DE1050768B - Process for the preparation of phenylthionophosphonic acid esters - Google Patents
Process for the preparation of phenylthionophosphonic acid estersInfo
- Publication number
- DE1050768B DE1050768B DENDAT1050768D DE1050768DA DE1050768B DE 1050768 B DE1050768 B DE 1050768B DE NDAT1050768 D DENDAT1050768 D DE NDAT1050768D DE 1050768D A DE1050768D A DE 1050768DA DE 1050768 B DE1050768 B DE 1050768B
- Authority
- DE
- Germany
- Prior art keywords
- benzene
- ecm
- acid esters
- sodium
- preparation
- 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
- NAKDJXIEBCHXIZ-UHFFFAOYSA-N dihydroxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical class OP(O)(=S)C1=CC=CC=C1 NAKDJXIEBCHXIZ-UHFFFAOYSA-N 0.000 title claims description 3
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- -1 phenyl thionophosphonic acid alkyl ester halides Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241001454295 Tetranychidae Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- DKTRZBWXGOPYIX-UHFFFAOYSA-N 3-chloro-4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C(Cl)=C1 DKTRZBWXGOPYIX-UHFFFAOYSA-N 0.000 description 1
- JUIKCULGDIZNDI-UHFFFAOYSA-N 4-chloro-3-nitrophenol Chemical compound OC1=CC=C(Cl)C([N+]([O-])=O)=C1 JUIKCULGDIZNDI-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 102100026197 C-type lectin domain family 2 member D Human genes 0.000 description 1
- WEQVLSZDHCLFPN-UHFFFAOYSA-N COP(C)(O)=S.Cl Chemical compound COP(C)(O)=S.Cl WEQVLSZDHCLFPN-UHFFFAOYSA-N 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- 101000912615 Homo sapiens C-type lectin domain family 2 member D Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HNPPKZRZKDKXDO-UHFFFAOYSA-N n,n-dimethylformamide;propan-2-one Chemical compound CC(C)=O.CN(C)C=O HNPPKZRZKDKXDO-UHFFFAOYSA-N 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with hydroxyaryl compounds
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
DEUTSCHESGERMAN
Aus dei USA -Patentschrift 2 503 390 smdOAlkylo nitrophcnyltliionophosphonsaureester bekannt Diesen Phosphonsaurecstein kommt eine beachtliche insekti/ide Wirksamkeit zu, und ein Veittctei diesei Stoffklasse hat auch untei dei Bezeichnung EPiST Eingang in die Praxis gefundenFrom U.S. Patent 2,503,390 smdOAlkylo nitrophcnyltliionophosphonsaureester known these Phosphonsaurecstein comes with a considerable insecti / ide Effectiveness to, and a Veittctei diesei The substance class also has the designation EPiST Found its way into the practice
Es wuide nun gefunden, daß man zu hochwirksamen Veibmdungen ähnliche! Art, die sich bei teilweise geunger Toxi/itat dutch eine bessere insektizide Wnksamkeit auszeichnen, gelangt, wenn man Phenylthionophosphonsauicalkylestei halogenide mit solchen Phenolen umsetzt, die außer det Nitiogilippe auch noch Halogen im Molekül enthalten bzw in denen nur Halogenatome als Substituenten enthalten sind Folgendes Reaktionsschema möge das \^crfahren erläuternIt has now been found that one is too highly effective Similar messages! Kind of that at partial geunger Toxi / itat dutch a better insecticidal Distinguishing effectiveness comes when you Phenylthionophosphonsauicalkylestei halide with converts such phenols, except for the Nitiogilippe also contain halogen in the molecule or in which only contain halogen atoms as substituents explain
J R'
P — Hal + OH —^ Jl - -> JR '
P - Hal + OH - ^ Jl - ->
RORO
OH-OH-
P — 0—,P - 0-,
4-R'4-R '
In diesen Foimeln bedeutet R einen vorzugsweise niederen Alkyliest, W bedeutet em odci mchicic Halogenatome oder Nittogruppen, wobei im Falle einer Nitrogruppe mindestens em weiteies llalogenatom im Kein enthalten sein mußIn these formulas, R denotes a preferably lower alkyl ester, W denotes em odci mchicic halogen atoms or nito groups, in the case of a nitro group at least em further halogen atom must be included in the zero
