US3911058A

US3911058A - O-(1,2-dibromo-2,2-dichloro-ethyl)-phosphoric acid diester-amides

Info

Publication number: US3911058A
Application number: US432775A
Authority: US
Inventors: Wilhelm Sirrenberg; Ingeborg Hammann; Bernhard Homeyer
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1973-01-19
Filing date: 1974-01-10
Publication date: 1975-10-07
Anticipated expiration: 1992-10-07
Also published as: GB1410314A; HU167095B; FR2214697A1; NL7400660A; IL44016A; DE2302569A1; LU69189A1; JPS49108022A; DD110750A5; BE809905A; DK133338B; AU6460874A; RO63675A; FR2214697B1; ATA36574A; IL44016A0; ZA74383B; IE38766B1; JPS49101545A; BR7400390D0

Abstract

O-(1,2-dibromo-2,2-dichloro-ethyl)-phosphoric acid diesteramides of the formula

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.

Description

Sirrenberg et al.

[54] O-( 1,2-DlBROMO-2,2-DlCHLORO-ETHYL)- PHOSPHORIC ACID DlESTER-AMIDES [75] Inventors: Wilhelm Sirrenberg, Sprockhoeverl;

Ingeborg l-lammann, Cologne; Bernhard Homeyer, Opladen, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Jan. 10,1974

[21] App], No: 432,775

[30] Foreign Application Priority Data Jan. I9, I973 Germany 2302569 {52] US. Cl. 260/950; 260/956; 260/959; 424/217; 424/219; 424/220 [5 I] Int. Cl. AOlN 9/36; C07F 9/24 [58] Field of Search 260/950, 956, 959

[56] References Cited UNITED STATES PATENTS 3,584,085 6/I97I Hartmann 260/959 X FOREIGN PATENTS OR APPLICATIONS 592,764 2/I960 Canada H 260/959 Primary E.mminer-Richard L, Raymond Attorney, Agent, or Fz'rmBurgess, Dinklage & Sprung [57] ABSTRACT O-( I ,2-dibromo-2,2-dichloro-ethyl)-phosphoric diesteramides of the formula Oct. 7, 1975 acid moiety, 0r phenylalkyl, and

R and R each independently is hydrogen or alkyl of I to 8 carbon atoms, or R and R" together with the nitrogen atom form a flve-membercd or six-membered heterocyclic ring,

which possess insecticidal, acaricidal, fungicidal. tickicidal and microbicidai properties.

7 Claims, N0 Drawings O-( l,2-DIBROMO-2,2-DICHLORO-ETHYL)- PHOSPHORIC ACID DlISTER-ANIIDES The present invention relates to and has for its objects the provision of particular new O-(alkyl, haloalkyl, alkenyl, alkoxyalkyl or phenylalkyl)-O( l,2- dibromo-Z,Z-dichloro-ethyl )-N-( mono or di-substituted)-phosphoric acid diester-amides, which possess insecticidal, acaricidal, fungicidal, tickicidal or microbicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersibleyarrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids, fungi, ticks and microbes, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification DOS l,567,076 and US. Pat. No. 3,068,270 that O-haloalkylphosphoric acid esters, for example 0,0- diethyl-(Compound A) or 0,0-dimethyl-O-( l ,2- dibromo-2,2-dichloroethyl)-phosphoric acid ester (Compound B), possess an insecticidal activity.

The present invention provides O-haloalkylphosphoric acid ester-amides of the general formula u t I P-OCHBrCCl- Br R N m in which R is alkyl of l to l2 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 l to 8 carbon atoms, or R' and R" together with the nitrogen ring form a five-membered or six-membered heterocyclic ring. Preferably, R is alkyl of l to l0 carbons atoms, lower alkenyl of 2 to 4 carbon atoms, alkoxyalkyl with l to 4 carbon atoms per alkyl or alkoxy moiety, chloromethyl, chloroethyl or phenyl-lower alkyl with l to 3 carbon atoms in the alkyl moiety; and R and R are hydrogen or alkyl of l to 6 carbon atoms or form, together with the nitrogen atom, a piperidine, pyrrolidine, morpholine or thiomorpholine ring.

