IL34448A - Phosphoric,thionophosphoric,phosphonic and thionophosphonic acid esters,ester amides and diamides,their production and their use as insecticides,acaricides and fungicides - Google Patents
Phosphoric,thionophosphoric,phosphonic and thionophosphonic acid esters,ester amides and diamides,their production and their use as insecticides,acaricides and fungicidesInfo
- Publication number
- IL34448A IL34448A IL34448A IL3444870A IL34448A IL 34448 A IL34448 A IL 34448A IL 34448 A IL34448 A IL 34448A IL 3444870 A IL3444870 A IL 3444870A IL 34448 A IL34448 A IL 34448A
- Authority
- IL
- Israel
- Prior art keywords
- compound
- formula
- carbon atoms
- active compound
- alkyl
- Prior art date
Links
- -1 ester amides Chemical class 0.000 title claims description 23
- 239000002253 acid Substances 0.000 title claims description 17
- 230000000895 acaricidal effect Effects 0.000 title claims description 8
- 150000002148 esters Chemical class 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001470 diamides Chemical class 0.000 title claims description 3
- 239000000417 fungicide Substances 0.000 title description 3
- 239000002917 insecticide Substances 0.000 title description 3
- 239000000642 acaricide Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 153
- 230000006378 damage Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 241000238631 Hexapoda Species 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 241000607479 Yersinia pestis Species 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 230000000749 insecticidal effect Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 241000233866 Fungi Species 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 4
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 239000011734 sodium Chemical group 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- DYUMBFTYRJMAFK-UHFFFAOYSA-N 3-cyano-2-pyridone Chemical class OC1=NC=CC=C1C#N DYUMBFTYRJMAFK-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004094 surface-active agent Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 244000045947 parasite Species 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 2
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- 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
- 235000013312 flour Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000974 larvacidal effect Effects 0.000 description 1
- 229920005610 lignin Polymers 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
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- FUWGSUOSJRCEIV-UHFFFAOYSA-N phosphonothioic O,O-acid Chemical class OP(O)=S FUWGSUOSJRCEIV-UHFFFAOYSA-N 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
Landscapes
- 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
Description
ni'iosi ηΐ'ΐκρκ ,ο*ρηπ ^aips am «riB»wn Phosphoric, thlono hosphoric, phosphonlc and thiono-phosphonic acid esters, ester amides and dlamides, their production and their use as insecticides, acarieides and fungicides C: 52727 The present invention relates to certain new phosphoric-(phosphonic)- and thionophosphoric-(phosphonic)-acid esters, -ester amides and -diamides, to a process for their production and to their use as insecticides, acaricides and fungicides.
It is already known that ( thio-)phosphonic acid esters of 2-hydroxypyridine like the O-ethylphenyl-thionophosphonic acid ester of 2-hydroxy-3-cyano-6-methyl-pyridine display insect-icidal, acaricidal and nematocidal properties (compare British Patent Specification 1,058,457 and Published Japanese Patent Applications 13,079/63 and 16,297/64). Against this, it cannot be deduced from the literature mentioned whether the products disclosed therein also possess a special aphicidal and larvicidal action.
The invention provides new phosphoric-(phosphonic)- and thionophosphoric-(phosphonic)-acid esters, ester amides and diamides of the general formula in which R2 is aryl or straight-chain or branched alkyl with 1 to 6 carbon atoms , R^ is hydrogen or methyl, R is straight-chain or branched alkyl with 1 to 6 carbon atoms, 1 is straight-chain or branched alkyl with 1 to 6 carbon atoms or alkoxy, mono- or dialkyl-amino or, if R2 is aryl or alkyl with 2 to 6 carbon atoms, R.^ may be aryl, X is oxygen or sulphur, and of a compound of the formula (I) in which either a 2-hydroxy 3-cyano-pyridine derivative of the general formula is reacted with a (thiono)phosphoric (phosphonic) acid diamide, -ester amide or -ester halide of the general formula or a 2-halogeno-3-cyano-pyridine derivative of the general formula is reacted with a ( thiono)phosphoric(phosphonic)-acid or salt of the general formula RY in which Hal is chlorine or bromine and M is hydrogen, sodium, potassium or ammonium.
Surprisingly, the new compounds of the invention are distinguished from the known (thio) phosphonic acid esters of 3-hydroxypyridine and the O-ethyl-phenylthiophosphonic acid ester of 2-hydroxy-3-cyano-6-methylpyridine of analogous constitution and similar direction of activity by an increased insecticidal, acaricidal and fungicidal, especially aphicidal ces cc rd the η If for example 2-hydroxy-3-cyano-6-methylpyridine and Ο,Ο-dipropylphosphoric acid ester chloride are used as starting substances, the course of the reaction can be shown by the following formula scheme: The phosphoric acid derivates and 3-cyanopyridines to be used as starting substances in the process according to the invention are unambiguously generally defined by the above general formulae (III) and (V), and (II) and (IV), respectively.
