DE2358760A1 - O,S-dialkyl O-(3,5,6-trichloro-2-pyridyl) dithiophosphates - with high insecticidal and acaricidal activity, but low toxicity to mammals - Google Patents
O,S-dialkyl O-(3,5,6-trichloro-2-pyridyl) dithiophosphates - with high insecticidal and acaricidal activity, but low toxicity to mammalsInfo
- Publication number
- DE2358760A1 DE2358760A1 DE2358760A DE2358760A DE2358760A1 DE 2358760 A1 DE2358760 A1 DE 2358760A1 DE 2358760 A DE2358760 A DE 2358760A DE 2358760 A DE2358760 A DE 2358760A DE 2358760 A1 DE2358760 A1 DE 2358760A1
- Authority
- DE
- Germany
- Prior art keywords
- compounds according
- dithiophosphates
- formula
- acid
- trichloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 238000003860 storage 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Zentralbereich Patente, Marken und LizenzenCentral area of patents, trademarks and licenses
Pyridindithiophosphorsäureester, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Insektizide und : Akarizide Pyridinedithiophosphoric acid esters, process for their preparation and their use as insecticides and : acaricides
Die vorliegende Erfindung betrifft neue Pyridindithiophosphorsäureester, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Insektizide und. Akarizide.The present invention relates to new pyridinedithiophosphoric acid esters, a process for their production and their use as insecticides and. Acaricides.
Es ist bereits bekannt, daß Pyridinthiophosphorsäureester, z.B. 0,0-Diäthyl-0-_J,5,6-trichlorpyridin(2.)yl_7-thionophosphorsäureester, gute insektizide Eigenschaften besitzen (vergleiche USA-Patentschrift 3.244.586). Diese Verbindungen haben jedoch eine hohe Warmblütertoxizität.It is already known that pyridinthiophosphoric acid esters, e.g. 0,0-diethyl-0-_J, 5,6-trichloropyridin (2.) yl_7-thionophosphoric acid ester, have good insecticidal properties (see US Pat. No. 3,244,586). These However, compounds have high toxicity to warm blooded animals.
Es wurde nun gefunden, daß die neuen Pyridindithiophosphorsäureester der lOrmelIt has now been found that the new pyridinedithiophosphoric acid ester the lOrmel
S' 0IS ' 0 I.
(I) Gl(I) Eq
in welcherin which
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R und R1 gleiche oder verschiedene Alkylreste mit je 1 bis 4 Kohlenstoffatomen bedeuten,R and R 1 are identical or different alkyl radicals each having 1 to 4 carbon atoms,
eine sehr gute insektizide und akarizide Wirksamkeit und darüber hinaus eine geringe Yiarmblütertoxizität aufweisen. have a very good insecticidal and acaricidal effectiveness and, in addition, a low blood toxicity.
Weiterhin wurde gefunden, .daß die neuen Pyridindithiophosphorsäureester der Konstitution (I) erhalten werden, wenn man OjS-Dialkylthionothiolphosphorsäureesterhalogenide der FormelIt has also been found that the new pyridinedithiophosphoric acid esters of constitution (I) can be obtained if OjS-dialkylthionothiolphosphoric acid ester halides the formula
R1SR 1 S
iP-Hal (II)iP-Hal (II)
in welcherin which
R und R1 die oben genannte Bedeutung haben und Hai ein Halogen-, vorzugsweise Chloratom bedeutet,R and R 1 have the meaning given above and Hal is a halogen, preferably chlorine atom,
mit 2-Hydroxy-3,5»6-triehlorpyridin der Formelwith 2-hydroxy-3,5 »6-triehlorpyridine of the formula
(III)(III)
in Gegenwart eines Säureakzeptors oder in Form ihrer Alkali-, Erdalkali oder Ammoniumsalze umsetzt.in the presence of an acid acceptor or in the form of their alkali, alkaline earth or ammonium salts.
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Ueberraschenderweise besitzen die erfindungsgemäßen Pyridind!thiophosphorsäureester eine bessere insektizide Wirkung.bei wesentlich geringerer Warmblütertoxizität als vorbekannte Verbindungen analoger Konstitution und gleicher Wirkungsrichtung.Surprisingly, the pyridine thiophosphoric acid esters according to the invention have a better insecticidal effect. with significantly lower warm-blooded toxicity as previously known compounds of analogous constitution and the same direction of action.
