DE2053713A1 - 1-phenyl-2-cyano-2-chlorovinylphosphoric triesters - as insecticides and acaricides from trialkylphosphites and dichlorobenzoyl-acetonitri - Google Patents

Abstract

Phosphoric esters of the formula (I) : (where R = 1-5C alkyl and R1 is Ph opt. substd. by halogen or 1-4C(alkyl or alkoxy)) are insecticides and acaricides of low phytotoxicity, are prepd. by reacting trialkyl-phosphites with alpha, alpha-dichlorobenzoylacetonitriles in inert solvents, pref. at 50-85 degrees.

Description

1-Phenyl-2-cyano-2-chlorovinyl-phosphoric acid triester, method for Their manufacture and their use as insecticides and acaricides The present The invention relates to new 1-phenyl-2-cyano-2-chlorovinyl-phosphoric acid triester, which have insecticidal and acaricidal properties and a process for their preparation.

It is already known that 1-phenyl-2-chlorovinylphosphoric acid ester, e.g. the 0- [1- (2 ', 4', 5'-trichlorophenyl) -2-chlorovinyl7-0,0-dimethylphosphoric acid ester and 1-alkyl-2-phenyl-2-cyanovinylthionophosphoric acid ester, such as the O, O-diethyl-O- (1 methyl-2-phenyl-2-cyanovinyl) -thionophosphoric acid ester, an insecticidal effect See U.S. Patent 3,102,842 and Y. Nishizawa, Bull.Agr.chem.Soc.Japan 25, 61 (1961) and Japanese published patent application 2.926 (196017.

It has now been found that the new 1-phenyl-2-cyano-2-chlorovinylphosphoric acid triesters of the formula (I) in which R is a straight-chain or branched alkyl radical having 1 to 5 carbon atoms and R is a phenyl radical optionally substituted by halogen atoms, A1EY1 or alkoxy groups each having 1 to 4 carbon atoms, have strong insecticidal, acaricidal and sometimes fungicidal properties.

The general formula (I) includes the corresponding cis and trans isomers of constitution (II) and (III) and mixtures of these two components. s R1 Cl R1 Cd / \ 0-i (OR) 2 NO / NU o-P1 (oR) 2 0 0 cis (II) trans (III) It has also been found that the 1-phenyl-2-cyano-2-chlorovinylphosphoric acid meters of the constitution (I) are obtained when trialkylphosphites of the formula (IV) with d,, -1ichlorobenzoylacetonitriles of the formula (V) in which formulas R and R1 are as defined above.

Surprisingly, the 1-phenyl-2-cyano-2-chlorovinylphosphoric acid triesters according to the invention are notable by a considerably better insecticidal and acaricidal effect than the known 1-phenyl-2-chlorovinylphosphoric and 1-alkyl-2-phenyl-2-cyanovinylthionophosphoric acid triesters analogous constitution and the same type of effect. The substances according to the invention thus represent a real asset to technology.

If, for example, triethyl phosphite and d-dichlorobenzoylacetonitrile are used as starting materials, the course of the reaction can be represented by the following equation: The starting materials to be used are clearly and generally defined by the formulas (IV) and (V). R is preferably a straight-chain or branched alkyl radical having 1 to 3 carbon atoms, such as methyl, ethyl, n- or iso-propyl, while R1 is preferably one optionally substituted by chlorine or bromine, an alkyl or alkoxy radical having 1 to 3 carbon atoms Represents phenyl radical.

As examples of phosphites or benzoylacetonitrile derivatives to be used according to the process are specifically mentioned: trimethyl, triethyl, tripropyl and tri-isopropyl phosphite and 4-chloro, 4-bromine, 4-methyl, 4-thyl, 4-propyl, 4-iso-propyl, 4-methoxy, 4-thoxy, 4-propoxy, 4-iso-propoxy, 2-chloro, 2-bromine, 2-methyl, 2-ethyl, 2-iso-propyl, 2-methoxy and 2-ethoxybenz oyl- dichloroacetonitrile.

The phosphites required as starting materials are known and can according to usual methods as well as the benzoylaceto, Nltril derivatives getting produced. The latter are made from benzoylacetonitrile and sulfonyl chloride available at elevated temperatures.

The manufacturing process is preferred with the use of more suitable ones Solvent or diluent carried out. As such, practically all inert ones come organic solvents in question. These include above all aliphatic and aromatic Hydrocarbons such as benzene, toluene, xylene, gasoline, ethers such as diethyl and dibutyl ether, dioxane, and also ketones, for example acetone, methylethyl-, methyl-isopropyl and methyl isobutyl ketone, as well as nitriles such as acetonitrile and propionitrile.

The reaction temperature can vary within a relatively wide range will. In general, one works between 0 and 1500C, preferably at 50 to 850C.

The reaction is generally carried out under normal pressure.

The starting materials are usually used to carry out the process in an equimolar ratio. An excess of one or the other reaction component does not bring any significant advantages. The reaction is preferred in the presence of a made of the above solvents at the specified temperatures, and the reaction mixture after several hours of stirring - if necessary with heating - worked up in the usual way.

