DE2409462A1 - 0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES - Google Patents
0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDESInfo
- Publication number
- DE2409462A1 DE2409462A1 DE2409462A DE2409462A DE2409462A1 DE 2409462 A1 DE2409462 A1 DE 2409462A1 DE 2409462 A DE2409462 A DE 2409462A DE 2409462 A DE2409462 A DE 2409462A DE 2409462 A1 DE2409462 A1 DE 2409462A1
- Authority
- DE
- Germany
- Prior art keywords
- ethyl
- propyl
- active ingredient
- formula
- compounds according
- 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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- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BGJMXJAEITUIDV-UHFFFAOYSA-N ethylperoxy-hydroxy-propoxy-sulfanylidene-lambda5-phosphane Chemical compound C(C)OOP(OCCC)(O)=S BGJMXJAEITUIDV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- YYJNOYZRYGDPNH-MFKUBSTISA-N fenpyroximate Chemical compound C=1C=C(C(=O)OC(C)(C)C)C=CC=1CO/N=C/C=1C(C)=NN(C)C=1OC1=CC=CC=C1 YYJNOYZRYGDPNH-MFKUBSTISA-N 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000020044 madeira Nutrition 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N methyl iso-propyl ketone Natural products CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000391 smoking effect Effects 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
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- 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
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Zentralbereich Patente, Marken und LizenzenCentral area of patents, trademarks and licenses
Hu/Hg 5Q9 Leverkusen, BayerwerkHu / Hg 5Q 9 Leverkusen, Bayerwerk
O-Äthyl-O-n-propyl-O-vinyl-thionophosphorsäureester, Verfahren zu ihrer Herstellung und ihre Verwendung als Insektizide und N AkarizideO-ethyl-on-propyl-O-vinyl-thionophosphoric acid ester, process for their preparation and their use as insecticides and N acaricides
Die vorliegende Erfindung betrifft neue O-Äthyl-O-n-propyl-O-vinyl-thiophosphorsäureester, Verfahren zu ihrer Herstellung und ihre Verwendung als Insektizide und Akarizide.The present invention relates to new O-ethyl-O-n-propyl-O-vinyl-thiophosphoric acid ester, Process for their preparation and their use as insecticides and acaricides.
Es ist bereits bekannt, daß 0,0-Dialkyl-0-cyano-vinyl(thiono)-phosphorsäureester, z.B. 0,0-Diäthyl-0-/T-(4f-methyl- bzw. -4'-chlorphenyl)-2-cyano-vinyl7-phosphorsäureester und O,O-Diäthyl-0-/T-(2'-methyl- bzw. -2'-ChIOr- bzw. -2',5'-dichlor- oder -4'-methoxyphenyl)-2-cyanovinyl7-thionophosphorsäureester insektizide und akarizide Eigenschaften besitzen (vgl. deutsche Offen-Iegungsschrift 2 030 509).It is already known that 0,0-dialkyl-0-cyano-vinyl (thiono) -phosphoric acid ester, e.g. 0,0-diethyl-0- / T- (4 f -methyl- or -4'-chlorophenyl) - 2-cyano-vinyl7-phosphoric acid ester and O, O-diethyl-0- / T- (2'-methyl- or -2'-Chlor- or -2 ', 5'-dichloro- or -4'-methoxyphenyl ) -2-cyanovinyl7-thionophosphoric acid esters have insecticidal and acaricidal properties (cf. German Offenlegungsschrift 2 030 509).
Es wurde gefunden, daß die neuen O-Äthyl-0-n-propyl-O-vinylthionophosphorsäureester der FormelIt has been found that the new O-ethyl-0-n-propyl-O-vinylthionophosphoric acid ester the formula
(D(D
. S I \n I. S I \ n I.
^P-O-C=CH-CN^ P-O-C = CH-CN
in welcherin which
R und R1 gleiche oder verschiedene Alkyl- oder Alkoxy-R and R 1 identical or different alkyl or alkoxy
reste mit jeweils 1 bis 4 C-Atomen oder Halogenradicals each with 1 to 4 carbon atoms or halogen
Le A 15 5oo - 1 -Le A 15 5oo - 1 -
509840/1100509840/1100
bedeuten, und
K darüber hinaus für Wasserstoff steht,mean, and
K also stands for hydrogen,
eine ausgezeichnete insektizide, auch bodeninsektizide und akarizide Wirkung besitzen.have an excellent insecticidal, also soil insecticidal and acaricidal effect.
Die allgemeine Formel (I) schließt dabei die entsprechenden eis-, und trans-Isomeren der Konstitution (II) und (III) und Mischungen dieser Komponenten ein:The general formula (I) includes the corresponding cis and trans isomers of the constitution (II) and (III) and Mixtures of these components:
C2H5O SC 2 H 5 OS
J Γ\ C* Π XJ Γ\ QJ Γ \ C * Π XJ Γ \ Q
^ £5°\ fi C2H5°\J^ £ 5 ° \ fi C 2 H 5 ° \ J
P-O ,CN P-O HP-O, CN P-O H
/"< y* pi TT f\' / "<y * pi TT f \ ' C* Γ*C * Γ *
\H 3 7\ H 3 7
R R'R R '
(H) (III)(H) (III)
Weiterhin wurde gefunden, daß die neuen O-Äthyl-0-n-propyl-O-vinyl-thionophosphorsäureester der Konstitution (I) erhalten werden, wenn man O-Äthyl-0-n-propylthionophosphorsäurediesterhalogenide der FormelIt has also been found that the new O-ethyl-0-n-propyl-O-vinyl-thionophosphoric acid ester of constitution (I) can be obtained when using O-ethyl-0-n-propylthionophosphoric acid diester halides the formula
NP-HaI N P-HaI
in welcherin which
Hal ein Halogen-, vorzugsweise Chloratom, bedeutet,Hal is a halogen, preferably chlorine atom,
mit CJ-Cyanacetophenon-Derivaten (Benzoylacetonitrilen) der Formel (V) bzw. deren Enolform der Formel (Va)with CJ-cyanoacetophenone derivatives (benzoylacetonitriles) der Formula (V) or its enol form of the formula (Va)
Le A 15 5oo - 2 -Le A 15 5oo - 2 -
509840/1100509840/1100
NC-CH2-C=O . NC-CH=C-OMNC-CH 2 -C = O. NC-CH = C-OM
"bzw."respectively.
(V) (Va)(V) (Va)
in welcherin which
R und R1 die oben angegebene Bedeutung haben und M ein Alkali-, Erdalkali- oder Ammoniumäquivalent bedeutet,R and R 1 have the meaning given above and M is an alkali, alkaline earth or ammonium equivalent,
gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Lösungsmittels umsetzt.optionally in the presence of an acid acceptor and optionally reacts in the presence of a solvent.