Die erfindungsgemäßen Stoffe stellen somit eine echte Bereicherung der Technik dar.The substances according to the invention thus represent a real one Enrichment of technology.
Verwendet man beispielsweise O-Aethyl-S-sec.-butyl-thionothiolphosphorsäurediesterchlorid und das JTatriumsalz des 2-Hydroxy-3,5,6-trichlorpyridins als Ausgangsstoffe, so kann der Reaktionsverlauf durch folgendes S1 ormelschema wiedergegeben werden:If, for example O-ethyl-S-sec-butyl-thionothiolphosphorsäurediesterchlorid and JTatriumsalz of 2-hydroxy-3,5,6-trichlorpyridins as starting materials, the course of the reaction can be represented by the following S 1 ormelschema:
S
C2H5O χ „^ + Sa0 J^-σΐ Säureakzeptor S.
C 2 H 5 O χ "^ + Sa0 J ^ -σΐ acid acceptor
. NaC1 . NaC1
C2H5OxS WC 2 H 5 O x SW
SeC-C4H9S' N-=/SeC-C 4 H 9 S 'N - = /
ClCl
Die verfahrensgemäß verwendbaren Ausgangsstoffe sind durch die Pormeln (II) und (III) allgemein eindeutig definiert. In der Formel (II) stehen R und R1 vorzugsweise für geradkettiges oder verzweigtes Alkyl mit 1 bis 3 Kohlenstoffatomen.The starting materials which can be used according to the process are generally clearly defined by the formulas (II) and (III). In formula (II), R and R 1 preferably represent straight-chain or branched alkyl having 1 to 3 carbon atoms.
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Die als Ausgangsstoffe zu verwendenden O,S-Dialkylthionothiolphosphorsäureesterhalogenide (II) sind in der Literatur beschrieben und nach üblichen Verfahren zugänglich (vergleiche UdSSR-Patentschrift 184.863 und bekanntgemachte Japanische Patentanmeldung 5536/72), ebenso wie das 2-Hydroxy-3,5,6-trichlorpyridin /vergleiche Recueil des Traveaux Chimiques des Pays Bas 70. (1951), S. 182_7«The O, S-dialkylthionothiolphosphoric acid ester halides to be used as starting materials (II) are described in the literature and can be obtained by customary methods (See USSR patent specification 184,863 and published Japanese patent application 5536/72), as well as the 2-hydroxy-3,5,6-trichloropyridine / compare Recueil des Traveaux Chimiques des Pays Bas 70. (1951), p. 182_7 «
Als Beispiele für die Ο,Β-Dialkylthionothiolphosphorsäurediesterhalogenide (II) seien im einzelnen genannt:As examples of the Ο, Β-dialkylthionothiolphosphoric acid diester halides (II) are mentioned in detail:
0,3-Dimethyl-, O,S-Diäthyl-, O,S-Di-n-propyl-, O,S-Diiso-propyl-, O-Äthyl-S-n-propyl-, O-Äthyl-S-iso-propyl-, O-n-Propyl-S-iso-propylthionothiolphosphorsäurediesterchlorid bzw. -bromid.0,3-dimethyl-, O, S-diethyl-, O, S-di-n-propyl-, O, S-diiso-propyl-, O-ethyl-S-n-propyl-, O-ethyl-S-iso-propyl-, O-n-propyl-S-iso-propylthionothiolphosphoric acid diester chloride or bromide.
Das Herstellungsverfahren wird bevorzugt unter Mitverwendung geeigneter Lösungs- und Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Solventien infrage. Hierzu gehören insbesondere aliphatische und aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Benzin, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, oder Äther, z.B. Diäthyl— und Dibutyläther, Dioxan, ferner Ketone, beispielsweise Aceton, Methyläthyl-, Methylisopropyl- und Methylisobutylketon, außerdem Nitrile, wie Aceto- und Propionitril.The production process is preferably carried out using suitable solvents and diluents. Practically all inert organic solvents can be used as such. This includes in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, Methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ethers, e.g. diethyl and dibutyl ethers, Dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also nitriles, such as aceto- and propionitrile.
Als Säureakzeptoren können alle üblichen Säurebindemittel Verwendung finden. Besonders bewährt haben sich Alkalicarbonate und -alkoholate, wie Natrium- und Kaliumcarbonat, -methylat bzw. -äthylat, ferner aliphatische, aromatische oder heterocyclische Amine, beispielsweise Triethylamin, Dimethylamin, Dimethy!anilin, Dirnethylbenzylamin und Pyridin.All customary acid binders can be used as acid acceptors. Alkali carbonates have proven particularly useful and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethyl aniline, dimethylbenzylamine and pyridine.