Die voigenannte Reaktion wird zweckmäßig in einem ineiten Losungsmittel, wie ζ B in niederen aliphatischen Alkoholen, Aceton, Benzol, Toluol, Xylol od a, duichgefuhit Sie soll weiter etwa bei Raumtempeiatur bzw leicht erhöhten Tempeiatuicn stattfinden An Stelle eines Saurebmdemittcls, wie ζ B Pottasche, Soda, Natronlauge und Alkabalkoholat, können auch die Phenolate heigcstellt weiden und diese mit den Phcnylthionophosphonsauiealkylcstethalogeniden zur Reaktion gebracht werden Als besonders voiteilhaft fur eine erfolgreiche Durchfuhiung der Reaktion hat sich der Zusatz von Kupferpulver, bevoizugt in Foim von Kupfei bionze heiausgestellt The aforementioned reaction is conveniently carried out in an internal solvent, such as ζ B in lower ones aliphatic alcohols, acetone, benzene, toluene, xylene od a, duichgefuhit You should continue about with Room temperature or slightly increased tempeiatuicn take place in place of a sour message, such as ζ B potash, soda, caustic soda and alcoholate, the phenolates can also graze and these with the Phcnylthionophosphonsauiealkylstethalogeniden Reacted as particularly beneficial for a successful implementation The reaction has been exposed to the addition of copper powder, favored in Foim by Kupfei bionze
Die neuen Verbindungen sind Schädlingsbekämpfungsmittel, die sich duich eine her\otiagendc insektizide Wiiksamkeit auszeichnen, teilweise kommt ihnen eine ausgezeichnete sjstemische Wirksamkeit Verfahren zur Herstellung von PhenylthionophosphonsaureesternThe new compounds are pesticides, which duich a her \ otiagendc insecticidal Distinguish criticality, sometimes comes them an excellent systemic effectiveness Process for the preparation of phenylthionophosphonic acid esters
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk
Dr Gerhard Schrader, Wuppertal-Cronenberg, ist als Erfinder genannt wordenDr Gerhard Schrader, Wuppertal-Cronenberg, has been named as the inventor
zu Die Anwendung der eifindungsgemaßen Verbindungen geschieht in der fur Phosphoi säureester üblichen Alt und Weise, d h bevorzugt in Kombination mit geeigneten festen oder flussigen inerten Streck- oder Veidunnungsmitteln Als solche seien beispielsweise genannt Talkum, Kreide, Bentomt, Kieselgui u dgl odei, falls es sich um flüssige Mittel handelt, Wassci, bevorzugt in Veibindung mit einem geeigneten Emulgator und einem organischen Losungsvermittler, wie 7 B Dimethylformamid oder Acetonto The application of the compounds according to the invention happens in the case of phosphoic acid esters usual alt and manner, i.e. preferably in combination with suitable solid or liquid inert diluents or thinning agents. As such for example called talc, chalk, Bentomt, Kieselgui u like odei, if it is a liquid agent acts, Wassci, preferably in connection with one suitable emulsifier and an organic solubilizer, such as 7 B or dimethylformamide acetone
OC2H5 OC 2 H 5
-Cl-Cl
NO,NO,
44 g (0,25 Mol) 3-Nitro-4-chlorphenol 111 400 ecm Benzol werden bei Zimmertemperatur mit 13,5 g (0,25 Mol) Natriummcthylat in 55 ecm Methanol versetzt Nach dem volligen Abdestilheren von Benzol und A4 ethanol (zuletzt untei Vakuum) weiden 440 ecm Methylethylketon zugefügt Sodann laßt man bei 30° C 55 g (0,25 Mol) Plienylthionophosphonsauieathylesterchloi id zutropfen, halt noch 1 Stunde bei 50 bis 60° C und aibeitet dann in gewohnter AVeise auf, es wird ein biauniotes öl eihalten Ausbeute 25 g An dei Ratte zeigt dei Estei eine mittleie Toxizitat von 50 mg/kg Spinnmilben weiden mit O,Ol°/oigen Losungen zu 100°/o abgetötet 0 l°/oigc Losungen toten Raupen 100%ig ab44 g (0.25 mole) 3-nitro-4-chlorophenol 111,400 ecm 13.5 g (0.25 mol) of sodium methylate in 55 ecm of methanol are added to benzene at room temperature After the benzene has been completely distilled off and A4 ethanol (last under vacuum) graze 440 ecm of methyl ethyl ketone are then added at 30 ° C 55 g (0.25 mol) of plienylthionophosphonic acid ethyl ester chloride add drop by drop, hold at 50 to 60 ° C for another hour and then proceed as usual AVeise it will yield a biauniote oil 25 g on the rat, dei Estei shows a mean Toxicity of 50 mg / kg spider mites graze with 100% of the 0.1% solution has been killed, 0% of the solution Solutions kill caterpillars 100%