Preferably, R^ s phenyl or alkyl with 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, n- butyl, iso-butyl, sec.-butyl or tert.-butyl; R is alkyl with 1 to 4 carbon atoms; is alkyl, alkoxy, monoalkylamino or dialkylamino with 1 to 4 carbon atoms in each alkyl group or, if R2 is phenyl or alkyl with 2 to 4 carbon atoms, R^ may be phenyl; and Y is oxygen, monoalkylami o with 1 to 4 carbon atoms, or NH-.
As examples of 3-cyano-pyridines of formula (II)or (IV) which can be used as starting materials, the following may be mentioned individually: The 2-halogeno-3-cyano and 2-hydroxy-3- cyano derivatives of 5, 6-dimethyl-, 6-methyl-, -ethyl-, -n-propyl-, iso-propyl-, -n-butyl-,-iso-butyl-, -sec.-butyl-, -tert .-butyl- or -phenyl-pyridine- Examples of (thiono)phosphoric(phosphonic)-acid-diamides or -ester halides which may be reacted according to the (dipropyl)-, and -(N,N-di-isopropyl)-phosphoric acid diamide chloride and the corresponding thiono analogues, N,N-dimethyl-O-methyl-, -O-eth l-, -O-propyl-, -O-isopropyl-, N,N-diethyl-O-methyl-, -O-ethyl-, -O-propyl-, -O-isopropyl-, -O-butyl-and Ν,Ν-di-isopropyl-O-methyl-phosphoric acid ester amide chloride and the corresponding thiono compounds, and also bis-(N-methyl-)-, -(N-ethyl-)- and -(N-isopropyl)-phosphoric . acid diamide chloride, N-methyl-O-methyl-, N-methyl-O-ethyl-, N-ethyl-O-ethyl-, N-isopropyl-O-ethyl-phosphoric acid ester amide chloride and their thiono analogues, O-methyl-methane-, 0-ethy1-ethane-, O-iso-propyl-ethane- and 0-ethyl-O-butane-phosphonic acid ester chloride and the thiono analogues, 0-methyl-phenyl-, O-ethyl-phenyl- and O-iso-propyl-phenyl-( thiono)phosphonic acid ester chloride, 0,0-dimethyl-, 0,0-diethyl-, 0-methyl-O-ethyl-, 0-ethyl-O-isopropylphosphoric acid ester chloride, Ν,Ν-dimethyl-methane-, N,N-dimethyl-ethane-, Ν,Ν-dimethyl-phenyl-, N-methyl-methane-, N^methyl-ethane-, N-methyl-isopropane-, N-iso-propyl-phenyl-phosphonic acid ester amide chloride and their thio analogues as well as N-methyl-N* ,Ν' -dimethyl- and N-methyl-N* ,N'-diethyl-phosphoric acid diamide chloride.
The ( thiono)phosphoric(phosphonic)-acid derivatives of formula (III) or (V), to be used as starting substances, are known and can be manufactured according to usual methods, as can the 2-hydroxy-3-cyano-pyridine derivatives of formula (II) which are in part already described in the literature and which are for example obtainable from 1,3-ketoaldehydes and cyanacetamide . The 2-halogeno-3-cyano-pyridine derivatives of formula (IV) can be easily obtained in very good yields by reaction of the corresponding hydroxy compounds with phosphorus oxychloride and dimethylaniline. solvent. Possible solvents include all organic solvents which are inert towards the reaction components. These solvents for example include aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, benzine, toluene, xylene, chlorobenzene , chloroform, carbon tetrachloride, ethers, such as diethyl ether or dibutyl ether, dioxane, and also ketones and nitriles, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; acetonitrile is preferably used.
The reaction may be carried out in the presence of an acid binding agent. All usual acid-binding agents can be used. However, alkali metal carbonates, for example sodium or potassium carbonate, alkali metal alcoholates, for example sodium or potassium methylate or ethylate, aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularly suitable.
The reaction temperatures can be varied within a wide range. In general the reaction is carried out at 40 to 120°C, preferably 70 to 90°C.
The reactions are in general allowed to take place at normal pressure.
In carrying out the processes, substantially equimolar amounts of the reagents may be reacted in one of the solvents mentioned, optionally in the presence of an acid-binding agent, at the temperatures indicated. In most cases the mixture is subsequently further stirred for some hours at elevated temperature and the batch then worked up according to usual methods.
