IE41802B1

IE41802B1 - Novel (thiono) (thiol) phosphoric (phosphonic) acid esters and ester-amides and their use as insecticides and acaricides

Info

Publication number: IE41802B1
Application number: IE2103/75A
Authority: IE
Original assignee: Bayer Ag
Priority date: 1974-09-27
Filing date: 1975-09-26
Publication date: 1980-03-26
Also published as: NO753096L; BE833817A; AR206235A1; ATA738275A; OA05119A; DD123054A5; AT333309B; ZA756125B; IL48164A0; DE2446218A1; IT1042788B; MY7800475A; HU173152B; SE7510766L; DE2446218C2; BR7506244A; CA1033738A; DK140063C; ES441324A1; TR18513A

Abstract

Novel pyridazinyl(thiono)(thio)phosphates(phosphonates) or -phosphoramidates(phosphonamidates) of the formula I are obtained by reacting a suitably substituted phosphorus-halogen compound with a suitably substituted 3-hydroxy-1,6-dihydropyridazinone compound with the elimination of hydrogen halide. In the formula I, R denotes alkyl having 1-6 C atoms, R' denotes phenyl, alkyl having 1-4 C atoms, alkoxy having 1-6 C atoms, alkylthio having 1-6 C atoms, monoalkylamino or dialkylamino having 1-4 C atoms per alkyl, R'' and R''' denote H or CH3, R denotes hydrogen, halogen, a nitro group or haloalkyl having 1-3 C atoms, X denotes oxygen or sulphur, and n denotes 1 to 4. The novel compounds have a very good insecticidal and acaricidal activity combined with a low phytotoxicity and toxicity to warm-blooded animals.

Description

The present invention relates to certain new pyridazinyl (thiono)(thiol)phosphoric(phosphonic) acid esters and esteramides’, to a process for their preparation and to their use as insecticides and acaricides.

It is already known that 0,0-dialkyl-O-pyridazinyl* thionophoSphoric aoid esters, for example Q-tl-phenyi-t,6dihydro-6-oxo-pyridazin(3)yl]-» 0-[l-hydr0xymethyl-1,6dihydro-6-oxo-pyridazin(3)yi]“, 0-[l-(N,H-dimethylaminometlyl)-1,6-dihydro-6-oxb-pyridazin(3)yl]- and 0-[l-(p10 methylphenyl)-t,6-dihydro-6-oxo-pyridazin(3)yl]-0,0diethylthionophosphoric acid esters possess insecticidal and acaricidal properties [see U.S. Patent Specification 2,759,937, Japanese published Patent Application 20,025/72 and Journal of Organic Chemistry, volume 26, No.9 (1961), pages 3,382-3,386].

The present invention provides, as new compounds, the pyridazinyl(thiono)(thiol)phosphoric(phosphonic) acid esters and ester-amides of the general formula in whioh R is alkyl with 1 to 6 carbon atoms, R' is phenyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 - carbon atoms or monoalkylamino or dialkylamino - 2 41802 with 1 to 4 carbon atoms in the or each alkyl group R and R*, which may be identical or different, are each hydrogen or methyl, and JiF ie hydrogen, halogen, nitro or halogenoalkyl with Ϊ to 3 carbon atoms, n is' an integer from 1 to 4 and X is oxygen or sulphur.

Ihe compounds of the formula (I) have been found to possess strong insecticidal and acaricidal properties. to Preferably S ifl straight-chain or branched alkyl with to 5 (especially 1 to 4) carbon atoms, R1 is phenyl, straight-chain or branched alkyl with 1 to 3 (especially t or 2) carbon atoms, straight-chain or branched alkoxy or aikythio, each with 1 to 5 (especially 1 to 4)carbon atoms, or monoalkylamino or dialkylamino with t to 3 (especially 1 or 2) carbon atoms per alkyl group R*7 is hydrogen, chlorine, nitro or trifluoromethyl, and» Is 1 »2 or 3 (especially 1).

The intention also provides a process for the preparation of a pyridazinyl(thiono)(thiol)phosphorio(phoBphonic) acid ester or ester-amide of the formula (I), in whieh a (thiono) (thiol)phosphoric(phosphonie) acid ester halide or esteramide halide of the general formula '· BO * J>jP-Hal (II), R·^ in which R, R’ and X have the above-mentioned meanings and Hal is halogen, is reacted with a 1-phenyl-3-hydroxy-1,6-dihydro-pyridazihone(6) derivative of the general formula - 3 41802 (in) in which Rr R1, R1V, and n have the above-mentioned meanings, if appropriate in the presence of a solvent or diluent, and if appropriate in the presence of an acid acceptor.

Surprisingly, the pyridazinyl(thiono)(thiol)phosphoric(phosphonic) acid esters and eBter-amides according to the invention exhibit a better insecticidal and acaricidal action than the previously known 0,0-diethyl-O-pyridazinyl10 thionophosphoric acid ester derivatives of analogous structure and of the same type of action.