809 750/493809 750/493
V-P-OV-P-O
OC,HK OC, H K
ClCl
40 g (0,2 Mol) 2,4,5-Trichlorphenol in 200 ecm Benzol gelöst, werden bei Zimmertemperatur mit 11g (0,2MoI) Natriummcthylat in etwa 50 ecm Methanol versetzt. Benzol und Methanol werden azeotrop abdcstillicrt und der letzte Rest an Lösungsmitteln im Vakuum abgezogen. Anschließend wird das erhaltene Natriumtrichlorphcnolat mit 200 ecm Methyläthylketon versetzt, und zu der erhaltenen Lösung läßt man 44 g (0,2 Moi) Phcnyithionophosphonsäurcäthylcsterchlorid in 30 ecm Benzol langsam unter gelinder Außenkühlung zutropfcn. Hierauf hält man 1 Stunde bei 6O0C, kühlt dann ab und wäscht mit Eiswasser und darauf mit verdünnter Sodalösung; man trocknet mit Natriumsulfat, zieht das Lösungsmittel ab und erhält ein fast farbloses öl, das sich im Hochvakuum destillieren läßt (Fp. 0,02/125 bis 13O0C). Ausbeute: 49 g. An der Ratte per os zeigt der Elster eine mittlere Toxizität von 100 mg/kg. Raupen und Spinnmilben werden mit 0,l%igen Lösungen sicher abgetötet. Der Ester hat eine ausgesprochen ovizide Wirkung auf die Eier der roten Spinne.40 g (0.2 mol) of 2,4,5-trichlorophenol dissolved in 200 ecm of benzene are mixed with 11 g (0.2 mol) of sodium methylate in about 50 ecm of methanol at room temperature. Benzene and methanol are azeotropically distilled off and the last residue of solvents is drawn off in vacuo. 200 ml of methyl ethyl ketone are then added to the sodium trichlorophosphonate obtained, and 44 g (0.2 mol) of phinithionophosphonic acid ethyl ester chloride in 30 ml of benzene are slowly added dropwise to the resulting solution with gentle external cooling. Then you hold for 1 hour at 6O 0 C, then cooled and washed with ice water and then with dilute sodium carbonate solution; is dried with sodium sulfate, the solvent is stripped off to give an almost colorless oil which can be distilled under high vacuum (mp. 0.02 / 125 to 13O 0 C). Yield: 49 g. The magpie showed a mean toxicity of 100 mg / kg in the rat per os. Caterpillars and spider mites are safely killed with 0.1% solutions. The ester has a pronounced ovicidal effect on the eggs of the red spider.
/ V — O—f Λ—NO, / V - O — f Λ — NO,
schlämmt. Dazu gibt man bei 50° C 42 g 2,4-Dichlorphenol, gelöst in 50ecm Benzol. Nach etwa 1'/2 Stunden ist das Natrium in Lösung gegangen. Dann gibt man bei 50° C 37 g Phenylthionopliosphonsäurcäthylesterchloric! hinzu und erwärmt noch IV2 Stunden auf 50 bis 55° C. Man läßt das Reaktionsprodukt auf Zimmertemperatur abkühlen und gibt es in 300 ecm Eiswasser. Die benzolische Lösung wird abgetrennt und mit Natriumsulfat getrocknet. Nach dem Abdestillieren des Lösemittels erhält man 65 g des neuen Esters als gelbes, wasserunlösliches öl, das sich auch im Hochvakuum nicht destillieren läßt. Ausbeute 75°/o der Theorie.slurries. To this are added 42 g of 2,4-dichlorophenol at 50 ° C, dissolved in 50 cm benzene. After about 1/2 hour the sodium has gone into solution. Then 37 g of Phenylthionopliosphonsäurcäthylesterchloric are added at 50 ° C! added and heated to 50 to 55 ° C. for another IV2 hours. The reaction product is allowed to dissolve Cool down to room temperature and put it in 300 ecm ice water. The benzene solution is separated off and dried with sodium sulfate. After the solvent has been distilled off, 65 g of the new one are obtained Esters as a yellow, water-insoluble oil that cannot be distilled even in a high vacuum. yield 75 per cent of theory.
OC9H5 OC 9 H 5
ClCl
57 g Phenylthionophosphonsäureäthylesterchlorid gibt man unter Rühren zu 43 g 3-Chlor-4-nitrophenol ■—■ angeschlämmt mit 40 g trockenem und gepulvertem Kaliumkarbonat und 1 g Kupferpulver in 150 ecm Äthylmcthylkcion — bei 8O0C. Man erwärmt noch 3 Stunden unter Ruhren bei 80° C, kühlt dann auf Zimmertemperatur ab, saugt die Salze ab und wäscht die ölige Schicht mit einer 4°/oigen Bikarbonatlösung neutral. Dann wird das erhaltene Öl mit Natriumsulfat getrocknet. Nach dem Entfernen des Lösungsmittels im Vakuum erhält man 65 g des neuen listers als viskoses, gelbes Öl. Ausbeute 73% der Theorie.57 g Phenylthionophosphonsäureäthylesterchlorid are added with stirring to 43 g of 3-chloro-4-nitrophenol ■ - ■ slurried with 40 grams of dried and powdered potassium carbonate and 1 g of copper powder in 150 cc Äthylmcthylkcion - at 8O 0 C. It is heated for 3 hours under stirring at 80 ° C, then cools down to room temperature, sucks off the salts and washes the oily layer neutral with a 4% bicarbonate solution. Then the oil obtained is dried with sodium sulfate. After removing the solvent in vacuo, 65 g of the new listers are obtained as a viscous, yellow oil. Yield 73% of theory.
An der Ratte per os zeigt der neue Ester eine DL50 von 100 mg/kg. Spinnmilben werden mit O.Ol°/oigen Lösungen lOO°/oig abgetötet. Die Verbindung hat eine ausgesprochene o\'izidc Wirkung auf die Eier der loten Spinne.The new ester shows a DL 50 of 100 mg / kg in the rat per os. Spider mites are killed with 100% solutions of 100%. The compound has a pronounced o \ 'izidc effect on the eggs of the loose spider.
-P —O-P —O
>—Cl> —Cl
OC2H5 OC 2 H 5
In 100 ecm Benzol schlämmt man 6 g Natriumpulver an. Bei 50° C gibt man dazu eine Lösung von 33 g 4-Chlorphenol in 50 ecm Benzol. Nach 1'/2StUndigem Rühren ist das Natrium in Lösung gegangen.6 g of sodium powder are slurried in 100 ecm of benzene. A solution of is added at 50 ° C 33 g of 4-chlorophenol in 50 ecm of benzene. After an hour and a half Stirring the sodium has gone into solution.
Man tropft dann unter weiterem Rühren bei 55° C 57 g Phcnylthionophosphonsäureäthylesterchlorid zu und rührt noch 2 Stunden bei 55 bis 60° C nach. Dann arbeitet man in üblicher Weise auf und erhält 60 g des neuen Esters als wasserunlösliches, schwach gelbes öl. Ausbeute 77% der Theorie.57 g of Phcnylthionophosphonsäureäthylesterchlorid are then added dropwise with further stirring at 55 ° C and stir at 55 to 60 ° C. for a further 2 hours. Then you work up in the usual way and get 60 g of the new ester as a water-insoluble, pale yellow oil. Yield 77% of theory.