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Statt in Gegenwart von Säurebindemitteln zu arbeiten, ist es ebenso gut möglich, zunächst Salze, vorzugsweise die Alkali- oder Ammoniumsalze des 2-Hydroxy-3,5,6-trichlor-pyridins (III) in Substanz herzustellen und diese anschließend weiter umzusetzen.Instead of working in the presence of acid binders, it is just as well possible to first use salts, preferably the alkali or ammonium salts of 2-hydroxy-3,5,6-trichloropyridine (III) to produce in substance and then to implement it further.
Die Reaktionstemperatur kann innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man zwischen O und 100, vorzugsweise bei 10 bis 60 C.The reaction temperature can be within a greater Range can be varied. In general, one works between 0 and 100, preferably at 10 to 60 C.
Die Umsetzung wird im allgemeinen bei Normaldruck vorgenommen. The reaction is generally carried out under normal pressure.
Zur Durchführung des Verfahrens vereinigt man vorzugsweise äquimolare Mengen der Reaktionskomponenten bei den angegebenen Temperaturen gegebenenfalls in Gegenwart eines Säurealczeptors und eines der oben genannten Lösungsmittel. Nach mehrstündiger Reaktion bei erhöhten Temperaturen kühlt man die Mischung ab, gießt sie in Wasser und nimmt das sich ausscheidende Öl in. einem organischen Lösungsmittel, z.B. Methylenchlorid, .auf„ Die organische Phase wird mit Wasser, verdünnter Natronlauge, dann nochmals mit Wasser gewaschen9 nach dem Trocknen das Lösungsmittel unter vermindertem Druck entfernt und der Rückstand "andestilliert".To carry out the process, equimolar amounts of the reaction components are preferably combined at the stated temperatures, if appropriate in the presence of an acid acceptor and one of the abovementioned solvents. After several hours reaction at elevated temperatures, the mixture is cooled, poured into water and takes the precipitating oil in. An organic solvent such as methylene chloride, .to "The organic phase is washed with water, dilute sodium hydroxide solution, then washed again with water 9 after drying, the solvent is removed under reduced pressure and the residue is "partially distilled".
Die neuen Verbindungen fallen zum Teil in Form von Ölen ans die sich meist nicht unzersetzt destillieren lassen, Jedoch durch sogenanntes "Andestillieren", d.h.. durch längeres Erhitzen unter vermindertem Druck auf mäßig erhöhte Temperaturen von den letzten flüchtigen AnteilenThe new compounds are the usually can not be distilled without decomposition, but "incipient distillation", that is partly in the form of oils to s. by prolonged heating under reduced pressure to moderately elevated temperatures of the last volatile components
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1 ffS Ci Ö "9 "^i / (TU!1 ffS Ci Ö "9 " ^ i / (TU!
1 SJ SJ CS & ΰ> e SiJ ·1 SJ SJ CS &ΰ> e SiJ
befreit und auf diese Weise gereinigt werden. Zu ihrer Charakterisierung dient der Brechungsindex.freed and purified in this way. The refractive index is used to characterize them.
Wie bereits mehrfach erwähnt, zeichnen sich die erfindungsgemäßen Pyridindithiophösphorsäureester durch eine
hervorragende insektizide und akarizide Wirksamkeit
bei geringer Warmblutertoxizität aus. Die erfindungsgemäßen
Stoffe können sowohl gegen pflanzenschädigende Insekten und Milben als auch gegen Hygiene- und Vorratsschädlinge
eingesetzt werden. Aus diesem Grunde finden die neuen Verbindungen im Pflanzenschutz sowie auf dem Hygiene- und
Vorratsschutzsektor als Schädlingsbekämpfungsmittel Verwendung.As already mentioned several times, the pyridinedithiophosphoric acid esters according to the invention are distinguished by an excellent insecticidal and acaricidal activity
with low warm blood toxicity. The substances according to the invention can be used both against insects and mites which are harmful to plants and against hygiene and storage pests. For this reason, the new compounds are used as pesticides in crop protection and in the hygiene and stored products sector.
