IL44016A - O-haloalkylphosphoric acid ester-amides,their preparation and their use as insecticides and acaricides - Google Patents

Abstract

O-(1,2-dibromo-2,2-dichloro-ethyl)-phosphoric acid diesteramides of the formula ROO PARALLEL ANGLE P-O-CHBr-CCl2Br R' ANGLE N R'' (I) in which R is alkyl of 1 to 12 carbon atoms, halo-lower alkyl, alkenyl with 2 to 6 carbon atoms, alkoxyalkyl with up to 6 carbon atoms per alkyl and alkoxy moiety, or phenylalkyl, and R' and R'' each independently is hydrogen or alkyl of 1 to 8 carbon atoms, or R' and R'' together with the nitrogen atom form a five-membered or six-membered heterocyclic ring, WHICH POSSESS INSECTICIDAL, ACARICIDAL, FUNGICIDAL, TICKICIDAL AND MICROBICIDAL PROPERTIES. [US3911058A]

Description

on acid their preparation and their as insecticides or acaricides The present invention relates to certain new acid to a process for their preparation and to their use as insecticides or It is already known that acid for example or acid possess an insecticidal activity German Offenlegungsschrift Published and Patent Specification British Patent Specification 784986 relates to a broad group of esters and ester amides of phosphoric acids having the formula O wherein and among aryloxy or alkylamido and are halogen may be and and are among hydrogen or halogen The known compounds are useful biocides and medicaments and some of them are insecticides or The present invention relates to certain selected phosphoric acid ester amides although covered by the above generic formula have not yet been The acid of the present invention have the general formula in which R is alkyl with 1 to 12 carbon haloalkyl with 1 to 4 carbon alkenyl with 2 to 6 carbon alkoxyalkyl to 6 carbon atoms per alkyl and alkoxy moiety or and and which can be the same or are hydrogen or alkyl ith 1 to 8 carbon or and together with the nitrogen atom form a or saturated heterocyclic ring selected from piperidine and R is alkyl with 1 to 10 carbon alkenyl with 2 to carbon alkoxyalkyl with 1 to 4 carbon atoms per alkyl or alkoxy chloromethyl chloroethyl or phenylalkyl with 1 to 3 carbon atoms in the alkyl and and are hydrogen or alkyl with 1 to 6 carbon atoms or together with the nitrogen a piperidine or pyrrolidine The invention also provides a process for the production of an acid of the formula in which an acid of the general formula in which and have the abovementioned is optionally in the presence of a or an acid of the formula 0 in which Hal is preferably is reacted with an alcohol of the general formula ROH in which R has the abovementioned in the form of an alkali metal alkaline earth metal salt or ammonium salt or in the presence of an and the resulting intermediate is optionally without intermediate with an amine of the general formula in and have the in the presence of an the acid amides according to the invention have a better c idal and acaricidal action than previously known compounds of analogous structure and of the same type of for the compounds of the present invention have been found to be more effective against biting and sucking insects such as the diamond moth or bean aphid as well as against flies such as the vinegar fly then compounds of a similar structure known from Patent Specification Examples E and the new compounds contribute to reducing the constant demand for new preparations in the field of The demand arises from the fact that the commercially available agents have to meet higher and higher particularly with respect to the protection of the such as low toxicity to animals and low rapid degradation in and on the plant with short times which have to elapse between application of the pesticide and and activity against resistant pests If phoric acid and bromine or acid ester ethanol and dimeth are used as starting the course of the reactions of the two process variants can be represented by the followin formula agent Acid binding agent The formulae to provide an unambiguous general definition of the starting compounds to be acid ester dichloride required as the starting material for the process variant can be prepared from acid ester dichloride for in German Offenlegungsschrift Published and The acid amides required as starting compounds for process variant are known from the literature published Netherlands Patent Applications 67 16721 and 68 and are easily obtainable on an industrial The following may be mentioned as examples of phosphoric acid to be reacted in the and phosphoric acid and the corresponding and piperidine The alcohols or amines required as starting substances are from the literature and can easily be prepared on an industrial The following may be mentioned individually as examples or or 2 propoxybutyl or butoxybutyl benzyl phenethyl alcohol and and also diethylamine ter Both variants of the process of the invention are preferably carried out in the presence of a solvent term includes a mere Practically all inert organic solvents can be used for this These in particular include aliphatic and aromatic for example methylene carbon tetrachloride and chlorobenzene for example diethyl dibutyl ether and for example methyl ethyl methyl isopropyl ketone and methyl isobutyl and for example acetonitrile and propionitrile All customary agents can be used as acid