US3903207A - N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters - Google Patents

N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters Download PDF

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Publication number
US3903207A
US3903207A US240282A US24028272A US3903207A US 3903207 A US3903207 A US 3903207A US 240282 A US240282 A US 240282A US 24028272 A US24028272 A US 24028272A US 3903207 A US3903207 A US 3903207A
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compound
formula
iminoformic
dialkyl
thiono
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Hellmut Hoffmann
Ingeborg Hammann
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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
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines

Definitions

  • the present invention relates to and has for its objects the provision of particular ne N-(O,S-dialkyl (thiono)-thiolphosphoryl)-iminoformic acid alkyl esters which possess insecticidal and acaricidal properties.
  • active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such'compounds in a new way es- (Ila) pecially for combating pests. e.g. insects and acarids. with other and further objects becoming apparent from a study of the within specification and accompanying examples.
  • N-(0,0-dialkylphosphoryl)- imino-dithiocarbonic acid dialkyl esters such as N- (0,0-diethylphosphoryl )-imino-dithiocarbonic acid diethyl ester (Compound A) have insecticidal properties.
  • the present invention provides N-(O.S-dialkyl(thionothiolphosphoryl) iminoformic acid alkyl esters of the formula in which X is oxygen or sulfur, and R, R and R" each independently is lower alkyl with l to 6 carbon atoms.
  • R and R each is a straight chain or branched lower alkyl with l to 4 carbon atoms, such as methyl, ethyl, npropyl, isopropyl, n-butyl. isobutyl, sec.-butyl or tert.-butyl, and R" is a lower alkyl with l-3 carbon atoms.
  • the compounds according to the invention have a rather better insecticidal, especially sys temic and acaricidal activity than the known N-(0.0- dialkylphosphoryl)-iminodithio carbonic acid dialkyl esters of analogous constitution and the same direction of activity. They therefore represent a genuine enrichment of the art.
  • the invention also provides a process for the produc tion of a N-(O.S-dialkyl-(thiono)-thiolph0sphoryl- )imino formic acid alkyl esters of the formula (I) in which an O,S-dialkyl-(thiono)-thiolphosphoric acid ester amide of the formula in which X, R and R have the meanings stated above,
  • i 2 is reacted with an ortho-formic acid alkyl ester of the formula in which i R has the meaning stated above.
  • Examples of the compounds of formulae (II) and (III) include: O.S-dimethyl-. ().S-diethyl-. O.S-di-npropyl-. O.S-di-isopropyl-. ().S-di-nbutyl-. O.S-di-sec.- butyl-, O.S-di-isobutyl-, O.S-ditert.-but ⁇ 'l'. O-mcthyl- S-ethyl-, O-methyl-S-n-propyL, O-methyl-S-isopropyl- O-methyl-S-n-butyl-.
  • the process according to the present invention can be carried out with the use of a solvent, which term includes a mere diluent. Preferably, however, no solvent is used for the reaction.
  • an acid catalyst may be used.
  • p-toluene-sulfonic acid for example p-toluene-sulfonic acid.
  • reaction temperatures can be varied over a wide range.
  • the reaction is carried out at about l()0-2()()C, preferably about l4()l6()C.
  • reaction is carried out at normal pressure.
  • the compounds of the invention are in most cases i obtained as colorless or slightly yellow oils which can mostly be distilled without decomposition. If not, they can be freed from volatile impurities by .slight distilla tion, that is, longer heating to moderately elevated temperatures under reduced pressure.
  • the refractive index is particularly useful for theircharacterization.
  • the compounds of the invention are distinguished by outstanding insecticidal and acaricidal effectiveness against crop pests.
  • hygiene pests and pests of stored products have a good activity against both sucking and biting insects and mites (Acarina). They are at the same time only slightly phyto toxic and have a five-fold to 10-fold lower toxicity to warm-blooded animals than do the compounds from which they are derived.
  • the compounds of the invention can-the-reforebe used successfully as pesticides in crop protectioniand the protection of stored products as well as in the field of hygiene. 1
  • aphids such as the green peach aphid (Nlvzus pursicuu). the bean aphid (Durull's fir/nu). the bird cherry aphid (Rlmpuloxiplumi pm).
  • pea aphid Mm-rm'ip/mm pisi
  • potato aphid Mucrm-ip/mm salami/Mil
  • the currant gall aphid Crypmmyzus kmisv/u'lfi
  • the rosy apple aphid SappuphLs' nzuli
  • the mealy plum aphid Hyulupu'rus urumlinis
  • Mygm' ('w'usi) in addition. scales and mealybugs (Coccina). for example the.