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Zu den saugenden Insekten gehören im wesentlichen Blattläuse (Aphidae) wie die grüne Pfirsichblattlaus (Myzus persicae), die schwarze Bohnen- (Doralis fabae), Hafer- (Rhopalosiphum padi), Erbsen- (Macrosiphum pisi) und Kartoffellaus (Macrosiphum solanifolii), ferner die Johannisbeergallen- (Cryptomyzus korschelti), mehlige Apfel- (Sappaphis mali), mehlige Pflaumen-(Hyalopterus arundinis) und schwarze Kirschenblattlaus (Myzus cerasi), außerdem Schild- und Schmierläuse (Coccina), z.B. die Efeuschild- (Aspidiotus hederae) und Napfschildlaus (Lecanium hesperidum) sowie die Schmierlaus (Pseudococcus maritimus); Blasenfüße (Thysanoptera) wie Hercinothrips femoralie und Wanzen, beispielweeise die Rüben- (Piesma quadrata), Baumwoll-(Dysdercus intermedius), Bett- (Cimex lectularius), Raub-(Rhodnius prolixus) und Chagaswanze (Triatoma infestans), ferner Zikaden, wie Euscelis bilobatus und Nephotettix bipunctatus. The sucking insects essentially include aphids (Aphidae) such as the green peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato mouse (Macrosiphum solanifolii) the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as scale and mealybugs (Coccina), e.g. the ivy shield (Aspidiotus hederae) and the cupfish (Lecanium hesperidum) and the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralie and bed bugs, for example beet bugs (Piesma quadrata), cotton bugs (Dysdercus intermedius), bed bugs (Cimex lectularius), predatory bugs (Rhodnius prolixus) and Chagas bug (Triatoma infestans), and also cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus.
Bei den beißenden Insekten wären vor allem zu nennen Schmetterlingsraupen (Lepidoptera) wie die Kohlschabe (Plutella maculipennis), der Schwammspinner (Lymantria dispar), Goldafter (Euproctis chrysorrhoea) und Ringelspinner (Malacosoina neustria), weiterhin die Kohl- (Mamestra brassicae) und die Saateule (Agrotis segetum), der große Kohlweißling (Pieris brassicae), kleine Frostspanner (Cheimatobia brumata), Eichenwickler (Tortrix viridana), der Heer- (Laphygma frugiperda) und aegyptische Baumwollwurm (Prodenia litura), ferner die Gespinst-(Hyponomeuta padella), Mehl- (Ephestia kühniella ) und große Wachsmotte (Galleria.mellonella),Among the biting insects, butterfly caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden eel (Euproctis chrysorrhoea) and ring moth (Malacosoina neustria), furthermore the cabbage (Mamestra brassicae) and the brassicae Seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frost worms (Cheimatobia brumata), oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian cotton worms (Prodenia litura padella), also the web (Hyponomeuta padella) , Flour (Ephestia kühniella) and large wax moth (Galleria.mellonella),
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Weiterhin zählen zu den beißenden Insekten Käfer (Coleoptera) ζ·Β. Korn- (Sitophilus granarius = Calandra granaria), Kartoffel- (Leptinotarsa decemlineata), Ampfer- (Gastrophysa viridula), Meerrettichblatt- (Phaedon cochleariae), Rapsglanz-(Meligethes aeneus), Himbeer- (Byturus tomentosus), Speisebohnen- (Bruchidius s Acanthoscelides obtectus), Speck-(Dermestes frischi), Khapra- (Trogoderma granarium), rotbrauner Reismehl- (Tribolium castaneum), Mais- (Calandra oder Sitophilus zeamais), Brot- (Stegobium paniceum), gemeiner Mehl- (Tenebrio molitor) und Getreideplattkäfer (Oryzaephilus surinamensis), aber auch im Boden lebende Arten z. B. Drahtwttrmer (Agriotes spec.) und Engerlinge (Melolontha melolontha); Schaben wie die Deutsche (Blattella germanica), Amerikanische (Periplaneta americana), Madeira- (Leucophaea oder Rhyparobia madera·), Orientalische (Blatte orientalis), Riesen- (Blaberus giganteus) und schwarze Riesenschabe (Blaberus fuscus) sowie Henschoutedenia flexivitta; ferner Orthopteren z.B. das Heimchen (Oryllus domesticus)j Termiten wie die Erdtermite (Reticulitermes flavipes) und Hymenopteren wie Ameisen, beispielsweise die Wiesenameise (Lasius niger).The biting insects also include beetles (Coleoptera) ζ · Β. Corn (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table bean (Bruchidius s Acanthoscelides obtectus), bacon (Dermestes frischi), khapra (Trogoderma granarium) Rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. B. Wirewttrmer (Agriotes spec.) and grubs (Melolontha melolontha); Cockroaches like that German (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia madera), Oriental (Blatte orientalis), giant (Blaberus giganteus) and black giant cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Oryllus domesticus) j termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).