Some of the substances according to the invention are produced as crystalline compounds and others in the form of last volatile constituents by so-called "slight distillation", that is to say prolonged heating to moderately elevated temperatures under reduced pressure, and can be purified in this manner. The refractive index and the elementary analysis above all serve for the characterisation of the substances.
As already briefly mentioned above, the new products are distinguished by an outstanding activity against plant pests, hygiene pests and pests of stored products, especially against biting and sucking insects and mites. At the same time they possess a fungicidal activity, especially against phytopatho-genic fungi on rice plants, for example Piricularia oryzae, and only a low phytotoxicity. The pesticidal effect starts rapidly and lasts for a long time. As regards their insect-icidal and acaricidal properties the products according to the present invention are unmistakably superior to the known active substances of analogous constitution and thus represent a genuine enrichment of the art.
For these reasons, the compounds according to the invention may be successfully employed as pesticides in plant protection and in the protection of stored products and in the hygiene field.
To the sucking insects there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosi-phum padi.), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii) , the currant gall aphid (Cryptomyzus korschelti), the mealy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) thrips (Thysanoptera) , such as Hercinothrips femoralis , and bugs, for example the beet bug (Piesma quadrata) , the cotton bug (Dysdercus intermedius), the bed bug (Gimex lectularius), the assassin bug (Rhodnius prolixus) and Ghagas' bug (Triatoma infestans) and, further, cicadas, such as Buscelis bilobatus and Nephotettix bipunctatus.
In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis) , the gipsy moth (Lymantria dispar) , the brown-tail moth (Euproctis chrysorr-hoea) and tent caterpillar (Malacosoma neustria) ; further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum) , the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata) , the green oak tortrix moth (Tortrix viridana) , the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura) , the ermine moth (Hyponomeuta padella) , the Mediterranean flour moth (Bphestia kuhniella) and greater wax moth (Galleria mellon-ella) .
Also to be classed with the biting insects are beetles ( Coleoptera) , for example the granary weevil (Sitophilus granarius = Calandra granaria) , the Colorado beetle (Leptinotarsa decemlineata) , the dock beetle (Gastrophysa viridula) , the mustard beetle (Phaedon cochleariae) , the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius = Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum) , the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum) , the yellow mealworm (Tenebrio molitor) but also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha) ; cockroaches, such as the German cockroach (Blattella germanica) , American cockroach (Periplaneta americana), Madeira cockroach(IOAicophaea or Rhyparobia madeirae), Oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger) .
The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster) , the Mediterranea fruit fly (Ceratitis capitata) , the house fly (Musca domestica), the little house fly (Fannia canicularis) , the black blow fly (Phormia aegina) and bluebottle fly (Galliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yello : fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles Stephens! ).
With the mites (Acari) there are classed, in particular, the spider mites ( Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pilbsus = Panonychus ulmi), blister mites, for example the currant blister mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus) ; finally, ticks, such as the relapsing fever tick (Ornithodorus moubata) . products, especially flies and midges, the process products are furthermore distinguished by an outstanding residual effec on timber and clay and by a good stability to alkali on lime-washed substrates.
The active compounds according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes or benzene, chlorinated aromatic hydrocarbons, such as chlorobenzenes, paraffins, such as mineral oil fractions, alcohols, such as methanol or butanol, or strongly polar solvents, such as dimethyl formamide or dimethyl sulphoxide, as well as water.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc or chalk, or ground synthetic minerals, such as highly-dispersed silicic acid or silicates.
Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers , such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates and aryl sulphonates; and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.
The active compounds accordin to the invention may be present in the formulations in admixture with other active compounds.
The active substance concentrations can be varied within a wide range for actual application. In general, concentrations of 0.00001 fo to 20 preferably of 0.01 # to 5 are used .
The active substances can be used as such or in the form of their formulatL ons or of the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, spraying powders, pastes, soluble powders, dusting agents and granules. They are applied in the usual manner, for example by pouring, spraying, atomising, fumigating, scattering, dusting and gassing.
In the veterinary medicine field the products are successfully employed against parasites of warm-blooded animals, particularly diptera larvae such as larvae of Lucilia cuprina, Lucilia sericat and Chrysomyia chloropyga. The dermal application in the veterinary field may take place in known manner, for example by dipping, spraying, pouring-on and powdering.
The invention therefore provides an insecticidal, acaricidal or fungicidal composition containing as active ingredient a compound according to the invention in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The invention also provides a method of combating insect, acarid or fungus pests which comprises applying to the pests or their habitat a compound according to the invention alone or in the form of a composition containing as active ingredient a compound according to the invention in admixture with a solid or liquid diluent or carrier.