überraschenderweise zeichnen sich die eriindungsgemäßen O-Äthyl-O-n-propyl-O-vinyl-thionophosphorsäureester (i) durch eine bessere insektizide, auch bodeninsektizide und akarizide Wirkung bei geringer Warmblütertoxizitat gegenüber vorbekannten Verbindungen analoger Konstitution und gleicher Wirkungsrichtung aus. Die erfindungsgemäßen Stoffe stellen somit eine echte Bereicherung der Technik dar.Surprisingly, those according to the invention stand out O-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid ester (i) a better insecticidal, also soil insecticidal and acaricidal effect with low warm-blooded toxicity compared to previously known ones Compounds of analogous constitution and the same direction of action. The substances according to the invention thus represent a a real asset to technology.
Verwendet man z.B. O-Äthyl-0-n-propyl-thionophosphorsäurediesterchlorid und cJ-Cyan-2-methylacetophenon bzw. das entsprechende Natriumsalz als Ausgangsstoffe, so kann der Reaktionsablauf durch d.ie folgenden Formeischeraatä wiedergegeben werden:If, for example, O-ethyl-0-n-propyl-thionophosphoric acid diester chloride is used and cJ-cyano-2-methylacetophenone or the corresponding If sodium salt is used as the starting material, the course of the reaction can be represented by the following formulas will:
Le A 15 5o.o - 3 -Le A 15 5o.o - 3 -
§09840/1100§09840 / 1100
P-C1 + NC-CH2-C-P-C1 + NC-CH 2 -C-
CH,CH,
P-O-C=CHCNP-O-C = CHCN
P-Cl + NC-CH=C-P-Cl + NC-CH = C-
CHCH
■A■ A
Das als Ausgangsmaterial zu verwendende O-Äthyl-0-n-propylthionophosphorsäurediesterhalogenid (IV), die Ketoverbindungen (V) und deren Enolform sind durch die obigen Formeln eindeutig allgemein definiert. Vorzugsweise stehen in den Formeln (V) und (Va) jedoch:The O-ethyl-0-n-propylthionophosphoric acid diester halide to be used as the starting material (IV), the keto compounds (V) and its enol form are clear from the above formulas generally defined. However, the formulas (V) and (Va) preferably contain:
R für Wasserstoff, Methyl, Äthyl, Methoxy, ithoxy, Chlor,R for hydrogen, methyl, ethyl, methoxy, ithoxy, chlorine,
Brom oder Fluor und
R1 für Methyl, Äthyl, Methoxy, Äthoxy, Chlor, Brom oder Fluor;Bromine or fluorine and
R 1 represents methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine;
insbesondere bedeutet
R Wasserstoff und
R1 Methyl, Äthyl, Methoxy, Äthoxy, Chlor, Brom, Fluorin particular means
R hydrogen and
R 1 methyl, ethyl, methoxy, ethoxy, chlorine, bromine, fluorine
oderor
R Methyl, Äthyl und
R' Methyl, Äthyl, Chlor, Brom, Fluor,R methyl, ethyl and
R 'methyl, ethyl, chlorine, bromine, fluorine,
oder R und Rf Chlor, Brom und Fluor.or R and R f are chlorine, bromine and fluorine.
Le A 15 5ooLe A 15 5oo
509 8AO/1100509 8AO / 1100
Das als Ausgangsstoff zu verwendende O-Äthyl-0-n-propylthionophosphorsäurediesterchlorid (IV) ist in der Literatur beschrieben und nach üblichen Methoden zugänglich, ebenso wie die iij-Cyanacetophenone (V) bzw. deren Enolform (Va) (vgl. deutsche Offenlegungsschrift 2 o3o 5o9)> welche nach prinzipiell bekannten Verfahren hergestellt werden können, z. B. indem manThe O-ethyl-0-n-propylthionophosphoric acid diester chloride to be used as the starting material (IV) is described in the literature and accessible by customary methods, as well like the iij-cyanoacetophenones (V) or their enol form (Va) (see German Offenlegungsschrift 2 o3o 5o9)> which after methods known in principle can be produced, e.g. B. by
a) Acetonitril mit Phenylcarbonsäureestern in Gegenwart von Alkoholaten bei erhöhten Temperaturen gegebenenfalls in einem Lösungsmittel umsetzt und anschließend das Reaktionsgemisch mit Säuren behandelt: a) Acetonitrile with phenyl carboxylic acid esters in the presence of alcoholates at elevated temperatures, if appropriate in a solvent and then the reaction mixture is treated with acids:
R . 1) Alkoholat 0R. 1) alcoholate 0
s. *———» Ils. * ——— »Il
CH,-CN + <* ^-CO9AIk 2) Erwärmen NC-CH9-CCH, -CN + <* ^ -CO 9 AIk 2) heating NC-CH 9 -C
π ι ^x- 'π ι ^ x- '
3)3)
oderor
b) die entsprechenden Pheny!verbindungen mit Acetylchlorid in Gegenwart von Aluminiumchlorid umsetzt, das Zwischenprodukt bromiert und schließlich das Brom gegen die Cyangruppe austauscht: b) the corresponding phenyl compounds with acetyl chloride in Reacts the presence of aluminum chloride, the intermediate product is brominated and finally the bromine is exchanged for the cyano group:
-H + CH3-C-Cl I^ CH3-C-// -% -H + CH 3 -C-Cl I ^ CH 3 -C - // -%
H0C C-//H 0 C C - //
-^=^ R1 R R1 - ^ = ^ R 1 RR 1
fr ?l r-^* NaCNf r ? l r- ^ * NaCN
HoC b-(/ ^V v NC-CH=C-ONaHoC b - (/ ^ V v NC-CH = C-ONa
2 \ V ^2 \ V ^
Le A 15 5oo - 5 -Le A 15 5oo - 5 -
5098A0/11005098A0 / 1100
c) entsprechend substituierte aromatische Nitrile mit Acetonitril in Gegenwart eines Alkalimetalls umsetzt und das entstehende Ketimin mit Säure spaltet:c) reacting appropriately substituted aromatic nitriles with acetonitrile in the presence of an alkali metal and that resulting ketimine splits with acid:
NH j NH j
NHNH
Na R , ^ [j SäureNa R, ^ [j acid
,-C-C, -C-C
\V-CN + CH5CN . ^V ^-C-CH2-CN .\ V-CN + CH 5 CN. ^ V ^ -C-CH 2 -CN.
R1' RR 1 'R
R MR M
A-C-CH2-CN
RAC-CH 2 -CN
R.