The new compounds are not only active against insects and mites which damage plants but are also active against pests harmful to health and peets of stored products end, in.ths veterinary medicine field, against animal ectoparasites, for example parasitic.fly larvae. Accordingly, they represent an enrichment of the art.

If, for example, O-ethyl-O-eec.-butyl-thionophosphoric acid diester chloride and 1-(3,5-bis-trifluoromethylphenyl)20 3-hydroxy-6-QXO-pyridazine are used as starting materials, the course of the reaction can be represented by the following equation: - 4 aec c2h5o .-C^HgO s )?-ci 41808 FjC CF, Acid acceptor -HOI 7C2H5° V-0 sec.-C^HgO The (thiono)(thiol)phosphoric(phosphonic) acid ester halides and ester-amide halides (II) are known and can he prepared according to processes described in the literature, as can the 1-phenyl-3-hydroxy-1,6-dihydro-6-oxo-pyridazine derivatives (III), which can be prepared, for example, from the correspondingly substituted phenylhydrazines, dissolved in dilute hydrochloric acid, by reaction with maleic anhydride in accordance with the following equation: cf3 .fi-CH / N ''C-CH .IV wherein rv R and n have the above-mentioned meanings.

The following may be mentioned as examples of (thiono) (thiol)phosphoric(phosphonic) acid ester halides and ester15 amide halides to be reacted in accordance with the process: Ο,Ο-dimethyl-, 0,0-diethyl-, Ο,Ο-di-n-propyl-, 0,0-di-isepropyl-, 0,0-di-n-butyl-, Ο,Ο-di-isobutyl-, 0,0-di-sec.5 butyl-, 0,0-di-tert.-butyl-, Ο-ethyl-O-n-propyl-, 0-ethylΟ-isopropyl-, 0-n-butyl-0-ethyl-, O-ethyl-O-sec.-butyland O-ethyl-O-methylphosphoric acid diester chlorides and the corresponding thiono analogues; Ο-methyl-, 0-ethyl·-, 0-npropyl-, O-isopropyl-, Ο-η-butyl-, 0-sec.-butyl-, 0-isobutyland Q-tert.-butyl-methane-, ethane-, η-propane-, isopropaneand phenylphosphonic acid ester chlorides and the corresponding thiono analogues; O,S-dimethyl-, 0,S-diethyl, 0,S-di-n-propyl-, 0,3-di-isopropyl-, O,S-di-n-butyl-, O,S-diisobutyl-, O,S-di-tert.-butyl-, Ο-ethyl-S-n-propyl-, O-ethylS-isopropyl-, O-ethyl-S-n-butyl-, O-ethyl-S-sec.-butyl-, . 0-n-propyl-S-ethyl-, O-n-propyl-S-isopropyl-, O-n-butyl-S-npropyl- and 0-sec.-butyl-S-ethyl-thiolophosphoric acid diester chlorides and the corresponding thiono analogues; and 0-methylΝ-methyl-, .0-ethyl-N-methyl-, Ο-η-propyl-N-methyl-, 0-isopropyl-N-methyl-, Ο-η-butyl-N-methyl-, 0-sec.-butyl-N-methyl-, O-methyl-N-ethyl-, Ο-ethyl-N-ethyl-, O-n-propyl-N-ethyl-, O-isopropyl-N-ethyl-, Ο-η-butyl-N-ethyl-, 0-sec.-butyl-Nethyl-, O-methyl-N-n-propyl-, O-ethyl-N-η-propyl-, 0-n-propylΝ-η-propyl-, O-isopropyl-N-ethyl- andO-tert.-butyl-N-ethylphosphoric acid ester-amide chlorides,, the corresponding thiono analogues and the corresponding dialkylamide-monoester chlorides.

The following may be mentioned as examples of the 1-pheny13-hydroxy-l,6-dihydro-6-oxo-pyridazine derivatives (III) to be employed: 1-(2- and 3-trifluoromethyl-, 3,5-bis-trifluoromethyl-, 2-tri£luoromethyl-4-chlor0-, 2-chloro-5-trifluoromethyl-, 2-nitro-4-trifluoromethyl- and 5-chloro-3-trifluoromethylphenyl)-3-hydroxy-1,6-dihydro-6-oxo-pyridazines, as well as the' corresponding 4- and 5-methyl derivatives.

The process for the preparation of the compounds - 6 41803 according to the invention is preferahly carried out in the. presence of a suitable solvent or diluent. Practically all inert organic solvents can be used for this purpose, especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzene, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxan; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as acetonitrile and propionitrile.