Surprisingly, the O-haloalkylphosphoric acid esteramides according to the invention have a better insecticidal, especially soil-insecticidal, and acaricidal action than previously known compounds of analogous structure and of the same type of action. The products according to the present invention thus represent a genuine enrichment of the art. Furthermore, the new compounds contribute to satisfying the constant demand for new preparations in the field of pesticides. The demand arises from the fact that the commercially available agents have to meet higher and higher standards, particularly with respect to the protection of the environment, such as low toxicity to warm-blooded animals and low phytotoxicity, rapid degradation in and on the plant with short times which have to elapse between application of the pesticide and harvesting, and activity against resistant pests.

The invention also provides a process for the production of an O-haloalkylphosphoric acid ester-amide of the formula (I) in which a. an O-dichlorovinylphosphoric acid ester-amide of the general formula PO-CH=CCI2 "J R' in which R, R and R" have the abovementioned meanings,

is brominated, optionally in the presence of a catalyst, or b. an O( l,2-dibromo-2,2-dichloroethyl )-phosphoric acid ester-dihalide of the formula 0 ll Hal POCHBrCCl,Br (1m in which Hal is halogen, preferably chlorine, is reacted with an alcohol of the general formula ROH in which R has the abovementioned meaning, in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt or in the presence of an acidbinding agent, and the resulting intermediate is reacted, optionally without intermediate isolation, with an amine of the general formula -Continued c rgo u P*0CHBr CCl Br cl O4 l,Z-dibromo-Z,Z-dichloroethyl )-phosphoric acid ester dichloride required as the starting material for the process variant (b) can be prepared from bromine and O-(2,2-dichlorovinyl)-phosphoric acid ester dichloride, described in German Published Specification DOS 1,903,168.

The O-( 2,2-dichlorovinyl)-phosphoric acid ester amides (ll required as starting compounds for process variant (a) are known from the literature (compare published Netherlands Patent Applications 67,16721 and 68,06396) and are easily obtainable on an indus trial scale,

The following may be mentioned as examples of O- vinylphosphoric acid ester-amides to be reacted in the process:

O-mcthyl-, O-ethyl-, O-n-propyl-, O-iso-propyl-, O-nbutyl-, O-isobutyl-, Osec. butyl-, O-tert.-butyl-,

O-pentyl-, O-hexyl-, O-heptyl-, O-octyl-, O-dccyl-, 0-2- ethylbuty1-, O-2,2-dimethyl-butyl-, O-2,2-dimcthy|hexyl-, O-2,Z-dimethyloctyl-, O-vinyl-, O-allyl-, O-butenyl-, O-chloromethyl-,

O-chloroethyl, O-benzyl-, O-phenethyl-, O-isophenpropyl-, O-methoxy-methyl-, O- methoxyethyl-, O-methoxypropyl-, O-methoxybutyL, O-ethoxymethyl-, O-ethoxyethyl-, O-ethoxrp py O-ethoxybutyl, On-propoxymethyl-, npropoxyethyl-, O-iso-propoxyethyland O-nbutoxyethyl-O-( 2,2dichlorovinyl )-phosphoric acid ester-amide and the corresponding N-methyl, N.N-dimeth vl, N-ethyl, N,N-diethyl, N-n-propyl,

N,N-di-n-pr0pyl, Nisopropyl, N,N-di-iso-propyl,

N-n-butyl, N-iso-butyl, N-tert.-butyl, N-sec.-butyl,

N-pentyl, pyrrolidine, piperazine and piperidine derivatives The alcohols (1V) or amines (V) required as starting substances are known from the literature and can easily be prepared on an industrial scale. The following may be mentioned individually as examples thereof: methanol, ethand, nor iso-propanol, n-, sec.-, isoor ten.- butanol, pentanol, hexanol, heptanol, octanol, decanol,