Als Beispiele für die verwendbaren cj-Cyanacetoph'enon-Derivate (V) bzw. deren Enolform (Va) seien im einzelnen genannt:As examples of the usable cj-cyanoacetoph'enone derivatives (V) or their enol form (Va) are mentioned in detail:
2-Methyl-, 2-Äthyl-, 2-Methoxy-, 2-Äthoxy-, 2-Chlor-, 2-Brom-, 2-Fluor-, 3-Methyl-·, 3-Äthyl-, 3-Methoxy-, 3-Äthoxy-, 3-Chlor-, 3-Brom-, 3-Pluor-, 4-Methyl-, 4-Äthyl-, 4-Methoxy-, 4-Äthoxy-, 4-Chlor-, 4-Brom-, 4-Fluor-, 2,5-Dichlor-, 2,5-Dibrom-, 4,5-Dibrom-, 4,6-Dimethyl-, 4,6-Diäthyl-W-cyano-acetophenon sowie die entsprechenden Natriumsalze der Enolform.2-methyl, 2-ethyl, 2-methoxy, 2-ethoxy, 2-chloro, 2-bromine, 2-fluoro, 3-methyl, 3-ethyl, 3-methoxy , 3-ethoxy, 3-chlorine, 3-bromine, 3-fluorine, 4-methyl, 4-ethyl, 4-methoxy, 4-ethoxy, 4-chlorine, 4-bromine , 4-fluoro, 2,5-dichloro, 2,5-dibromo, 4,5-dibromo, 4,6-dimethyl, 4,6-diethyl-W-cyano-acetophenone and the corresponding sodium salts of Enol form.
Das Herstellungsverfahren wird bevorzugt unter Mitverwendung geeigneter Lösungs- und Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Solventien infrage. Hierzu gehören insbesondere aliphatisch^ und aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Benzin, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, oder Äther, z. B.The production process is preferably carried out using suitable solvents and diluents. Practically all inert organic solvents can be used as such. These include in particular aliphatic ^ and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ethers, e.g. B.
Le A 15 5oo - 6 -Le A 15 5oo - 6 -
509840/1100509840/1100
Diäthyl- und Dibutyläther, Dioxan, ferner Ketone, beispielsweise Aceton, Methyläthyl-, Methylisopropyl- und Methy}.isobutylketon, außerdem Nitrile, wie Aceto- und Propionitril.Diethyl and dibutyl ethers, dioxane, and 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 Triäthylamin, Trimethylamin, 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, trimethylamine, dimethyl aniline, dimethylbenzylamine and pyridine.
Die Reaktionstemperatur kann innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man zwischen 0 und loo, vorzugsweise bei 2o bis 55 C.The reaction temperature can be varied within a relatively wide range. Generally one works between 0 and loo, preferably at 2o to 55 C.
Die Umsetzung läßt ruan im allgemeinen bei Normaldruck ablaufen. The reaction can generally proceed at normal pressure.
Zur Durchführung des Verfahrens setzt man die Ausgangsstoffe im allgemeinen in äquimolaren Verhältnissen ein. Ein Überschuß der einen oder anderen Reaktionskomponente bringt im allgemeinen keine wesentlichen Vorteile. Die Umsetzung wird bevorzugt in Anwesenheit eines der oben genannten Solventien gegebenenfalls in Gegenwart eines Säureakzeptors bei den angegebenen Temperaturen vorgenommen. Nach ein- bis mehrstündiger Reaktionsdauer, meist bei erhöhter Temperatur, kühlt man den Ansatz ab und gießt das Reaktionsgemisch in ein organisches Lösungsmittel, z. B. Toluol. Anschließend wird die Reaktionsmischung in üblicher Weise durch Waschen mit einer gesättigten Natriumbicarbonatlösung und Wasser, Trocknen der organischen Phase, Verdampfen des Lösungsmittels und gegebenenfalls Destillation des Rückstandes aufgearbeitet.To carry out the process, the starting materials are generally employed in equimolar proportions. An excess one or the other reaction component generally has no significant advantages. The implementation is preferred in the presence of one of the abovementioned solvents, if appropriate in the presence of an acid acceptor for the specified ones Temperatures made. After a reaction time of one to several hours, usually at an elevated temperature, the is cooled Approach and pour the reaction mixture into an organic solvent, for. B. toluene. The reaction mixture is then in the usual manner by washing with a saturated Sodium bicarbonate solution and water, drying of the organic phase, evaporation of the solvent and optionally Worked up distillation of the residue.
Die neuen Verbindungen fallen in Form von Ölen an, die sich meist nicht unzersetzt destillieren lassen, jedoch durchThe new compounds are obtained in the form of oils which, in most cases, cannot be distilled undecomposed, but through
Le A 15 5oo - 7 -Le A 15 5oo - 7 -
509840/1100509840/1100
sogenanntes "Andestillieren", d* h. längeres Erhitzen unter vermindertem Druck auf mäßig erhöhte Temperaturen von den letzten flüchtigen Anteilen befreit und auf diese Weise gereinigt werden können. Zu ihrer Charakterisierung dient der Brechungsindex.so-called "Andes tillieren", d * h. prolonged heating under reduced pressure to moderately elevated temperatures freed from the last volatile constituents and cleaned in this way. The refractive index is used to characterize them.
Wie bereits mehrfach erwähnt, zeichnen sich die erfindungsgemäßen O-Äthyl-O-n-propyl-O-vinyl-thionophosphorsäureester durch eine hervorragende insektizide, auch bodeninsektizide und akarizide Wirksamkeit aus. Sie wirken dabei gegenüber Pflanzen-, Hygiene- und" Vorratsschädlingen und besitzen bei sehr geringer Phytotoxizität sowohl eine gute Wirkung gegen saugende als auch fressende Insekten.As already mentioned several times, the O-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid esters according to the invention are distinguished by an excellent insecticidal, also soil insecticidal and acaricidal effectiveness. They act against plant, hygiene and "storage pests" and contribute to very low phytotoxicity and a good effect against sucking as well as eating insects.
Aus diesem Grunde können die erfindungsgemäßen Verbindungen mit Erfolg im Pflanzenschutz sowie, auf dem Hygiene- und Vor ratsschutzsektor eingesetzt werden.For this reason, the compounds according to the invention can be used successfully in crop protection as well as on hygiene and before Council protection sector are used.