All customary acid-binding agents can be used as acid acceptors. Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate, potassium carbonate, sodium methylate and ethylate and potassium methylate and ethylate, have proved particularly suitable, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly wide range, . Xn general, the reaction is carried out at between 0° and 12O°O, preferably at 40° to 60°0* To cany out the process, the starting materials are in general employed in substantially equimolar amounts . An excess of one or other component in general produces no significant advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents, if appropriate in the presence of an acid aoceptor, at the indicated temperatures. After a reaction time of one or more hours, in most cases at elevated temperatures, the reaction batch is coolea to room temperature, an organic solvent, for - 7 41802 example toluene, is added, and the organic phase is worked up in accordance with customary methods, for example washing, . drying and distillation.

The new compounds, are frequently obtained in the form of oils which mostly cannot he distilled without decomposition hut are freed from the last volatile constituents hy so-called slight distillation, that is to say by prolonged heating under reduced pressure to moderately elevated temperatures, and are purified in this way. They are characterised hy the refractive index. Some of the products are obtained in a crystalline form; in that case, they can he characterised by their melting point.

As has already been mentioned, the pyridazinyl(thiono) (thiol)phosphoric(phosphonic) acid esters and ester-amides according to the invention are distinguished by an excellent insecticidal and acaricidal activity. They are not only active against plant peate, pests harmful to health and peste of stored products but also, in the veterinary medicine field, against animal parasites (ectoparasites), such as parasitic fly larvae. They combine a low phytotoxicity with a good action against both sucking and biting insects and against motes..

For this reason, the compounds according to the invention can be employed with success as pesticides in plant protection and in the hygiene field, the field of protection of stored products and the veterinary field.

The economically important pests in agriculture and forestry, as well as pests of stored products, pests destructive of materials a,nd pests harmful to health, include: from the order of the Isopoda. for example, Oniscus asellus. - 8 41802 Arffladillidinm vulgare and Porcellio scaber; from the order of the Diploda. for example, Blaniulus guttulatus; from the order of the Ohllopoda. for example, Geophilus carpophagus. and Scutigera spec.; from the order of the Symphyla, for example, Scatigerella immaculate; from the order of the Arachnids, foi* example, Scorpio maur.ua and latrodeotus mactans; from the order of the Aparina.· for example, Aoarus sire.

Argas reflexus, Ornithodoros moubata. Dermanysaus galllnae. Briphyes ribia. Phyllocoptruta oleivora. Boophilus mioroplus. Shinicephalus evertei. garcoptes scabiei. Tarsonemus apeoi, Bryobla praetioaa. Panonyohua oitri. Panonyohua ulmi. Tetraaychua tumidus and Tetranychus urtinaa: from the order of the Ihyaanura. for example, Deplsma aaooharina; from the order of the Oollembola, for example, Onyohiurua armatus; from the order of the Orthoptera. for example, Blatta orientalis. Periplaneta americana. Deucophaea maderae. Blattella germanica, Acheta domestlcus. Gryllotalpha spec., locusta migratoria migratorioides. Melanoplus differentialis and Schistoceroa gregaria; from the order of the Dermaptera. for example, Porflcala aurjcularla; from the order of the leotera. for example, Reticulltermes spec,; from the order of the Anoplura. for example, Phylloxera vastatrix. PemphjguB epee, and Pediculue humanus corporis; from the order of the Thysanoptera. for example, Hercinothrips femoralis and ThripB tabaci; from the order of the Heteroptera. for example, Burygaster spec., Dysdercus intermedius. Piesma quadrata. 0-imex le_ctularius. Rhodnius prolixus and Triatoma spec.; from the order of the Homoptera. for example, Aleurodes brassicae. Bemlsia tabaci. Trialeurodes vaporariorum.Aphis gosgypii. Breviooryne brassicae. Oryptomycus ribia. Doralis' - 9 41802 fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis. Macrosiphua avenae. Myzus oerasi. Myzus persicae. Phorodon humuli, Rhosalosiphum padi. Empoaaca spec., Buscelis bllobatus. Nephotettix cincticeps. Lecanium corni, Saissetia oleae. Laodelphax striatellus, ffllaparvata lugens, Aonidiella aurantii. Aspidiotus hederae, Pseudococcus spec, and Pgylla spec.; from the order of the Lepidoptera. for example, Pectinophora gossypiella. Bupalus pinlarius. Oheimatobia brumata. Lithocolletis blancardella. Hyponomeuta padella, Plutella aacullpennls. Malacosoma neustria. Euproctls chry sorrhoea. Lymantria spec., Buccalatrlx thurberiella. PhyllOcnlBtiB citrella. Agrotia spec., Euxoa spec., geltia spec., Barias insulana, Heliothis spec., Laphygma exigua, Mamestra brassicae. Pattolis flammea, Prodenia litura. Spodoptera spec.. Trichoplusia ni. Oarpocapsa pomonella. Pieris.