The substances according to the invention usually fall in the form of colorless to weakly yellow colored, viscous, water-insoluble oils that do not distill without decomposition leave, but by so-called "distilling", i.e. by prolonged heating reduced pressure to moderately elevated temperatures from the last volatile components can be freed and cleaned in this way. To their The main characterization is the refractive index.

As already mentioned several times, the new 1-phenyl-2-cyano-2-chlorovinylphosphoric acid triesters stand out due to its excellent insecticidal and acaricidal effectiveness against plant, Hygiene and storage pests. They both have a good effect against sucking and eating infections and mites (acarina). At the same time wise they have a low phytotoxicity and partly also fungicidal properties.

For these reasons, the compounds of the present invention are successful as a pesticide in the protection of plants and stored products as well as in the hygiene sector used.

The sucking insects mainly include aphids (Aphidae) like the green peach aphid (myzus persicae), the black bean (Doralis fabae), HaSer (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato lice (Macrosiphum solanifolii), also the currant gall (Cryptomysus 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); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and Wanzein, for example beetroot (Piesma quadrata), cotton (Dysdercus intermedius), bed (Cimex lectularius), predatory (Rhodnius prolixus) and Chagaswanse (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

he biting insects should be mentioned above all by caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the swain moth (Lymantria dispar), golden afters (Euproctis chrysorrhoea) 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 are among the biting insects beetles (Coleoptera) e.g. corn (Sitophilus granarius = Calandra granaria), potato (leptinotarsa decemlineata), dock-Castrophysa 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 (Stegobium paniceum), common meal beetle (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. wireworms (Agriotes spec.) and white grubs (Melolontha melolontha); Cockroaches like the German (BlaUella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia madeirae), Oriental (Blatta orientalis), giant cockroach (Blaberus giganteus) and black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; furthermore orthoptera e.g. the cricket (Acheta domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera like ants, for example the meadow ant (Iasius niger).

The liptera essentially comprise flies like the dew (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata) room (Musca domestica), bran house fly (Fannia canicularis), gloss fly (Phormia aegina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcitrans); also mosquitoes, e.g. Mosquitoes such as the yellow fever mosquito (Aedes aegypti), house mosquito (Culex pipiens) and nalaria mosquito (Anopheles stephenei).

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 Flies and mosquitoes, the process products are also characterized by excellent Residual effect on wood and clay as well as good alkali stability on limed Documents from.

Depending on their useful purpose, the new active ingredients can be incorporated into the common formulations, such as solutions, emulsions, suspensions, Powders, pastes and granulates. These are manufactured in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers, optionally using surface-active agents i.e. emulsifiers and / or dispersants, e.g. in the case of the use of Water as an extender, optionally organic solvents as auxiliary solvents can be used. 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 stone sockets (e.g. kaolins, clays, talc, chalk) and synthetic ones Rock flour (e.g. highly dispersed silica, silicates); as emulsifier: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene petroleum alcohol ol ether, e.g. 3. Alkyl aryl polyglycol ethers, alkyl sulfonates and aryl sulfonates; as Dispersants: 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 to 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,: narcotics and granules can be used. It is used in the usual way, e.g. by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, Pouring, pickling or encrusting.

The material 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-5.ow-Vclume process (ULV) should be used where possible, formulations up to 95 or even the Apply 100% active ingredient alone.

Example A Phaedon larvae 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.

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

After the specified times, the death rate is determined in ffi. 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 1 below: Table 1 (Phaedon larvae test) Vactive substances active substance concentration degree of destruction tration in ffi in% after 3 days CH3 C l! (NC) C = C 3 0.1 0.01 0 t, 3 OP S. (known) NC (Cl) C = C /> ° 0 01 10000 0.01 100 0 NO (01) 0 = 0 00: 001011 110o0 OP (OC2H5) 2 0.001 45 0 Cl NC (Cl) C = C / 0.1 100 OP t 100 POH3) 2 Tab 1 le 1 (continued) (Phaedon larvae test) Active ingredients Active ingredient concentration degree of destruction tration in ß in P after 3 days Cl .C NC (C1) C = C / 0.1 100 0.01 100 OP (OC2Hs) 2 0 S OCH3 3 NC (Cl) C ~ C / 0.1 100 0-f1 (00113) 2 0.01 95 0 STILL3 NC (CI) C = C, 0.1 100 0, \ 01 0 70 OP (OC2R5) 2 0 Example B Myzus test (contact effect) Solvent: 3 parts by weight of acetone 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 desired concentration.