Z-methylbutanol, Z-ethylbutanol, 2,2-

dimethylbutanol, Z-ethylhexanol, dimethylhexanol, 2,2 dimethyloctanol, vinyl. allyl, butenyl, chloromethyl, chloroethyl, methoxymethyl, ethoxyethy], propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, ethoxybutyl, propoxybutyl or butoxybutyl alcohol, benzyl alcohol, phenethyl alcohol and l-phenylpropanol-(3) and also ammonia, methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, iso-propylamine, di-npropylamine, di-iso-propylamine, n-butylamine,

di-n-butylamine, iso-butylamine, di-iso-butylamine,

sec.-butylamine, di-sec.-butylamine, tert.- butylamine, di-tert.-butylamine, pentylamine and hexylamine, as well as ethyl-n-propylamine, ethyl-iso-propylamine, piperidine, piperazine, pyrrolidine, morpholine and thiomorpholine,

Both variants of the process of the invention are preferably carried out in the presence of a solvent which term includes a mere diluent. Practically all inert organic solvents can be used for this purpose. These in particular include aliphatic and aromatic optionally chlorinated hydrocarbons, for example benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone', and nitriles, for example acetonitrile and propionitrile.

All customary acid-binding agents can be used as acid acceptors in process variant (h). Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate, sodium methylate or ethylate and potassium methylate or ethylate, and aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularly satisfactory.

Finally, an excess of the particular amine (V) employed can also serve as the acid-binding agent.

In variant (a), l,l -dimethyl-l,l'-dicyanoazoethane, for example, can serve as a catalyst.

The reaction temperature can be varied over a wide range. In both process variants, the reaction is generally carried out at 0 to preferably 15 to 45C. Generally the reaction is allowed to take place under normal pressure.

In order to carry out process variant (a), the bromine is generally reacted in 5 to 15% excess with the O- dichlorovinylphosphoric acid ester-amide (ll), optionally in the presence of a catalyst, for example l,ldimethyl-l,1'-dicyanoazoethane, in one of the indicated solvents and at the indicated temperatures. After completion of the reaction, the excess bromine may be eluted with sodium bisulfite solution and the reaction mixture purified in the usual way by washing, drying and distillation.

In process variant (b), the phosphoric acid esterdihalide ([11) may be mixed with the appropriate alcohol (1V) in the presence of an acid-binding agent and a solvent, at the indicated temperatures, for one or more hours and a solution of the amine (V) and fresh acid-binding agent may then be added dropwise. After completion of the reaction, the salt-like precipitate which has separated out may be either filtered off or eluted with water and the filtrate worked up in the usual manner by washing, drying and concentration or distillation.

Some of the new compounds are obtained in the form of oils which mostly can not be distilled without decomposition but can be freed of the last volatile constituents, and thus be purified, by so-called slight distillation, that is to say prolonged heating under reduced pressure to moderately raised temperatures. They are characterized by the refractive index. Some of the compounds may be obtained in a crystalline form, with a sharp melting point.

The O-haloalkylphosphoric acid ester-amides according to the invention are distinguished by outstanding insecticidal, especially soil-insecticidal, and acaricidal activity against plant pests, hygiene pests and pests of stored products. They couple a low phytotoxicity with a good action against sucking and biting insects and in addition some of the compounds display a fungicidal, tickicidal and/or microbiocidal action. For this reason, 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 products.

To the sucking insects there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Mac-rusiphum pisi), and the potato aphid (Macrosiphum solumfolii), the currant gall aphid (Cryptomyzus kursclzelrz'), the rosy apple aphid (Sappap/zis mall), the mealy plum aphid (Hyulopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the Oleander scale (Aspidiorus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudatoccus murin'mus); thrips ("llzysanopteray such as Her-cine llirips fenwralis, and bugs, for example the beet bug (Piexmu quudruta), the red cotton bug (Dysdericus in Iermedius), the bed bug (Cl'mex lecrularius), the assassin bug Rlmdnius prolixux) and C hagas bug (7)"z'at0mu lnfexmns) and, further, cicadas, such as Euscelis bz'lobams and Neplzotemx bipunctatus.