II Spec., Chilo spec., Pyrausta nubilalis, Epheatia kuhniella. Galleria mellonella, Cacoeoia podana. Capua retioulana. Chorlstoneura fumiferana. Olysia amblguella. Homona magnanima. and. Tortrix virldana: from the order of the Ooleontera. for example, Anobium punctatum. Rhizopertha dominlca, Bruchidius obteotus. Acanthoscelides obteotus. Hylotrupes balulus. Agelastlca alni. Leptinotarsa decemlineata. Phaedon coohleariae. Diabrotloa spec., Psylliodes chrysocephala, Bpilachna yarivestis. Atomaria Spec., Oryzaephilus surinamensis, Anthonomus spec., Sltophilus spec., Otiorrhynchus sulcatus. Cosmopolites sordidus. Oeuthorrhynchus assimilis. Hypera postlca. Permeates epee.. Trogoderma spec., AnthrenuB spec., Attagenus spec., LyCtus spec., Meligethes aeneus, Ptinus spec., Miptus hololeucus. Gibbium paylloldes, Tribolium spec., Tenebrio molitor. Agriotes spec., Conoderus spec., Melolontha - 10. 41802 melolontha. Amphimallus solstitialis and Ooatelytra zealandica; from the order of the Hymenoptera. for example Diprion spec,, Hoplocampa spec., Daslus spec., Monomorium pharaonis and Vespa spec.; from the order of the Diptera. for example, Aedes spec., Anopheles spec., Oulex spec., Drosophila, melanogaster. Musca domestjoa. Fannia spec., Stpmoxys calcitrana. Hypoderma spec., Sibio hortulans. Oacinella frit. Fhormia spec., Fegomyia hyoscyami. Calllphora, erythrooephala. lucilia epee., Chryaomvia spec., Oeratitis oapitata, Dacus oleae and Tipuia paludosa; and from the order of the Siphonaptera. for example, Xenopsylla oheopia.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions, for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils as well as U1V cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents of carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foamforming agents. In the case of the use of water as an extender, organic solvents can, for exampie, also be uBed as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic and alicyclic hydrocarbons, such -as cyolo5 hexane or paraffins, for example mineral oil fractions, alcohols, suoh as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, Such as dimethyl formamide, dimethyl sulphoxide or 1ύ acetoftitrile, as Well as water.

By liquefied gaseous diluents or carriers are meant liquids which would he gaseous at normal temperatures and pressures, for example propellants, such as halogenated hydrocarbons, for example Freon (trademark).

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clayB, talc, chalk,. quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as Well as albumin hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be present In the formulations as a mixture with other active compounds. - 12 41802 The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent.

The active compounds can be employed as such, in the form of their formulations· or as the use forms prepared therefrom. They may be used in the customary manner, for example by squirting, spraying, atomising, dusting, scattering, fumigating, gassing, watering, dressing or encrusting.

The active-compound concentrations in the ready-to-use preparations can be varied within fairly wide ranges. In general they are from 0.0001 to 10%, preferably from 0.01 to 1%, by weight.

The active compounds can also be used with good success in the ultra-low-volume (U1V) method where it is possible to apply formulations of up to 95% active compound or even to use the active compound by itself.

When used against pests harmful to health and pests of stored products, the active compounds are distinguished by an excellent residual action on wood and clay, as well as a good stability to alkali on limed Bubstrates.

The present invention also provides an inseotieidal or acaricidal composition containing as active ingredient a compound of the present invention in admixture with a Solid or liquefied gaseous diluent or oarrier or in admixture with a liquid diluent or oarrier containing a surface-active agent. ..

The present invention also provides a method of combating insects or aoarids which comprises applying to the insects or aoarids or to a habitat thereof a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by insects or acarids by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

The pesticidal activity of the present compounds is illustrated in the following bioteSt Examples.

Example A Plutella test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the conoentrate was diluted with water to the desired concentration.

Cabbage leaves (Brassica oleraoea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella maoulipennis).

After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the caterpillars were killed whereas 0% means that none of the caterpillars were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be Been -1441802 from the following tables Table A (Plutella test) Active compound Active compound Degree of desconcentration truction in % ........ in $ after 5 days S-P(0C2H5)2 0.1 0.01 100 ,n-ch2-oh (known) s.p(0C2h5)2 0.1 0.01 100 r-CH2-N(CH3)2 (known) s«p(och3)2 0.1 0.01 100 100 - 15 41802 Table A (continued).

