IL43535A - Mono- di- or trithiophosphonylmethyl-1,3,4-oxadiazoles and their use as pesticides - Google Patents

Description

43535/3 MONO-, PI- OR TRITHIOPHOSPHONVLMETHYL, T , 3,4-OXADIAZOLES AND THEIR USE AS PESTICIDES is - 4,3 ,1 - ^na^iaDia - unimo IN Ή - "mn 43535/3 Subject of the present invention are mono-di- or trithiophosphonyV oxadiazoles methyl -1 ,3, -©-*νβ*ο}€« having the general formula in which R is (C,-C4) alkyl, (C^) haloalkyl, (C8-C6) cycloalkyl, (Cg-Cg) cycloalkenyl; phenyl, optionally substituted by methoxy; bicycloheptenyl or benzyl R1 is alkyl, optionally substituted by halogen, nitro, cyano or a radical having the formula: -P (0R3)2 . or -P (R3)2 or 0 0 (Cg-C^) alkenyl, optionally substituted by halogen; (C3) alkinyl, (C2-Cg) alkoxyalkyl, (C^-C3) alkyl me rcapto- alkyl, ( g-Cg) cycloalkyl, phenyl, halophenyl, trlfluoro- the formula R2 is'(C|-C4) alkyl, (Cg-C^) alkoxyalkyl, phenyl or halophenyl, R3 is methyl or ethyl, and X and Y are oxygen or sulfur.

Besidss the meanings specified in the examples, the symbols R, .| and R2 may preferably have the following meanings: R: isopropyl, sec. butyl, β-Phloroethyl or cyclopentyl. : n-pentyl, n-hexyl ; .2.2.2- trichloroethyl , 2 f 3-dibromo propyl crotyl; cyclopentyl; 2-, 3- or -bromophenyl , 2.3-» 2,6-, or 315-dicb.lorophenyl or -dibromophenyl ; R : ethyl, me thoxymeth l , ' 3-niethoxypr0pyl , 2-ethoxyethyl ; phenyl; 2- or ^-chlor-ophenyl , 2,k~ or 2 ; 6-dichlorophenyl . 2-, 3- or -bromophenyl.

The compounds of the formula I are prepared by reacting compounds havin or their salts, if necessary in the preserice of an acid-binding' agent, with 2-halogenome thyl- 1 , 3 > ^-oxdiazoles having the formula in which Hal repr-esents preferably chlorine or bromine.

As salts of compounds having the formula HI the alkaline metal salts, alkaline earth metal salts or ammonium salts or salts, of organic bases are especially used. In case that the free compounds are used, acid-binding agents must be added, siich as alkali metal hydroxides, alcoholates or carbonates, ammonia or tert. nitrogen bases such as triethylamine , dimethyl aniline, pyridine, or quinoline.

Generally, the compounds having the formula III are used in slightly excessive quantities of up to 1 0 70. In principle it is possible to use excess halogenomethyl-oxdiazole , as well but neither technically nor economically is there any advantage.

The reaction is performed in a temperature range between room temperature and the decomposition temperature of the final products, respectively the temperature at which secondary reactionSbetween excess starting material and the reaction end product may occur i.e. . between 20° and 1 00°C, preferably between . .30°C and 80°C. The reaction, being mostly, exothermic, can be carried through without solvents. However, in order to guarantee a better temperature control, the reaction is generally performed in solvents inert in respect to the starting materials As solvents are suitable, besides . the reaction products themselves, especially low aliphatic alcohols having from 1 - carbon, atoms, low aliphatic ketones such as, for instance, acetone or methyl ethyl ketone, short chain aliphatic nitriles, ethers such as , for example, tetrabydrofurane or glycol dimethyl ether, amides of low aliphatic carboxylic acids such as dimethyl form-amide or dimethyl acetamide or water when water-soluble starting/materials are used. In some cases it may also be advantageous to use aromatic hydrocarbons or chlorinated aliphatic hydrocarbons with or without small quantities of the above mentioned solvents as solubilizers .

