DE1026323B - Process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphoric acid esters - Google Patents
Process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphoric acid estersInfo
- Publication number
- DE1026323B DE1026323B DEF18573A DEF0018573A DE1026323B DE 1026323 B DE1026323 B DE 1026323B DE F18573 A DEF18573 A DE F18573A DE F0018573 A DEF0018573 A DE F0018573A DE 1026323 B DE1026323 B DE 1026323B
- Authority
- DE
- Germany
- Prior art keywords
- phenyl
- dialkyl
- acid esters
- preparation
- insecticidally active
- 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
- 150000002148 esters Chemical class 0.000 title claims description 6
- 239000002253 acid Substances 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 4
- JKIFPWHZEZQCQA-UHFFFAOYSA-N 2-nitrobenzenethiol Chemical class [O-][N+](=O)C1=CC=CC=C1S JKIFPWHZEZQCQA-UHFFFAOYSA-N 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 241001454295 Tetranychidae Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UCQRPBLOYKRHFQ-UHFFFAOYSA-N CCOP(O)([ClH]CC)=S Chemical compound CCOP(O)([ClH]CC)=S UCQRPBLOYKRHFQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- -1 thiol phosphoric acid esters Chemical class 0.000 description 2
- HBCSOCHVMJKLLO-UHFFFAOYSA-N 3-nitrobenzenethiol Chemical compound [O-][N+](=O)C1=CC=CC(S)=C1 HBCSOCHVMJKLLO-UHFFFAOYSA-N 0.000 description 1
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010626 work up procedure Methods 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
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)
Description
Verfahren zur Herstellung von insekticid wirksamen O,O-Dialkyl-S-phenyl-thionothiolphosphorsäureestern Es wurde gefunden, daß man insekticid wirksame 0,0 - Dialkyl - S - phenyl - thiono - thiolphosphorsäureester durch Umsetzung von Dialkylthionophosphorsäurechloriden mit substituierten Phenylmercaptanen dadurch herstellen kann, daß als substituierte Phenylmercaptane Nitrophenylmercaptane, die gegebenenfalls im Phenylrest durch Halogen oder Alkylreste weitersubstituiert sind, verwendet werden.A process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphorsäureestern It has been found that one insecticidally effective 0,0 - dialkyl - S - phenyl - thiono - can be prepared by reacting thiolphosphorsäureester Dialkylthionophosphorsäurechloriden with substituted phenylmercaptans in that the substituted phenyl mercaptans used are nitrophenyl mercaptans which are optionally further substituted in the phenyl radical by halogen or alkyl radicals.
Die neuen Thionothiolphosphate zeichnen sich durch hohe Beständigkeit gegen hydrolytische Einflüsse und durch sehr gute kontaktinsekticide Wirkungen aus. Gegenüber den vergleichbaren Thiolphosphorsäureestern, die z. B. aus der deutschen Patentschrift 817 753 bekannt sind, zeigen die neuen Thiono-thiolphosphorsäureester eine wesentlich geringere Toxizität gegenüber Warmblütern.The new thionothiol phosphates are characterized by high resistance against hydrolytic influences and through very good contact insecticidal effects. Compared to the comparable thiol phosphoric acid esters that z. B. from the German Patent 817 753 are known, show the new thionothiolphosphoric acid ester significantly lower toxicity to warm-blooded animals.