Die Dipteren umfassen im wesentlichen Fliegen wie die Tau-(Drosophila melanogaster), Mittelmeerfrucht- (Ceratitis capitata), Stuben- (Musca domestica), kleine Stuben- (Fannia canicularis), Glanz- (Phormia regina) und Schmeißfliege (Calliphora erythrocephala) sowie den Wadenstecher (Stomoxys calcitrans); ferner Mücken, z.B. Stechmücken wie die Gelbfieber- (Aedes aegypti), Haus- (Culex pipiens) und Malariamücke (Anopheles Stephens!)o The Diptera essentially include flies such as the dew (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicularis), glossy (Phormia regina) and blowfly (Calliphora erythrocephala) as well the calf stick (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles Stephens!) etc.
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Zu den Milben (Acari) zählen besonders die Spinnmilben (Tetranychidae) wie die Bohnen- (Tetranychus telarius = " Tetranychus althaeae oder Tetranychus urticae) und die Obstbaumspinnmilbe (Paratetranychus pilosus = Panonychus ulmi), Gallmilben, z.B. die Johannisbeergallmilbe (Eriophyes ribis) und Tarsonemiden "bsispielsweise die Triebspitzenmilbe (Hemitarsonemus latus) und Cyclamenmilbe (Tarsonemus pallidus); schließlich Zecken wie die Lederzecke (Ornithodorus moubata).The mites (Acari) include spider mites in particular (Tetranychidae) like the bean (Tetranychus telarius = " Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), Gall mites, e.g. the currant gall mite (Eriophyes ribis) and tarsonemids, e.g. the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).
Bei der Anwendung gegen Hygiene- und Vorratsschädlinge, besonders Fliegen und Mücken,- zeichnen sich die Verfahrensprodukte außerdem durch ein© hervorragende Residualwirkung auf Holz und Ton sowie eine gute Alkalistabilität auf gekalkten Unterlagen aus»When used against hygiene pests and pests, particularly flies and mosquitoes - the process products are also distinguished by a © excellent residual action on wood and clay and a good stability to alkali on limed substrates "
Le A 15 562 - '8 Le A 15 562 - '8
Die erfindungsgemäßen Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln s also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als HilfslÖsungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, Benzol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid,The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are prepared in known manner, for example by mixing the active compounds with extenders s that is liquid solvents, pressurized liquefied gases and / or solid carriers, optionally with the use of surfactants, that is emulsifiers and / or dispersants and / or foam-forming agents. If water is used as an extender, organic solvents, for example, can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride,
aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionens Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und.unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe, z.B. Freon; als feste Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluciuiuiaoxid und Silikate; als Emulgier- und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren» wie PoIyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol-Ä'ther, z.B. Alkylaryl-polyglyko 1-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z.B. Lignin, Sulfitablaugen und Methylcellulose. Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in MiscliiHig mit anderen bekannten Wirkstoffen vorliegen.aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, s alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons, for example freon; as solid carrier substances: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as highly disperse silica, aluminum oxide and silicates; as emulsifiers and / or foam-producing agents: nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglyco 1 ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose. The active ingredients according to the invention can be present in the formulations mixed with other known active ingredients.
MJk 15—362 - 9 -MJk 15-362 - 9 -
533323/0966533323/0966
Die Formulierlangen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %. The formulation lengths generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 %.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder in den daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Emulsionen9 Schäume, Suspensionen, Pulver, Pasten, lösliche Pulver, Stäubmittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Verspritzen, Versprühen, Vernebeln', Verstäuben, Verstreuen, Verräuchern, Vergasen, Gießen, Beizen oder Inkrustieren. The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready solutions, emulsions 9 foams, suspensions, powders, pastes, soluble powders, dusting agents and granules. They are used in the customary manner, for example by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zube- reitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10 %, vorzugsweise zwischen 0,01 und 1 %. ■The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1 %. ■
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wo es möglich ist, Formulierungen bis zu 95 % oder sogar den 100 %-Igen Wirkstoff allein auszubringen.The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations of up to 95% or even the 100% active ingredient alone.