The invention also provides crops protected from damage growing, a compound according to the invention was applied alone or in admixture with a solid or liquid diluent or carrier.
The outstanding insecticidal and acaricidal activity of the new products can be seen from the followin examples: Example A Phaedon larvae test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether .
To produce a suitable preparation of active compound, 1 part b 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.
Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochleariae) .
After the specified periods of time, the degree of destruction is determined as a percentage: 100 means that all the beetle larvae are killed. 0 means that none of the beetle larvae are killed.
The active compounds, the concentration of the active compounds, the times of evaluation and the results can be' seen from the following Table 1.
T a b l e 1 (contd) (Phaedon larvae test) .
Active compound Active compound Degree of (constitution) concentration destruction in fo in after 3 days a b l e 1 (contd) (Phaedon larvae test) Active compound Active compound Degree of ( constitution) concentration destruction in °/o in after 3 days (CH50) 2 a l e 1 ( contd) (Phaedon larvae test) Active compound , Active compound Degree of (constitution) concentration destruction in in °fa after 3 days (02H50)2 N G NC (G2H50) a l e 1 (contd) (Phaedon larvae test) Active compound Degree of concentration destruction in ° in after. 3 days (nG5H70)2P-0 a l e 1 ( contd) (Phaedon larvae test) Active compound Active compound Degree of (constitution) concentration destruction in o in " after 3 days Example B Myzus test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of 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.
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.
After the specified periods of time, the degree of destruction is determined as a percentage: 100 means that all the aphids are killed whereas ΟΌ means that none of the aphids are killed.
The active compounds, the concentrations of the active T a b l e 2 (Myzus test) Active compound Degree of concentration destruction in o in c/o after 24 hours 0.1 100 S " _ 0.01 100 (ic3V)2 p-°-r 0>001 20 N 0.0001 0 (known) (33) NG (known) (34) (35) 0.0001 20 T a b l e 2 (continuation) (Myzus Test) ee of ruction after 24 hours NO 0.1 100 (6) 0.00001 60 b 1 e 2 (continuation ( yzus Test) Active compound Active compound Degree of ( constitution) concentration destruction in o in fo after 24 hours (39) b 1 e 2 ( continuati (Myzus Test) Active compound Active compound Degree of ( constitution) concentration destruction in in °/o after 24 hours NC G¾ 0.1 100 C2H50 0.01 100 0.001 90 iC-^O (40) (42) 0.0001 20 C T a b l e 2 (continuation) (Myzus test) Active compound Active compound Degree of ( constitution) concentration destruction in o in v/o after 24 hours (44) T a b l e 2 ( continuation) (Myzus test) Active compound Active compound Degree of (constitution) concentration destruction in °/o after 24 hours Example G Doralis test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of 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 (Vicia faba) which have been heavily infested with the bean aphid (Doralis fabae) are sprayed with the preparation of the active compound until dripping wet.
After the specified periods of. time, the degree of destruction is determined as a percentage. 1005» means that all the aphids are killed; 0 means that none of the aphids are killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3' T b l e (Doralis Test) Active compound Active compound Decree of ( constitution) concentration .destruction in io in 7' after 24 hours (known) (45) 0.000.1 50 (46) NC T a b l e 3 ' (continuation) (Doralis Test) Active compound Active compound . Degree of (constitution) concentration destruction in fc in °o after 24 hours Example D Tetranychus test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of 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 so obtained is diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris), which have a height of approximately 10-30 cm. , are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetranychus urticae) in all After the specified periods of time, 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 0J¾ means that none of the spider mites are killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 4: T a b l e 4 (Tetranychus Test) Active compound Active compound Degree of ( constitution) concentration destruction in °/o in i after 48 hours (known) (known) ""¾ 0.1 0 T a l e 4 (continuat on) (Tetranychus Test) Active compound Active compound Degree of ( constitution) concentration destruction in jS. in "A after 48 ■ hours T a b l e 4 (continuation) (Tetranychus Test) Active compound Active compound Degree of ( constitution) concentration destruction in <° in after 48 hours (16) a b l e 4 ( continuation) (Tetranychus Test) Active compound Degree of concentration destruction in o in fo after 48 hours HC (50) C2H0 Example E Critical concentration test/soil insects Test insect: cabbage fly maggots (Phorbia brassicae) Solvent: 3 parts by weight of acetone Enulsifier: 1 part by weight of alkylarylpolygl col ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concen- tration. The preparation of active compound is intimately mixed with the soil. The concentration of the active compound in the preparation is of practically no importance; only the amount by weight of active compound per unit volume of soil, which is given in p.p.m., (e.g. mg/l), is decisive. The soil is filled into , pots and the pots are left to stand at room temperature. After 24 hours, the test animals are put into the treated soil, and after a further 48 hours the degree of effectiveness of the active compound is determined as a percentage by counting the dead and living test insects. The degree of effectiveness is 100?S when all the test insects have been killed; it is QFo when exactly as many test insects are still alive as in the case of the control.