The process may be performed by various methods which are principally known, such as are described, for example, in the general preparation methods A - D of the Examples. The 2-halogen 1 , 3 > ^ -oxdiazole s used for this purpose may be prepared according to Elderfieid "Heterocyclic compounds " , vol.7» pg« 526- 52 by A number of related thio hosphoric and dithiophosphoric acid derivatives are described in German schriften 1 963 6?2 and 1 9^2 993. These compounds are, however, less active against many pests than the invention compounds. splitting off water from corresponding 1 -Iialogenacetyl-2-acyl-hydrazides or according to German "Offenlegungsscbrift" 2.047.464 and 2.0 . 5 from corresponding acyl.bydra.zide s with haloacetic acids in the presence of phosphorus halides. The dithiophosphonic acid anhydrides used for this purpose, being partially unknown, may be obtained according to the general process described in Houben-Weyl, 4th edition vol.XIl/l, pg.. 16.

' The compounds claimed by the present invention are efficient insecticidal , acaricidal and nematocidal agents.

Th Because of their properties and their good tolerability to plants they are useful for combating numerous insect pests on crop plants. ■" They can be used successfully against both sticking and biting insects, for example, against members of the following classes or families: Tettigonioideae Bruchidae Acridoideae Curculionidae Gryllidae Bostrychidae Gryllotalpidae Carabidae Blattidae . Cassidinae Reduviidae Tineidae Pyrrhocoriae Noctuidae Cimicidae Lymantriidae Penta.tomidae Pyralidae .

Delpha.cidae Geomet idae Cicadellidae Hy onomoi tidae Aphidoideae Pieridae Psylloideae Tortricidsie Aleurodidae Culicidae Diaspididae Tipulidae Coccidae Stomoxydae Pseudococcidae Tabanidae Scarabae idae Tephritidae Oermes idae Muse idae Coc cine 11 idae Calliphorinae Tenebrionidae Cecidomyiidae Chrysomelidae Pulicidae The comiDOunds act also against many types of mites (Acarinae), for example against members of the families Tetra-nychidae , Derrnanys sidae , Tarsonemidae and Eriophyidae.

The novel compounds are furthermore useful for combating plant nematodes such as Meloidogynes spp. , Heterodora spp.

Ditylenchus spp. , Pratylenchus spp. , Paratylenchus spp. , Anguina spp. , Helicotylenchus spp., Tylenchorhynchus spp. , Rotylenchulus spp. , Tylenchulus spp. , Radopholus spp. , Belonolaismus spp. , Trichodorus spp. , Longid rus spp. , Aphelenchoides spp. , Xiphi-nema spp.

Among the pests against ΛΛΙΧΟΙΙ the invention compounds are active are the following: beetle species suc as strawtary blossom weevil (Anthonomus rubi), the Mexican bean beetle (Epilachna varivestis), the Colorado beetle (Leptinotarsa decemlineata) , the grain (Calandra granaria), mealworm (Tenebrio molitor) ; larvae of the codling moth (Carpocapsa pomonella) , of the green oak leaf roller (Tortrix viridana)-, of the tortrix moth (Capua reticulane) , of the Asiatic cotton moth (Prodenia litura), of the corn borer (Ostri ia nubilalis); aphids, such as the bean aphid (Doralis . fabae ), the green peach aphid (Myzodes persicae), the wooly aphid (Eriosonia lanigerura) ; cicadae such as Nilapar-vata lugens and Nephotettix bipunctata; bugs sucking on plants such as- cotton stainers (Oncopeltus fasciatus and Dysdercus fasciatus); locusts such as the North African variety of Locusta migratoria; cockroach varieties impeaching hygiene such as Perxplaneta americana and Phyllodromia gei^manica ; spider mite varieties such as Tetranychus urticae and Metatetranychus ulmi .

Due to the systemic properties of the compounds well hidden noxious insects can be combated, too, for example aphids living inside galls such as the mealy apple aphid (Yezabura communis) and Anuraphis roseus.