Außerdem sind die erfindungsgemäßen Verbindungen auch den aus der deutschen Patentschrift 885 176 her bekannten Verbindungen überlegen, und zwar sowohl hinsichtlich der Toxizität als auch hinsichtlich einer besseren Wirksamkeit. Aus der folgenden Gegenüberstellung sind diese Tatsachen zu ersehen: Verglichen wurden der erfindungsgemäße Dithiophosphorsäureester mit dem aus der deutschen Patentschrift 817 753 her bekannten Ester und dem aus der deutschen Patentschrift 885 176 her bekannten Ester Folgende Werte wurden gefunden: Toxizität Ratte per os DL" 50 mg ,!kg I ... Spinnmilben . . . . . . . . 0,001 o!0 1000o Raupen . . . . . . . . . . . . 0,10/0 100 0/0 Toxizität Ratte per os DL" 2,5 mg/kg 1I ... Spinnmilben . . . . . . . . 0,010/0 1000/0 Raupen . . . . . . . . . . . . 0,1% keine Wirkung Toxizität Ratte per os DL" 20 mg/kg III ... Spinnmilben . . . . . . . . 0,005 0/0 1000/, Raupen ............ keine Wirkung Beispiel 1 43 g p-Nitrothiophenol werden in 100 ccm wasserfreiem Pyridin gelöst. Unter Rühren gibt man, bei Zimmertemperatur beginnend, 76 g 0,0-Diäthylthionophosphorsäuremonochlorid hinzu. Man sorgt durch Kühlen dafür, daß die Temperatur nicht über ,40°C steigt. Nach dem ,Ausreagieren läßt man noch 1 bis 2 Stunden weiterrühren und gießt dann das Reaktionsprodukt in 100 ccm konzentrierte Salzsäure, die mit 50 g Eisstückchen versetzt ist. Das ausgeschiedene Rohprodukt wird ausgeäthert, und die Ätherschicht wird ein- bis zweimal mit einer 5 °/jgen wäßrigen Bicarbonatlösung gewaschen. Dann wird die ätherische Schicht mit Natriumsulfat getrocknet, filtriert und der Äther abdestilliert. Bei 1 mm Hg bei einer Badtemperatur von 70°C wird der Rückstand einige Stunden stehengelassen, bis der Rückstand in der Kälte kristallisch erstarrt. Das kristalline Rohprodukt wird aus Äthylalkohol- umkristallisiert. Man erhält 64 g (entsprechend 80 % der Theorie) des neuen Esters in Form von farblosen langen Nadeln, die bei 49°C schmelzen. Beispiel 2 115 g Nitrothiophenol werden in 150 ccm wasserfreiem Pyridin gelöst. Unter Rühren gibt man, bei 10°C beginnend, 115 g Diäthylthionophosphorsäuremonochlorid hinzu. Man hält die Temperatur weiter 2 Stunden bei etwa 40°C. Dann arbeitet man, wie im Beispiel 1 angegeben, auf und erhält nach dem Abdestillieren des Lösemittels 214 g des rohen Thionothiolphosphates in Form eines gelben, wasserunlöslichen Öles. Das Präparat läßt sich im Hochvakuum destillieren. Kp. ",os m,/105 bis 108°C. Beispiel 3 Wie im Beispiel 1 beschrieben, werden 80 g m-Nitrothiophenol in einem Gemisch von 20 ccm Triäthylamin und 100ccm wasserfreiem Pyridin gelöst. Dann gibt man,wie in den Beispielen 1 und 2 beschrieben, 95 g Diäthylthionophosphorsäuremonochlorid bei 40°C hinzu und hält die Temperatur noch 3 Stunden bei 40°C. Nach dem üblichen Aufarbeiten werden 150 g rohes Thionothiolphosphat erhalten. Das wasserunlösliche gelbe Öl läßt sich auch im Hochvakuum nur unter Zersetzung destillieren.In addition, the compounds according to the invention are also superior to the compounds known from German patent specification 885 176, both in terms of toxicity and in terms of better effectiveness. These facts can be seen from the following comparison: The dithiophosphoric acid ester according to the invention was compared with the ester known from German Patent 817 753 and the ester known from German patent specification 885 176 The following values were found: Toxicity rat per os DL "50 mg ,! Kg I ... Spider mites........ 0.001 o! 0 1000o caterpillars........... 0.10 / 0 100 0/0 Toxicity rat per os DL "2.5 mg / kg 1I ... spider mites. . . . . . . . 0.010 / 0 1000/0 caterpillars. . . . . . . . . . . . 0.1% no effect Toxicity rat per os DL "20 mg / kg III ... spider mites ........ 0.005 0/0 1000 /, caterpillars ............ none Effect example 1 43 g of p-nitrothiophenol are dissolved in 100 cc of anhydrous pyridine. Starting at room temperature, 76 g of 0,0-diethylthionophosphoric acid monochloride are added with stirring. It is ensured by cooling that the temperature does not rise above .40 ° C. After the reaction is complete, the mixture is left to stir for a further 1 to 2 hours and the reaction product is then poured into 100 cc of concentrated hydrochloric acid to which 50 g of ice pieces are added. The precipitated crude product is extracted with ether, and the ether layer is washed once or twice with a 5% aqueous bicarbonate solution. Then the ethereal layer is dried with sodium sulfate, filtered and the ether is distilled off. At 1 mm Hg and a bath temperature of 70 ° C., the residue is left to stand for a few hours until the residue solidifies crystalline in the cold. The crystalline crude product is recrystallized from ethyl alcohol. 64 g (corresponding to 80 % of theory) of the new ester are obtained in the form of colorless long needles which melt at 49.degree. Example 2 115 g of nitrothiophenol are dissolved in 150 cc of anhydrous pyridine. 115 g of diethylthionophosphoric acid monochloride are added with stirring, starting at 10 ° C. The temperature is maintained at about 40 ° C. for a further 2 hours. Then work is carried out as indicated in Example 1 and, after the solvent has been distilled off, 214 g of the crude thionothiol phosphate are obtained in the form of a yellow, water-insoluble oil. The preparation can be distilled in a high vacuum. Kp. ", Os m, / 105 to 108 ° C. Example 3 As described in Example 1, 80 g of m-nitrothiophenol are dissolved in a mixture of 20 cc of triethylamine and 100 cc of anhydrous pyridine. Then, as described in Examples 1 and 2, 95 g of diethylthionophosphoric acid monochloride are added at 40 ° C. and the temperature is maintained at 40 ° C. for a further 3 hours. After the usual work-up, 150 g of crude thionothiol phosphate are obtained. The water-insoluble yellow oil can only be distilled under high vacuum with decomposition.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF18573A DE1026323B (en) | 1955-10-04 | 1955-10-04 | Process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphoric acid esters |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF18573A DE1026323B (en) | 1955-10-04 | 1955-10-04 | Process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphoric acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1026323B true DE1026323B (en) | 1958-03-20 |
Family
ID=7089006
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF18573A Pending DE1026323B (en) | 1955-10-04 | 1955-10-04 | Process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphoric acid esters |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1026323B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1154486B (en) * | 1961-03-28 | 1963-09-19 | Bayer Ag | Process for the preparation of insecticidally active dialkylthiophosphoric acid esters |
DE1182659B (en) * | 1961-04-04 | 1964-12-03 | Monsanto Co | Process for the preparation of alkylthiophosphonic acid aryl esters |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE817753C (en) * | 1949-07-10 | 1951-10-18 | Bayer Ag | Process for the preparation of S-nitrophenyl-0, 0-dialkylthiophosphates |
DE885176C (en) * | 1951-10-02 | 1953-08-03 | Bayer Ag | Pest repellants |
-
1955
- 1955-10-04 DE DEF18573A patent/DE1026323B/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE817753C (en) * | 1949-07-10 | 1951-10-18 | Bayer Ag | Process for the preparation of S-nitrophenyl-0, 0-dialkylthiophosphates |
DE885176C (en) * | 1951-10-02 | 1953-08-03 | Bayer Ag | Pest repellants |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1154486B (en) * | 1961-03-28 | 1963-09-19 | Bayer Ag | Process for the preparation of insecticidally active dialkylthiophosphoric acid esters |
DE1182659B (en) * | 1961-04-04 | 1964-12-03 | Monsanto Co | Process for the preparation of alkylthiophosphonic acid aryl esters |
DE1226363B (en) * | 1961-04-04 | 1966-10-06 | Monsanto Co | Insecticides containing alkylthiophosphonic auryl esters |
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