In the ease of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipemiis), the gypsy moth (Lymamria dispar), the browntail moth (Euprocris clirysorrhuea) and tent caterpillar (Maluc'usumu neustriu); further the cabbage moth (Mumestru bramic-ae) and the cutworm (Agrotis .s'egemm), the large white butterfly (Pieris Brassicae), the small winter moth (Cheimalobia hrumula), the green oak tortrix moth (Turtrix viridana), the fall armyworm Laplrvgma frugiperdu) and cotton worm (Pmdenia limru), the ermine moth (H vponomeula padella), the Mediterranean flour moth (Epheslia kz'l/zniella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Culeupteru), for example the granary weevil (Situplzllm granarlus Calandra granaria), the Colorado beetle (Leprinolarsu decemlineum), the dock beetle (Gaslmphysu i'iridula), the mustard beetle (Plzaedun cochlear-me), the blossom beetle (Meligerlzes aeneus'), the raspberry beetle (Bylurus mmerzmsus), the bean weevil (Bruclu'dius Acanllzosc'elides obtectus), the leather beetle (Hermes-res fliSf/li), the khapra beetle (Tmgudermu granurium), the flour beetle (Tribolium cuxtaneum), the northern corn billbug (Calandru or Simplzilus zeamuis), the drugstore beetle (Slegohium paniceum), the yellow mealworm (Tenehriu molitur), and the saw-toothed grain beetle (Oi vzaephllur surina- IlltllAlS), and also species living in the soil, for example wireworms (Agrimes spec.) and larvae of the cockchafer (Melulonlhu melulonrlm); cockroaches, such as the German cockroach (Blarrella germanica), American cockroach (Periplanera americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blarta orienlalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivirra; further, Orlhoptera, for example the house cricket (Ac/zeta domesticus); termites such as the eastern subterranean termite (Reticulr'rermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly (Drosopln'la melanogaster), the Mediterranean fruit fly (Ceratitis capitam), the house fly (Musca domestica), the little house fly (Fannie: canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora eryrlzrocephala) as well as the stable fly (Smmoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypli the northern house mosquito (Cu/ex pipiens) and the malaria mosquito (Anopheles step/tense).

With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranyc'hus urricae) and the European red mite (Paraterranychus pilosus Panonychur ulmi), gall mites, for example the blackcurrant gall mite (i Eriophyes ribis) and tarsonemicls, for example the broad mite (Hemitursonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornitlzodorus muubam).

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the compounds of the invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or ex tenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsiflable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc. halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc), cycloalkanes (e.g. cyclohexane, etc), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (eg glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone methyl isobutyl ketone, cyclohexanone, etc), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, atta pulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc. whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates. alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearatc, sodium olcate, etc); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose. etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, fungicides, tickicides and microbicides, or bactericides, rodenticides, nematocides, herbicides, fertilizers. growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0. l-957r by weight, and preferably 0.590% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0000 l] preferably 0.0ll7r. by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount ofthe active compound which is effec tive for the purpose in question and which is generally between about ().()U0l-95.7r, and preferably 0.0l-957r, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment. in finely divided form, e.g. average particle diameter offrom 50-100 microns, or even less. i.e. mist form, for example by airplane crop spraying techniquesv Only up to at most about a few liters/hectare are needed, and often amounts only up to about l5 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about by weight of the active compound or even the active substance alone, e .g. about 20-1007: by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids, fungi, ticks and bacteria, and more particularly methods of combating at least one of insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (e) such fungi, (d) such ticks, (e) such bac teria, and (f) the corresponding habitat thereof, i.ev the locus to be protected, a correspondingly conbative or toxic amount, i.e. an insecticidally, acaridically, fungi cidally, tickicidally or bactericidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, gassing, dressing, or encrusting, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 PO-CHBrCCl,Br CH=;\

