DE2006020A1 - 6-oxopyridazinylmethyl thiophosphates, pesticides - Google Patents

Abstract

Cpds. of formula: (where R and R1 are 1-6C alkyl; R2 is Me or Ph) are insecticides, acaricides and rodenticides, and may be prepd. by reacting an N-halomethyl-pyridazinone with the alkali(ne earth) metal or NH4 salt of the appropriate alkyldithiophosphonic acid alkyl ester.

Description

6-Oxo-pyridazinmethyl-dithiophosphonic acid ester, a process for theirsr Manufacture and their use as insecticides and acaricides The present The invention relates to new 6-oxo-pyridazine methyl-dithiophosphonic acid esters, which are insecticidal and have acaricidal properties and a method for their preparation.

It is already known (see German Auslegeschrift 1.106.766 and Belgian patent 580.175) that 6-Oxopyridazinmethyl-dithiophosphorsäureester, such as O, O-diethyl-S- (1,6-dihydro-3-methyl- or -5-phenyl-6-oxo-1-pyridazinylmethyl) -dithiophosphoric acid ester, have insecticidal and acaricidal properties.

It has now been found that the new 6-oxo-pyridazflnmethyldithiophosphonic acid esters of the general formula (I) in which R and R1 are the same or different and for a straight chain or. branched lower alkyl radical with 1 to 6 carbon atoms and R2 is a methyl or phenyl group means strong insecticidal, acaricidal, but also rodenticidal properties.

It has also been found that compounds of the above constitution (I) are obtained if dithiophosphonic acid salts of the general formula (II) in which R and R1 have the meaning given above and M is an alkali, alkaline earth or ammonium equivalent with N-halomethylpyridazinones of the general structure (III) where R2 has the meaning given above and Hal represents a halogen atom.

The 6-oxopyridazine methyl dithiophosphonic acid esters according to the invention surprisingly show a considerably higher insecticidal and acaricidal effect than the constitutional analogues 6-Oxo-pyridazinmethyl-dithiophosphoric acid ester of the prior art. The invention Fabrics are a real asset to technology.

If ethyl-O-ethyl-dithiophosphonic acid potassium and 1-chloromethyl-1,6-dihydro-3-methyl-6-oxopyridazine are used as starting materials, the course of the reaction can be represented by the following equation: The starting materials to be used are generally clearly defined by the formulas (II) and (III).

However, R and R1 are preferably straight or branched lower alkyl radical with 1 to 4 carbon atoms, such as methyl, ethyl, n- and iso-propyl, n-, sec.-, tert.- and iso-butyl, while Hal prefers a chlorine atom and M a potassium, Represents sodium or ammonium ion.

Examples of dithiophosphonic acid salts which can be used are in detail called: O, P-methyl-, O, P-ethyl-, O, P-iso-propyl-, O, P-tert-butyl-, O-methyl-P-ethyl (-propyl-, -iso-propyl, -butyl) -, O-ethyl-P-propyl (-iso-propyl, -tert.butyl) -, O-iso-propyl-P-butyl or O-butyl-P-ethyldithiophosphonic acid alkali, alkaline earth or ammonium salts.

The dithiophosphonic acid salts to be used as starting materials (II) and halomethylpyridazinones (III) have already been described in the literature and can be produced according to methods that are known per se.

As an solvent or diluent when carrying out the process all inert organic solvents can be used.

These include especially aliphatic and aromatic, if appropriate chlorinated hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, Chloroform, carbon tetrachloride, chlorobenzene, ethers, e.g. diethyl and dibutyl ethers, Dioxane, also ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also nitriles, such as acetonitrile.

The reaction temperatures can be within a wide range can be varied. The starting components are usually combined at room temperature and then heating the mix and then generally to 30 to 70, preferably 40 up to 50 ° C.

The reaction is generally carried out under normal pressure.