acceptors in process variant Alkali metal carbonates and alkali metal such as sodium carbonate and assium sodium meth late or eth late and potassium methylate or and aromatic or cyclic for example trieth lamine dimethylamine dimeth dimethylbenzylamine and have proved particularly an excess of the particular amine employed can also serve as the In variant for can serve as a The reaction temperature can be varied over a wide In both process the is generally carried out at 0 to preferably 15 to Generally the reaction is allowed to take place under normal In order to carry out process variant the bromine is generally reacted in 5 to 15 excess the Le A 14 779 7 vinylphosphoric acid optionally in the presence of a for example in one of the indicated solvents and at the indicated After completion of the the excess bromine may be eluted with sodium bisulphite solution and the reaction mixture purified in the usual way by drying and In process variant the phosphoric acid dihalide may be mixed with the appropriate alcohol in the presence of an agent and a at the indicated for one or more hours and a solution of the amine and fresh agent may then be added After completion of the the precipitate which has separated out may be either filtered off or eluted with water and the filtrate worked up in the usual manner by drying and centration or Some of the new compounds are obtained in the form of oils which can mostly not be distilled without position but can be freed of the last volatile and thus be by that is to say prolonged heating under reduced pressure to moderately raised They are characterised by the refractive Some of the compounds may be obtained a crystalline with a sharp melting The acid according to the invention are distinguished by outstanding especially and acaricidal activity against plant hygiene pests and pests of stored They couple a low phytotoxicity with a good action against sucking play a tickicidal microbiocidal For this the compounds according to the invention can be employed successfully as pesticides in plant protection and in the hygiene field and the field of protection of stored To the sucking insects there in the aphids such as the green peach aphid the bean aphid the bird cherry aphid the pea aphid pisi and the potato aphid the currant gall aphid the rosy apple aphid phis the mealy plum aphid and the cherry in scales and mealybugs example the oleander scale t s hederae and the soft scale as well as the grape mealybug thrips such as Hercinothrips and for example the beet bug the red cotton bug the bed bug the assassin bug prolixus and Chagas bug such as Buscelis bilobatus and hotettix bipunctatus In the case of the biting above all there should be mentioned butterfly caterpillars such as the moth maculipennis the gipsy moth the moth and tent caterpillar the cabbage moth a brassicae and the cutworm the large white butterfly the winter moth the oak tortrix and cotton the ermine moth the Mediterranean flour moth and greater wax moth Also to be classed with the biting insects are beetles for example the granary weevil philus granarius Galandra the Colorado beetle the dock beetle mustard beetle the blossom beetle the raspberry beetle the bean weevil celides the leather beetle the khapra beetle the flour beetle the northern corn billbug or Sitophilus zeamais the drugstore beetle the yellow mealworm and the grain beetle but also species living in the for example wireworms and larvae of the cockchafer such as the German cockroach American cockroach Madeira cockroach phaea or oriental cockroach the giant cockroach and the black giant cockroach f scus as well as denia for example the house cricket termites such as the eastern terranean termite and Hymenoptera such as for example the garden ant The Diptera comprise essentially the such as the vinegar fly the Mediterranean fruit fly the house fly Phormia and bluebottle fly as well as the stable for example mosquitoes such as the yellow fever mosquito the northern house mosquito and the malaria mosquito With the mites there are in the spider mites such as the spotted spider mite and the European red mite ran chus pilosus Panonychus gall for example the blackcurrant gall mite and for example the broad mite tarsonemus and the cyclamen mite such as the relapsing fever tick orus When applied against hygiene pests and pests of stored particularly flies and the compounds of the invention are also distinguished by an outstanding residual activity on wood and as well as a good stability to alkali on The active compounds according to the present invention can be converted into the usual such as pastes and These may be produced in known for example by mixing the active compounds with that liquid or solid or liquefied gaseous diluents or optionally with the use of that emulsifying agents dispersing foam forming In the case of the use of water as an organic solvents for also be used as auxiliary used aromatic such as benzene or alkyl chlorinated aromatic or aliphatic such as chloroethylenes or methylene aliphatic such as hexane or for example mineral oil such as butanol or glycol as well as their ethers and such as methyl ethyl methyl isobutyl ketone or or strongly polar such as dimethyl dimethyl sulphoxide or acetonitrile as well as