35 g (0.15 mole) of O-methyl-O-(2,2-dichlorovinyl)- N,N-dimethylphosphoric acid diester-amide were dissolved in 250 cc of carbon tetrachloride. l g of l,] dimethyl-l,l '-dicyanoazoethane were first added to this solution, and thereafter 26.2 g of bromine dissolved in l00 cc of carbon tetrachloride were added dropwise at 20 to 30C. The batch was subsequently stirred for a further 3 hours at 30C and was then poured into ice water. Excess bromine was removed by washing with a dilute aqueous sodium sulfite solution. This was followed by a wash with very dilute sodium hydroxide solution. Finally, the batch was washed twice with 300 cc of water each time and was dried over sodium sulfate. After removing the drying agent, the solvent was evaporated undcr reduced pressure. 40.5 g (68.5% of theory) of O-methyl-O-(l,2-dibromo-2,2- dichloroethyl)-N,N-dimethylphosphoric acid diesteramide remained as a light brown oil of refractive index n 1.5149.

EXAMPLE 2 Four hundred g of bromine were added dropwise over the course of 1 hour to a solution of 572 g (2.47 moles) of O-(2.2-dichlorovinyl )-phosphoric acid esterdichloride (known from German Published Specification DOS l,903,l68) in 800 g of carbon tetrachloride and l g of l,l '-dimethyl-l,l '-dicyano-azoethane at 50 to 55C and the batch was stirred for four hours at this temperature. After two hours, a further 1 g of 1.1- dimethyl-l ,l '-dicyanoazoethane was added to the mixture and after completion of the reaction the solvent was evaporated under reduced pressure, during which process the bath temperature did not exceed 40C, the residue, after cooling, was stirred with 300 cc of petroleum ether, the solution was cooled to C and the O- l ,2-dibromo-2,2-dichloroethyl )-phosphoric acid esterdichloride was filtered off. Melting point: 56C; the yield was 870 g (90% of theory).

78 g (0.2 mole) of O-( l,2-dibromo-2.Z-dichloroethyl)-phosphoric acid ester-dichloride were dissolved in 200 cc of benzene. A second solution consisting of IO g of ethanol and 2] g of triethylamine in 50 cc of 5 benzene was added dropwise to this solution at to C. After completion of the addition, the batch was stirred for a further half hour at C and then cooled to 20C and treated dropwise with a solution of 12 g of iso-propylamine and 2] g of triethylamine in cc of benzene. To complete the reaction the mixture was stirred for a further half hour at 30C. Thereafter the triethylammonium hydrochloride which had precipitated was separated off and the benzene solution was washed three times with 300 cc of water. After drying and concentration 67 g (79.5% of theory) of O-ethyl- O-( l ,2-dibromo-2,2-dichloroethyl )-N-isopropylphosphoric acid diester-amide remained in the form of an oil which solidified aftcr standing for some time and then had a melting point of C.

Table 1 -Continued P-OCHBr(Cl Br (I) R N Physical properties in or Yicld (pd R R R" melting (/1 of N0 point |"C]) theory) 126 n-C H.,OCH -CH H lst)C;;H 1.4900 61.5 127 n-C,H..OCH CH H nC,,H., 1.4900 64 12s n-C,H OCH- CH H tea-(3Hn 1,4395 59 129 n-C,H ,OCH CH H iso-C H 1.4900 68.5 nu n-C,H..0 CH CH CH CH 1.4919 65 131 nC H,,O-CH CH 6 H (3H,. 1.42470 64 132 n--C.,H OCH CH nC; H n-C H 1.4830 73 133 iS0C; H n-C; H n-C H 1.4879 67 134 CH2=CHCH2 CH, 1.5229 57 EXAMPLE 4 Table 2-Continued Critical concentration test/soil insects ('lcnehrio molitor test) Test insect: Tenebrio molitor gigs: 9;; Solvent: 3 parts by weight of acetone an active compound concentration of tEmulSlfief. 1 part by weight of alkylaryl polyglycol Acme compound 2U 10 5 ppm 8 tit.