(Plutella test) Active compound Active compound Degree of desconcentration truction in % . in % after 3 days SaP(0C2H5)2. 100 100 0.1 0.01 100 (3) (8) 0.1 0.01 0.1 0.01 100 100 100 100 Table A (continued) (flute11a test) Active compound Active compound Degree of desconcentration truction in % in % after 3 days S»P' I ,OCH3 'OC^Hy-n 0.1 0.01 100 100 CP, 0.1 0.01 100 too S=Pi .0¾ •OCjHy-n (7) 0.1 0.01 100 100 (Isomer mixture) Table A (continued) (Plutella test) Active compound Active compound Degree of desconcentration truction in % in # after 3 dayB S.P(0C2Hc)2 I 0.1 0.01 100 (16) (14·) (17) 0.1 0.01 0.1 0.01 100 100 100 100 (isomer mixture) - 18 41802 Table A (continued) (Plutella test) Active compound Active compound Degree of desooncentration truction in % in after 3 days (21) 0.1 0.01 100 100 100 100 (20) 0.1 0.01 100 100 S«p^ - 19 41802 Table A (continued) (Plutella test) Active compound Active compound Degree of desconcentration truction in % in %after 3 days 100 100 (28) 0.1 0.01 100 100 ^QCgH« «ft (27) NO, 0.1 0.01 100 100 Example,B laphygma test Solvents 3 parts by weight of acetone 10 Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier - 20 41802 and the concentrate was diluted with water to the desired concentration.

Cotton leaves (G-ossypium hirsutum) were sprayed with the preparation of the active compound until dew-moist and were then infested with caterpillars of the owlet moth (Laphygma exigua).

After the specified periods of time, the degree of destruction in was determined. 100% means that all caterpillars had been killed whilst 0% indicates that no caterpillars had been killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the table which follows; Table B (laphygma test) Active compound Active compound Degree of desconcentration truction in % truction in % after 3 days in % S-P(0C2H5)2 N-CH2-0H 0.1 0.01 0.001 100 (known) S«P(OC21^)2 0.1 0.01 100 (known) - 21 41803 Table Β (continued) (lauhygma test) Active compound Active compound Degree of desconcentration truction in % in % after 3 days s«p(0C2h5)2 0.1 0.01 0.001 100 100 (known) s=p(oc2h5)2 J-G0.1 0.01 0.001 •CH, 100 100 (known) S»P(OC2H5)2 (4) (1) 0.1 0.01 0.001 0.1 0.01 0.001 100 100 100 100 100 (28) 0.1 0.01 0.001 100 100 100 S*P— - 22 41802 Example C Myzus teat (contact action) Solvent; 3 parts by weight of acetone Emulsifier; 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage plants (Srassioa olegacea) which had been heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction was determined as a percentage; 100% means that all the aphids were killed whereas 0% means that none of the aphids were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: Table 0 (Myzus test) Active compound Active compound Degree of deeconcentration truction in % . in .% . after 1 day 0.1 100 0.01 75 0.001 0 S-P( OCgHj)., (known) Table 0 (continued) (Myzus test) Active compound Active compound Degree of desconcentration truction in % 'in % after 1 day 0.1 0.01 0,001 100 s-p(oc2h5)2 -CH2-N(CH3)2 (known) s=p(oc2h5)2 (known) s=p(oc2h5)2 0.1 100 (known) 100 - 24 41802 Table C (continued) (Mvzus test) Active compound Active compound Degree of desconcentration truction in % in %after 1 day S=P I > 2rt5 (8) 0.1 0.01 0.001 100 100 100 Tetranvchus test (resistant) Solvents 3 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglyool ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and tha concentrate was diluted with water to the desired concentration.

Bean plants (Phaseplus vulgaris), which had a height of approximately 10-30 cm, were sprayed with the preparation of ths active compound until dripping wet. These bean plants were heavily infested with the two-spotted spider mite (Tetranvchus urtioae) in all stages of development.

After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the spider mites were killed whereas 0% means that none Of the spider mites were killed.

The active compounds, the concentrations of the active 418 0 2 compounds, the evaluation times and the results can he seen from the following table: Table D (Tetranychus test) Active compound Active compound Degree of desconcentration truction in % ____in % after. 2 days s=p(oc2h5)2 (known) S=P(OC2HR) '2 0.1 0.01 n-ch2-n(ch3)2 (known) s=p(oc2h5)2 (known) - 26 418 0 2 Table D (continued) (Tetranychus test) Active compound ,Active compound Degree of des'concentration truction in % in % after 2 days s-p(oc2H5)2 (known) 0.1 0.01 100 s^oczn5)z (1) (3) 0.1 0.01 0.1 0.01 100 100 100 Table D (continued) (Tetranychus test) Active compound Active compound Degree of desooncentration truction in 0 in % after 2 days 100 100 100 100 0.1 0.01 0.001 100 - 28 41802 Example Ε ΙΒ100 test Test animals: Sitophilus granarius Solvent: Acetone parts by weight of the active compound were taken up in 1,000 parts by volume of the solvent. The solution so obtained was diluted with further solvent to the desired concentrations. 2*5 ml of the solution of the active compound were pipetted into a Petri dish. On the bottom of the Petri dish there wae a filter paper with a diameter of about 9.5 cm.

The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per ο m of filter paper varied with the concentration of the solution of active compound. About 25 test animals were then placed in the Petri dish and it was covered with a glass lid.

The condition of the test animals was observed 3 days after the commencement of the experiments. The destruction, in %, was determined. 100% denotes that all the test animals had been killed; 0% denotes that no test animals had been killed.