By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and aerosol such as halogenated As solid diluents or there are preferably used ground natural such as or diatomaceous or ground synthetic such as silicic alumina or Preferred examples of emulsifying and agents include and anionic such as acid alcohol for example alk larylpol l col alkyl alkyl sulphates and sulphonates as well as albumin hydrolyzation and preferred examples of dispersing agents include sulphite waste liquors and methyl The active compounds according to the invention can be used as a mixture with other active The formulations in general contain from to 95 per The active compounds can be employed as such or in the of their formulations or the use forms prepared such as soluble dusting agents and They may be applied in the customary for example by dressing or The compositions may be diluted for actual and the active compound concentrations in the preparations can be varied within wide In they are from to preferably to by eight The active compounds can also be used with good success in the volume method where it is possible to apply formulations of up to strength or even the strength active compound by The invention therefore provides an insecticidal or acaricidal composition containing as active ingredient a compound according to the invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a agent The invantion also provides a method of combating insect or acarid pests which comprises applying to the pests or a habitat thereof a compound according to the invention alone or in the form of a composition containing as active ingredient a compound according to the invention in admixture with a diluent or The invention also provides crops protected from immediately prior to during the time of the a compound according to the invention was applied alone or in admixture with a diluent or It will seen that the usual methods of providing a harvested crop may be improved by the present The compounds according to the and the preparation and use of the compounds according to the are illustrated by the following Example A test parts by weight of acetone 1 part by weight of alk laryl polyglycol ether To produce a suitable preparation of active 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 Cabbage plants which had been heavily infested with peach aphids were sprayed with the preparation of the active compound until dripping After the specified periods of the degree of destruction was determined as a means that all the aphids were killed whereas means that none of the aphids were The active the concentrations of the active the evaluation times and the results can be seen from the following Table Table 1 Active compound Active compound Degree of concentration in after in Example B Critical concentration insects Test Tenebrio molitor 3 parts by weight of acetone 1 part by weight of alk laryl polyglycol To produce a suitable preparation of active 1 part by weight of active compound was mixed with the stated amount of the stated amount of emulsifier was added and the concentrate was diluted with water to the desired The preparation of active compound was timately mixed with The concentration of the active compound in the preparation was of practically no only the amount by weight of active compound per unit volume of which was given in ppm example was The soil was filled into pots and the pots were left to stand at room After 24 the test animals were introduced into the treated soil and after a further 48 hours the degree of effectiveness of the active compound was determined in by counting the dead and live test The degree of destruction was if all test insects had been killed and was if just as many test insects were still alive as in the case of the The active the amounts used and the results can be seen from the following Table Table 2 molitor Degree of truction in at an active compound concentration of Active compound 10 5 CH 5 90 50 Table 2 molitor Degree of truction in at an active compound concentration of Active compound 20 10 5 Example C Tetranvchus test parts by weight of acetone 1 part by weight of alk laryl polyglycol ether To produce a suitable preparation of active 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of desired Bean plants vulgaris which had a height of approximately were sprayed with the preparation of the active compound until dripping These bean plants were heavily infested with the common or spider mite etranvchus in all stages of After the specified periods of the ness of the preparation of active compound was determined by counting the dead The degree of destruction thus obtained was expressed as a 100 means that all the spider mites were killed whereas means that none of the spider mites were The active the concentrations of the active the evaluation times and the results can be seen from the following Table Table 3 Active Degree compound of truction tration in in after 2 days Active compound 95 0 Br Table 3 Active compound Degree Active compound of tration truction in 96 in after 2 days CCl Br 100 98 Br 98 98 H Br Table coutinued us Active Active of truction in in after 2 days Table compound Active tructi n in i af er 2 100 90 Table Active compound compound in ion in 2 days Example D Drosophila test 3 parts by weight of