To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed CH HCCI- Br 100 60 with the stated amount of solvent, the stated amount of r emulsifier was added and the concentrate was diluted 2 with water to the desired concentration. 30 C H W The preparation of active compound was intimately 7 p o H CC|2Br mo 80 30 1 mixed with soil. The concentratlon of the active com- C1 r- 1; pound in the preparation was of practically no impor- [18) r lance; 2

v H only the amount by we ght of active compound per CH unit volume of soil, WhlCh was given in ppm (for ex- O HCCl Br 90 50 ample mg/l was decisive. The soil was filled into (C H Br pots and the pots were left to stand at room tem- A 5 I (52) perature. After 24 hours. the test animals were in CQHS H troduced into the treated soil and after a further 48 0 hours the degree of effectiveness of the active com- C H NH Q 100 IOU 5tJ pound was detemiined in "/1 by counting the dead Br and live test insects. The degree of destruction was (46) 100% if all test insects had been killed and was 0% ifjust as many test insects were still alive as in th CH,, Case of the control. 1 (CH H N OfHCCl,Br 100 100 so The active compounds, the amounts used and the re- 2 Br sults can be seen from the following Table 2: C H (47) CH;, O?HCCl Br 100 51) Table 2 C,H,,NH Br (4 (Tcncbrio molitor test) 55 Degree of destruction in "/r at an active mmpuund CH -O-ifH-CChBr lUU 100 50 concentration of C H B Active compound 20 l0 5 ppm 2 CH N r l CH" (49) sec.( H O W CH3 'O\ OCH([CI 100 30 Cl: 0 O u i-C;.H;NH I E 47 r Br CH, r r i l C H (known) (B) 2 5- -O- H-CCLBr 100 50 OiHC'Cl-,Br 0 0 (1 CH;

H,-,O r CH LH--l\l (92) r (known) (A) EXAMPLE 5 Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: l 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 concentrate was diluted with water to the desired concentration.

Bean plants (Plzaseolus vulgaris), which had a height of approximately l0-3O cm. were sprayed with the preparation of the active compound until dripping wet. These bean plants were heavily infested with the common or two-spotted spider mite (Tetranyc/zus urricae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound was determined by counting the dead mites. The degree of destruction thus obtained was expressed as a percentage: i007 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 compounds, the evaluation times and the results can be seen from the following Table 3:

Table 3 (Tetrunychus test) Active Degree compound of desconecntruction [ration in'lr in'/? after Active compound 2 days 0 CH. 01 95 j o- H-CCl Br 0.01 0 011 0 r (known) (H) CH; O-CH. -c1-1. ii 0.1 100 i z 0 H Cc'1. .Br 0.01 as C.H.-O-CH. CH 0.1 100 x O\ -o-- 11*cc1 13r 0.01 99 (H -NH Br (H41 f i-C; H; 0.1 100 l o HCCl. .Br 0.01 93 ("HM-NH c H 0.1 100 I -o H-(Cl Br 0,01 15 CH;;-NH

Br 34) on ll 01 100 P "HCCL Br 0.01 c 11, NH

Br (10) iC.H T 0.1 99 i -o H-CChBr 0.01 99 C.,H4-,N

CH.- if 0.1 100 O P--O* H cu1. .Br 0.01 C,H;NH l

c H d 0.1 911 i i-0 H cc1. ,Br 0.01 911 C:,H7NH T (36 1 i-C H.- ll 01 o* H-CChBr 0.01 91 c H NH T 1-1 l 0.1 100 CH P 0 H-CChBr 0.01 100 C3H1N 0.001 25 i-c. H. 0.1 100 i o HCCl. Br 0.01 98 i-c,.H. NH

(Tclrunychus test) EXAMPLE 6 2. A compound according to claim I in which R is alkyl of l to l() carbon atoms, alkenyl of 2 to 4 carbon atoms, alkoxyalkyl with l to 4 carbon atoms per alkyl or alkoxy moiety. chloromethy], chloroethyl or phenylalkyl with l to 3 carbon atoms in the alkyl moiety; and R and R" each independently is hydrogen or alkyl of l to 6 carbon atoms.

3. A compound according to claim 1 wherein such compound is O-ethyl-O-( |,2-dibromo-2,2-dichloroethyl)-N-ethylphosphoric acid diester-amide of the for- Myzus test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: I 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 10 diluted with water to the desired concentration.