In den nachstehenden Anwendungsbeispielen A bis F wurden die erfindungsgemäßen Wirkstoffe hinsichtlich ihrer Wirksamkeit gegen eine Reihe von Pflanzenschädlingen im Vergleich zu den mit (A) bis (F) bezeichneten bekannten O,O-Dialkyl-0-cyanovinyl(thiono)phosphorsäureestern der folgenden Konstitution getestet:In the following application examples A to F, the active ingredients according to the invention were tested in terms of their effectiveness against a number of plant pests in comparison to the known O, O-dialkyl-0-cyanovinyl (thiono) phosphoric acid esters designated with (A) to (F) the following constitution tested:
OCH,OCH,
S ηS η
(A) (C2H5O)2P-O-C=CH-CN (B) (C2H5O)2P-O-C=CH-CN(A) (C 2 H 5 O) 2 POC = CH-CN (B) (C 2 H 5 O) 2 POC = CH-CN
CH,CH,
(C) (C2H5O)2P-O-C=CH-CN (D) (C2H5O)2P-O-C=CH-CN(C) (C 2 H 5 O) 2 POC = CH-CN (D) (C 2 H 5 O) 2 POC = CH-CN
(E) (C2H5O)2P-O-C=CH-CN (F) (C2H5O)2P-O-C=CH-CN(E) (C 2 H 5 O) 2 POC = CH-CN (F) (C 2 H 5 O) 2 POC = CH-CN
Le A 15 500Le A 15 500
509840/1100509840/1100
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 Kartoflellaus (Macrosiphum
solanifolii), ferner die Johannisbeergallen- (Cryptomyzus korschelti), mehlige Apfel- (Sappaphis mall), 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 mainly include aphids
(Aphidae) such as the green peach aphid (Myzus persicae),
the black bean (Doralis fabae), oat (Rhopalosiphum
padi), pea (Macrosiphum pisi) and potato peas (Macrosiphum solanifolii), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mall), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as black cherry aphid (Myzus cerasi) - and mealybugs (Coccina), for example the ivy shield louse (Aspidiotus hederae) and cup scale louse (Lecanium hesperidum) as well as 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 bugs (Triatoma infestans),
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 (Malacosoma 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) and golden juices should be mentioned in particular
(Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frost moth (Cheimatobia brumata), oak moth (Tortrix viridana), the Army (Laphygma frugiperda) and Egyptian cotton worms (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones
Wax moth (Galleria mellonella),
Le A 15 5oo - 9 -Le A 15 5oo - 9 -
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Weiterhin zählen zu den beißenden Insekten Käfer (Coleoptera) z.B. Korn- (Sitophilus granarius = Calandra granaria), Kartoffel- (Leptinotarsa decemlineata), Ampfer- (Gastrophysa viridula), Meerrettichblatt- (Phaedon cochleariae), Rapsglanz-(Meligethes aeneus), Himbeer- (Byturus tomentosus), Speisebohnen- (Bruchidius = Acanthoscelides obtectus), Speck-(Dermestes frischl), 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. Drahtwürmer (Agriotes spec.) und Engerlinge (Melolontha melolontha); Schaben wie die Deutsche (HLsttella germanica), Amerikanische (Periplaneta americana), Madeira- (Leucophaea oder Rhyparobia maderae), Orientalische (Blatta orientalis), Riesen- (Blaberus giganteus) und schwarze Riesenschabe (Blaberus fuscus) sowie Henschoutedenia flexivitta; ferner Orthopteren z.B. das Heimchen (Gryllus domesticus); Termiten wie die Erdtermite (Reticulitermes flavipes) und Hymenopteren wie Ameisen, beispielsweise die Wiesenameise (Lasius niger).Furthermore, the biting insects include beetles (Coleoptera) e.g. grain (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes Frischl), Khapra- (Trogoderma granarium), red-brown 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 such. B. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like that German (HLsttella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant cockroach (Blaberus giganteus) and black cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Gryllus domesticus); 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 stephensi)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 stephensi) etc.
Le A It 5oo - Io -Le A It 5oo - Io -
509840/1100509840/1100
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 Tarsoneraiden beispielsweise die Triebspitzenmilbe (Hemitarsonemus latus) und Cyclamenmilbe (Tarsonemus pallidus); schließlich Zecken wie die Lederzecke (Ornithodorus moubata).The mites (Acari) include especially the spider mites (Tetranychidae) such as 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 tarsoneraids, 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 eine hervorragende Residualwirkung auf Holz und Ton sowie eine gute Alkalistabilität auf gekalkten Unterlagen aus.When used against hygiene and storage pests, especially flies and mosquitoes, the process products are also characterized by an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.
509840/1100509840/1100
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, 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 ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solids Carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Using water 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. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methy1-äthylketon, 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, Aluminiumoxid und Silikate; als Emulgier- und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren, wie PoIyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglykol-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z.B. Lignin, Sulfitablaugen und Methylcellulose. Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen. Le a. 15 5oo - 12 -aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, 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; by 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 powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, 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 polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose. The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds. Le a. 15 5oo - 12 -
509840/1100509840/1100
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 % .The formulations 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, Emulsionen, 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 ingredients can be used as such, in the form of their formulations or in the application forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, Powders, pastes, soluble powders, dusts and granules can be applied. The application happens in the usual way, e.g. by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen 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 %-±gen 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 5oo - 13 -Le A 15 5oo - 13 -
509 8AO/1100509 8AO / 1100
?£09462? £ 09462
Beispiel A
Drosophila-Test Example A.
Drosophila test
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.
1 cm der Wirkstoffzubereitung wird auf eine Filter papierscheibe mit 7 cm Durchmesser aufpipettiert. Man Ie ■ diese naß auf die Öffnung.eines Glasgefäßes, in dem si h rjG Taufliegen (Drosophila melanogaster) befinden und be . jI;-*- sie mit einer Glasplatte.1 cm of the active compound preparation is pipetted onto a filter paper disk with a diameter of 7 cm. One Ie ■ this wet to the Öffnung.eines glass vessel located in the si h r jG fruit flies (Drosophila melanogaster) and be. jI; - * - them with a glass plate.
Nach den angegebenen Zeiten bestimmt man die A^t: L, ng in %. Dabei bedeutet 100 %, daß alle Fliegen abgetötet --Ien.After the specified times, the A ^ t: L, ng is determined in %. 100 % means that all flies have been killed --Ien.
Wirkstoffe, Wirkstoff konzentrat ionen, Auswertung ., . Abtötungsgrad gehen aus der nachfolgenden TabelActive ingredients, active ingredient concentrations, evaluation.,. The degree of death can be found in the following table
Le A 15 5oo -H-Le A 15 5oo -H-
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Tabelle 1
(Drosophila-Test) Table 1
(Drosophila test)
Wirkstoff Wirkstoff- AbtötungsgradActive ingredient active ingredient kill rate
konzentration in # nach in ia 1 Tagconcentration in # after in generally 1 day
(A) o,o1 20(A) o, o1 20
(5) o,o1 1oo(5) o, o1 1oo
o,oo1 100o, oo1 100
(2) o,o1 1oo(2) o, o1 1oo
o,oo1 100o, oo1 100
Ie A 15 5oo - 15 -Ie A 15 5oo - 15 -
509840/1100509840/1100
Beispiel B
Plutella-Test Example B.
Plutella test
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.For the production of an appropriate preparation of active substance mixed 1 part by weight of active ingredient is diluted with the stated amount of solvent and the stated amount of emulsifier the concentrate with water to the desired concentration.
Mit der Wirkstoffzubereitung besprüht man Kohlblätter (Brassica oleracea) taufeucht und besetzt sie mit Raupen der Kohlschabe (Plutella maculipennis).Cabbage leaves are sprayed with the active compound preparation (Brassica oleracea) becomes dewy and populates them with caterpillars of the cabbage moth (Plutella maculipennis).
