DE1668911A1 - Furfuryl thio or dithiophosphonic acid esters and process for their preparation - Google Patents

Description

Furfuryl-thio- or -dithiophosphonic acid esters and processes for their Production The present invention relates to new furfurylthio or dithiophosphonaic acid esters with insecticidal and acaricidal properties and processes for their preparation.

In well-known Japanese patent application 5438/65 i.a. already 0, 0-dialkyl-0-or-S-furfuryl-thio- and -dithiophosphoric acid ester described, which, due to their acaricidal properties, are used as mite control agents should find. The last-mentioned compounds have a further pesticidal effect not.

It has now been found that the hitherto unknown furfuryl-thio- or dithiophosphonic acid esters of the general formula (I) have excellent insecticidal and acaricidal effectiveness.

In the above formula, R and R 'are the same or different Alkyl groups each with 1 to 6 carbon atoms, R also stands for the Phenylreet, while X and Y represent oxygen or sulfur atoms, where however, at least one of the last-mentioned symbols means sulfur.

As was also found, furfuryl-thio or.

-dithiophosphonic acid ester of the above structure (I) obtained in a smooth and with good yields proceeding reaction if either furfuryl alcohol with alkyl- or phenyl-thionophosphonic acid-0-alkyl ester halides of the formula (II) or 2- (furanyl) methyl halides with alkyl resp.

Phenyl-O-alkyl-thiol- or -thionothiolphosphona acids of the formula (III) implements.

In the formulas (II) and (III), symbols R, R 'and Y have the following meaning given above, while Hal stands for a halogen atom.

The course of the process-related conversions is illustrated by the following reaction scheme (IV): where the symbols R, R ', Y and Hal have the same meaning as given above.

In the aforementioned formulas, however, R preferably represents alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n- and iso-propyl, butyl, iso- or sec-butyl-, also for the shenylrent.

R 'preferably also denotes lower alkyl having 1 to 4 carbon atoms, e.g. methyl, ithyl, propyl, butyl, where -R and R 'are identical or different can, and Hal is a precautionary chlorato.

The necessary for carrying out the process according to formula scheme (IV) Starting materials furfuryl alcohol or 2- (furanyl) methyl halide are made from known in the literature and easily accessible on a technical scale.

The reaction according to the method is preferably used with more suitable ones Solvent or diluent carried out. All of these are practically all inert organic solvents or mixtures thereof, such as ethers, for example Diethyl or di-n-butyl ether and dioxane, and also ketones, e.g. B. acetone, methyl ethyl, Methyl isopropyl and methyl isobutyl ketone; low-boiling aliphatic alcohols, z. B. methanol, ethanol and polar solvents such as dimethylformamide or sulfoxide.

However, they may have proven particularly useful for the stated purpose halogenated aromatic and aliphatic hydrocarbons, e.g. B. benzene, gasoline, Toluene, chlorobenzene, xylene and nitriles such as aceto- and propionitrile and mixtures of these solvents.

Furthermore, the process according to the implementation is preferably allowed in Expire presence of acid acceptors.

Practically all customary acid binders can be used for this purpose Find. Tertiary aromatic or heterocyclic compounds have proven particularly suitable Amines, e.g. B.

Triethylamine, dimethylaniline or pyridine, and also alkali metal alcoholates and carbonates, such as potassium and sodium methylate or ethylate, sodium and potassium carbonate.

The reaction temperature can be varied within a broader range. Generally one works between 20 and 100 ° C (or the boiling point of the mixture), preferably at 40 to 80 ° C. The starting materials to be converted according to the process as well as the auxiliary substances (acid binders) are generally in stoichiometric Quantities applied. After combining the starting components, it is advantageous to use the Mix for a longer time to complete the conversion (about 10 to 15 Hours), if necessary after-heating with stirring. This way of working gives the process products with excellent yields and excellent purity.

The furfuryl thio or dithiophosphonic acid esters according to the invention usually fall in the form less to pale yellow, more viscous, less water-insoluble Oils that can usually be distilled without decomposition under greatly reduced pressure. If this is not possible, they can be distilled by so-called. H. short-term The last volatile components are heated in a vacuum to moderately elevated temperatures freed and purified in this way. For their more detailed characterization serves the refractive index.

As mentioned briefly above, the process products stand out due to excellent insecticidal and acaricidal effectiveness against eating and sucking Ineects as well as against mites. In that regard, they are inventions Compounds those described in the published Japanese patent application 5438/65 Far superior to products of an analogous constitution.

They represent a real enrichment of the technology.