The active compounds, the amounts applied and the results can be seen from the followin Table 5 '· T a b l e 5 (Phorbia brassicae Test) Active compound Ac ( constitution) co on 0 (known) (33) (known) (34) NG y 100 G2H5 20 100 90 Example F: Test on parasitic fly larvae Solvents: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether In order to manufacture an appropriate active compound preparation, 30 parts by weight of the active compound in question are mixed with the stated amount of solvent containing the abovementioned proportion of emulsifier, and the concentrate thus obtained is diluted to the desired concentration with water.
About 20 fly larvae (Chrysomyia chloropyga, lucilia sericata or Lucilia cuprina) are introduced into a test tube which contains 2 ml of the active compound preparation absorbed in cottonwool. After 48 hours the degree of destruction in <> is determined. Here Of* denotes that all larvae, have been killed. 0?S denotes that no larvae whatsoever have been killed..
The active compounds tested, use concentrations and test results can be seen from Table 6 belo : ·· . ·.. . a b l e 6 a b l e 6 (continued) Active compound Active compound Degree of (constitution) concentration destruction in ppm in °fi 3 =-50 Example G Piricularia test: liquid preparation of active compound Solvent: 4 parts by weight of acetone Dispersing agent: 0.05 part by weight of sodium oleate Other additives: 0.2 part by weight of gelatine Water: 95.75 parts by weight The amount of active compound required for the desired concentration in the spray liquor is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water containing the stated additives. rice plants about 14 days old are sprayed with the spray liquor until dripping wet. The plants remain in a greenhouse at temperatures of 22 to 24°C and a relative atmospheric humidity of about 70?ί until they are dry. They are /then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Piriculari . oryzae and placed in, a chamber at 24-26°C and 100?¾ relative atmospheric humidity. days after inoculation, the infestation of all the leaves present at the time of inoculation is determined as a percentage of the · untreated but also inoculated control plants. Q?° means no infestation; means that the infestation is exactly as great in the case of the control plants., The active compounds, the concentrations of the active compounds and the results can be seen from the following Table T a l e 7 Piricularia Test/liquid ive compound concentration Active compound Infection in of infection ( constitution) of the untreated control at an active compound concentration '(in fo) of 0.05 0.025 (3) (55) T a l e 7 Piricularia Test/liquid active compound concentration Active compound Infection in of infection (constitution) of the untreated control at an active compound concentration (in fo) of 0.05 0.025 (10) (45) (56) (57) Example 1. 49 g (0.3 mol) of 2-hydroxy-3-cyan-6-isopropylpyridine are boiled for 30 minutes under reflux with 42 g of finely powdered dry potassium carbonate in 500 ml of acetonitrile. 52 g (0.3 mol) of 0-ethyl-ethane-thionophosphonic acid ester chloride are then added to the mixture at 70°C whilst stirring and the mixture is stirred for a further three hours at elevated temperature. Thereafter the reaction mixture is treated with 500 ml of benzene and the benzene solution is washed with water, 2 N sodium hydroxide solution and again with water to remove the soluble products. After drying the organic phase over sodium sulphate and evaporating off the solvent, a yellowish oil remains which is freed of volatile constituents by "initial distillation" at 70°C/0.01 mm Hg. 82 g (92 o of theory) of 0-ethyl-0-[ 3-cyan-6-isopropyl-pyridyl (2) ]-ethanethionophosphonic acid ester having a refractive index n = 1.5273 are obtained.
Calculated for Gi3Hig 202PS (molecular weight 298.3): N P S Found: 9.23 10.68 10.75 Example 2: ■A 55.6 g of finely powdered sodium salt of 2-hydroxy-3-cyan-6-isopropyl-pyridine are suspended in 500 ml of acetonit-rile and thereafter the procedure described in Example 1 is followed. The yield is 79 g (88 of theory) of 0-ethyl-0-[ 3-cyan-6-isopropylpyridyl-( 2) J-ethanethionophosphonic acid ester. The compound is identical with the product obtained according to Example 1 in thin layer chromatography and also on the basis of the nuclear resonance spectrum and IR spectrum.
The sodium salt of the 2-hydroxy-3-cyan-6-isopropyl-pyridine required as the starting material can be obtained by suspending 2-hydroxy-3-cyan-6-isopropyl-pyridine in hot ethan-ol, adding the equimolar amount of a solution of sodium raethy-late in methanol dropwise to this suspension whilst stirring, warming the mixture for 30 minutes to 60 - 70°C and then evaporating off the alcohol. The solid residue is stirred with benzene and the benzene solution is again evaporated, finally on a boiling water-bath at 10 mm Hg. The product thus obtained can irimediatel be reacted further.
Tables 8 to 13 give the properties of a number of compounds obtained by methods analogous to. hose which have just been described.
The compounds are all of the formula (I) as indicated below In all these tables, the group X I YR of formula (I) is identified under the heading ¾.
In table 8, R2 is methyl and R^ is also methyl.
In table 9, 2 is methyl and is hydrogen. b 1 R is iso ro l and is h dro en.
In table 12, 2 is phenyl and R^ is hydrogen.
In table 13, R2 is tertiary butyl and R^ is hydrogen. 12 233 - 43 - Table 8 Yield (#) Melti g point N . of theory [°C] calculated found calcula -P /C2H5 39 78 9.85 9.78 10.92 \0C2H5 Table 8 (continuation) Z Yield (#) Melting point 22 N of theory [°C] D calculated found calcula P(OG3H?n)2 1.5130 8.53 8.11. 9.45 P(0C3H?i)2 43 80 8.53 8.80 9.45 Table 8 (continuation) Yield (#). Melting point 22 „. of theory [°C] D calculated found calcula V (OC3H?i)2 30 45 8.96 8.71 9.94 Table 9 Z Yield io Melting point N of theory [°C] D calculated found calculat 0 .P(0C2H5)2 78 23°/1.4880 -PtOC L- 70 42 9.79 9.73 10.84 5 0 - (θσ3Η?η)2 78 25°/l.4840 9.39 8.81 10.40 S I -P(0C,H^n)o 86 25°/1.5960 8.90 8.20 9.91 l . 0 1 -P(0C H i) 65 56 9.39 9.22 10.40 Table 9 (continuation) H Yield Melting point ηβ N of theory [°C] calculated found calcul 64 24°/1.5337 10.39 9.89 11.46 0C2H5 Table 9 (continuation jj/N(cV; 32 70 15.61 15.51 11.5 ^OC2H5 Table 10 /°2H5 -P 92 22°/l.5273 9.39 9.23 10.40 OG2H5 0 II -P (OC H ) 40 22°/l.4900 9.39 9.45 10.38 O -P (0C2H5)2 73 22°/1.5140 8.91 8.83 9.85 -P 59 22°/l.5271 9.85 9.96 10.92 C2H5 Table 10 (continuation) Yield Melting point ¾ N of theory [°GJ calculated found calcula 87 24°/l.4829 8.58 8.49 9.52 P (OG3H?i)2 87 24°/l.5022 8.18 8.19 9.07 60 26°/1.5051 8.53 8.49 9.45 Table 10 (continuation) -P (0G3H7i)2 89 24°/l.4787 8.58 8.15 Table 11 Yield io nD N P of theory calculated found calculated -PiOCH^ 64 24°/l.5305 10.31 ■P(0G2H5)2 82 24°/l.5091 8.53 8.51 9.45 ■P(OC5H7n)2 89 24°/l.4772 71 24°/l.5023 7.86 7.56 8.70 ■P(OG3H7i)2 90 24°/l.4801 8.23 8.36 9.12 ■P(0C3H?i)2 88 24°/l.4980 7.86 7.62 8.70 Table 11 (continuation) >0H3 70 24°/1.5221 9.39 9.31 ' OC2H5 I /C2H5 P. 70 24°/l.5217 8.97 8.70 ^OC H 92 24°/1.5245 8.58 8.62 9.52 Table 11 (continuation) Yield 1o nD N P of theory calculated found calculated S -C6H5 -P: 78 24VI.5632 7.77 7.72 OC2H5 -P 88 24V1.4959 13.50 13.15 9.95 N(CH3)2 »/H CH3 2 -P, 93 melting n 18.05 17.94 9.98 N(CH5)2 point 67 C Table 12 -P(0C2H5)2 50 88 8.43 8.38 9.38 \J1 -P(0C2H5)2 50 64 8.04 8.15 8.89 Table 12 (continuation) 0 1 -P(OC,H„n) 63 51 7.77 7.73 8.59 —3 I -PiOC^i) 56 75 7.77 7.59 8.59 -P.. 56 113 8.80 8.89 9.73 OG2H5 Table 12 (continuatio ? N(CH5)2 - 71 175 16.96 16.40 9.37 N(GH3)2 Table 15 Yield # 24 N P of theory D calculated found calculated •P(OG2H5)2 69 1.5001 •P(0C2H5)2 78 1.5153 8.53 8.17 9.43 0 .PiOC^ ^ 82 1.4850 8.23 8.09 9.10 Table 15 (continuation) Yield of theory D calculated ound calcula e 76 1.5660 7.77 7.66 8.59
Claims (70)
1. Phosphoric-(phosphonic)- and thionophosphoric-(phosphonic) -acid esters, ester amides and diamides of the general formula in which R2 is aryl or straight-chain or branched alkyl with 1 to 6 carbon atoms, R^ is hydrogen or methyl, R is straight-chain or branched alkyl with 1 to 6 carbon atoms , R^ is straight-chain or branched alkyl with 1 to 6 carbon atoms or alkoxy, monoalkylamino or dialkylamino or, if 2 is aryl or alkyl with 2 to 6 carbon atoms, ^ may be aryl, X is oxygen or sulphur, and Y is oxygen, monoalkylamino or NH-.
2. Compounds according to claim 1 in which R^ is phenyl or alkyl with 1 to 4 carbon atoms; R is alkyl with 1 to 4 carbon atoms; R1 is alkyl, alkoxy, monoalkylamino or dialkylamino with 1 to 4 carbon atoms in each alkyl group or, if R2 is phenyl or alkyl with 2 to 4 carbon atoms, 1 may be phenyl; and Y is oxygen, monoalkylamino with 1 to 4 carbon atoms or H-.
3. The compound of the formula
4. The compound of the formula
5. The compound of the formula
6. The compound of the formula
7. The compound of the formula
8. The compound of the formula
9. The compound of the formula
10. The compound of the formula
11. The compound of the formula
12. The compound of the formula
13. The compound of the formula
14. The compound of the formula
15. The compound of the formula
16. The compound of the formula
17. The compound of the formula
18. The compound of the formula
19. The compound of the formula
20. The compound of the formula
21. The compound of the formula (
22. The compound of the formula
23. The compound of the formula
24. The compound of the formula
25. The compound of the formula
26. The compound of the formula
27. The compound of the formula
28. The compound of the formula
29. The compound of the formula
30. The compound of the formula G
31. The compound of the formula
32. The compound of the formula
33. The compound of the formula (
34. The compound of the formula
35. The compound of the formula NC
36. The compound of the formula NC
37. The compound of the formula
38. The compound of the formula (
39. The compound of the formula iC3H70^:P-0 CH3
40. The compound of the formula
41. The compound of the formula
42. The compound of the formula NG S (43) C2H5- II •P-0 GH(GH^) , C2H50
43. The compound of the formula NC (44) (C2H50)2 -0 N %CH -CH(C¾ V) 2
44. The compound of the formula (
45. The compound of the formula
46. The compound of the formula
47. The compound of the formula
48. The compound of the formula
49. The compound of the formula NG
50. The compound of the formula
51. The compound of the formula
52. The compound of the formula
53. The compound of the formula
54. A process for the production of a compound according to any of claims 1 - 53 in which either a 2-hydroxy-3-cyano-pyri-dine derivative of the general formula is reacted with a (thiono) phosphoric (phosphonic)-acid ester, ester amide or diamide halide of the general formula or a 2-halogeno-3-cyano-pyridine derivative of the general formula is reacted with a (thio) phosphoric (phosphonic)-acid or salt of the general formula R, R^, R2, R^, X and Y have the same meaning as in Claim 1, whilst Hal is chlorine or bromine and M is hydrogen, sodium, potassium or ammonium.
55. A process according to claim 54 in which the compound of formula (II) or (IV) is one of these hereinbefore specifically mentioned.
56. A process according to claim 54 or 55 in which the compound of formula (III) or (V) is one of these hereinbefore specifically mentioned.
57. A process according to any of claims 54 - 56 in which the reaction is carried out in the presence of an acid-binding agent.
58. A process according to any of claims 54 - 57 in which the reaction is carried out in the presence of a solvent.
59. A process according to claim 58 in which the solvent is acetonitrile.
60. A process according to any of claims 54 - 59 in which the reaction is carried out at 40 - 120°C.
61. A process according to claim 60 in which the reaction is carried out at 70 - 90°C.
62. A process for the production of a compound according to claim 1, substantially as hereinbefore described in Example 1 or 2.