acetone 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active 1 part by weight of the active compound was mixed with the stated aaount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the 1 era of the solution of active compound was pipetted on a filter paper with a diameter of 7 The wet paper was placed on top of an open Petri dish containing 50 vinegar flies and was covered with a glass After the specified periods of the degree of destruction was determined as a means that all the flies were killed whereas means that none of the flies were The active the concentrations of the active the evaluation times and the results can be seen from the following Table Table 4 Active compound Active compound Degree of concentration in destruction by weight in after 1 day Example E Plutella test 3 parts by weight of acetone 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active 1 part by weight of the active compound was mixed with the stated aiaount of solvent containing the stated amount of emmlsifier and the concentrate was diluted with water to the desired Cabbage leaves were sprayed with the preparation of the active compound until dew and were then infested with caterpillars of the moth After the specified periods of the degree of destruction was determined as a means that all the caterpillars were killed whereas that none of the caterpillars were The active the concentrations of the active the evaluation times and the results can be seen the following Table 5 Active compound Active compound Degree of concentration destruction in by weight in after 3 days O Br 100 30 Active compound Active Degree of concentration destruction in by weight in after 3 days Example F 3 parts by weight of acetone 1 part by weight of alk laryl polyglycol ether To produce a suitable preparation of active 1 part by weight of the active was mixed with the stated amount of solvent containing the stated amount of emulsi and the concentrate was diluted with water to the desired Bean plants strongly infested with bean aphids are watered with the solution of the active compound in such a manner that the solution penetrates into the soil without wetting the leaves of the bean The active compound is taken up by the plant from the soil and thus reaches the attacked After the specified periods of the degree of destruction was determined as a means that all the aphids were killed whereas means that of the aphids were The active the concentrations of the Table 6 test Active compound Active compound Degree of concentration destruction in by weight in after 4 days Br 0 1 CH CH 35 g of acid were dissolved in 250 cm of carbon 1 g of were added to this solution and 3 thereafter g of bromine dissolved in 100 cm of carbon 23d tetrachloride were added dropwise at 20 to The batch was subsequently stirred for a further hours at and was then poured into ice Excess bromine was removed by washing with a dilute aqueous sodium sulphite This was followed by a wash with very dilute sodium hydroxide the batch was washed twice with 300 of water at a time and was dried over sodium After removing the drying the solvent was evaporated under reduced g of of lphosphoric acid remained 20 as a light brcwn oil of refractive index Example 2 78 g of acid were dissolved in 200 of A second solution consisting of 10 g of ethanol and 21 g of triethylamine in 50 of benzene was added dropwise to this solution at 20 to After completion of the the batch was stirred for a further half hour at and then cooled to and treated dropwise with a solution of 12 g of and 21 g 3 of triethylamine in 50 of To complete the reaction the mixture was stirred for a further half hour at Thereafter the lammonium hydrochloride which had precipitated was separated off and the benzene solution was washed three times with 300 of After drying acid remained in the form of an oil which solidified after standing for some time and then had a melting point of The following compounds of the formula can be manufactured analogously to the description in Example 1 l ies Yield of H 77 CH5 H H 50 C H 45 H H 58 H 4 9 R R 83 60 H 67 H H H H sec 4 9 H C 67 G3H7 67 H 67 H 67 H 79 H 67 H 62 H3 61 H 58 H H H 59 Yield melting point R H 57 H sec 5 j H 60 69 68 sec H 61 sec H H 63 sec H aec H sec sec H 64 sec sec H 68 H 71 H 71 H H sec H 65 2 H Physical properties Yield of R melting H 69 H sec 61 H H 69 GH5 G2H5 H 60 H 41 H H 52 H 56 H CH5 49 H GH 57 H 59 H H H H 65 H 65 H 67 H 69 H 62 H 77 H 35 H H 54 H 92 5 5 5 5 5 5 5 Physical properties or Yield melting of Λ point H CH3 69 73 H 71 H 69 H 78 3 74 74 H 61 H 64 H 59 H 4 9 65 64 73 67 H 57 The preparation of the acid re uired as starting products can be for according to the following 400 g of bromine were added dropwise over the course of 1 hour to a solution of 572 g mols of acid from German Offenlegungsschrift Published in 800 g of carbon tetrachloride and 1 g of at 5 to and the batch was stirred for four hours at this After two a further 1 g of was added to the mixture and after completion of the reaction the solvent was evaporated under reduced during which process the bath temperature did not exceed the after was stirred with 300 of petroleum the solution was cooled to and the acid dichloride was filtered Melting the was 870 g of insufficientOCRQuality