Cabbage plants (Brasxic-a oleracea) which had been mum: heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active com- C2H',)0\ pound until dripping wet. X5 2 After the specified periods of time, the degree of de- H\ .struction was determined as a percentage: l007r means C,,H

that all the aphids were killed whereas 0% means that none of the aphids were killed. 4. A compound according to claim I wherein such The active compounds, the concentrations of the accompound is O-isopropyl-O-( l,2-dibromo-2,2- tive compounds, the evaluation times and the results dichloro-ethyl)-N-methylphosphoric acid diestercan be seen from the following Table 4: amide of the formula:

Table 4 (My7us test) Active compound Active compound Degree of destruction concentration in 9? after I day in 7! H. if

PO H-CC|:Br 0.1 100 c u o (ml r 0.001 0 (known) (A) c HE,()VCH. .-CHZ

' 0\ o HCCl. .Br u.| mu (H;,-NH I out as r l).ll(]l in t- H.. if

I 0\ o H CCL Br 0.] m0 (H -NH f um m0 Br (1.001 35 I34) H u.| 100 H 001 100 (H H P- o-- H-CChBr 0.0m 2m FtyH qv l It will be appreciated that the instant specification CH and examples are set forth by way of illustration and not limitation and that various modifications and H\ changes may be made without departing from the spirit 5 and scope of the present invention.

What is claimed is: A 2 dib -2 2 di h| h 5. A compound according to claim I wherein such phosphoric acid dicster-amide of the formula compound is O-isopr0pyl- L Q- dichloro-ethyl)-N-ethyl-phosphoric acid diester-amide of the formula:

H\ in which C2H/ I R is alkyl of l to l2 carbon atoms, halo-lower alkyl, alkenyl with 2 to 6 carbon atoms, alkoxyalkyl with up to 6 carbon atoms per alkyl and alkoxy moiety. 6. A compound according to claim 1 wherein such or phenylalkyl. and compound is O-sec.butyl-O-( l ,2-dibromo-2,2- R' and R" each independently is hydrogen or alkyl dichloro-ethyl) N-isopropylphosphoric acid diesterof l to 8 carbon atoms. amide of the formula:

dichloro-ethyl)-N-methyl-phosphric acid diester- SCCC;H| amlde of the formula. k A CHK QH. 5 -O-CHBrCCl Br 7. A compound according to claim I wherein such (2H,, compound is O-methoxyethyI-O-(l.2-dibrom0-2,2-

Claims

1. AN O-(1,2DIBROMO-2,2-DICHLORO-ETHYL)-PHOSPHORIC ACID DIESTER-AMIDE OF THE FORMULA

2. A compound according to claim 1 in which R is alkyl of 1 to 10 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms per alkyl or alkoxy moiety, chloromethyl, chloroethyl or phenylalkyl with 1 to 3 carbon atoms in the alkyl moiety; and R'' and R'''' each independently is hydrogen or alkyl of 1 to 6 carbon atoms.

3. A compound according to claim 1 wherein such compound is O-ethyl-O-(1,2-dibromo-2,2-dichloro-ethyl)-N-ethylphosphoric acid diester-amide of the formula:

4. A compound according to claim 1 wherein such compound is O-isopropyl-O-(1,2-dibromo-2,2-dichloro-ethyl)-N-methylphosphoric acid diester-amide of the formula:

5. A compound according to claim 1 wherein such compound is O-isopropyl-O-(1,2-dibromo-2,2-dichloro-ethyl)-N-ethyl-phosphoric acid diester-amide of the formula:

6. A compound according to claim 1 wherein such compound is O-sec.-butyl-O-(1,2-dibromo-2,2-dichloro-ethyl)-N-isopropyl-phosphoric acid diester-amide of the formula:

7. A compound according to claim 1 wherein such compound is O-methoxyethyl-O-(1,2-dibromo-2,2-dichloro-ethyl)-N-methyl-phosphoric acid diester-amide of the formula: