DE1063157B - Process for the preparation of thiophosphoric acid esters - Google Patents
Process for the preparation of thiophosphoric acid estersInfo
- Publication number
- DE1063157B DE1063157B DEF26848A DEF0026848A DE1063157B DE 1063157 B DE1063157 B DE 1063157B DE F26848 A DEF26848 A DE F26848A DE F0026848 A DEF0026848 A DE F0026848A DE 1063157 B DE1063157 B DE 1063157B
- Authority
- DE
- Germany
- Prior art keywords
- acid esters
- preparation
- thiophosphoric acid
- ester
- toxicity
- 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
- 238000000034 method Methods 0.000 title claims description 5
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- -1 mercaptomethyl halides Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical group 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000256118 Aedes aegypti Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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 Thiophosphorsäureestern 0,0-Dialkylthio- bzw. -dithiophosphorsäureester, in denen der am Schwefel befindliche Esterrest ein Acylphenylrest, z. B. der Acetophenylrest, ist, sind bisher aus der Literatur nicht bekannt.Process for the preparation of thiophosphoric acid esters 0,0-dialkylthio- or -dithiophosphoric acid esters, in which the ester residue located on the sulfur is a Acylphenyl radical, e.g. B. the acetophenyl radical, are not yet from the literature known.
Es wurde gefunden, daß man zu dieser Gruppe sehr wirksamer Thiophosphor- bzw. Dithiophosphorsäureester gelangen kann, wenn man entsprechende Acylphenylmercaptomethylhalegenide mit Salzen von 0,0-Dialkylthio- bzw. -dithiophosphorsäureestern umsetzt. Diese Umsetzung wird bevorzugt bei Raumtemperatur bzw. leicht erhöhter Temperatur und in Gegenwart inerter Lösungs- bzw. Verdünnungsmittel durchgeführt.It has been found that this group of very effective thiophosphorus or dithiophosphoric acid ester can arrive if one uses corresponding acylphenylmercaptomethylhalegenide with salts of 0,0-dialkylthio- or dithiophosphoric acid esters. This implementation is preferred at room temperature or slightly elevated temperature and in the presence inert solvent or diluent carried out.
Die Anwendung der neuen Verbindungen geschieht in prinzipiell bekannter Weise, nämlich in Kombination mit festen oder flüssigen Streck- oder Verdünnungsmitteln. Als solche Streckmittel haben sich vor allem Kreide, Talkum, Bentonite und Kieselgur bewährt. Falls flüssige Kombinationen angewandt werden sollen, bestehen diese vorzugsweise aus wäßrigen Emulsionen, die unter Mitverwendung geeigneter Lösungshilfsmittel und handelsüblicher Emulgatoren leicht aus den vorstehenden Verbindungen hergestellt werden können.The new compounds are used in a manner that is known in principle Way, namely in combination with solid or liquid extenders or diluents. Chalk, talc, bentonite and kieselguhr have proven to be the most common such extenders proven. If liquid combinations are to be used, these preferably exist from aqueous emulsions, with the use of suitable solubilizers and commercially available emulsifiers are easily made from the above compounds can be.
Gegenüber den aus der deutschen Patentschrift 957 213 bekannten Thiophosphorsäureestem zeichnen sich die erfindungsgemäß erhältlichen Verbindungen durch eine bessere Wirksamkeit gegen Fliegenmaden bei gleichzeitig geringerer Toxizität gegen Warmblüter aus, wie aus der nachfolgenden Tabelle ersichtlich ist.Compared to the thiophosphoric acid esters known from German patent specification 957 213 the compounds obtainable according to the invention are distinguished by a better effectiveness against fly maggots with lower toxicity against warm-blooded animals, such as can be seen in the table below.
Verglichen wurden der verfahrensgemäß erhältliche Ester der Formel
(I)
und der aus der deutschen Patentschrift 957 213 bekannte Ester der Formel (II)
Ausbeute: 64 g, entsprechend 951)%1) der Theorie. Toxizität: Ratte per 1)s DL51) 25 mg/kg.Yield: 64 g, corresponding to 951)% 1) of theory. Toxicity: rat per 1) s DL51) 25 mg / kg.