63. Compounds according to claim 1 whenever prepared by a process according to any of claims 54 - 62.
64. An insecticidal, acaricidal or fungicidal composition containing as active ingredient a compound according to any of claims 1 - 53 or 63 in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
65. A composition according to claim 64 containing from 0.1
66. A method of combating insect, acarid or fungus pests which comprises applying to the pests or a habitat thereof a compound according to any of claims 1 - 53 or 63 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 - 53 or 63 in admixture with a solid or liquid diluent or carrier.
67. A method according to claim 66 in which a composition is used containing from 0.0001 to 2Qff<> of the active compound, by weight.
68. A method according to claim 66 or 67 in which the active compound is applied to an area of agriculture.
69. A method according to claim 66 or 67 in which the active compound is applied against parasites of domestic animals.
70. Crops protected from damage by insect, acarid or fungus pests being grown in areas in which, immediately prior to and/or during the time of the growing, a compound according to any of claims 1 - 53 or 63 was applied alone or in admixture with a solid or liquid diluent or carrier.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691927643 DE1927643A1 (en) | 1969-05-30 | 1969-05-30 | Phosphorus (phosphonic) or thionophosphorus (phosphonic) acid esters, ester amides or diamides, processes for their preparation and their use as insecticides, acaricides and fungicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL34448A0 IL34448A0 (en) | 1970-07-19 |
| IL34448A true IL34448A (en) | 1973-01-30 |
Family
ID=5735668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL34448A IL34448A (en) | 1969-05-30 | 1970-05-04 | Phosphoric,thionophosphoric,phosphonic and thionophosphonic acid esters,ester amides and diamides,their production and their use as insecticides,acaricides and fungicides |
Country Status (15)
| Country | Link |
|---|---|
| JP (2) | JPS526342B1 (en) |
| AT (1) | AT297027B (en) |
| BE (1) | BE751171A (en) |
| CH (1) | CH498157A (en) |
| CS (1) | CS161749B2 (en) |
| DE (1) | DE1927643A1 (en) |
| DK (1) | DK128121B (en) |
| ES (1) | ES380220A1 (en) |
| FR (1) | FR2043833A1 (en) |
| GB (1) | GB1263652A (en) |
| IL (1) | IL34448A (en) |
| NL (1) | NL7007733A (en) |
| PL (1) | PL69776B1 (en) |
| RO (1) | RO58847A (en) |
| SU (1) | SU460631A3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3445465A1 (en) * | 1984-12-13 | 1986-06-19 | Bayer Ag, 5090 Leverkusen | PYRIMIDINYL THIONOPHOSPHORIC ACID ESTER |
-
1969
- 1969-05-30 DE DE19691927643 patent/DE1927643A1/en active Pending
-
1970
- 1970-05-01 CH CH660070A patent/CH498157A/en not_active IP Right Cessation
- 1970-05-04 IL IL34448A patent/IL34448A/en unknown
- 1970-05-14 RO RO63358A patent/RO58847A/ro unknown
- 1970-05-28 NL NL7007733A patent/NL7007733A/xx unknown
- 1970-05-28 JP JP45045255A patent/JPS526342B1/ja active Pending
- 1970-05-28 JP JP45045254A patent/JPS4817277B1/ja active Pending
- 1970-05-29 AT AT481470A patent/AT297027B/en not_active IP Right Cessation
- 1970-05-29 SU SU1443808A patent/SU460631A3/en active
- 1970-05-29 BE BE751171D patent/BE751171A/en unknown
- 1970-05-29 DK DK278870AA patent/DK128121B/en unknown
- 1970-05-29 FR FR7019721A patent/FR2043833A1/fr not_active Withdrawn
- 1970-05-29 PL PL1970140959A patent/PL69776B1/pl unknown
- 1970-05-29 GB GB26028/70A patent/GB1263652A/en not_active Expired
- 1970-05-29 CS CS3788A patent/CS161749B2/cs unknown
- 1970-05-30 ES ES380220A patent/ES380220A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SU460631A3 (en) | 1975-02-15 |
| GB1263652A (en) | 1972-02-16 |
| DK128121B (en) | 1974-03-04 |
| IL34448A0 (en) | 1970-07-19 |
| FR2043833A1 (en) | 1971-02-19 |
| BE751171A (en) | 1970-11-30 |
| CH498157A (en) | 1970-10-31 |
| ES380220A1 (en) | 1972-08-16 |
| AT297027B (en) | 1972-03-10 |
| DE1927643A1 (en) | 1970-12-03 |
| JPS526342B1 (en) | 1977-02-21 |
| NL7007733A (en) | 1970-12-02 |
| RO58847A (en) | 1976-03-15 |
| PL69776B1 (en) | 1973-08-31 |
| CS161749B2 (en) | 1975-06-10 |
| JPS4817277B1 (en) | 1973-05-28 |
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