Claims (15)

1. 0-haloalk;/l-phosphoric acid ester-amides of the •areneral formula RO 0 It \ P-O-CHBr-CCl Br / (I) \ in which R is alkyl with 1 to 12 carbon atoms, haloalkyl with 1 to 4 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkoxyalkyl with up to 6 carbon atoms per alkyl and alkoxy moiety or phenylalkyl, and R' and R", which can be the same or different, are hydrogen or alkyl with 1 to 8 carbon atoms, or R' and R" together with the nitrogen atom form a 5- membered or 6-membered saturated heterocyclic ring, selected from piperidine and pyrrolidine.

2. Compound according to claim 1 in which R is allcyl with 1 to 10 carbon atoms, alkenyl with 2 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms per alkyl or alkoxy moiety, chloronethyl, chloroethyl or phenylalkyl with 1 to 3 carbon atoms in the alkyl moiety; and H* and R" are hydrogen or alkyl with 1 to 6 carbon atoms or form, together with the nitrogen atom, a piperidine or pyrrolidine ring.

3. Each of the compounds according to claim 1 hereinbefore specifically identified.

4. A process for the production of a compound according to any of claims 1-3 in which (a) an O-dichlorovinylphosphoric acid ester-amide of the general formula Le A 14 779 - 3 - R" in which R, R1 and R" have the meanings given in claim 1, is brominated, or (b) an 0-(l,2,-dibromo-2,2-dichloroethyl)-phosphoric acid ester-dihalide of the formula 0 Hal2P-0-CHBr-CCl2Br (III) in which Hal is halogen, is reacted with an alcohol of the general formula ROH (IV) in which R has the meaning given in claim 1, in the form of an allcali meaL salt, alkaline earth metal salt or ammonium salt or in the presence of an acid binding agent, and the resulting intermediate is reacted with an amine of the general formula in which R' and R" have the meanings given in claim 1, in the presence of an acid-binding agent.

5. A process according to claim 4(a) in which the compound of formula (II) is any of those hereinbefore specifically identified. #

6. A process according to claim 4(a) or 5 in which the bromination is carried out in the presence of a brominated- catalyst .

7. A process according to claim 4(b) in which the 5 compounds of formulae (IV) and (V) are any of those hereinbefore specifically identified.

8. A process according to any of claims 4-7 in which the reaction or reactions is or are effected at 15-45°C.

9. A process for the production of a compound according 10 to claim 1 substantially as hereinbefore described in any of Examples 1-3.

10. Compounds according to claim 1 whenever prepared by a process according to any of claims 4-9.

11. An insecticidal or acaricidal composition containing ^ as active ingredient a compound according to any of claims 1-3 or 10 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

12. A composition according to claim 11 containing from 20 0.1 to 95/'·' of the active compound by weight.

13. A method of combating insect or acarid pests which comprises applying to the pests or a habitat thereof a compound according to any of claims 1-3 or 10 alone or in the form of a composition containing as active ingredient a 25 compound according to any of claims 1-3 or 10 in admixture with a diluent or carrier.

14. A method according to claim 13 in which a composition is used containing from 0.0001 to 10^ of the active compound, by weight. 30

15. Crops protected from damage by insects or acarids by during the time of the growing, a compound according to any of claims 1-3 or 10 was applied alone or in admixture with a diluent or carrier. far fh*/ Applicants