The products according to the invention have only a low level of warm-blooded animals and Phytotoxicity. The pesticidal effect sets in quickly and lasts for a long time. For this Basically, the compounds which can be prepared according to the invention can be used successfully in plants and animals Store protection as well as in the hygiene sector to combat harmful sucking agents and eating insects and dipteras as well as against mites (acarina).

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 Kirechen aphid (Myzus cerasi), also shield and mealybugs (Coccina), z. B. the ivy shield (Aspidiotus hederae) and cup scale (Lecanium hesperidum) and the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and bedbugs, for example the beet (Piesma (quadrata), cotton (Dysdercue intermedius), bed (Cimes lectularius), predatory (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

The most biting insects were caterpillars (Lepidoptera) such as the Kohlachabe (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden after (Euproctis chrysorrhoea) and ringed moth (Malacoaoma 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 Heur (Laphygma frugiperda) and Egyptian Cotton fluff (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia Kühniella) and large guard moth (Galleria mellonella).

The biting insects also include beetles (Coleoptera) see B. Corn (Sitophilus granarius-Calandra granaria), potato (Leptinotarsa decemlineata), Dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapaglance (Meligethes aeneus), raspberry (Byturus tomentosus), table beans (Bruchidius = Acanthoscelidea obtectus), bacon (Dermestes frischi), khapra (Trogoderma granarium), red-brown Rice flour (Tribolium castaneum), Maiw (Calandra or Sitophilus zeamais), bread (Stegobium panicum), common meal beetle (Tenebrio molitor) and flat grain beetle (Oxyzaephilus surinamensis)), but also species living in the ground such. B. Wireworms (Agriotes spec.) and white grubs (Melolontha melolontha); Cockroaches like the Germans (Blatella germanica), American (Periplaneta americana), Madeira (Laucophaea or Rhyparobia madeirae), Oriental (Blatta orientalis), giant (Blaberus giganteus) and black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also orthopedic z. B. that House crickets (Gryllus 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 (deratitis capitata), room (Musca @ domestica), small house fly (Fannia canicularis), glossy 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 Upinn mites (Tetranychidae) like the bean (Tetranychus telariue-Tetranychus althaeae or Tetranychus urticae) and the obat tree apin mite (Paratetranychus pilosus-Panonychus ulmi), gall mites z. B. the common mite (Eriophyes ribis) and tarsonemids for example the shoot tip (Hemitarsonemus latue) and cyclamen mite (Tarsonemus pallidus) ; after all, ticks like that 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 granulates. These are made in a known manner, e.g. B. by mixing the active ingredients with extenders, d. H. liquid solvents and / or solids Carriers, possibly with the use of surface-active agents Emulsifiers and / or dispersants, where z. B. in the case of the use of water as an extender, optionally organic solvents as auxiliary solvents can be used. Essentially, liquid solvents can be used : 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. kaolin, 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 dispersants: e.g. B. lignin, sulphite waste liquors and methylcelluloae.

The active ingredients according to the invention can be used as a mixture in the formulations 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 active ingredient concentrations can be varied over a wide range will. In general, concentrations of 0.00001% to 20% are used, preferably from 0.01% to 5%.

The active ingredients can be used as such, in the form of their formulations or 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 used. It is used in the usual way, e.g. by pouring, spraying, misting, varnishing, scattering, dusting, gasifying.

The excellent insecticidal and acaricidal effectiveness of the products of the process is evident from the following application examples: Example A. Myzus test (contact effect) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether for the production of an appropriate preparation of active ingredients 1 part by weight of active ingredient is mixed with the specified amount of solvent, that contains the specified amount of emulsifier, and dilute the concentrate with water to the desired concentration.

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

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

Active ingredients, active ingredient concentrations, evaluation times and results are shown in the table below: T abe 1 1 e 1 Myzus test Active ingredient active ingredient concentration degree of destruction (Constitution) tration in% in% 24 hours CH-CH nn S CH C-CH2-SP (OC2H5) 2 0, 1 0 0 2-2 li) 2 (known comparator preparation) CH-CH nns r'C25 0.1 100 CXH XC CH2 SP \ 0 01 98 0 OC2H5 CH-CH 0 0 CH C-CH2-SP CS 5 0 1 100 0 CH-ClI S "" n H CH C-CHp-0-P "" 0, 1,100 Oc2H 5 ogoi 100 2 5 CH-CH MHS ß TT tt, n CH C-CH2-0-P qu 0 1 100 ,. 0 / Example B Doralis test (systemic action) Solvent: 3 parts by weight of acetone 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 desired concentration.