When going through the process, the reactants are mostly used in an equimolar ratio. An excess of one or the other component does not bring any significant advantages. The implementation is - as already mentioned - expedient made in a suitable solvent at elevated temperature. After this the reaction has ended, the batch is worked by pouring it into water and shaking it out with an organic solvent in a manner known in principle.

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 let, however, by so-called incipient distillation, i.e. by prolonged heating reduced pressure to moderately elevated temperatures from the last volatile components freed and purified in this way. For their characterization serves before especially the refractive index.

As already mentioned above, the compounds according to the invention are distinguished with excellent insecticidal and acaricidal properties. Furthermore they partly own

a rodenticidal effect. Therefore, find the new active ingredients to combat harmful, sucking and biting insects and mites, especially in plant protection Use.

The eager insects mainly include aphids (Aphidae) like the green peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), strawberry (Macrosiphum pisi) and potato lice (Nacrosiphum solanirolli), also the currant gall (Cryptomysus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinie) and black Cherry aphid (Myzus cerasi), also scale and mealybugs (Coccina), see B. the ivy shield (Aspidiotus hederae) and cup scale (Lecanium hesperidum) as well the mealybug (Pseudococcus maritimus); Bladder feet (Thysanopters) such as Hercinothrips fermoralis and Wansen, for example the beet (Piesma quadrata), cotton (Dysdercus intermedius), bed bug (Cimez lectularius), predatory bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

:. Among the biting insects, the most important moths would be moths (Lepidoptera) such as the Kohlachabe (Plutella maculipennis), the gypsy moth (Lymantris dispar), golden after (Euproctis chrysorrhosa) and ringed moth (Malacosoma neuetria), furthermore the tohl- (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris braseicae), small frost moth (Cheimatobia brumata), Oak moth (fortrix viridana), the army (Iaphygma 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 (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 zeainais), bread (Stegobium paniceum), common meal beetle (2enebrio 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 German (Blatilla 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 wit 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), glans 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 Xalariamiicke (Anopheles stephensi).

The mites (Acari) include in particular the spider mites (Tetanychidae) 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 (Ornithodorue 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 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. 3. 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 aesthetic rock flour (e.g. highly dispersed Silicic acid, silicates); as emulsifier: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene petroleum alcohol ethers, see B. Alkylaryl polyglycol ether, Alkyl sulfonates and aryl sulfonates; as a dispersant: e.g. lignin, sulphite waste liquors and methyl cellulose.

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

The formulations generally contain between (), 1 and d 95 Weight percent 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 application 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 splashing, spraying. Fogging, dusting, scattering, smoking, gasifying, Pouring, pickling or encrusting.

The substance 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 process (ULV) used where possible, formulations up to 95% or even to apply the 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, with the active ingredient preparation you spray cabbage leaves (Brassica oleracea) dripping wet and populate them with mustard beetle larvae (Phaedon cochleariae).

After the specified times, the degree of destruction is determined in «. 100% means that all of the beetle larvae have been killed. O% 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) Active ingredient active ingredient concentration degree of destruction in, % occurred after 3 days S 0.1 100 (C, H, O) 1 0.01 80 , PS-CH2- 0.001 0 (known) CH9 SNX 0.1 100 PS CH2-N 0.01 100 C2H5 ° / W 0.001 30 CH3 0.1 100 C2H5 N51, I 0.01 100 PS-CH2-N s C2H50 1 0.1 100 Where 0.1 100 g NX 0.01 100 C2H5 5sP-S-CH2- j 0.001 100 C2H50 V Example B Drosophila test 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 stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

1 cm3 of the active ingredient preparation is applied to a filter paper disk with 7 cm diameter pipetted on. They are placed wet on a glass in which there are fifty fruit flies (Drosophila melanogaster) are located and covered with a glass plate.

After the specified times, jnan determines the destruction in *.

100% means that all flies have been killed, O * means that no flyers were killed.