The excellent root-systemic properties of the compounds allow for their use as insecticidal and acaricidal granules, so that the protection of the growing youn plants against the actions of aphids, spider mites, larvae etc. is guaranteed for weeks if the granules are dispersed simultaneously with, the seed such as cotton, broad beans etc.

Therefore, subject of the invention are also pesticidal agents which contain as active agent compounds having the formula I. For this purpose , the compounds having the general formula I may be formulated in the usual admixtures with solid or "liquid inert carrier substances, adhesives, wetting and dispersing agents, or grinding auxiliairies , as wettable powders, emulsion concentrates, granules etc.

As , carrier material, mineral substances may be used, such ■ as · aluminium silicates, argillaceous earths, kao3.in, chalks, siliceous chalks, talcum, kieselguhr or hydra.ted silicic acids, or preparations of these mineral substances with special additives, for example chalk with sodium stearate. As carrier material for liquid preparations, all usual and suitable organic solvents may be employed, for example toluene , xylene , diacetone alcohol, isophorone, gasolines, paraffin oils, dioxan, dimethyl formamide , dimethyl sulphoxide , ethyl acetate, butyl acetate, te trahydrofuran , chlorobenzene and the like.

As adhesives, there may be used glue-like cellulose products or polyvinyl alcohols.

As wetting agents, all suitable emulsifiers may be used, such as oxethylated alkylphenols , salts of aryl- or alkylaryl-sulphonic acids, salts of ethoxylated benzenesulphonic acids, or soaps . .

Suitable dispersing agents are cellulose pitch (salts of stilphite waste liquors), salts of naphthalenesul Aphonic acid or, in certain cases, hydrated silicic acids or also kieselguhr.

As grinding auxiliaries , suitable inorganic or organic salts, such as sodium sulphate, ammonium sulphate, sodium carbonate, sodium bicarbonate, sodium thiosulphate , sodium stearate, sodium acetate may be used.

The pesticidal compositions may optionally be mixed with other insecticidal , nematocidal and/or fungicidal agents. These pesticidal compositions are containing, generally, from 1 to 95 i° of compounds having the formula 1".

The following Examples illustrate the invention.

Preparation procedure A: Acco equimolar . quantities of dithiopbosphonic acid anhydride and of alcaline metal alcoholate II in a 5 to 10 fold quantity of alcohol were mixed together and stirred for a period of from 5 minutes to 1 hour, thus obtaining the intermediate product according to formula III. Subseqiently, equimolar quantities of a 2-halogenomethyl-oxdiazole having the general formula IV were added and the whole was heated to temperatures between 20° and 80°C for a period from 10 minutes to 5 hours, depending on the reaction. For working-up, the alkali metal halide was separated by suction filtration, the solvent eliminated by distillation and the residue .dissolved in another solvent immiscible with water. This, solution was washed several times with. water, dried and concentrated. General].y the esters were obtained as oils which cannot be distilled without decomposition occurring. The following compounds were prepared according to this process : General preparation procedure B: According to the reactio equation a dithiophosphonic acid anhydride I was stirred together with stoichiometric quantities of a phenol, a thiophenol, an alcohol, a glycol or mercaptan II in a solvent being inert under the reaction conditions and immiscible with water (for example CH2Ci2, toluol), heated to from 60° - 110°C and reacted with the equimolar quantity of a tert. base B (for example tri-ethylamine, pyridine). To the intermediate product III thus prepared there was added a stoichiometric quantity of 2-halo-genomethylox-rdiazole IV. The reaction usually took .place within from 10 minutes to 5 hours at temperatures of from 20 - 110°C, respectively the boiling point of the solvent used.

The work-up was performed by washing out the amine-salt with water, drying the organic phase e.g. with sodium sulfate and eliminating the solvent by distillation.

The reaction products were usuall obtained as oils which cannot be subjected to distillation without decomposition.