The active compounds, the concentrations of the active compounds, the test animals and the results can be seen from the following table: - 29 41802 Table Ε (ID^qq test/Sitophilus granarius) Active compound Active compound Degree of desconcentration truction in % in % S^OCgH^ ό jf-0H2-N(CH5)2 (known) 0.2 S=P(002H5)2 0.2 -cai2-0H (known) s=p(oc2h5)2 0.2 100 0.02 0 (known) 0.2 100 0.02 100 0.2 100 0.02 100 - 30 41802 Table (continued) (LD100 test/Sitophilus granarius) Active compound Active compound Degree of desconcentration truction in % in % 0.2 100 0.02 100 0.2 100 0.02 100 8»P(002H5)2 ° NO, 0.2 0.02 100 100 100 100 - 31 41802 Example F 1^100 f°r biptera II Test animals: Aedes aegypti Solvent: Acetone 2 parts by weight of active compound were dissolved in 1,000 parts by volume of solvent. The solution so obtained was diluted with further solvent to the desired lower concentrations. 2.5 ml of the solution of active compound, were pipetted into a Petri dish. On the bottom of the Petri dish there was a filter paper with a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound 2 per m of filter paper varied with the concentration of the solution of active compound. About 25 test animals were then placed in the Petri dish and it was covered with a glass lid.

The condition of the test animals was continuously observed. .The time which was necessary for 100% destruction was determined.

The test animals, the active compounds, the concentrations of the active compounds and the times at which there .was 100% destruction can be seen from the fon owing tables - 32 41802 Table F (M100 test for diptera/Aedes aegypti) Active compound Active compound ΙΤ,θθ in minu-tes Sw »» % (hrs) S*P(0G2H5)2 ό 0.2 0.02 180' hrs 0% (known) 0.2 0.02 120' hrs 0% (known) 0.2 0.02 120' 180' 0.2 0.02 0.002 0.2 0.02 0.002 120' 120' hrs 70% 60' 120' 180' - 33 41802 Example & 1T1OO test for Diptera Test animals: Musca domestica Solvent: Acetone 2parts by weight of ective compound were dissolved in 1,000 parts by volume of solvent. The solution so obtained, was diluted with further solvent to the desired lower concentrations, 2,5 ml of the solution of active compound were pipetted into a Petri dish. On the bottom of the' Petri dish there was a filter paper with a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per m of filter paper varied with the concentration of the solution of active compound. About .25 test animals were then placed in the Petri dish and it was covered with a glass lid.

The condition of the test animals wa& continuously observed. The time which was necessary for 100% destruction was determined.

The test animals, the active compounds, the concentrations of the active compounds and the times at which there was 100% destruction can be seen from the following table: - 34 418 0 2 (LTinn test for diptera/Musca domestics) 100 Active compound Active compound ϋ'.θθ in minutes concentration in in icentration (-) or hours the solution, (hrs) s=p(oo2h5)2 (known) s=p(oc2h5)2 (known) 0.2 0.02 0.2 0.02 0.2 0,02 60' hrs 100' hrs ' 80' Example B Test with parasitic fly larvae Solvent: 35 partB by weight of ethylene polyglycol monomethyl ether Emulsifier! 35 parts by weight of nonylphenol polyglycol ether To produce a suitable preparation of active compound, parts by weight of the active substance in question were mixed with the stated amount of solvent which contained the above-mentioned proportion of emulsifier and the concentrate thus obtained was diluted with water to the desired concen- 35 41802 tration.

About 20 fly larvae (lucilia cuprina) were introduced into a test tube which contained approx. 2 cnr of horse muscle. 0.5 ml of the preparation of active compound was applied to this horse meat. After 24.hours, the degree of destruction in % was determined. 100% means that all the larvae had been killed and 0% means that no larvae had been killed.

The active compounds investigated, the concentrations of the active compounds used and the results obtained can be seen from the table which follows: Table H (Test with parasitic fly larvae/lucilia cuprina res.) Active compound Active compound Degree of desconcentration truction in % 100 · 100 30 >50 100 too ^50 - 36 41802 T a b 1 e H (continued) (Test with parasitic fly larvae/Lucilia cuprlna res.) Active compound Active compound Degree of desconcentration truction in % in ppm S=P 8=2(001^), 100 100 100 100 100 100 100 100 (isomer mixture) The process of this invention is illustrated in the following Preparative Examples: s=*p(og2h5)2 (1) A mixture of 25«6 g (0.1 mole) of 1-(3-trifluoromethylphenyl)-3-hydhoxy-1,6-dihydropyridazinohe-(6), 20.7 g (0.15 mole) of potassium carbonate, 18.8 g (0.1 mole) of 0,0-diethylthionophoephorlc aoid diester chloride and 300 ml of acetonitrile was stirred for 4 hours at 50°C. It was then cooled to room temperature and, after addition of 400 ml of toluene, was extracted by shaking with twice 300 ml of- water. The organic phase was nernr-tod off, dried over sodium sulphate and freed from the solvent in vacuo. The residue was subjected to slight distillation. This gave 33.4 g (82% of theory) of 0,0-dietfiyl-0-[l-(3-trifluoromethylphenyl)1,6-dihydropyridaz-(6)-on-(3)-yl]-thionophosohorie acid ester in the form of a yellow oil having a refractive index n^2 of 1.5240.