With the preparation of the active compound are bean plants (Vicia faba) which are heavily infested with the black bean louse (Doralis fabae), angegoesen, see above that the active compound preparation penetrates the soil without the bitterness of the bean plants to wet. The active ingredient is absorbed from the soil by the bean plants and so arrives at the infected leaves.

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 2 below: Tables 1 1 e 2 Doralis test Active ingredient active ingredient concentration degree of destruction (Constitution) tration in in after 4 days CH - CH nn CH C-CH2-0-P (OC2Hs) 2 0 (known comparator preparation) CH CE Mu g CH C-CH-QP 2 5 0, 1 100 0 00 0, 01 100 2 5 Example C Tetranychus test Solvent: 3 parts by weight of acetone Eatulsifier: 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 stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

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

After the times indicated, the effectiveness of the active ingredient preparation by counting out the dead animals. The degree of destruction thus obtained becomes given in%. 100% means that all spider mites have been killed, 0% means that no spider mites were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below: Table 3 Tetranychus test Active ingredient active ingredient concentration degree of destruction in% (Constitution) tration in% after 48 hours CH - CH MM g \ 0/2 \ OC2H5 Or 2 w OC2H5 The following examples illustrate the invention: Example 1: 75 g (0.75 mol) of furfuryl alcohol are dissolved in 400 cc of benzene with the addition of 64 g of pyridine. 129 g of ethylthionophosphonic acid 0-ethyl ester chloride are added to this solution with stirring at room temperature. The temperature of the mixture rises to 40 ° C. The reaction mixture is then stirred for a further 12 hours. The latter is then washed twice with 100 cc of dilute hydrochloric acid each time, the benzene solution is separated off, dried over sodium sulfate and fractionally distilled. 85 g (49,96 of theory) of the ethylthionophosphonic acid 0-ethyl-O-furfuryl (2) ester are obtained as a water-insoluble oil with a boiling point of 0.01 78 ° C. and a refractive index nD22 = 1.5033.

Example 2s 75 g (0.75 mol) of furfuryl alcohol are added with the addition of 64 g of pyridine in 400 cc of benzene and 165 g of phenyl-thionophosphonic acid-0-ethyl ester chloride are added dropwise to this solution, starting at room temperature. The temperature of the mixture rises to 40 ° C. The latter is stirred for a further 12 hours and then worked up as in Example 1. 147 g (69% of theory) of the phenylthionophosphonic acid 0-ethyl-0-furfuryl (2) ester in the form of a slightly yellowish, water-insoluble oil with a boiling point of 0.01 150 ° C. and a refractive index nD22 = 1 are obtained , 5562 received.

Example 3: 105 g (0.75 mol) of 2- (furanyl) methyl chloride are added dropwise with vigorous stirring to a solution of 165 g of ethyl-O-ethyl-thionothiolphosphonic acid potassium in 600 cem acetonitrile and the mixture is warmed up for a further 2 hours after the addition 60 ° C. The reaction mixture is then diluted with 500 cc of benzene. The benzolate solution is washed with 300 cem water, dried over sodium sulfate and the solvent is distilled off under reduced pressure. In the fractional distillation of the residue, the ethyl-thionothiolphosphonic acid-O-ethyl-S-furfuryl (2) ester is obtained as a colorless, water-insoluble oil with a boiling point of 0.018600 and a refractive index n2D = 1.5562. The yield is 170 g (91% of theory).

Claims (5)

Claims: 1. Furfuryl thio or dithiophosphonic acid ester of the formula in which R and X 'denote identical or different alkyl groups each having 1 to 6 carbon atoms, R darder also denotes the phenyl radical, while X and Y represent oxygen or sulfur atoms, but at least one of the last-mentioned symbols is sulfur. 2. Process for the production of thio or. Dithiophosphonic acid esters, characterized in that furfuryl alcohol is mixed with alkyl or. Phenyl-thionophosphonic acid-O-alkyl-ester halides of the formula or 2- (furanyl) methyl halides with alkyl or. Phenyl-0-alkylthiol or thionothiolphosphonic acids of the formula reacted, where R, R 'and Y have the meaning given in claim 1, while Hal stands for a halogen atom. 3. Insecticidal and acaricidal agents, characterized by a content of furfuryl-thio- or -dithiophosphonic acid esters according to claim 1. 4. A method for combating insects and mites, characterized in that that one furfuryl-thio or. dithiophosphonic acid ester according to claim 1 on insects and / or mites or lets its habitat act. 5. Process for the production of insecticidal and acaricidal agents, characterized in that furfuryl-thio- or dithiophosphonic acid esters according to Claim 1 mixes with extenders and / or surface-active agents.