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

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

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US3911058A
US3911058A US432775A US43277574A US3911058A US 3911058 A US3911058 A US 3911058A US 432775 A US432775 A US 432775A US 43277574 A US43277574 A US 43277574A US 3911058 A US3911058 A US 3911058A
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ethyl
carbon atoms
alkyl
dibromo
dichloro
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Wilhelm Sirrenberg
Ingeborg Hammann
Bernhard Homeyer
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds

Definitions

  • 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,
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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,
  • Both variants of the process of the invention are preferably carried out in the presence of a solvent which term includes a mere diluent.
  • 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.
  • aliphatic and aromatic optionally chlorinated hydrocarbons for example benzene, toluene,
  • 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.
  • 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.
  • 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.
  • a catalyst for example l,ldimethyl-l,1'-dicyanoazoethane
  • the excess bromine may be eluted with sodium bisulfite solution and the reaction mixture purified in the usual way by washing, drying and distillation.
  • 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.
  • 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.
  • aphids 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 (Pseudatocc
  • butterfly caterpillars 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)
  • beetles 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 Simplzi
  • 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).
  • mosquitoes such as the yellow fever mosquito (Aedes aegypli the northern house mosquito (Cu/ex pipiens) and the malaria mosquito (Anopheles step/tense).
  • mites 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).
  • the spider mites 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)
  • the compounds of the invention 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.
  • 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
  • conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsiflable concentrates,
  • 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.
  • 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.
  • 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.
  • ground natural minerals e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, atta pulgite, montmorillonite, kieselguhr, etc.
  • ground synthetic minerals e.g.
  • 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.
  • 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,
  • 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
  • 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.
  • 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.
  • 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.
  • pests e.g. insects, acarids, fungi, ticks and bacteria
  • 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
  • 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.
  • 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.
  • O-(2.2-dichlorovinyl )-phosphoric acid esterdichloride known from German Published Specification DOS l,903,l68
  • 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.
  • 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.
  • a compound according to claim 1 wherein such compound is O-ethyl-O-(
  • 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.
  • 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:
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US432775A 1973-01-19 1974-01-10 O-(1,2-dibromo-2,2-dichloro-ethyl)-phosphoric acid diester-amides Expired - Lifetime US3911058A (en)

Applications Claiming Priority (1)

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DE2302569A DE2302569A1 (de) 1973-01-19 1973-01-19 0-halogenalkylphosphorsaeureesteramide, verfahren zu ihrer herstellung und ihre verwendung als insektizide und akarizide

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US (1) US3911058A (tr)
JP (2) JPS49108022A (tr)
AT (1) ATA36574A (tr)
AU (1) AU6460874A (tr)
BE (1) BE809905A (tr)
BR (1) BR7400390D0 (tr)
DD (1) DD110750A5 (tr)
DE (1) DE2302569A1 (tr)
DK (1) DK133338C (tr)
FR (1) FR2214697B1 (tr)
GB (1) GB1410314A (tr)
HU (1) HU167095B (tr)
IE (1) IE38766B1 (tr)
IL (1) IL44016A (tr)
LU (1) LU69189A1 (tr)
NL (1) NL7400660A (tr)
RO (1) RO63675A (tr)
TR (1) TR17602A (tr)
ZA (1) ZA74383B (tr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6384261B1 (en) * 1996-03-26 2002-05-07 Texas Biotechnology Corporation Phosphoramidates, phosphinic amides and related compounds and the use thereof to modulate the activity of endothelin

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3584085A (en) * 1967-07-18 1971-06-08 Atlas Chem Ind Phosphoramidates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB784986A (en) * 1952-10-29 1957-10-23 Fmc Corp Manufacture of organic phosphorus compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3584085A (en) * 1967-07-18 1971-06-08 Atlas Chem Ind Phosphoramidates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6384261B1 (en) * 1996-03-26 2002-05-07 Texas Biotechnology Corporation Phosphoramidates, phosphinic amides and related compounds and the use thereof to modulate the activity of endothelin

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GB1410314A (en) 1975-10-15
HU167095B (tr) 1975-08-28
FR2214697A1 (tr) 1974-08-19
NL7400660A (tr) 1974-07-23
IL44016A (en) 1977-01-31
DE2302569A1 (de) 1974-07-25
LU69189A1 (tr) 1974-08-19
JPS49108022A (tr) 1974-10-14
DD110750A5 (tr) 1975-01-12
BE809905A (fr) 1974-07-18
DK133338B (da) 1976-05-03
AU6460874A (en) 1975-07-17
RO63675A (fr) 1978-10-15
FR2214697B1 (tr) 1977-08-26
ATA36574A (de) 1975-07-15
IL44016A0 (en) 1974-05-16
ZA74383B (en) 1974-11-27
IE38766B1 (en) 1978-05-24
JPS49101545A (tr) 1974-09-25
BR7400390D0 (pt) 1974-08-22
IE38766L (en) 1974-07-19
DK133338C (da) 1976-09-27
TR17602A (tr) 1975-07-23

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