The following compounds were prepared, accordin to method B: General preparation procedure C; According to the reaction equation equimolar quantities of an alkali metal salt or an ammonium •salt of t io- or dithiophosphonic acid monoesters III and of a 2-chloro-methyloxdiazole IV were heated to 60° - 90°C or about 30 minutes in an appropriate solvent (such as for example ethanol, acetonitrile or glycol dimethyl ether). Subsequently, the solvent was eliminated by distillation, the residue taken u in a solvent immiscible with water, and worked-up in analogy to method A.

The following compounds were prepared according to this method: General preparation procedure D; According to the reaction equation a op osphon c ac d an y r e was reac ed w at least the •10 stoichiometric quantity of a hydroxy! compound II. The dithiophosphonic acid monoester, formed with heat generation, was dissolved in a solution of stoichiometric quantities . of an alka-tL metal hydroxide in water. After having added stoichiometric quantities of a 2-chloromethyl- 1 , 3 > -oxdiazole IV to the solutim 5 of salt III, the reaction mixture was heated to temperatures between 50° - 100°C for periods from 10 minutes to 2 hours. The • ' separated oil was taken up by an inert solvent such as methylene chloride or toluol and separated from the aqueous solution. .

After drying the organic phase with one of the usually used 20 drying agents such as - for example - sodium sulfate or calcium chloride the solvent was eliminated by distillation, whereby the reaction product was generally obtained as an oil.

The following compounds were prepared according to this process : E X A M P L E S OF A P P L I C A T I O · " ■ E X A M P L E I; ' Bean pl-ants being heavily infested with spider mites (Tetranychus urticae) were drip- sprayed with the aqueous dilution of an emulsdion concentrate contiining 0.003 wt. of the active compound according to Example 25· Subsequently, the plants were placed in a greenhouse at 20°C. Upon checking by inicorscope 8 days after the spraying, all the mobile and immobile phases of the mite population were destroyed.

Upon testing in the same way the compounds according to Examples 2k, 32, 26, k, 5, 3.1 , 3, kO , 38, 35, 39, 3^ and 2 proved to be 'equally efficient.

E X A M P L E II: . Potted young apple trees being heavily infested by a strain of fruit-tree red spider (Metatetranychus ulmi ) resistent to phosphoric acid esters were sprayed to dripping wetness with an j aqueois dilution of an emulsion concentrate containing 0.01.25 wt$ of the active compound according to Example 31 , and subsequently placed in a green-house at 20°C. Upon checking by microscope 8 days after spraying, all the mobile and immobile phases of the fruit-tree red spider had bee destroyed.

Upon testing in the same way the compounds according to Examples 2k, 26 and 3 proved to be equally efficient.

However, the following phosphoric acid esters, even, though applied in high concentrations of the active agents, were entirely inefficient: phenkaptone Ο. 25 w.t.70 cone. no effect denieton-S-methyl O.O wt.70 cone. no effect dimethoate 0.05 wt.^o cone. ' no effect E X A M P L E, III ; ■ The systemic properties of the active compounds were proved by the following, test . arrangement : The roots of broad beans (Vicia faba) , the above-ground growing parts of which were being sucked by 200 - 300 aphids, were wrapped in a plastics bag so as to eliminate the gas phase effect. 1 0 ml of an aqueous dilution of an emulsion concentrate were then dispersed in the root area of the plants, the concentrate containing 0. 1 25 nig of the active compound according to Example 25 · The plants were placed in a greenhouse at 20°C.

The active agent was rapidly absorbed by the roots and carried to the above-ground growing parts of the plants.

Upon checking 3 days after the application, all the aphids had been destroyed.

Upon tetdrig in the same way, the active compounds according -to Examples 2h , 26 , h, 3 9-hd 3 proved to be equally efficient.

E A M P L E IV: By a similar method and at a similar concentration as described for Example III broad beans being heavily infested by spider mites (Tetranychus urticae) were treated.

Upon chacking 8 days after having applied the active οοηΐ· pound according to Example 25 ». all the mobile and immobile phases were destroyed. The same good effect was obtained by using the compounds according to Example 2h , 26 and 31 in the test arrangement as described.

E X A M P L E V: Potted young cotton plants (Cossypium spec.) being infested with African cotton stainers (Dysdercus fasciatus) (5 plants each infested with 20 insects) were sprayed to dripping wetness with an aqieous dilution of a wettable powder concentrate containing O.OO6 wt.0 of the active compound according to Example 4. Subsequently, the plants with the cotton stainers were put in cylindrical gaze cages and placed in a greenhouse at 22°C. · Upon checking after 48 hours, all the "cotton stainers had been destroyed.

The same testing method proved the compounds according to Examples 24, 23, 26, 31, 3, 40, 33, 37, 35, 39, 36, 3, 34, 42, · 1 and 2 to e equally efficient.

E X A M P L E VI; Larvae (3^d phase) of the Asian cotton moth (Prodenia litura) and cotton leaves were sprayed with a determined quantity . of an aqueous dilution of an emulsion concentrate . containing the active compound according to Example 35 and subsequently, placed i the laboratory at 22°C in open vessels (5 vessels with 10 larvae each).

A concentration of 2 0.0024 mg/cm of the active agent was sufficient for destroying all the test insects within the specified lapse of time.

When using the same test arrangement, the active compounds according to Example 24, 25, 26 and 3 were equally efficient.

E A M P L E VII: Larvae (4th phase) of the Mexican bean beetle (Epilachna varivestis) and leaves of dwarf bush beans (Phaseolus vulgaris) were sprayed with a determined quantity (corresponding to an E A M P L E III;' - . ·, The systemic properties of the active compounds were proved by the following test arrangement.: The roots of broad beans (Vicia . faba) , the above-ground growing parts of which were being sucked, by 200 - 300 aphids, were wrapped in a plastics bag so as to eliminate the gas phase effect. 1 0 ml of an aqueous dilution of an emulsion concentrate were then dispersed in the root area of the plants, the concentrate containing 0. 1 25 mg of the. active compound according to Example 25 · The plants were placed in a greenhouse at 20°C. The active agent lias rapidly absorbed by the roots and carried to the above-ground growing parts of the plants.

Upon checking 3 days after the application, all the aphids had been destroyed.

Upo teting in the same way, the active compounds according -to Examples 24, 26 , , 31 and 3 proved to be equally efficient.

E X A M P L E IV: ' , By a similar method and at a similar concentration as described for Example III broad beans being heavily infested by spider mites (Tetranychus urticae) were treated.

Upon chacking 8 days after having applied the active coin-pound according to Example 25 , all the mobile and immobile phases were destroyed. The same good effect was obtained by using the compounds according to Example 24, 26 and 31 in the test arrangement as described.

E X A M P L E V: . ■ .

Potted young cotton plants (Gossypium spec . ) being infested with African cotton stainers (Dysdercus fasciatus) (5 plants each infested with 20 insects) were sprayed to dripping wetness with an aqueous dilution of a wettable powder concentrate containing O.OO6 wt.$ of the active compound according to Example 4 Subsequently, the plants with the, cotton stainers were put in cylindrical gaze cages and placed in a greenhouse at 22°C.

Upon checking after 48 hours, all the cotton stainers had been destroyed.

The same testing method proved the compounds accordin to Examples 24, 25, 26, 31, 3, 40, 33, 37, 35, 39, 36, 3, 3 , 2, 1 and 2 to be equally efficient.

E X A M P L E VI : Larvae (3rd phase) of the Asian cotton moth (Prodenia litura) and cotton leaves were sprayed with a determined quantity of an aqueous dilution of an emulsion concentrate containing the active compound according to Example 35 and subsequently placed in the laboratory at 22°C in open vessels ( vessels wit 10 larvae each).

A concentration of 0.0024 mg/.cni 2 of the active agent was sufficient for destroying. all the test insects within the specified lapse of time.

When using the . same test arrangement, the active compounds according to Example .24, 25, 26 and 3 were equally efficient.