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

After the specified times, the degree of destruction is determined to be 6.4. 100 means that all aphids have been killed, 0 ffi means that no aphids were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below: Table 2 (Myzus test) active ingredient active ingredient concentration degree of destruction tration in ffi in% 1 day Cl w Cl (Cl) HC = C \% Cl OP (OCH3) 2 0 (known) 0 CH3 0.1 98 (CN) GC 0.01 20 sO-P (OC2H5) 2 S. (known) p NC (Cl) C = C \ 0.1 1CO 0.01 99 0-P11 (OCH3) 2 0 R (Di) 0.1 100 NC (Cl) CC 0.01 100 0.001 50 0f (0C2H5) 2 0 Cl (½ 0.1 100 NC (Cl) C = C 0.01 99 O-POC, H,) 2 Ä 1 99 O 17 19 0 Example C Phorodon / resistant test (contact effect) 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 narrow emulsifier and the concentrate is diluted with water to the desired concentration.

Hop plants (Humulus lupulus), which are heavily infested by the hop aphid (Phorodon humuli / resistant), Splattered dripping wet.

After the specified times, the degree of destruction is determined in ffi. 100% means that all aphids have been killed, 0 0/06 means that no aphids were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below: Table 3 (Phorodon humuli / resistant) irtoffe active ingredient concentration degree of destruction tration in% in% 1 day C2T! 0, 30 CP-OC = C (CN) Cf; HFj 0.1 30 CpH5G t 0.02 25 CH3 (known) CH3 ° P-0-C = CH (Cl) CH3 Cl 1 0.1 5o ICl 0.02 10 0.02 10 Cl (known) CH3 O, 0 = POC = C (C1) CN 0.1 100 CH3O 1 0.02 90 ici 0.004 70 C2H50, Q 0.1 100 6-P-O-C = C (Cl) CN 0.02 100 C2H50 1 0.004 95 0.0008 70 Tab 1 1 e 3 (continued) (Phorodon humuli / resistant) Active ingredients Active ingredient concentration degree of destruction tration in% in% 1 day C2Hg 0 Q 2 5 POC = C (Cl) CN 0.1 C2H50 8 0.02 93 v ici 0.004 65 Cl Manufacturing examples 24.9 g (0.15 mol) of triethyl phosphite are added dropwise at 50 ° C. to a solution of 32.1 g (Q, 15 mol) of O (-dichlbrbenzoylacetonitrile in 100 ml of toluene, the reaction temperature is then increased to 80 ° C. and the batch is then cooled 2 hours from.

The reaction mixture is diluted with 200 ml of benzene, then with ten percent Washed sodium bicarbonate solution and dried over sodium sulfate. After peeling of the solvent 24 remains a yellow oil with the refractive index nD = 1.5171.

The yield is 41 g (87% of theory). Analysis: Calculated for C13H15ClNO4P (molecular weight 315.5) 4.4%; found 4.1, '.

The following connections can be established in an analogous manner: Constitution refractive index yield (% of theory) NC (Cl) C-9-OP (OCH3) 2 4 4 3 1.4852 75 oil NC (Cl) C = lC-oP (oC2H5) 2 n22 nD22 i) = 1.5251 89 CH3 Constitution refractive index yield (% of theory) NC (S1) C = COP (OCH27 n23 = 1.5594 68 OCtI3 0CF13 0 n23 NC (Cl) C = C1-0- (0C2H5) 2 n23 = 1.5370 83 y STILL, NC (Cl) C = IC-O-P (OCH3) 20 = 1.5527 62 1½; ' Cl 0 II 26 = n26 NC (Cl) C = IC-OP (OC2H5) 2 n26 = 1.5282 97 Cl Cl The * -Dichlorobenzoylacetonitriles required as starting materials can be obtained, for example, as follows: 300 g (2.22 mol) of sulfuryl chloride in 200 ml of CC14 are added dropwise at 500 ° C. to a solution of 145 g (1 mol) of benzoylacetonitrile in 600 ml of carbon tetrachloride and the mixture is then refluxed for 8 hours. After cooling, the reaction mixture is washed with ten percent sodium bicarbonate solution, dried over sodium sulfate, then the solvent is drawn off and the viscous residue that remains is distilled. A colorless oil is obtained; Bp 2/106 ° C with the refractive index nD = 1.5550.

The yield is 135 g (63% of theory).

The following starting products can be synthesized in the same way: Yield: 26% of theory; colorless oil; Bp 2 / 120-1250a; n25 = 1.5535 D Yield: 54% of theory; colorless oil; Bp 2/16000; 25 nD = 1.5783 Yield: 55% of theory; colorless crystals; Bp 2/120-123 ° C

Claims (6)

Claims 1. 1-phenyl-2-cyano-2-chlorovinylphosphoric acid triester of the formula in which R is a straight-chain or branched alkyl radical having 1 to 5 carbon atoms and R is a phenyl radical optionally substituted by halogen atoms, alkyl or alkoxy groups each having 1 to 4 carbon atoms. 2. Process for the preparation of 1-phenyl-2-cyano-2-chlorovinylphosphoric acid triesters, characterized in that trialkyl-phosphites of the formula with rX, -dichlorobenzoylacetonitriles of the formula in which formulas R and R1 have the meaning given in claim 1. 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 the mentioned pests or allows their living space to 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.