US3840541A - O-pyrazolopyrimidine-(thiono)-phosphoric-(phosphonic or phosphinic)-acid esters or ester-amides - Google Patents

O-pyrazolopyrimidine-(thiono)-phosphoric-(phosphonic or phosphinic)-acid esters or ester-amides Download PDF

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US3840541A
US3840541A US00263075A US26307572A US3840541A US 3840541 A US3840541 A US 3840541A US 00263075 A US00263075 A US 00263075A US 26307572 A US26307572 A US 26307572A US 3840541 A US3840541 A US 3840541A
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butyl
compound
phosphoric
active
propyl
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R Coelln
I Hammann
G Unterstenhoefer
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings

Definitions

  • R is alkyl or alkoxy With 1 to 6 carbon atoms, or phenyl, or a monoalkylamino or dialkylamino group with up to 6 carbon atoms per alkyl moiety,
  • R is hydrogen or halogen
  • X is oxygen or sulfur
  • the present invention relates to and has for its objects the provision of particular new O-pyrazolopyrirnidine- (thiono) phosphoric (phosphonic or phosphinic) -acid esters or ester amides, i.e.
  • O-pyrazolopyrimidine (thiono) phosphoric-(phosphonic or phosphinic)-acid esters for example 0,0- diethyl O (5,7 dimethylpyrazolo[1,5 a]pyrirnidin (2)yl)-thiono-phosphoric acid ester (Compound A) and 0,0-diethyl-O-(3-chloro- (Compound B) or -3-bromo- 5,7 dimethylpyrazolo-[1,5 a] pyrimidin(2)ylphosphoric acid ester (Compound C), display a pesticidal action, especially an insecticidal and acaricidal action.
  • thiono phosphoric-(phosphonic or phosphinic)-acid esters
  • the present invention provides O-pyrazolopyrimidine- (thono) phosphoric (phosphonic or phosphinic) -acid esters or ester-amides of the general formula "ice in which R is alkoxy or alkyl with 1 to 6 carbon atoms,
  • R is alkyl or alkoxy with 1 to 6 carbon atoms, or phenyl, or a monoalkylamino or dialkylamino group with up to 6 carbon atoms per alkyl moiety,
  • R is hydrogen or halogen
  • X is oxygen or sulfur.
  • the compounds of the invention show a considerably higher insecticidal and acaricidal action than the previously known compounds of analogous structure and the same type of action.
  • the substances according to the invention thus represent a genuine enrichment of the art.
  • R is straight-chain or branched lower alkyl with 1 to 4 carbon atoms, such as methyl, ethyl, nor isopropyl, n-, sec.-, tert.- or iso-butyl, or straight-chain or branched lower alkoxy with 1 to 4 carbon atoms, for example methoxy, ethoxy, nor iso-propoxy or n-, sec.-, tert.- or iso-butoxy; R is such lower alkyl or alkoxy, or phenyl, or mono-lower alkylamino or di-lower alkylamino with up to 4 carbon atoms in each alkyl moiety, such as a monomethylamino, monoethylamino, mono isopropylamino, mono-n-propylarnino, mono n butylamino, mono-sec.- butylamino, mono-iso-butylamino, mono-tert.-buty
  • (thiono)-phosphoric-(phosphonic or phosphinic)-acid esters or ester-amides of the formula (I) which can be used, the following may be mentioned individually: 0,0-dimethyl-, 0,0-diethyl-, QO-di-n-propyl-, 0,0-di-iso-propyl-, 0,0-di-n-butyl-, 0,0-di-iso-butyl-, 0,0-di-sec.-butyl-, 0,0-di-tert.-butyl-, O-methyl-O- ethyl-, O-methyl-O-n-propyl-, O-methyl-O-isopropyl-, O- methy1-O-n-butyl-, O-ethyl-O-n-propyl-, O-ethyl-O-isopropyl-, O-ethyl-O-n-butyl-, O-ethyl-O-
  • di-iso-butane-, di-sec.-butane, di-tert.-butane-, methanebutaneand methane-benzene phosphinic acid-ester also O,N-dimethyl, O-methyl-N-ethyl-, O-methyl-.N-n-propyl-, O-methyl-N-iso-propyl-, O-methyl-N-n-butyl-, O-methyl- N-sec.-butyl-, O-methyl-N-iso-butyl-, O-methyl-N-tert.- butyl-, O-ethyl-N-methyl-, O-ethyl-'N-ethyl-, O-ethyl-N-npropyl-, O ethyl N iso propyl-, O-ethyl-N-n-butyl-, O-ethyl-N-sec.-butyl-, O-eth
  • butyl N ethyl-, O-tert.- butyl-N-n-propyl-, O-tert.-butyl N iso-propyl-, O-sec.- butyl-N-ethyl-, O-sec.-butyl-N-n-propyl-, O-sec.-butyl-N- iso-propylor O-sec.-butyl-N-n-butyl-phosphoric acid ester amide, as well as the corresponding dialkylamino ester amide and their thiono analogue esters of 2-hydroxypyrazolo[1,5-a]pyrimidine or its 3-chloroor 3-bromo derivative.
  • the invention also provides a process for the production of an O-pyrazolopyrimidine-(thiono)-phosphoric-(phosphonic or phosphinic)-acid ester or ester-amide of the formula (I) in which a (thiono)-phosphoric-(phosphonic or phosphinic)-acid ester halide or ester-amide halide of the general formula in which R R and X have the above-mentioned meanings, and Hal is halogen, preferably chlorine or bromine,
  • the unsubstituted 2 hydroXy-pyrazolo[1,5-a] pyrimidine is obtained from a solution of 3-aminopyrazolone-(5) in ethanol and water, which has been saturated with HCl gas at 0 C., by reaction with 1,1,3,3-tetramethoxypropane.
  • the products halogenated in the 3-position are obtained therefrom by halogenation.
  • the process of the invention is preferably carried out with the use of a solvent which term includes a mere dil-.