Nach den angegebenen Zeiten wird der Abtötungsgrad in % bestimmt. Dabei bedeutet 100 %, daß alle Raupen getötet wurden, während 0 % angibt, daß keine Raupen getötet wurden.After the specified times, the degree of destruction is determined in % . 100% means that all of the caterpillars have been killed, while 0 % indicates that no caterpillars have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle 2 hervor:Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below:
Le A 15 5oo - 16 -Le A 15 5oo - 16 -
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Tabelle 2Table 2
konzentration
in <?» Active ingredient
concentration
in <? »
in io nach
3 TagenDegree of destruction
in io after
3 days
o,oo1o, o1
o, oo1
01oo
0
o,oo1o, o1
o, oo1
090
0
o,oo1o, o1
o, oo1
9o1oo
9o
o,oo1o, o1
o, oo1
1oo1oo
1oo
o,oo1o, o1
o, oo1
1oo1oo
1oo
o,oo1o, o1
o, oo1
1oo1oo
1oo
o,oo1o, o1
o, oo1
9o1oo
9o
ο,οοϊo, o1
ο, οοϊ
1oo1oo
1oo
o,oo1o, o1
o, oo1
8o1oo
8o
Le A 15 5ooLe A 15 5oo
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5098AO/11005098AO / 1100
Myzus-Test (Kontakt-Wirkung)Myzus test (contact effect)
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.To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.
Mit der Wirkstoffzubereitung werden Kohlpflanzen (Brassica oleracea), welche stark von der Pfirsichblattlaus (Myzus persicae) befallen sind, tropfnaß besprüht.Cabbage plants (Brassica oleracea), which are heavily infested by the peach aphid (Myzus persicae), sprayed until dripping wet.
Nach den angegebenen Zeiten wird der Abtötungsgrad in % bestimmt. Dabei bedeutet 100 %, daß alle Blattläuse abgetötet wurden, 0 % bedeutet, daß keine Blattläuse abgetötet wurden.After the specified times, the degree of destruction is determined in % . 100 % means that all aphids have been killed, 0 % means that none of the aphids have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle 3 hervor:Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below:
Le A 15 5oo - 18 -Le A 15 5oo - 18 -
509840/1 100509840/1 100
konzentration
in io "Active ingredient
concentration
in io
in $ nach
1 TagFrom the degree of mortality
in $ after
1 day
o,o1o, 1
o, o1
5048 ·
50
o,o1
o,oo1o, 1
o, o1
o, oo1
I00
I00I00
I00
I00
o,o1
o,oo1o, 1
o, o1
o, oo1
I00
95I00
I00
95
, ο, ο 1
o,oo1o, 1
, ο, ο 1
o, oo1
I00
7oI00
I00
7o
o,o1
o,oo1o, 1
o, o1
o, oo1
I00
I00I00
I00
I00
o,o1
o,oo10.1
o, o1
o, oo1
I00
95I00
I00
95
o,o1
ο, ο ο 1o, 1
o, o1
ο, ο ο 1
I00 ■
■9oI00
I00 ■
■ 9o
o,o1
O.oo1o, 1
o, o1
O.oo1
I00
95I00
I00
95
Le A 15 5ooLe A 15 5oo
- 19 -- 19 -
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74094627409462
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 dilute the concentrate with water to the desired concentration.
Mit der Wirkstoffzubereitung werden Bohnenpflanzen (Phaseolus 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.Bean plants (Phaseolus vulgaris), which are approximately 10 to 30 cm in height, sprayed to runoff. These bean plants are strong with everyone Developmental stages 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 wurdens 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 the spider mites have been killed s 0% means that none of the spider mites have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle 4 hervor:Active ingredients, active ingredient concentrations, evaluation times and The results are shown in Table 4 below:
Le A 15 5oo - 2o -Le A 15 5oo - 2o -
509840/1 100509840/1 100
Tabelle 4 (Tetranychus-Test) Table 4 (Tetranychus test)
WirkstoffActive ingredient
konzentration
in <fo Active ingredient
concentration
in <fo
in fo nach
2 TagenFrom the degree of mortality
in fo after
2 days
o,o1o, 1
o, o1
O9o
O
o,o1o, 1
o, o1
O6o
O
o,o1o, 1
o, o1
9598
95
o,o1.o, 1
o, o1.
981oo
98
o,o1■ o, 1
o, o1
9o95
9o
o,o1o, 1
o, o1
9599
95
(D)(D)
(E) (3) (5) (2) (4)(E) (3) (5) (2) (4)
Le A 15 5oo - 21 -Le A 15 5oo - 21 -
509840/1100509840/1100
Grenzkonzentrations-Test / BodeninsektenLimit concentration test / soil insects
Testinsekt: Tenebrio molitor-Larven im BodenTest insect: Tenebrio molitor larvae in the soil
Lösungsmittel: 3 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil AlkylarylpolyglykolätherSolvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu 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 stated amount of solvent, the stated amount of emulsifier and dilutes the concentrate with water to the desired concentration.
Me Wirkstoffzubereitung wird innig mit dem Boden vermischt. Dabei spielt die Konzentration des Wirkstoffes in der Zubereitung praktisch keine Rolle, entscheidend ist allein die Wirkstoffgewichtsmenge pro Yolumeneinheit Boden, welche in ppm angegeben wird (z. B. mg/1). Man füllt den Boden in Töpfe und läßt die Töpfe bei Räumtemperatur stehen. Mach 24 Stunden werden die Testtiere in den behandelten Boden gegeben und nach weiteren 48 Stunden wird der Wirkungsgrad des Wirkstoffes durch Auszählen der toten und lebenden Testinsekten in $ bestimmt.- Der Wirkungsgrad ist 1oo $, wenn alle Testinsekten abgetötet worden sind; er ist 0 $,· wenn noch genau so viele Testinsekten leben wie bei der Kontrolle.The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient by weight per volume unit of soil, which is given in ppm (e.g. mg / 1). You fill the soil in pots and leaves the pots at room temperature. The test animals are placed in the treated soil for 24 hours after a further 48 hours, the effectiveness of the active ingredient is determined by counting the dead and living test insects in $. The efficiency is $ 100 when all test insects have been killed; it is $ 0 if there are exactly that many Test insects live as in the control.
Wirkstoffe, Aufwandmengen und Resultate gehen aus der nachfolgenden Tabelle 5 hervor:Active ingredients, application rates and results are based on the following Table 5 shows:
Le A 15 5oo - 22 -Le A 15 5oo - 22 -
509840/1 1 00509840/1 1 00
Tabelle 5Table 5
(Bodeninsektizid-Test / Tenebrio molitor - Larven im Boden)(Soil insecticide test / Tenebrio molitor - larvae in the soil)
Wirkstoff Abtötungsgrad in % Active ingredient kill rate in %
bei einer Wirkstoffkonzentration von 2ο ppmat an active ingredient concentration of 2ο ppm
(F) 0(F) 0
(5) 100(5) 100
(7) 100(7) 100
(8) 100(8) 100
Le A 15 5oo - 23 -Le A 15 5oo - 23 -
5098AO/11005098AO / 1100
Grenzkonzentrations-Test / BodeninsektenLimit concentration test / soil insects
Testinsekt: Phorbia antiqua-Maden im BodenTest insect: Phorbia antiqua maggots in the soil
Lösungsmittel: 3 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil AlkylarylpοIyglykolatherSolvent: 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, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.For the production of an appropriate preparation of the active substance If 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and dilute the concentrate with water to the desired concentration.