The following Compounds of the formula could be prepared analogously: - 38 41802 ο crt W) C Φ ·Η fc-P ·-* Η Φ π) β +3 αΐ * τί W φ* Η Ό ϋ α) 00 ϋ τΙ •Η «Ρ co φ 0 >?>·π Χί «Η Ο ΡΜ Ρ Ο CM tA •4· IA n cn in 4 • « Η H IA IA lA r-l σ\ γΗ Ο ι—Ι ΙΑ <τ ΙΑ ΙΑ 00 Ν ΙΑ CM ΙΑ ιη • ΙΑ ΙΑ Η 0 • γΗ ·· Η Κ CO GO frQ0 fr IA NONflNcXa s $owa3iaNn $ 8« o no IA Φ & +» X ri a A © a o to 'ri § •ri jn Ph Ρ •ri ο a’ to o O flj Φ H & a · co o Η « {» -ΰ Ή £ HOC © 4! •Η &Λ Η'-'-Ρ (—1 C— ΙΑ Φ & 4- C— t— ω ΙΑ ΙΑ φ ΙΑ ft M3 t- Ο ΛΟ CM ω 4* ω 4* κο 4- 00 φ co οΐ ω W Ο ω ω co Μ ω Μ Μ Ώ w ό ο CO IA mtnmtntntntntntntninintntntn aaaaaaaaasaaaaaaa tn a a. a a a «as a a a Γ - aaaaaaaa o ts • * aP m aP a . in Tn a k\ ni ? aP a a a g •H I aT in in cP «. a o'· ω o tn tn fa iaSf aT o a o a FA ΙΑ ΙΑ IA JS O «nt aP a10 ar “n. £ Ow 8 8 8 8 J* 2° 8 8 cf cf cf 8 8 o S ο ϋ ο ο ϋ ϋ ϋ o ο ο ο ο ο ο ιη Nn-imiDNOmo η.νιλ·ϊημ3Ι< • Η Η Η Η Η Η Η - 39 41803 Φ -ΡΟ Ο+» a α Ιη ·η «Μ Ο Φ ft β Φ Π +3 ·Η cd-p Ό Η Φ ϊ3 ο * •Η Η ω φ Φ Φ rt rt β 3 -P +3 K Θ a p rt in φ Ο Φ O' tn a KY o in tn O o b· in ω in ω in m in • *rl • • • H—' H'-* H H (-1 WO WO WO WO WO β fl fi is * ΙΗ rt Ο •Η, tn p ft ft •HO 3 ra. ο O tii C£ CC (C s Et · Μ O MB pa H © •it m CM tn © cu m tn H tn in in in in • • < • « H rH rH rH rH WOWOWQ wrtwo c rt rt rtrt b- tn s b- CM r- in m • rH r- m wowp o\ in 5! CM c·* 0 is © tn tn ID 5 3 8 CM 10 ό co © © © © © © m © © w © w tn tn m tn tn -3· m tn tn tn KY tn CM KY KY w rH frl I—1 O fe fe 0 U ϋ ϋ © 0 I O a 1 as a IO m 10 CM a 1 in in oil a a KY KY a§ aS S3 © as © a a a a a a g33 ep3 © © a © a' a a a a a ) af f aT KY I aP aP jm aP cm ϋ I in in ffiw aP “k> ooo rt rt if· al· KY KS o o co co I I o «I w tn O O n w •H rt Ή I II in in in m 1 js in in in 1 is 1 t- tn tn © CC © © S3 © © © © a © © CM CM CM CM tn CM CM CM tn ky ϋ 1 u 1 ϋ t 0 1 ϋ 1 ϋ 1 ϋ I O 1 0 1 O a 1 0 1 © Ch 0 rH CM tn in 10 b- © 0\ rH rH CM CM CM CM CM CM CM CM CM CM - 40 41802 The 1-phenyl-3-hydroxy-6-oxo-pyridazine derivatives (III) required as starting materials can he prepared, for example, as follows: OH 176 g (1 mole) of 3-trifluoromethylphenylhydrazine (for preparation, see German Auslegeschrift (German Published Specification) 1,116,534) were dissolved in a mixture of 1,000 ml of water and 250 ml of concentrated hydrochloric acid and then 98 g (1 mole) of maleic anhydride were added at approx. 90°C. The mixture was then stirred for a further hour at 95-100°0 and after the reaction mixture had cooled, the product whioh had crystallised out wae filtered off. It oould be purified by dissolving it in dilute sodium hydroxide solution and reprecipitating with hydrochloric acid. This gave 210 g (82% of theory) of 1-(3-trifluoromethylphenyl)-3hydroxy-1,6-dihydropyridazinone-(6) in the form of a pale yellow-coloured powder of melting point 176°C.

The following compounds could be prepared analogouslys OH 88% yield; melting point 245°C (isaner mixture). 418 02 OH 65% yield; melting point 230°C 69% yield; melting point 174°0 40% yield; melting point 208°0

Claims

CLAIMS:

1.. Pyridazinyl(thiono)(thiol)phosphoric(phosphonicj acid esters and ester-amides of the general formula (I) in which R is alkyl with 1 to 6 carbon atoms, R' is phenyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 carbon atoms or monoalkylamlno or dialkylamino with 1 to 4 carbon atoms in the or each alkyl group, R M and R', which may be identical or different, are each hydrogen or methyl, TV R is hydrogen, halogen, nitro or halogenoalkyl with 1 to 3 carbon atoms, n is an integer from 1 to 4, and X is oxygen or sulphur.

2. Compounds aooording to claim 1, in whioh R is straightchain or branched alkyl with 1 to 5 carbon atoms, R' is phenyl, straight-chain or branched alkyl with 1 to 3 carbon atoms, straight-chain or branched alkoxy or alkylthio, each with 1 to. 5 oarbon atoms, or monoalkylamlno or dialkylamino with 1 to 3 oarbon atoms per alkyl group S' ia hydrogen, chlorine, nitro or trifluoromethyl, andnt 1.2-or 3.

3. The compound of the formula - 43 418 0 2 s=p(oc 2 h 5 ) 2 ' ό (1)

4. The compound of the formula (4)

5. The compound of the formula (8)

6. The compound of the formula s=p(oo 2 H 5 ) 2 (12)

7. The compound of.the formula (14)

8. The compound of the formula (23)

9. The compound of the formula ΌΗ, 3=P (24) - Ofl 3 H 7 i

10. The compound of the formula (28)

11. The compounds hereinbefore disclosed In Examples 2, 3, 5-7, 9-11, 13, 15-22, 25-27 and 29.

12. A prooese for the preparation of a pyridazinyl(thiono) (thiol)phosphoric(phosphonic) acid ester or ester amide according to any of claims 1 to 11, in which a (thiono)(thiol) (phosphoric)(phosphonic) acid ester halide or ester-amide halide of the general formula KO * JXP-Hal (II) H' - 45 41802 in which R, R' and X have the meanings stated in claim 1, and Hal is halogen, is reacted with a 1-phenyl-3-hydroxy-1,6-dihydropyridazinone-(6) derivative of the general formula in which R, R’,. R IV and n have the meanings stated in claim 1. 1J. A process according to claim 12 in which the reaction is effected in the presence of a diluent or solvent.

13. 14. A process according to claim 12 or 13 in which the reaction is effected in the presence of an acid acceptor.

14. 15. A process according to claim 14 in which the acid acceptor is an alkali metal carbonate, an alkali metal alcoholate or an aliphatic, aromatic or heterocyclic amine.

15. 16. A process according to any of claims 12 to 15, in which the reaotion is effected at between 0° and 120°C.

16. 17* A process according to claim 16, in which the reaction is effected at from 40° to. 60°Q.

17. 18. A prooess according to any of claims 12 to 17, in which the reactants are employed in substantially equimolar amounts.

18. 19. A process according to any of claims 12 to 18, in which the ester halide or ester-amide halide (ll) is one that is hereinbefore specifically mentioned.

19. 20. A process according to any of claims 12 to 19, in which - -46 41802 the pyridazinone derivative (ill) is one that is hereinbefore specifically mentioned.

20. 21. A process for the preparation of a compound according to claim 1, substantially as hereinbefore described in Example 1.

21. 22. Compounds according to claim 1 whenever prepared by a process according to any of claims 12 to 21.

22. 23. An insecticidal or acaricidal composition containing as active ingredient a compound according to any of claims 1 to 11 and 22 in admixture with a solid or liquefied gaseous diluent or oarrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

23. 24. A composition according to claim 23 containing from 0,1 to 95% of the active compound, by weight,

24. 25. A composition according to claim 24 containing from 0.5 to 90% of the active compound, by weight,

25. 26. A method of combating insects oraoarids which comprises applying to the insects or aoarids or to a habitat thereof a compound according to any of claimB 1 to 11 and 22 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 to 11 and 22 in admixture with a diluent or carrier.

26. 27. A method according to claim 26 in which a composition ia uBed containing from 0.0001 to 10% of the active compound, by weight.

27. 28. A method according to claim 27 in which a composition is used containing from 0.01 to 1% of the active compound, by weight.

28.

29. A method according to any of claims 26 to 28 in which the active compound is one of those hereinbefore mentioned in any - 47 41802 of Examples A to H.