  • inert organic solvents include, above all, aliphatic and aromatic, optionally chloronated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene; ethers, for example diethyl ether, dibutyl ether, dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone; nitriles, for example acetonitrile, propionitrile; and formamides, especially dimethyl-formamide.
  • hydrocarbons such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene
  • ethers for example diethyl ether, dibutyl ether, dioxane
  • Alkali carbonates and alcoholates such as sodium carbonate or potassium carbonate, sodium methylate or potassium methylate or sodium ethylate or potassium ethylate, as well as aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularly suitable.
  • the reaction temperature can be varied over a wide range. In general, the reaction is carried out at from about 0 to 0., preferably about 15 to 35 C. The reaction is generally carried out at normal pressure.
  • the starting substances are in most cases employed in equimolar ratios. An excess of one or other reactant does not produce any significant advantages.
  • the reaction is preferably carried out in the presence of one of the above-mentioned solvents and in the presence of an acid acceptor, at the temperatures indicated; after stirring for one or more hours at the indicated temperatures, the reaction mixture may be workedup by treating it with ice water. Thereupon, either the product already precipitates in solid form and is filtered off, washed and recrystallized if necessary, or the mixture is extracted with an organic solvent, preferably methylene chloride. After washing and drying the extract, the solvent is removed under reduced pressure and the oily residue is heated until slight distillation occurs.
  • an organic solvent preferably methylene chloride
  • the substances according to the invention are mostly obtained in a crystalline form and are characterized by their melting points. However, if they are obtained in the form of mostly yellowish-reddish oils, which cannot be distilled without decomposition, these may be freed of the remaining volatile constitutents by so-called slight distillation, that is to say prolonged heating under reduced pressure to moderately elevated temperatures, and may be purified in this way. In this case, their refractive indexes may be used to characterize them.
  • the new O-pyrazolopyrimidine (thiono) phosphoric (phosphonic or phosphinic)-acid esters or ester-amides are distinguished by an excellent insecticidal and acaricidal activity against crop pests, hygiene pests and pests of stored products. They possess a good action against both sucking and biting insects and mites (Acarimz). At the same time they display only a slight phytotoxicity; they also display some rodenticidal action.
  • the products according to the invention may be successfully employed as pesticides in the protection of crops and stored products, and in the hygiene field.
  • aphids such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Mqgrosiphum solanifolii), the currant gall aphid (Cryptom'y zus-korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry blackfly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the Oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Ps
  • butterfly caterpillars such as the diamond-back moth (Plutella 'p hey gypsy moth (Lymantrz'a dispar), the brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (A grotis segetum) the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworrn (Laphygma frugiperda) and cotton worm (Prodenz'a; litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kithniella) and; greater wax moth (Galleria
  • the Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogasfer), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.
  • mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.
  • 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 extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles 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
  • conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable 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.
  • 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, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g.
  • ground natural minerals e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, 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, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, 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, and rodenticides or fungicides, bactericides, 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, and rodenticides or fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc.