  • oleander scale (Avpidiums lu'dm-uc) and the soft scale (Lr't'u'nimn hcxpvrir/mn) as well as the grape mealybug (Pscmloummmurilimm' thrips ('lhysanoptera such 11Slhl't'ilIUl/IITIJXjtHlUI'U/iS. and bugs. for example the beet bug (Pies-um qumlrulu). the red cotton bug (Dyst/CIL'IM' imz'rmr'diux). the bed bug ((imex lcctulm'ius).
  • the browntail moth (Eupruclis ('/H ⁇ S()II'/ll)(tl) and tent caterpillar (Mulucosuma m'usl-riu); further. the cabbage moth (Ma/21mm: [)I'UAZS'IIUL) and the cutworm Agmris .s'cg etmiz the large white butterfly (Pieris brus- .viulc). the small winter moth (C/zainmmhiu bruimllu). the green oak tortrix moth Torn-ix ririzlunu).
  • the fall armyworm (Laplrvgmu ji'ugipw'du) and cotton worm (Pl'mle'niu Iimru).
  • the ermine moth (Hyponmneulu [)(ltlt'l/(l).
  • the Mediterranean flour moth (Iip/zestia kl'l'hmic/la) and greater was moth (Galleria nwllonellu); and the like.
  • beetles Colding insects contemplated herein are beetles (Coleoptera). for example the granary weevil (.S'iIop/zilux gramu'ius Culmulm grunuriu). the Colorado beetle (Leptinolursu decentlineuta). the dock beetle ((iusti'oplrnw riridul u). the mustard beetle (Plzuedon (och/curiae). the blossom beetle (Mcligellms ueneux). the raspberry beetle (Bylurus IOHMHIUSHS).
  • the bean weevil (Bruc/u'zlizmv Ac'un- !/i'u.i'celiz1cs obreclus the leathcr'bee tle ([)ermestesfi'ischi).
  • the k'hapra beetle (Tmgozlerma granurium);
  • flour beetle Trilmlium custaneum.
  • the northern corn billbug Calandra orSitophilus zcamais).
  • the drugstore beetle (Siege/2mm puniceum).
  • the yellow mealworm (Tenebrio n'zolimr) and the saw-toothed grain beetle 0r ⁇ 'zueplzilus .s'urimlmensis). and also species living in the soil. for example wireworms (Agriurs spec.) and larvae of the cockchafer (Melolont/za meIOlonr/zu); cockroaches. such as the German. cockroach"(B1auelIa germunica).
  • the house cricket Ac/zeta clunms'licus
  • termites such as the eastern subterranean termite (Reticulitermas'.fluripasd and Hy'menoptera such as ants.
  • gardenrant Lasius nigenh and the like.
  • the Diptera contemplated herein comprise essentially the flies. such as the vinegar fly (Drosop/zilu "161th nogaster). the Mediterranean fruit fly (Qln utitis cupitum). the house fly (Muscu domexticu). the little house fly (Fumziu canic'uluris). the black blow .fly (P/mrmiu rvginu) and bluebottle fly (Culliplmra (I' ⁇ I/lI'UCP/ltlld) as well as the stable fly (Smmarys c'ulcirrans); further. gnats. for example mosquitoes such as the yellow fever mosquito (Aedes uegypri). the northern house mosquito (Cu/ex pipiwis) and the malaria mosquito (Anopheles .stcphcnsi); and the like.
  • mosquitoes such as the yellow fever mosquito (Aedes uegypri). the northern house mosquito (Cu/
  • mites contemplated herein there are classed. in particular. the spider mites (Tetranyehidae) such as the two-spotted spider mite (Tetrunyclzus lelurills TLIIUII ⁇ '(']IIIS all/mule or Tbrrmrrclum urlic'ue) and the European red mite (Puratetrimyclzus pilosus Punmrvc/ms ulnu'). gall mites. for example the black currant gall mite (Eriop/rves ribis) and tarsonerriids.
  • the spider mites Tetranyehidae
  • the two-spotted spider mite Tetrunyclzus lelurills TLIIUII ⁇ '(']IIIS all/mule or Tbrrmrrclum urlic'ue
  • European red mite Puratetrimyclzus pilosus Punmrvc/ms
  • ticks such as the relapsing fever tiek.(()rni-- I/wzlorus muubura); and the like.
  • 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 extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier'vchicles such as gases. solutions. emulsions. suspensions, emulsifiable 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 extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier'vchicles such as gases. solutions. emulsions. suspensions,
  • sulfoxides e.g. dime'thyl'sulfoxide. ctc.
  • acetonitrile e.g. dime'thyl'sulfoxide. ctc.
  • kctones cg. acetone. methyl ethyl ketone. methyl isobutyl ketonc. cyclt'ihexanone. "ete'); "and/or water; as well as inert dispersible. finely divided solid carriers.
  • ground natural minerals e.g. kaolins. clays. alumina. silica, chalk', i.e. calcium carbonate. talc. attapulgite, montmorillonite. kiesclguhr. etc.
  • ground synthetic minerals e.g.
  • emulsifying agents such as nonionic'and- /or anionic emulsifying agents (cg. polyethylene oxide esters of fatty acids. polyethylene oxide ethers of fatty alcohols. alkyl sulfates. alkyl sulfonates. aryl sulfonates. etc.. and especially alkyl arylpolyglycol ethers. magne sium stearate. sodium ole-ate. 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/o with such solid and/or liquid dispersible carrieryeh icles. and/or with other knowncompatible active agents. especially plant protection agents such as other insecticides and acaricides. or rodenticides. fungicides, bacterieides. nematocides. herbicides. fertilizers, growthregulating 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 forusc.
  • carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1 95 71 by weight. and preferably 0.5-9()'/z by weight. of the mixture
  • carrier composition mixtures suitable for direct applicationor field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001 1 preferably ().()ll'/(. by weight of the mixture.
  • the present invention contemplatesover-all composi tions which comprises mixtures'of a conventional dispersihle carrier vehicle such as (l a dispersible inert finely divided carrier solid.
  • a dispersiblc carrier liquid such as an inertorg'anic solvent and/or water preferable including a surface-active effective amount of a carrier vehicle assistant.
  • a surface-active agent such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.()()l957(. and preferably (HM-95%. by weight of the mixture.
  • the active compounds can also be used in accor dance 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. c.g. average particle diameter of from 50-1 ()0 microns, or even less. i.e. mist form. for example by airplane crop spraying techniques. Only up to at most about a few liters/hectai'e are needed, and often amounts only up to about l5 to 1000 g/heetare. preferably to 600 g/hectare. are sufficient. In this process it is possible to ,use highly concentrated liquid compositions with said liquid carrier vehicles containingfrom about 20 to about by weight of the active compound or even the active 6 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 and acarids. which comprises applying to at least one of correspondingly (a) such insects. (b) such acarids. and (c) the corresponding habitat thereof. i.e. the locus to be protected. a correspondingly combative or toxic amount. i.e. an insecticidally or acaricidally 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. and the like.
  • EXAMPLE 1 Myzus Test (contact actionj Solvent: 3 parts by weight acetone Emulsifier: l part by weight alkylarylpolyglycol ether Toproduce a suitable preparation of active compound. 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is di luted with water to the desired concentration.
  • the degree of destruction is determined as. a percentage: 1007! means that all the aphids are killed whereas (l /r means that none of the aphids are killed.
  • i P N (1 -1 O(H.. 0.1 100 0.01 75 (H S H, O ⁇ ( i1 PN ('H()(H 0.1 100 0.01 95 (H S EXAMPLE 2 Doralis Test (systemic action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound. 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Bean plants which have been heavily infested with the bean aphid (Doralisfilluw) are watered with the preparation of the active compound so that the preparation of active compound penetrates into the soil without wetting the leaves of the bean plants.
  • the active compound is taken up by the bean plants from the soil and thus reaches the infested leaves.
  • the degree of destruction is determined as a percentage. 100% means that all the aphids are killed; 0% means that none of the aphids are killed.
  • Bean plants (P/iuseolus vul aris). which have a height of approximately 10-30 cm.. are sprayed with the prep-' aration of the active compound until dripping wet. These bean plants are heavily infested with spider mites (T(U't
  • the effectiveness of the preparation of active compound is determined by counting the dead mites.
  • the degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.
  • EXAMPLE 4 7 g (0.5 mole) of Omethyl-S-methyl-thiolphosphorie acid ester amide are heated to the boil under reflux for 4 hours with 92 g of orthoformic acid ethyl ester. Subsequently. the alcohol formed is distilled off and the residue is distilled. There are obtained 56 g (57% of theory) of the desired N-(O.S-dimethylthiolphosphoryl)-iminoformic acid ethyl ester of the boiling point 84C/O.()l mm Hg and the refractive index n,, 1.4892. LD rat per os approximately 200 mg/kg.
  • EXAMPLE 5 47 g (0.3 mole) of O-ethyl-S-methyl-thiolphosphoric acid ester amide and 55 g orthformic acid ethyl ester are heated to 150C for 4 hours; the alcohol forming is distilled off simultaneously. The residue is distilled and there are obtained 52 g (82% of theory) of the desired N-( O-ethyl-S-methyl-thiolphosphoryl )iminoformic acid ethyl ester of the boiling point 88C/().()l mm Hg and the refractive index n,, 1.4802. LD rat per 0s 50 mg/kg.
  • the compound according to claim 1 wherein such compound I is N-( O-ethyl-S-methylthiolphosphoryl iminoformic acid ethyl ester of the formula 5.
  • the compound according to claim 1 wherein such compound is N(O.S-dimethylthionothiolphosphoryl iminoformic acid ethyl ester of the formula 6.
  • the compound according to claim 1 whcrcin such compound is N-(O,S-dimcth'lthiolphosphoryl imin oformic acid methyl ester of the formula 7.