Spinnmilben werden mit 0,011)/1)iger Lösung 1001)/1)ig abgetötet. Beispiel 2 Dieser neue Ester wird erhalten, wenn man 60g 0,0-diäthylthionothiolphosphorsaures Ammonium in Aceton mit 41 g Chlormethyl-p-acetophenyl-sulfid (F. = 64°C) in Aceton analog dem Beispiel l umsetzt und wie dort angegeben aufarbeitet.Spider mites are killed with 0.011) / 1) iger solution 1001) / 1) ig. Example 2 This new ester is obtained if 60 g of ammonium 0,0-diethylthionothiolphosphoric acid are reacted in acetone with 41 g of chloromethyl-p-acetophenyl sulfide (mp = 64 ° C.) in acetone analogously to Example 1 and worked up as indicated there.
Ausbeute: 70g, entsprechend 99°/o der Theorie. Toxizität: Ratte per os DL" 250 mg/kg. Spinnmilben werden mit 0,01 °/jgen Lösungen sicher abgetötet. Beispiel 3 LäBt man 44 g 0,0-dimethylthionothiolphosphorsaures Ammonium mit 40 g Chlormethyl-p-acetophenyl-sulfid (F. = 64°C) nach der im Beispiel 1 erläuterten Methode reagieren, so erhält man nach der dort angegebenen Aufarbeitung 55 g des neuen Esters (entsprechend 85 % der Theorie) in Form eines hellgelben Öles.Yield: 70 g, corresponding to 99% of theory. Toxicity: rat per os DL "250 mg / kg. Spider mites are safely killed with 0.01% / yg solutions. Example 3 If 44 g of ammonium 0,0-dimethylthionothiolphosphoric acid are allowed to react with 40 g of chloromethyl-p-acetophenyl sulfide (mp = 64 ° C.) by the method explained in Example 1, 55 g of the new ester are obtained after the work-up indicated there (corresponding to 85 % of theory) in the form of a light yellow oil.
Toxizität: Ratte per os DL" 1000 mg/kg.Toxicity: rat per os DL "1000 mg / kg.
Fliegen werden mit 0,1 °; oigen Lösungen zu 1000/, abgetötet.Flies are 0.1 °; oigen solutions to 1000 /, killed.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF26848A DE1063157B (en) | 1958-10-18 | 1958-10-18 | Process for the preparation of thiophosphoric acid esters |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF26848A DE1063157B (en) | 1958-10-18 | 1958-10-18 | Process for the preparation of thiophosphoric acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1063157B true DE1063157B (en) | 1959-08-13 |
Family
ID=7092185
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF26848A Pending DE1063157B (en) | 1958-10-18 | 1958-10-18 | Process for the preparation of thiophosphoric acid esters |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1063157B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1137006B (en) * | 1960-02-18 | 1962-09-27 | Geigy Ag J R | Process for the preparation of the insecticidally active S-phenyl-mercaptomethyl-O, O-dimethyl-dithiophosphoric acid ester |
DE1276638B (en) * | 1965-04-09 | 1968-09-05 | Basf Ag | O, O-dialkyl-thionophosphoric acid ester |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE957213C (en) * | 1954-06-10 | 1957-01-31 | Geigy Ag J R | Process for the preparation of new thiolthionophosphoric acid esters |
-
1958
- 1958-10-18 DE DEF26848A patent/DE1063157B/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE957213C (en) * | 1954-06-10 | 1957-01-31 | Geigy Ag J R | Process for the preparation of new thiolthionophosphoric acid esters |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1137006B (en) * | 1960-02-18 | 1962-09-27 | Geigy Ag J R | Process for the preparation of the insecticidally active S-phenyl-mercaptomethyl-O, O-dimethyl-dithiophosphoric acid ester |
DE1276638B (en) * | 1965-04-09 | 1968-09-05 | Basf Ag | O, O-dialkyl-thionophosphoric acid ester |
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