Le A 15 562 - 10 - Le A 15 562 - 10 -
503823/0966503823/0966
Tetranychus-Test (resistent)Tetranychus test (resistant)
Lösungsmittel: 3 Gewichtsteile Aceton Emulgator : 1 Gewichtsteil AlkylarylpolyglykolatherSolvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und. der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration. Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and. the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.
Mit der Wirkstoff zubereitung werden Bohnenpflanzen (Ehaseolus vulgaris), die ungefähr eine Höhe von 10 bis 30 cm haben, tropfnaß besprüht. Diese Bohnenpflanzen sind stark mit allen Entwicklungsstadien der 'gemeinen Spinnmilbe oder Bohnenspinnmilbe (Tetranychus urticae) befallen.With the active ingredient preparation, bean plants (Ehaseolus vulgaris), which are approximately 10 to 30 cm in height, sprayed dripping wet. These bean plants are strong with everyone Stages of development of the common spider mite or bean spider mite (Tetranychus urticae).
Nach den angegebenen Zeiten wird die Wirksamkeit der Wirkstoffzubereitung bestimmt, indem man die toten Tiere auszählt. Der so erhaltene Abtötungsgrad wird in % angegeben. 100 % bedeutet, daß alle Spinnmilben abgetötet wurden, 0 % bedeutet, daß keine Spinnmilben abgetötet wurden.After the specified times, the effectiveness of the active compound preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in % . 100 % means that all spider mites have been killed, 0 % means that none of the spider mites have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle -\ hervor:Active ingredients, active ingredient concentrations, evaluation times and results are shown in the following table - \ :
Ie A 15 362 . - 11 - Ie A 15 362 . - 11 -
509823/0966509823/0966
Tabelle 1 (Tetranychus-Test) Table 1 (Tetranychus test)
Wirkstoff YJirkstoffkonzen- Abtötungsgrad inActive ingredient Y active ingredient concentration degree of destruction in
tration in fo nach 2 Tagentration in fo after 2 days
0,02 250.02 25
(bekannt)(known)
0,1 1000.1 100
0,02 ' 900.02 '90
Le A" 15 362 - 12Le A "15 362 - 12
Si"S82S /(D)SSSSi "S82S / (D) SSS
Beispiel B
Toxizitäts-Test / peroral Example B.
Toxicity test / perorally
Versuchstier: Auswertung nach:Test animal: evaluation according to:
Albinoratte (Rattus norvegicus) 7 TagenAlbino rat (Rattus norvegicus) 7 days
Zur Herstellung einer geeigneten Wirkstoffzubereitung vermischt man 3 Gewichtsteile Wirkstoff mit 2,8 Gewichtsteilen hochdisperser Kieselsäure und 4,2 Gewichtsteilen Talkum. Unter Zugabe von etwas pulverisiertem .Pflanzengummi stellt man aus diesem Wirkstoffkonzentrat durch Anreiben mit Wasser Suspensionen her, die in 1 ml Flüssigkeit die pro 100 g Tiergewicht zu appliaierende Wirkstoffmenge enthalten. Die Dosierung erfolgt nach Wägung der Versuchstiere volumetrisch. Appliziert wird mittels einer stählernen Knopfsonde per os. Die Auswertung erfolgt jeweils nach Ablauf der oben angegebenen Zeitspanne, gerechnet von der Applikation des Wirkstoffs. To produce a suitable preparation of active ingredient, 3 parts by weight of active ingredient are mixed with 2.8 parts by weight highly disperse silica and 4.2 parts by weight of talc. With the addition of some powdered vegetable gum one from this active ingredient concentrate by rubbing with water suspensions, which in 1 ml of liquid per 100 g Animal weight to be applied amount of active ingredient contained. The dosage takes place volumetrically after weighing the test animals. It is applied per os using a steel button probe. The evaluation is carried out in each case after the above specified period of time, calculated from the application of the active ingredient.
Die Bestimmung der LD^Q-Werte (Wirkstoffdosis, mit der 50 $ der behandelten Tiere abgetötet werden) erfolgt aus den Mortalitätswerten der in geometrischer Progression variierten Dosen in üblicher Weise.The determination of the LD ^ Q values (active ingredient dose, with the $ 50 of the treated animals are killed) is carried out from the mortality values which varied in geometric progression Doses in the usual way.