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  • Health & Medical Sciences (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US240282A 1971-04-06 1972-03-31 N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters Expired - Lifetime US3903207A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/553,873 US3957979A (en) 1971-04-06 1975-02-27 Pesticidal N-(O-S-dialkyl(thionol)-thiolPhosphoryl)-iminoformic acid alkyl esters

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Application Number Priority Date Filing Date Title
DE2116690A DE2116690C3 (de) 1971-04-06 1971-04-06 N-(O,S-Dialkyl (Mono) IhiolphosphoryO-iminoameisensäurealkylester, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Insektizide und Akarizide

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US (1) US3903207A (fr)
JP (1) JPS577157B1 (fr)
AT (1) AT307444B (fr)
AU (1) AU459589B2 (fr)
BE (1) BE781672A (fr)
BR (1) BR7202006D0 (fr)
CA (1) CA979916A (fr)
CH (1) CH571532A5 (fr)
DD (1) DD100476A5 (fr)
DE (1) DE2116690C3 (fr)
EG (1) EG10734A (fr)
ES (1) ES401483A1 (fr)
FR (1) FR2132478B1 (fr)
GB (1) GB1325656A (fr)
HU (1) HU163994B (fr)
IL (1) IL39123A (fr)
IT (1) IT967039B (fr)
NL (1) NL7204612A (fr)
PL (1) PL83529B1 (fr)
RO (1) RO62300A (fr)
TR (1) TR17269A (fr)
ZA (1) ZA722349B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4692436A (en) * 1985-05-14 1987-09-08 Nihon Tokushu Noyaku Seizo K.K. Phosphoroimidates as pesticides

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842527A (en) * 1954-10-06 1958-07-08 Rohm & Haas Vinyl ether derivatives of amidophosphate and amidothiophosphate esters, their polymers and processes for preparing them

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842527A (en) * 1954-10-06 1958-07-08 Rohm & Haas Vinyl ether derivatives of amidophosphate and amidothiophosphate esters, their polymers and processes for preparing them

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4692436A (en) * 1985-05-14 1987-09-08 Nihon Tokushu Noyaku Seizo K.K. Phosphoroimidates as pesticides

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AU459589B2 (en) 1975-03-06
RO62300A (fr) 1977-12-15
TR17269A (tr) 1975-03-24
DE2116690A1 (de) 1972-10-19
FR2132478A1 (fr) 1972-11-17
HU163994B (fr) 1973-12-28
AT307444B (de) 1973-05-25
EG10734A (en) 1976-04-30
CA979916A (en) 1975-12-16
AU4040172A (en) 1973-09-27
PL83529B1 (fr) 1975-12-31
ES401483A1 (es) 1975-02-16
BR7202006D0 (pt) 1973-12-20
BE781672A (fr) 1972-10-05
JPS577157B1 (fr) 1982-02-09
GB1325656A (en) 1973-08-08
DD100476A5 (de) 1973-09-20
NL7204612A (fr) 1972-10-10
IL39123A0 (en) 1972-06-28
DE2116690C3 (de) 1980-10-23
DE2116690B2 (de) 1980-02-28
CH571532A5 (fr) 1976-01-15
ZA722349B (en) 1972-12-27
FR2132478B1 (fr) 1978-03-03
IT967039B (it) 1974-02-28
IL39123A (en) 1974-11-29

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