Die Wirkstoffzubereitung wird innig mit dem Boden vermischt. Dabei spielt die Konzentration des Wirkstoffes in der Zubereitung praktisch keine Rolle, entscheidend ist allein die Wirkstoffgewichtsmenge pro Volumeneinheit Boden, welche in ppm angegeben wird (z. B. mg/1). Man füllt den Boden in Töpfe und läßt die Töpfe bei Raumtemperatur stehen. Nach 24 Stunden werden die Testtiere in den behandelten Boden gegeben und nach weiteren 48 Stunden wird der Wirkungsgrad des Wirkstoffes durch Auszählen der toten und lebenden Testinsekten in fo bestimmt. Der Wirkungsgrad ist 1oo fof wenn alle Testinsekten abgetötet worden sind; er ist 0 $, wenn noch genau so viele Testinsekten leben wie bei der Kontrolle.The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation plays practically no role here; the only decisive factor is the amount by weight of the active ingredient per unit volume of soil, which is given in ppm (e.g. mg / l). The bottom is filled into pots and the pots are left to stand at room temperature. After 24 hours the test animals are placed in the treated soil and after a further 48 hours the degree of effectiveness of the active ingredient is determined by counting the dead and living test insects in fo . The efficiency is 1oo fo f if all the test insects had been killed; it is $ 0 if just as many test insects are still alive as in the control.
Wirkstoffe, Aufwandmengen und Resultate gehen aus der nachfolgenden Tabelle 6 hervor:Active ingredients, application rates and results are based on the following Table 6 shows:
Le A 15 5oo - 24 -Le A 15 5oo - 24 -
509840/1100509840/1100
Tabelle 6Table 6
bei einer Wirkstoffkonzentration
von 2ο ppmDegree of destruction in%
at an active ingredient concentration
of 2ο ppm
Le A 15 5oo - 25 -Le A 15 5oo - 25 -
509840/1100509840/1100
HerstellungsbeispieleManufacturing examples
NC-CH-NC-CH-
S OC2H5 S OC 2 H 5
ο-κο-κ
χ r\rt TTχ r \ rt TT
Zu einer Mischung von 15,9 g (o,1 Mol) Gu -Cyan-2-methylacetophenon, 14,2 g (o,11 Mol) Kaliumcarbonat und 15o ml Acetonitril werden 2o,2 g (o,1 Mol) O-Äthyl-O-n-propyl-thionophosphorsäurediesterchlorid getropft. Man erwärmt die Reaktionsmischung anschließend 3 Stunden auf 5o°C, kühlt sie ab und gießt den Ansatz in 3oo ml Toluol. Die Toluollösung wird mit gesättigter Natriumbicarbonatlösung und Wasser gewaschen, über Natriumsulfat getrocknet und dann das Lösungsmittel unter vermindertem Druck abgezogen. Man erhält 28 g (86 $ der Theorie) O-Äthyl-0-n-propyl-0-/~1-(2'-methylphenyl)-2-cyanovinyl_7-'fchionophosphorsäureester als gelbes Öl mit demTo a mixture of 15.9 g (0.1 mol) of Gu -cyan-2-methylacetophenone, 14.2 g (0.11 mol) of potassium carbonate and 150 ml of acetonitrile are 2o.2 g (0.1 mol) of O-ethyl-O-n-propyl-thionophosphoric acid diester chloride dripped. The reaction mixture is then heated to 50 ° C. for 3 hours and then cooled and pour the batch into 300 ml of toluene. The toluene solution is washed with saturated sodium bicarbonate solution and water, dried over sodium sulfate and then the solvent is removed under reduced pressure. 28 g ($ 86 of the Theory) O-ethyl-0-n-propyl-0- / ~ 1- (2'-methylphenyl) -2-cyanovinyl_7-'fchionophosphorsäureester as yellow oil with that
25
Brechungsindex nD : 1,532o.25th
Refractive index n D : 1.532o.
In analoger Weise können die folgenden Verbindungen hergestellt werden:The following connections can be established in an analogous manner:
spiel
Nr,at
game
No,
indexRefractive
index
{ia der
Theorie)yield
{ia the
Theory)
>Cl
>
Le A 15 5ooLe A 15 5oo
- 26 -- 26 -
509840/1100509840/1100
Bei- Konstitution Brechungs- AusbeuteOn constitution refractive yield
spiel index (# dergame index (# the
Nr. Theorie)No theory)
: 1,535o 77: 1.535o 77
NC-CH=C „
ο-P
\( NC-CH = C "
ο-P
\ (
Cl
NC-CH= CCl
NC-CH = C
\ S 0CoHc \ S 0C o H c
Zu einer Suspension τοη 23,6 g (o,1 Mol) des Natriumsalzes des <L7-Cyan-2,5-dichloracetophenons in 2oo ml Acetonitril werden 2o,2 g (o,1 Mol) O-Äthyl-O-n-propyl-thionophosphorsäurediesterchlorid getropft. Man erwärmt das Eeaktionsgemisch 3 Stunden auf 5o°C, kühlt es ab und gießt den Ansatz in 3oo ml Toluol. Die Toluollösung wird mit gesättigter Natriumbicarbonatlösung und Wasser gewaschen, über Natriumsulfat getrocknet, dann wird das Lösungsmittel unter vermindertem Druck abgezogen. Man erhält 28,5 g (75 i° der Theorie) O-Äthyl-O-n-propyl-0-/~1 -(2 ', 5 ' -dichlorphenyl)-2-cyanovinyl /-"thionophosphorsaureester als Öl mit dem Brechungsindex n-p ι 1,5245.To a suspension of 23.6 g (0.1 mol) of the sodium salt of <L7-cyano-2,5-dichloroacetophenone in 2oo ml of acetonitrile, 2o.2 g (0.1 mol) of O-ethyl-on-propyl- thionophosphoric acid diester chloride was added dropwise. The reaction mixture is heated to 50 ° C. for 3 hours, cooled and the batch is poured into 300 ml of toluene. The toluene solution is washed with saturated sodium bicarbonate solution and water, dried over sodium sulfate, then the solvent is removed under reduced pressure. This gives 28.5 g (75 i ° of theory) of O-ethyl-On-propyl-0- / ~ 1 - (2 ', 5' -dichlorphenyl) -2-cyanovinyl / - "thionophosphorsaureester as an oil with the refractive index np ι 1.5245.
Le A 15 5oo - 27 -Le A 15 5oo - 27 -
509840/1100509840/1100
Analog werden die folgenden Verbindungen hergestellt:The following connections are made in the same way:
Beispiel
Nr.example
No.
Konstitution Brechungs- Ausbeute index (^ derConstitution refractive yield index (^ der
Theorie)Theory)
NC-CH=C SNC-CH = C S
N0-P N 0-P
n^: 1,519o 76n ^: 1.519o 76
ClCl
NC-CH=CNC-CH = C
S OCX PS OCX P
It1 3: 1,54o7 58It 1 3 : 1.54o7 58
CHCH
NC-CH=CNC-CH = C
S
IlS.