Active ingredients, active ingredient concentrations, evaluation times and degree of destruction are shown in Table 2 below: Table 2 (Drosophila test) Active ingredient active ingredient concentration degree of destruction tration in% in * after 24 hours CH3 S 0.1 20 (C2H50) 2P-S-CH2 W 0.1 20 (known) CH3 CH3 S -N'1 0.1 100 3 -CH2 C2H50 & CH3 2 5 oP ~ 8 ~ CR2 ~ t 0.1 100 c2H? Example C Myzus test (contact vWlrkung) 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 stated amount of solvent containing the stated amount of 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 in%. 100% means that all aphids have been killed, O% 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 stepped ion in in, 'after 24 hours CH3 So 0.01 99 (C2H50) 2P-S-CH2 N v O (known) CH3 0.01 100 C2H SN at 0.001 100 C2H50 / CH2-1> 0 Example D Doralis test (contact effect) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight 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 the desired concentration.

With the preparation of the active compound are bean plants (Vicia faba) which heavily infested by the black bean louse (Doralis fabae), sprayed until dripping wet.

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 4 below: Table 4 (Doralis fabae test) Active ingredient active ingredient concentration degree of destruction tration in in, 'after 24 hours S Üii 0.1 95 (CH30) 2P-S-CI2-0.01 20 (known) Sy 0.1 40 (02H5O) 2P "-8-CH2- '0.01 0 (known) C2H5 SN $ 0.1 100 2 (1 0.01 95 C2H50 Example E Tetranychus test 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 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 about 10 - 30 approx., sprayed dripping wet. These bean plants are strong with all stages of development of the common spider mite (Tetranychus urticae) infested.

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

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 5 below: Table 5 (Tetranychus test) Active ingredient active ingredient concentration degree of destruction stepped ion in, 'in fi after 48 hours S k 0.1 0 (CH30) 2P S-CH2 1 (known) 1 SR 0.1 0 (C2H.O) 11 011) (known) CH3 0.1 100 CH3, N <0.01 10-0 C2H50 CH2-Ng CH3 CH2 0.1 100 C2H5 S IH2- 0.01 100 C2H50 2 C2Ri0 W Example 1: 41 g (0.18 mol) of N-chloromethyl- [3-phenyl-pyridazon- (6)] are dissolved in 160 cc of acetone. After 45 g (0.216 mol) of potassium O, P-ethanedithiophosphonic acid have been introduced, the mixture is stirred 1 hour at 50 ° C and then pour it into water. The separated oil is taken up in benzene.

After washing the organic phase with sodium hydrogen carbonate solution the former is dried over sodium sulfate and the benzene is distilled off. It left behind 62 g (97.6% of theory) of ethyl-O-ethyl-S- [3-phenyl-pyridazin- (6) -2-yl-] dithiophosphonic acid ester in the form of a viscous, water-insoluble, orange-colored oil with the refractive index 24 1.6175.

Calculated for C15H19N2O2PS2 (molecular weight 354.4): N P S 7.90%; 8.77 %; 18.09%; Found: 8.35%; 8.74%; 18.19%.

Example 2: 116 g (0.6 mol) of O-ethyl-P-methyldithiophosphonic acid potassium are suspended or dissolved in 250 cc of acetone. After 80 g (0.5 mol) of N-chloromethyl- [3-methyl-pyridazon- (6)] have been introduced, the mixture is stirred for one hour at 40 to 50 ° C., after cooling it is poured into water and the oil which has separated out is taken in benzene, proceed as in Example 1 and obtain a yellow, water-insoluble oil with the refractive index nD21 = 1.5833.

The yield is 108 g (77.7% of theory) of methyl-O-ethyl-S- [3-methyl-pyridazon- (6) -2-yl-] dithiophosphonic acid ester.

The compound of the following constitution is obtained in an analogous manner as a yellow, water-insoluble oil with the refractive index nD21 = 1.5805.