-Cl-Cl
OCILOCIL
In 100 ecm Benzol schlämmt man 6 g Natriumpulver an. Dazu gibt man bei 55° C 33 g 4-Chlorphenol — gelöst in 50 ecm Benzol. Man hält die Temperatur bei 50° C 2 Stunden. Das Natrium ist dann gelöst. Dann tropft man unter gutem Rühren bei 50° C 53 g Phcnylthionophosphonsäurcmethylesterchlorid zu. Man rührt noch 1 Stunde bei 50 bis 55° C nach und gibt dann das Reald ionsprodukt in 250 ecm Eiswasser. Das abgeschiedene öl wird mit 150 ecm Benzol verdünnt, mit einer 4%igen Natriumbikarbonatlösung neutral gewaschen und getrocknet. Nach dem Abdestilliercn der Lösemittel bleiben 69 g des neuen Esters als schwach gelbes, wasserunlösliches öl zurück. Ausbeute 92% der Theorie.6 g of sodium powder are slurried in 100 ecm of benzene. 33 g of 4-chlorophenol are added at 55.degree - dissolved in 50 ecm benzene. The temperature is kept at 50 ° C. for 2 hours. The sodium is then solved. 53 g of methylthionophosphonic acid methyl ester chloride are then added dropwise at 50 ° C. with thorough stirring to. The mixture is stirred for a further 1 hour at 50 to 55 ° C. and the reaction product is then added in 250 ecm Ice water. The separated oil is diluted with 150 ecm benzene, with a 4% sodium bicarbonate solution washed neutral and dried. After the solvents have been distilled off, 69 g of des remain new ester as a pale yellow, water-insoluble oil. Yield 92% of theory.
6 g Natriumpulver werden in 100 ecm Benzol ange-6 g sodium powder are mixed in 100 ecm benzene
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1050768B true DE1050768B (en) | 1959-02-19 |
Family
ID=591103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1050768D Pending DE1050768B (en) | Process for the preparation of phenylthionophosphonic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1050768B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1150387B (en) * | 1960-10-05 | 1963-06-20 | Bayer Ag | Process for the production of di- or trithiophosphonic acid esters |
| DE1176653B (en) | 1961-01-27 | 1964-08-27 | Bayer Ag | Process for the production of (thiono) phosphonic (- in -) - acid esters |
| DE1198126B (en) * | 1959-09-04 | 1965-08-05 | Stauffer Chemical Co | Miticidal agent |
| US3202658A (en) * | 1959-02-28 | 1965-08-24 | Bayer Ag | Thionophosphonic acid esters and a process for their production |
| DE1214040B (en) * | 1960-07-20 | 1966-04-07 | Sumitomo Chemical Co | Insecticidal agent |
| DE1219026B (en) * | 1961-03-28 | 1966-06-16 | Bayer Ag | Process for the preparation of thionophosphonic acid esters |
| DE1226363B (en) * | 1961-04-04 | 1966-10-06 | Monsanto Co | Insecticides containing alkylthiophosphonic auryl esters |
| US4296108A (en) | 1979-08-24 | 1981-10-20 | Basf Aktiengesellschaft | 2,2-Dichlorocyclopropyl-methyl-phosphoric acid derivatives |
-
0
- DE DENDAT1050768D patent/DE1050768B/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3202658A (en) * | 1959-02-28 | 1965-08-24 | Bayer Ag | Thionophosphonic acid esters and a process for their production |
| DE1198126B (en) * | 1959-09-04 | 1965-08-05 | Stauffer Chemical Co | Miticidal agent |
| DE1214040B (en) * | 1960-07-20 | 1966-04-07 | Sumitomo Chemical Co | Insecticidal agent |
| DE1150387B (en) * | 1960-10-05 | 1963-06-20 | Bayer Ag | Process for the production of di- or trithiophosphonic acid esters |
| DE1176653B (en) | 1961-01-27 | 1964-08-27 | Bayer Ag | Process for the production of (thiono) phosphonic (- in -) - acid esters |
| DE1219026B (en) * | 1961-03-28 | 1966-06-16 | Bayer Ag | Process for the preparation of thionophosphonic acid esters |
| DE1226363B (en) * | 1961-04-04 | 1966-10-06 | Monsanto Co | Insecticides containing alkylthiophosphonic auryl esters |
| US4296108A (en) | 1979-08-24 | 1981-10-20 | Basf Aktiengesellschaft | 2,2-Dichlorocyclopropyl-methyl-phosphoric acid derivatives |
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