US3903207A - N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters - Google Patents
N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters Download PDFInfo
- 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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- US
- United States
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- compound
- formula
- iminoformic
- dialkyl
- thiono
- Prior art date
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- Expired - Lifetime
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- 239000002253 acid Substances 0.000 title claims abstract description 32
- 125000005907 alkyl ester group Chemical group 0.000 title abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 13
- -1 ester amide Chemical class 0.000 claims description 11
- 125000004494 ethyl ester group Chemical group 0.000 claims description 8
- 150000004702 methyl esters Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000895 acaricidal effect Effects 0.000 abstract description 6
- 230000000749 insecticidal effect Effects 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 11
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- 239000003995 emulsifying agent Substances 0.000 description 10
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- 239000003085 diluting agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
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- 239000000969 carrier Substances 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 2
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
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- 241001465754 Metazoa Species 0.000 description 1
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 description 1
- 241000810465 Myzus cerasi cerasi Species 0.000 description 1
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- 235000001537 Ribes X gardonianum Nutrition 0.000 description 1
- 235000001535 Ribes X utile Nutrition 0.000 description 1
- 235000016919 Ribes petraeum Nutrition 0.000 description 1
- 244000281247 Ribes rubrum Species 0.000 description 1
- 235000002355 Ribes spicatum Nutrition 0.000 description 1
- 241001237745 Salamis Species 0.000 description 1
- 241000254179 Sitophilus granarius Species 0.000 description 1
- 241000254154 Sitophilus zeamais Species 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 241000256251 Spodoptera frugiperda Species 0.000 description 1
- 241001177161 Stegobium paniceum Species 0.000 description 1
- 241001494115 Stomoxys calcitrans Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000254105 Tenebrio Species 0.000 description 1
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- 241000064240 Yponomeuta padellus Species 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- YYJNOYZRYGDPNH-MFKUBSTISA-N fenpyroximate Chemical compound C=1C=C(C(=O)OC(C)(C)C)C=CC=1CO/N=C/C=1C(C)=NN(C)C=1OC1=CC=CC=C1 YYJNOYZRYGDPNH-MFKUBSTISA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000003128 rodenticide Substances 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
-
- 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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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 |
Applications Claiming Priority (1)
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 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/553,873 Division US3957979A (en) | 1971-04-06 | 1975-02-27 | Pesticidal N-(O-S-dialkyl(thionol)-thiolPhosphoryl)-iminoformic acid alkyl esters |
Publications (1)
Publication Number | Publication Date |
---|---|
US3903207A true US3903207A (en) | 1975-09-02 |
Family
ID=5803981
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US240282A Expired - Lifetime US3903207A (en) | 1971-04-06 | 1972-03-31 | N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters |
Country Status (22)
Country | Link |
---|---|
US (1) | US3903207A (it) |
JP (1) | JPS577157B1 (it) |
AT (1) | AT307444B (it) |
AU (1) | AU459589B2 (it) |
BE (1) | BE781672A (it) |
BR (1) | BR7202006D0 (it) |
CA (1) | CA979916A (it) |
CH (1) | CH571532A5 (it) |
DD (1) | DD100476A5 (it) |
DE (1) | DE2116690C3 (it) |
EG (1) | EG10734A (it) |
ES (1) | ES401483A1 (it) |
FR (1) | FR2132478B1 (it) |
GB (1) | GB1325656A (it) |
HU (1) | HU163994B (it) |
IL (1) | IL39123A (it) |
IT (1) | IT967039B (it) |
NL (1) | NL7204612A (it) |
PL (1) | PL83529B1 (it) |
RO (1) | RO62300A (it) |
TR (1) | TR17269A (it) |
ZA (1) | ZA722349B (it) |
Cited By (1)
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)
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 |
-
1971
- 1971-04-06 DE DE2116690A patent/DE2116690C3/de not_active Expired
-
1972
- 1972-03-24 AU AU40401/72A patent/AU459589B2/en not_active Expired
- 1972-03-28 EG EG126/72A patent/EG10734A/xx active
- 1972-03-31 US US240282A patent/US3903207A/en not_active Expired - Lifetime
- 1972-03-31 RO RO197270348A patent/RO62300A/ro unknown
- 1972-04-03 IL IL7239123A patent/IL39123A/xx unknown
- 1972-04-04 IT IT89503/72A patent/IT967039B/it active
- 1972-04-04 CH CH493072A patent/CH571532A5/xx not_active IP Right Cessation
- 1972-04-04 TR TR17269A patent/TR17269A/xx unknown
- 1972-04-05 BE BE781672A patent/BE781672A/xx unknown
- 1972-04-05 GB GB1563872A patent/GB1325656A/en not_active Expired
- 1972-04-05 DD DD162158A patent/DD100476A5/xx unknown
- 1972-04-05 JP JP3360072A patent/JPS577157B1/ja active Pending
- 1972-04-05 CA CA138,900A patent/CA979916A/en not_active Expired
- 1972-04-05 PL PL1972154566A patent/PL83529B1/pl unknown
- 1972-04-05 ES ES401483A patent/ES401483A1/es not_active Expired
- 1972-04-06 NL NL7204612A patent/NL7204612A/xx not_active Application Discontinuation
- 1972-04-06 AT AT295772A patent/AT307444B/de not_active IP Right Cessation
- 1972-04-06 FR FR7212084A patent/FR2132478B1/fr not_active Expired
- 1972-04-06 HU HUBA2723A patent/HU163994B/hu unknown
- 1972-04-06 BR BR722006A patent/BR7202006D0/pt unknown
- 1972-04-07 ZA ZA722349A patent/ZA722349B/xx unknown
Patent Citations (1)
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)
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 |
Also Published As
Publication number | Publication date |
---|---|
DE2116690C3 (de) | 1980-10-23 |
IT967039B (it) | 1974-02-28 |
PL83529B1 (it) | 1975-12-31 |
RO62300A (fr) | 1977-12-15 |
TR17269A (tr) | 1975-03-24 |
GB1325656A (en) | 1973-08-08 |
BR7202006D0 (pt) | 1973-12-20 |
NL7204612A (it) | 1972-10-10 |
ZA722349B (en) | 1972-12-27 |
CH571532A5 (it) | 1976-01-15 |
IL39123A0 (en) | 1972-06-28 |
IL39123A (en) | 1974-11-29 |
EG10734A (en) | 1976-04-30 |
FR2132478B1 (it) | 1978-03-03 |
AU4040172A (en) | 1973-09-27 |
ES401483A1 (es) | 1975-02-16 |
DE2116690B2 (de) | 1980-02-28 |
AU459589B2 (en) | 1975-03-06 |
FR2132478A1 (it) | 1972-11-17 |
JPS577157B1 (it) | 1982-02-09 |
BE781672A (fr) | 1972-10-05 |
DE2116690A1 (de) | 1972-10-19 |
AT307444B (de) | 1973-05-25 |
CA979916A (en) | 1975-12-16 |
HU163994B (it) | 1973-12-28 |
DD100476A5 (de) | 1973-09-20 |
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