  • carrier composition mixtures in which the active compound is present in an amount substantially between about 0.195% by weight, and preferably 0.5% 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 0.0001-10%, preferably 0.014%, 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 of the active compound which is effective for the purpose in question and which is generally between about 0.0001-%, and preferably 0.01-95 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, eg average particle diameter of from 50 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liter/hectare are needed, and often amounts only up to about 15 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 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20100% by weight of the active compound.
  • the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids and rodents, 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, (c) such rodents, and (d) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally or rodenticidally 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.
  • concentration of the particular active compound utilized in admixture with the carrier vehicle will depend uopn the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.
  • EXAMPLE 1 A mixture of 99.0 g. (1 mole) of 3-aminopyrazolone, 750 ml. of ethanol and 100 ml. of concentrated hydrochloric acid is saturated with gaseous hydrogen chloride at C. Thereafter, 164.2 g. (1 mole) of 1,1,3,3-tetamethoxypropane are added dropwise to the mixture at an internal temperature of to 0 C. and the mixture is stirred for one hour without a cooling bath and for a further hour at 50 C.
  • the resulting yellow salt is filtered oil on a frit at 20 C. and is rinsed with ethanol and then dissolved in 1.2.1. of Water, and the solution is adjusted to a pH-value of 34 by adding sodium hydroxide solution.
  • the product which has precipitated is filtered off, repeatedly rinsed with water and dried. In this way, 101.0 g. (74.2% of theory) of 2-hydroxy-pyrazolo[1,5-a]pyrirnidine are obtained in the form of a pale reddish powder of melting point 176 to 177 C.
  • EXAMPLE 3 43.0 g. (0.25 mole) of 0,0-diethylph0sphoric acid ester chloride are added dropwise at room temperature to a mixture of 33.8 g. (0.25 mole) of 2-hydroxypyrazolo- [1,5-a1pyrimidine, 150 ml. of dimethylformamide and 27.5 g. of triethylamine, while cooling externally and stirring; the reaction mixture is allowed to continue reacting for 2 hours at room temperature, 350 ml. of ice-cold water are subsequently slowly added at below 10 C., and the batch is extracted by shaking with 200 ml. of methylene chloride. The organic phase is shaken with ml.
  • EXAMPLE 4 A solution of 135.2 g. (1 mole) of 2-hydroxy-pyrazolo- [1,5-a] pyrimidine and 40 g. (1 mole) of sodium hydroxide in 800 ml. of water is added to a solution of 282 g. (1 mole) of Chloroamine T in 2 l. of water at an internal temperature of 5 to 15 70., while stirring and cooling externally. After the mixture has been stirred for 1 hour at 15 to 20 C., it is treated with 60. g. of glacial acetic acidjand after a further hour it is brought to a pH-value of exactly 9 and the p-toluenesulfonamide formed is filtered off and rinsed with water. 150 ml.
  • Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dew moist and are then infested with caterpillars of the diamondback moth (Plutella maculipennis).
  • the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas 0% means that none of the caterpillars are killed.
  • the active compounds, the concentrations of the active 50 3 C1 8: gg compounds, the evaluation times and the results can be H 0001 70 seen from the following Table 10 N 0.1 100 'rABLEs o1 0.01 100 [Myzus Test/normally sensitive] 01H; S 0. 001 100 ⁇ ll 0. 0001 40 Concen- Degree P-O N tration oi oi de- N active struction CaHsO vigmpound i111 apier- BIOBD.
  • Solvent 3 parts by weight acetone 2 7 0H
  • Emulsifier 1 part by weight alkylaryl polyglycol ether. (known) 7
  • N 0 1 g 1 part by weight of the active compound is mixed with S m 85 the stated amount of solvent containing the stated amount (CH) ⁇ 1 of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.
  • Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.
  • the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.
  • Hop plants (H umulus lupulus) which have been heavily infested with the hop aphid (Phorodon humuli) resistant, are sprayed with the preparation of the active compound until dripping wet.
  • the degree of destruction is determined as a percentage: 100% means that all the aphids were killed; 0% means that none of the aphids were killed.
  • O-pyrazolopyrimidine (thiono) phosphoric- (phosphonic or phosphinic)-acid ester of the formula in which R is alkoxy or alkyl with 1 to 6 carbon atoms,
  • R is alkyl or alkoxy with 1 to 6 carbon atoms or phenyl or monoalkylamino or dialkylamino with up to 6 carbon atoms in each alkyl moiety
  • R is hydrogen or halogen
  • X is oxygen or sulfur.
  • R is lower alkyl or alkoxy
  • R is lower alkyl or alkoxy
  • phenyl mono-lower alkylamino or di-lower alkylamino
  • R is hydrogen, chlori e o bromi e.