Il
Ii/ OCpH5 Ii / OCpH 5
: 1,5272 71: 1.5272 71
NC-CH=CNC-CH = C
Cl 0CoHc Cl 0C o H c
0-P0-P
n^: 1,5372n ^: 1.5372
Le A 155ooLe A 155oo
- 28 -- 28 -
5098A0/110 05098A0 / 110 0
/9/ 9
Die als Ausgangsverbindungen zu verwendenden CL>-Cyanacetophenon-Derivate (V) bzw. deren Enolform (Ta) können beispielsweise nach folgender Methode gewonnen werden:The CL> -cyanacetophenone derivatives to be used as starting compounds (V) or its enol form (Ta) can be obtained, for example, by the following method:
NC-OH=C-ONaNC-OH = C-ONa
Zu 26,8 g (o,1 Mol) 2',5f-Dichlor-2-bromacetophenon (Herstellung aus p-Dichlorbenzol und Acetylchlorid nach Friedel-Crafts und anschließend Bromierung in Äther) in 3o ml Äthanol tropft man unter Rühren eine Lösung von 1o,8 g Natriumcyanid in 2o ml Wasser und 2o ml Äthanol, wobei die Temperatur der Mischung bis auf 5o°C ansteigt. Man rührt den Ansatz 15 Minuten nach, kühlt ihn auf 1o°C ab und saugt das ausgefallene Salz scharf ab. Es wird mit Äther nachgewaschen und 5 Stunden bei 1oo bis 11O0C unter vermindertem Druck getrocknet. Man erhält so 19,5 g (85 io der Theorie) eines beigen Pulvers vom Schmelzpunkt >3oo°C.A solution is added dropwise with stirring to 26.8 g (0.1 mol) of 2 ', 5 f- dichloro-2-bromoacetophenone (prepared from p-dichlorobenzene and acetyl chloride according to Friedel-Crafts and then bromination in ether) in 3o ml of ethanol of 10.8 g of sodium cyanide in 2o ml of water and 2o ml of ethanol, the temperature of the mixture rising to 5o ° C. The batch is stirred for 15 minutes, cooled to 10 ° C. and the precipitated salt is sharply filtered off with suction. It is washed with ether and dried for 5 hours at 1oo to 11O 0 C under reduced pressure. Are thus obtained 19.5 g (85 io of theory) of a beige powder of melting point> 3oo ° C.
In analoger Weise sind auch die folgenden Qj-Cyanacetophenone bzw. deren Natriumsalze zugänglich: The following Qj -cyanacetophenones and their sodium salts are also accessible in an analogous manner:
Konstitutionconstitution
Ausbeute {<fo der Theorie)Yield {<fo the theory)
Physikalische Eigenschaften (Siedepunkt,
Schmelzpunkt) Physical properties (boiling point,
Melting point)
NC-CH2-CO-NC-CH 2 -CO-
6868
5353
Le A 15 5ooLe A 15 5oo
- 29 -- 29 -
1290C129 0 C
75-780C75-78 0 C
509840/1100509840/1100
Konstitution Ausbeute {io der Theorie)Constitution yield (io of theory)
Physikalische Eigenschaften (Siedepunkt, Schmelzpunkt)Physical properties (boiling point, melting point)
NC-CH2-CO-NC-CH 2 -CO-
4343
125125
NC-CH2-CO-NC-CH 2 -CO-
35 15o-16o°C/4 Torr35 15o-16o ° C / 4 Torr
NC-CH2-CO-NC-CH 2 -CO-
Vy-CH. 33Vy-CH. 33
1oo°C100 ° C
NC-CH2-CO-//NC-CH 2 -CO - //
720C72 0 C
CHCH
NC-CH2-CO-NC-CH 2 -CO-
3737
84 - 85 C84-85 C.
ONa NC-CH=C- // ONa NC-CH = C- //
7777
NC-CH2-CO-^NC-CH 2 -CO- ^
OCH, 71OCH, 71
880C88 0 C
ΟΗ,ΟΟΗ, Ο
NC-CH2-CO-NC-CH 2 -CO-
5o5o
670C67 0 C
Le A 15 5ooLe A 15 5oo
- 3o -- 3o -
509840/1 1 00509840/1 1 00
74094627409462
Konstitution Ausbeute PhysikalischeConstitution Yield Physical
($ der Eigenschaften Theorie) (Siedepunkt, Schmelzpunkt)($ of the property theory) (boiling point, Melting point)
NaONaO
NC-CH=C-/ Vci 51NC-CH = C- / Vci 51
ClCl
NaO
NC-CH=C- /~Λ -F 75 284°CNaO
NC-CH = C- / ~ Λ -F 75 284 ° C
Na(J
NC-CH=C-/' VBr 82Well (J
NC-CH = C- / 'VBr 82
Le A 15 5oo - 31 -Le A 15 5oo - 31 -
509840/1100509840/1100
(Zersetzung)(Decomposition)
ιNaO
ι
'Br'Br
NaO NC-CH=C-//NaO NC-CH = C - //
7777
NC-CH2-CO-NC-CH 2 -CO-
-CH-CH
CH,CH,
2o2o
740C74 0 C
NC-CH2-CO-NC-CH 2 -CO-
-C3H7-I-C 3 H 7 -I
1818th
560C56 0 C
NC-CH2-CO-NC-CH 2 -CO-
CH,CH,
CH,CH,
Le A 15 5ooLe A 15 5oo
2222nd
710C71 0 C
509840/ 1 100509840/1 100
Claims (6)
NC-CH=G-OMor their enol form of the formula
NC-CH = G-OM
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2409462A DE2409462A1 (en) | 1974-02-27 | 1974-02-27 | 0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES |
AR257787A AR206422A1 (en) | 1974-02-27 | 1975-01-01 | NEW O-ETHYL-ON-PROPYL-O- (1-PHENYL-2-CYANE) -VINYL ESTERS OF THIONOPHOSPHORIC ACID OF APPLICATIONS SUCH AS INSECTICIDES AND ACARICIDES WITH THE EXCLUSION OF EVERYTHING THAT IMPLIES THE APPLICATION OF PHARMACOLOGICAL AND CONDITIONAL PROCEDURES OR VETERINARY PROCEDURES GET THEM |
BR1071/75A BR7501071A (en) | 1974-02-27 | 1975-02-21 | PROCESS FOR THE PRODUCTION OF O-ETHYL-O-N-PROPYL-O-VINYL THIONOPHOPHOSPHORIC ACID AND INSECTICIDES AND ACARICIDES BASED ON THESE |
IL46688A IL46688A (en) | 1974-02-27 | 1975-02-24 | Thionophosphoric acid esters their preparation and their use as insecticides and acaricides |
DD184402A DD118513A5 (en) | 1974-02-27 | 1975-02-25 | |
AU78550/75A AU7855075A (en) | 1974-02-27 | 1975-02-25 | O-ethyl-o-npropyl-o-vinyl-thionophosphoric acid esters |
JP50022504A JPS50117752A (en) | 1974-02-27 | 1975-02-25 | |
LU71912A LU71912A1 (en) | 1974-02-27 | 1975-02-25 | |
JP50022505A JPS50117940A (en) | 1974-02-27 | 1975-02-25 | |