The starting materials can be produced, for example, as follows: N-hydroxymethyl- [3-phenylpyridazone- (6)] 200 g (1.15 moles) of 3-phenylpyridazone- (6) [m.p .: 201-202 ° C.

manufactured according to Gabriel and Colman, Reports of the German Chemical Society ", Vol. 32, pages 399 to 400 (1899)] are suspended in 1200 ccm of 30% formaldehyde and heated from the water bath (80 to 90 ° C) with occasional stirring. After standing for about half an hour, the batch has solidified to form a thick 3rei with the formation of the N-hydroxymethyl compound. The product is allowed to cool, filtered off with suction, dried on clay plates and a colorless powder with a boiling point of 140 ° C. is obtained 205 g (88.2 of theory).

N-chloromethyl- [3-phenylpyridazon- (6)] 202 g (1 mol) of N-hydroxymethyl- [3-phenylpyridazon- (6)] are suspended in 1000 cc of methylene chloride. After adding 20 cc of dimethylformamide, 143 g (1.2 mol = 87 cc) of thionyl chloride are added dropwise to this suspension with occasional cooling at 20 to 30 ° C. After about one hour of stirring at 40 ° C, complete dissolution has taken place. After the solvent has been distilled off, colorless crystals remain, which are washed acid-free with water and melt at 1290C. The yield is 205 g (91.5% of theory).

N-hydroxymethyl- [3-methylpyridazon- (6)] 96 g (0.87 mol) 3-methylpyridazon- (6) p. 143 ° C, manufactured according to 0. Poppenberg, reports of the German Chemical Society, Vol. 34, page 3264 (1901)] dissolved in 288 cc formaldehyde (30%) on a water bath. After cooling down the mixture to 5 0C is sucked the crystals and washes them with a little ice-cold water. Mp 136 ° C.

The yield is 84 g (69.2% of theory).

Calculated for a molecular weight of 140.2; HHN 51.52%; 5.75%; 19.98%; Found: 51.5%; 6.0%; 20.4 ".

N-chloromethyl- [3-methylpyridazon- (6)] 70 g (0.5 mol) of N-hydroxymethyl- [3-methylpyridazon- (6)] are suspended in 350 cc of methylene chloride. This suspension is then added dropwise Addition of 3 cc of dimethylformamide at 250C, 72 g (0.6 mol = 44 ml) of thionyl chloride. Stirring for hours results in almost complete dissolution. A slight haze is removed by filtration and the residue after distilling off the solvent recrystallized from benzene (1 g / 2 ml). Pale yellow, crystal benzene-containing products are obtained Crystals with a melting point of 74 ° C, which rapidly release the benzene in the air and then at 940 ° C melt.

The yield is 60 g (86.5% of theory).

Calculated for molecular weight 158.6: N 01 17.66%; 22.36%; Found: 17.79 %; 22.52%

Claims (6)

Claims: 1) 6-Oxo-pyridazinmethyl-dithiophosphonic acid ester of the general formula in which R and R are identical or different, straight-chain or branched lower alkyl radicals having 1 to 6 carbon atoms, and R 2 is a methyl or phenyl group. 2) Process for the preparation of 6-oxo-pyridazinmethyldithiophosphonic acid esters, characterized in that one dithiophosphonic acid salts of the general formula in which R and R1 have the meaning given in claim 1 and M represents an alkali, alkaline earth or ammonium equivalent with §-halomethYlByridazinonen of the general formula wherein R2 has the meaning given in claim 1 and Hal is a halogen atom. implements 3) insecticidal and acaricidal agents, labeled by a content of 6-oxo-pyridazinmethyl-dithiophosphonic acid esters according to claim 1. 4) method for combating insects and mites, characterized in that that 6-Oxopyridazinmethyldithiophosphonsäureester according to claim 1 on insects and / or mites or their habitat can act. 5) Use of 6-Oxopyridazinmethyl-dithiophosphonsäureestern according to claim 1 for combating insects and / or mites. 6) processes for the preparation of insecticidal and acaricidal agents, characterized in that 6-oxopyridazine methyldithiophosphonic acid ester according to Claim 1 mixes with Streeimittcln and / or surface-active agents.