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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)
US00263075A 1971-06-24 1972-06-15 O-pyrazolopyrimidine-(thiono)-phosphoric-(phosphonic or phosphinic)-acid esters or ester-amides Expired - Lifetime US3840541A (en)

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Application Number Priority Date Filing Date Title
CA170,856A CA941022A (en) 1972-06-15 1973-05-09 Microwave heating apparatus

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DE2131298A DE2131298C3 (de) 1971-06-24 1971-06-24 O-Pyrazolopyrimidin-(thiono)-phosphor-(phosphon, phosphln)-saureester bzw. -esteramide, Verfahren zu ihrer Herstellung sowie diese als Insektizide und Alkarizide enthaltende Mittel

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US (1) US3840541A (da)
AT (1) AT308143B (da)
AU (1) AU470168B2 (da)
BE (1) BE785265A (da)
BR (1) BR7204068D0 (da)
CH (1) CH571529A5 (da)
CS (1) CS175430B2 (da)
DD (1) DD101167A5 (da)
DE (1) DE2131298C3 (da)
DK (1) DK133008C (da)
EG (1) EG10481A (da)
ES (1) ES404213A1 (da)
FR (1) FR2143450B1 (da)
GB (1) GB1391354A (da)
HU (1) HU163999B (da)
IL (1) IL39728A (da)
IT (1) IT961237B (da)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948926A (en) * 1971-12-30 1976-04-06 Saburo Kano O,O-Diethyl-2-(5-ethyl-6-bromothiazolo[3,2-b]-s-triazolyl)thionophosphate
US4067970A (en) * 1975-10-14 1978-01-10 Bayer Aktiengesellschaft Pesticidal O-ethyl-S-n-propyl-O[pyrazolo(1,5-a)-pyrimidin-(2) yl]-thionothiolphosphoric acid esters
US7288554B2 (en) 2001-08-15 2007-10-30 E.I. Du Pont De Nemours And Company Ortho-substituted aryl amides for controlling invertebrate pests

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2544938C2 (de) * 1975-10-07 1983-12-29 Bayer Ag, 5090 Leverkusen 0-Pyrazolopyrimidin-(thiono)- phosphor(phosphon)-säureester bzw. -esteramide, Verfahren zu ihrer Herstellung sowie ihre Verwendung zur Bekämpfung von Insekten, Milben und Nematoden

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948926A (en) * 1971-12-30 1976-04-06 Saburo Kano O,O-Diethyl-2-(5-ethyl-6-bromothiazolo[3,2-b]-s-triazolyl)thionophosphate
US4067970A (en) * 1975-10-14 1978-01-10 Bayer Aktiengesellschaft Pesticidal O-ethyl-S-n-propyl-O[pyrazolo(1,5-a)-pyrimidin-(2) yl]-thionothiolphosphoric acid esters
US7288554B2 (en) 2001-08-15 2007-10-30 E.I. Du Pont De Nemours And Company Ortho-substituted aryl amides for controlling invertebrate pests

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BR7204068D0 (pt) 1973-05-03
NL7208683A (da) 1972-12-28
CH571529A5 (da) 1976-01-15
FR2143450B1 (da) 1977-12-23
EG10481A (en) 1976-07-31
GB1391354A (en) 1975-04-23
DE2131298B2 (de) 1979-06-21
HU163999B (da) 1973-12-28
AU4371472A (en) 1974-01-03
DD101167A5 (da) 1973-10-20
ES404213A1 (es) 1975-05-16
FR2143450A1 (da) 1973-02-02
DE2131298A1 (de) 1972-12-28
DK133008C (da) 1976-08-09
ZA724332B (en) 1973-03-28
CS175430B2 (da) 1977-05-31
IT961237B (it) 1973-12-10
AT308143B (de) 1973-06-25
AU470168B2 (en) 1976-03-04
IL39728A0 (en) 1972-08-30
DK133008B (da) 1976-03-08
IL39728A (en) 1975-10-15
BE785265A (fr) 1972-12-22
DE2131298C3 (de) 1980-02-14

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