AT141775A AT329079B (en) | 1974-02-27 | 1975-02-25 | PROCESS FOR THE PRODUCTION OF NEW O-ATHYL-O-N-PROPYL -O- VINYL-THIONOPHOSPHORIC ACID ESTERS |
SE7502157A SE7502157L (en) | 1974-02-27 | 1975-02-26 | |
ZA00751200A ZA751200B (en) | 1974-02-27 | 1975-02-26 | Novel-o-ethyl-o-n-propyl-o-vinyl-thionophosphoric acid esters and their use as insecticides and acaricides |
GB803675A GB1457395A (en) | 1974-02-27 | 1975-02-26 | O-ethyl-o-n-propyl-o-1-aryl-2-cyano vinyl-thionophosphoric acid esters and their use as insecticides and acaricides |
BE153752A BE825995A (en) | 1974-02-27 | 1975-02-26 | NEW ESTERS OF O-ETHYL, O-N-VINYL OF THIONOPHOSPORIC ACID, THEURPROCEDE AND THEIR APPLICATION AS INSECTICIDES AND ACARICIDES |
NL7502342A NL7502342A (en) | 1974-02-27 | 1975-02-27 | PROCESS FOR PREPARING O-ETHYL O-N-PRO-PYL O-VINYLTHIONOPHOSPHORIC ESTERS AND THEIR USE AS INSECTICIDES AND ACARICIDES. |
FR7506152A FR2262043B1 (en) | 1974-02-27 | 1975-02-27 | |
DK76575A DK133988C (en) | 1974-02-27 | 1975-09-30 | INSECTICIDES AND ACARICIDES ACTIVE 0-ETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID RESIDENTS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2409462A DE2409462A1 (en) | 1974-02-27 | 1974-02-27 | 0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2409462A1 true DE2409462A1 (en) | 1975-10-02 |
Family
ID=5908628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2409462A Pending DE2409462A1 (en) | 1974-02-27 | 1974-02-27 | 0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES |
Country Status (16)
Country | Link |
---|---|
JP (2) | JPS50117752A (en) |
AR (1) | AR206422A1 (en) |
AT (1) | AT329079B (en) |
AU (1) | AU7855075A (en) |
BE (1) | BE825995A (en) |
BR (1) | BR7501071A (en) |
DD (1) | DD118513A5 (en) |
DE (1) | DE2409462A1 (en) |
DK (1) | DK133988C (en) |
FR (1) | FR2262043B1 (en) |
GB (1) | GB1457395A (en) |
IL (1) | IL46688A (en) |
LU (1) | LU71912A1 (en) |
NL (1) | NL7502342A (en) |
SE (1) | SE7502157L (en) |
ZA (1) | ZA751200B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0005228A1 (en) * | 1978-05-05 | 1979-11-14 | Bayer Ag | Process for the preparation of O,O-diethyl-0-(1-phenyl-2-cyano-propene-(1)-yl)-thionophosphoric acid ester |
US4197312A (en) | 1978-05-09 | 1980-04-08 | American Cyanamid Company | Alkali metal and alkaline earth metal salts of benzoylacetonitriles |
EP0033825A2 (en) * | 1980-01-17 | 1981-08-19 | Bayer Ag | 2-Cyano-vinyl-(thiono)(thiol)-phosphoric or phosphonic acid derivatives as endoparasiticidal agents |
-
1974
- 1974-02-27 DE DE2409462A patent/DE2409462A1/en active Pending
-
1975
- 1975-01-01 AR AR257787A patent/AR206422A1/en active
- 1975-02-21 BR BR1071/75A patent/BR7501071A/en unknown
- 1975-02-24 IL IL46688A patent/IL46688A/en unknown
- 1975-02-25 JP JP50022504A patent/JPS50117752A/ja active Pending
- 1975-02-25 DD DD184402A patent/DD118513A5/xx unknown
- 1975-02-25 JP JP50022505A patent/JPS50117940A/ja active Pending
- 1975-02-25 LU LU71912A patent/LU71912A1/xx unknown
- 1975-02-25 AT AT141775A patent/AT329079B/en not_active IP Right Cessation
- 1975-02-25 AU AU78550/75A patent/AU7855075A/en not_active Expired
- 1975-02-26 BE BE153752A patent/BE825995A/en unknown
- 1975-02-26 ZA ZA00751200A patent/ZA751200B/en unknown
- 1975-02-26 SE SE7502157A patent/SE7502157L/xx unknown
- 1975-02-26 GB GB803675A patent/GB1457395A/en not_active Expired
- 1975-02-27 NL NL7502342A patent/NL7502342A/en not_active Application Discontinuation
- 1975-02-27 FR FR7506152A patent/FR2262043B1/fr not_active Expired
- 1975-09-30 DK DK76575A patent/DK133988C/en active
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0005228A1 (en) * | 1978-05-05 | 1979-11-14 | Bayer Ag | Process for the preparation of O,O-diethyl-0-(1-phenyl-2-cyano-propene-(1)-yl)-thionophosphoric acid ester |
US4197312A (en) | 1978-05-09 | 1980-04-08 | American Cyanamid Company | Alkali metal and alkaline earth metal salts of benzoylacetonitriles |
EP0033825A2 (en) * | 1980-01-17 | 1981-08-19 | Bayer Ag | 2-Cyano-vinyl-(thiono)(thiol)-phosphoric or phosphonic acid derivatives as endoparasiticidal agents |
EP0033825A3 (en) * | 1980-01-17 | 1981-11-18 | Bayer Ag | 2-cyano-vinyl-(thiono)(thiol)-phosphoric or phosphonic acid derivatives as endoparasiticidal agents |
Also Published As
Publication number | Publication date |
---|---|
DK76575A (en) | 1975-10-27 |
GB1457395A (en) | 1976-12-01 |
IL46688A (en) | 1977-04-29 |
NL7502342A (en) | 1975-08-29 |
IL46688A0 (en) | 1975-04-25 |
DK133988C (en) | 1977-02-28 |
FR2262043A1 (en) | 1975-09-19 |
AR206422A1 (en) | 1976-07-23 |
LU71912A1 (en) | 1975-12-09 |
JPS50117752A (en) | 1975-09-16 |
BE825995A (en) | 1975-08-26 |
SE7502157L (en) | 1975-08-28 |
ZA751200B (en) | 1976-01-28 |
AT329079B (en) | 1976-04-26 |
BR7501071A (en) | 1975-12-02 |
DK133988B (en) | 1976-08-23 |
FR2262043B1 (en) | 1978-07-13 |
JPS50117940A (en) | 1975-09-16 |
DD118513A5 (en) | 1976-03-12 |
AU7855075A (en) | 1976-08-26 |
ATA141775A (en) | 1975-07-15 |
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