E X A M P L E VII: Larvae (4th phase), of ' the Mexican bean beetle (Epilachna varivestis) and leaves of dwarf bash beans (Phaseolus vulgaris) were sprayed with a determined quantity (corresponding to an - 35 - applied quantity of 600 ltr/ha i -;tlie field) of the aqueous dilution of an emulsion concentrate^ containing the active com-pound according to Example k , subsequently placed in the laboratory at 22°C in open vessels. 8. hours later the mortality rate was determined ( 5 vessels each containing 1 0 larvae). 2 The concentration of 0 . 003 mg/cm of active agent was sufficient for destroying the la.r\rae by 1 00 *o.

When using the compounds accordin to Examples 25 » 2.6, 3 11 33 » 37 » 38 » 36 and 2 in the same test arrangement, the results were equally good.

E X A M P L E VIII; In earth-filled rectangular plates (ho x 60 x 1 0 cms) seeds of broad beans (Vicia faba) were placed in drills; simultaneously a granular formulation containing the active, compound according to Example 35 a the rate of 5 wt.70 -corresponding to an applied quantity of 1 . 5 kg of active agent per hectare - was dispersed in the same drills which were then covered with earth. Subsequently, these plates ( 8 series) went to the greenhouse at 20°C. For the test period the earth was kept slightly humid.

Afte the germination of the seed and the plants having reached 1 0 to 1 5 cms height (= "\ days), same were heavily infested with spider mites (Tetranychus urticae).

Another week later (= 3 weeks after sowing) checking proved that the spider mites whic had crawled onto the plants, had been destroyed and that no population had been formed.

Further infections with spider mites in weekly intervals proved upon checking that in each case the spider mites were destroyed for a period of ip to TO weeks after the infection.

On control plants infested simultaneousl and left without treatment, the spider mites spread heavily and destroyed the plants.

Upon using the active compounds of Examples 3k, 39 > 25 arid 2k. for the same test arrangement, same proved to be equally efficient.

Granules containing 10 wto of " Carbofurane " did not produce any effect, though it was applied in twice the amount , of 3 kg of active agent per hectare, and while using the same test arrangement.

Claims (1)

VMI\T IS CLAIMED IS: .

1. in wh ■■. .. ' · R is g-Cg) .cycloalkyl, • ally substituted by - ' · benzyl ; -R. is '(C-j-C12) alkyl, optionally substituted by halogen, nitro: : cyano or a radical having the formula -P(OR3)2, ' or · "ρ(¾)2 or · 0 0 alogen; lkylmercapto- l, trifluoro- ■ formula 2 is (C1-C4) alkyl ,. (Cg-C^) alkoxyalkyl, phenyl or halophenyl, R3 is mthyl or ethyl, and X and Y are oxygen or sulfur. WHAT IS CLAIMED IS: Compounds having the formula in which R is (C-j -C4) alkyl, (Cj-C^) haloalkyl, (C5~Cg) ^cycloalkyl, (Cg-Cg) cycloalkenyl, phenyl, optionally substituted by methoxy, moreover bicyclo eptenyl or benzyl; R is (ci_ci2^ alky^» optionally substituted by halogen, nltro, cyano or a radical having the formula -P(0R3)2, or -p(¾)2 or 0 · 0 R3 is methyl or ethyl, and X and Y are oxygen or sulfur. -38- Process for preparing compounds according to claim 1, which comprises reacting a compound having the. formula or a salt thereof with 2-halogenomethyl- 1 , 3 » -ox'diazoles having the formula in which ' Hal represents preferably chlox^ine or bromine, the reaction optionally taking place in the presence of an acid-binding agent . Method of combating pests which comprises applying to the infested plants a pesticidally effective amount o a compound' of formula I. Λ pesticidal composition, which comprises a pesticidally effective amount of a compound . having the formula I, combined with usual formulation additives. COHEN ZEDE <& SPISBACH P. O, Box 33116 , Tel - Aviv Attorneys for Applicant