halides of the formula In general, R1 and R2 stand for identical or different, straight-chain or branched lower alkyl radicals, R1 also denotes a lower alkoxy or phenyl group, while 1 represents an oxygen or sulfur atom and Hal is a halogen atom. with cyanamide in the form of its alkali, alkaline earth or ammonium salts or in the presence of acid binders. 3) Insecticidal and acaricidal agents characterized by a content of phosphorus, phosphonic or thionophosphorus (- phosphonic) acid esters according to claim 1. 4) method for combating insects and mites, characterized in that that one phosphorus, phosphonic or thionophosphorus - (- phosphonic) acid esters according to Claim 1 on insects and / or mites or their habitat can act. 5) processes for the manufacture of insecticidal and acaricidal agents, characterized in that one phosphorus, phosphonic or. Thionophosphorus (- phosphonic) acid ester according to claim 1 mixed with extenders and / or surface-active agents. 6) Use of phosphorus, phosphonic or thionophosphorus (- phosphonic) acid esters according to claim 1 for combating insects and mites.