Le A 15 362 - 13 -Le A 15 362 - 13 -
50S823/096650S823 / 0966
Tabelle (loxizitäts-Test Albinoratt e/peroral) Table (loxicity test Albinoratt e / peroral)
LD_n-¥erte 50LD_ n - ¥ erte 50
Wirkstoff · (in mg/kg Körpergewicht)Active ingredient (in mg / kg body weight)
(bekannt)(known)
Cl ^xCl
C2H5°4 Λ X, 25°-5ΟΟ Cl ^ x Cl
C 2 H 5 ° 4 Λ X, 2 5 ° -5ΟΟ
Le A 15 362 - 14 - Le A 15 362 - 14 -
583823/0966583823/0966
m mm m
Beispiel 1; Q-V^ Example 1; Q - V ^
C2HC 2 H
n-C-H,,S 3 7n-C-H ,, S 3 7
Zu 10 g (0,05 MoI) des Natriumsalzes von 2-Hyd-roxy-3,5»6-trichlorpyridin in 200 ml trockenem Acetonitril tropft man bei 20 bis 25°C 10,4 g O-Äthyl-S-n-propylthionothiolphosphorsäurediesterchlorid. Die Mischling wird zur Vervollständigung der Reaktion noch 6 Stunden unter Rühren auf 600C erwärmt. Dann kühlt man sie ab, gießt das Reaktionsgemiseh in ca. 1 1 Wasser und nimmt das sich ausscheidende Öl in Methylenchlorid auf. Die organische Phase wird mit Wasser, verdünnter Natronlauge, anschließend nochmals mit Wasser gewaschen, über Natriumsulfat getrocknet, das Lösungsmittel unter vermindertem Druck entfernt und der verbleibende Rückstand andestilliert. Man erhält 6 g (31,5 i° der Theorie) O-Äthyl-S-n-propy1-0-/3,5,6-trichlorpyrid(2)yl_7-thionothiolphosphorsäureester mit dem Brechungsindex n-.: 1,5710,10.4 g of O-ethyl-Sn-propylthionothiolphosphoric acid diester chloride are added dropwise at 20 to 25 ° C. to 10 g (0.05 mol) of the sodium salt of 2-hydroxy-3,5 »6-trichloropyridine in 200 ml of dry acetonitrile. To complete the reaction, the hybrid is heated to 60 ° C. for a further 6 hours while stirring. They are then cooled, the reaction mixture is poured into about 1 liter of water and the oil which separates out is taken up in methylene chloride. The organic phase is washed with water, dilute sodium hydroxide solution, then again with water, dried over sodium sulfate, the solvent is removed under reduced pressure and the residue that remains is distilled off. This gives 6 g (31.5 i ° of theory) of O-ethyl-Sn-propy1-0- / 3,5,6-trichloropyrid (2) yl_7 thionothiolphosphorsäureester-n having the refractive index .: 1.5710,
Le A 15 362 - 15 - Le A 15 362 - 15 -
509823/0966509823/0966
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2358760A DE2358760A1 (en) | 1973-11-26 | 1973-11-26 | O,S-dialkyl O-(3,5,6-trichloro-2-pyridyl) dithiophosphates - with high insecticidal and acaricidal activity, but low toxicity to mammals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2358760A DE2358760A1 (en) | 1973-11-26 | 1973-11-26 | O,S-dialkyl O-(3,5,6-trichloro-2-pyridyl) dithiophosphates - with high insecticidal and acaricidal activity, but low toxicity to mammals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2358760A1 true DE2358760A1 (en) | 1975-06-05 |
Family
ID=5899052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2358760A Pending DE2358760A1 (en) | 1973-11-26 | 1973-11-26 | O,S-dialkyl O-(3,5,6-trichloro-2-pyridyl) dithiophosphates - with high insecticidal and acaricidal activity, but low toxicity to mammals |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2358760A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021041A1 (en) * | 1979-06-15 | 1981-01-07 | BASF Aktiengesellschaft | 6-Fluoropyridyl-(di)(thio)phosphoric acid esters, process for their preparation and their use in combating pests |
-
1973
- 1973-11-26 DE DE2358760A patent/DE2358760A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021041A1 (en) * | 1979-06-15 | 1981-01-07 | BASF Aktiengesellschaft | 6-Fluoropyridyl-(di)(thio)phosphoric acid esters, process for their preparation and their use in combating pests |
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