DE1119849B - Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters - Google Patents

Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters

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Publication number
DE1119849B
DE1119849B DEF28805A DEF0028805A DE1119849B DE 1119849 B DE1119849 B DE 1119849B DE F28805 A DEF28805 A DE F28805A DE F0028805 A DEF0028805 A DE F0028805A DE 1119849 B DE1119849 B DE 1119849B
Authority
DE
Germany
Prior art keywords
allyl
phosphoric acid
thiol
alkyl
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
Application number
DEF28805A
Other languages
German (de)
Inventor
Dr Dr H C Gerhard Schrader
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF28805A priority Critical patent/DE1119849B/en
Publication of DE1119849B publication Critical patent/DE1119849B/en
Pending legal-status Critical Current

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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 System
    • 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
    • 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 System
    • 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

Description

Verfahren zur Herstellung von O-AIlyl-O-alkyl-thiol-phosphorsäureestern Es wurde gefunden, daß man O-Allyl-O-alkylthiol-phosphorsäureester dadurch herstellen kann, daß man O-allyl-O-alkyl-thiol-phosphorsaure Salze mit gegebenenfalls substituierten Alkylchloriden umsetzt. Process for the preparation of O-Allyl-O-alkyl-thiol-phosphoric acid esters It has been found that O-allyl-O-alkylthiol-phosphoric acid esters can be produced in this way can that one O-allyl-O-alkyl-thiol-phosphoric acid salts with optionally substituted Reacts alkyl chlorides.

Die als Ausgangsmaterialien benötigten O-allyl-O-alkyl-thiol-phosphorsauren Salze können auf bequeme Art und Weise dadurch hergestellt werden, daß man an Diallylphosphit in Gegenwart von Alkalialkoholaten Schwefel anlagert. Hierbei entsteht nicht, wie erwartet werden müßte, das entsprechende O, O-diallyl-thionophosphorsaure Alkalisalz, sondern unter Austausch einer Allylgruppe gegen den Alkoholrest des verwendetenNatriumalkoholates das entsprechende O-allyl-O-alkyl-thionophosphorsaure Alkalisalz, das sich in seiner tautomeren Thiolform alkylieren läßt zu den neuen erfindungsgemäßen Verbindungen. The O-allyl-O-alkyl-thiol-phosphoric acids required as starting materials Salts can be conveniently prepared by reacting on diallyl phosphite accumulates sulfur in the presence of alkali alcoholates. This does not arise how would have to be expected, the corresponding O, O-diallyl-thionophosphoric acid alkali salt, but by exchanging an allyl group for the alcohol residue of the sodium alcoholate used the corresponding O-allyl-O-alkyl-thionophosphoric acid alkali salt, which is in his tautomeric thiol form can be alkylated to give the new compounds according to the invention.

Am Beispiel der Umsetzung des O, O-Diallylphosphits mit Schwefel und Natrium-methylat sowie der weiteren erfindungsgemäßen Reaktion des entstandenen O-allyl-O-methylthiol-phosphorsauren Na- triums mit einem gegebenenfalls substituierten Alkylhalogenid sei das Verfahren erläutert : In vorstehenden Gleichungen bedeutet R einen gegebenenfalls substituierten Alkylrest und X ein Halogenatom.The process is explained using the example of the reaction of O, O-diallyl phosphite with sulfur and sodium methylate and the further inventive reaction of the sodium O-allyl-O-methylthiol-phosphoric acid with an optionally substituted alkyl halide: In the above equations, R denotes an optionally substituted alkyl radical and X denotes a halogen atom.

Die erfindungsgemäß erhältlichen neuen Verbindungen stellen Schädlingsbekämpfungsmittel dar, die vor allem als Insektizide Verwendung finden sollen. The new compounds obtainable according to the invention represent pesticides which are to be used primarily as insecticides.

Ihre Anwendung geschieht auf prinzipiell bekannte Art und Weise, d. h. in Verbindung mit geeigneten festen oder flussigen Streck-oder Verdünnungsmitteln.They are used in a manner known in principle, i. H. in conjunction with suitable solid or liquid extenders or thinners.

Die gemäß Erfindung herstellbaren O-Allyl-O-alkylthiol-phosphorsäure-S-alkylester sind, wie aus den nachfolgenden Vergleichsversuchen eindeutig hervorgeht, den bekannten, analog gebauten O, O-Dialkylthiol-phosphorsäure-S-alkylestern hinsichtlich ihrer insektiziden Wirksamkeit deutlich überlegen. Es wurden verglichen : Der verfahrensgemäß herstellbare O-Allyl-O-methyl-thiol-phosphorsäure-S- (4-chlor- phenyl)-methylester der Formel mit dem bekannten O, O-Dimethyl-thiol-phosphorsäure-S-(4-chlorphenyl)-methylester der Formel Die Ergebnisse der Vergleichsversuche sind in der folgenden Tabelle zusammengefaßt. 0 0 CH30 CH2=CHCHZO P-S-CH2-S Cl P-S-CH2-S Anwendunggegen CH0-/CHO/ 3 Wirkstoffkonzen-Abtdtung Wirkstoffkonzentration Abtötung tration I I Fliegen........ 0, 0101, 50010 0, 010/0 1000/0 f 1 1000/, 0110/0 1000/0 Blattläuse 0, 01"/o00, 01"/. 100 °/. 0, 001 /0 100% 0, °/o 100°/o 0, °/0 100°/0 Spinnmilben.. 0, 01°/0 0 0, 01 °/0 100 °/o 00, 001% 100% Wie aus der Tabelle ersichtlich, wirkt der erfindungsgemäße Thiophosphorsäureester noch in solchen Konzentrationen 100°/oig abtötend auf Blattläuse und Spinnmilben, bei denen sich die analog gebaute bekannte Vergleichsverbindung bereits als völlig wirkungslos erweist. Bei der Anwendung gegen Fliegen zeigt das Verfahrensprodukt eine wesentlicheWirkungssteigerung gegenüber der Vergleichssubstanz.The O-allyl-O-alkylthiol-phosphoric acid S-alkyl esters which can be prepared according to the invention are, as is clearly evident from the following comparative experiments, clearly superior to the known, analogously constructed O, O-dialkylthiol-phosphoric acid S-alkyl esters with regard to their insecticidal effectiveness. The following were compared: The O-allyl-O-methyl-thiol-phosphoric acid S- (4-chlorophenyl) methyl ester of the formula which can be prepared according to the process with the known O, O-dimethyl-thiol-phosphoric acid-S- (4-chlorophenyl) -methyl ester of the formula The results of the comparative tests are summarized in the table below. 0 0 CH30 CH2 = CHCHZO PS-CH2-S Cl PS-CH2-S Application against CH0- / CHO / 3 Active ingredient concentration killing active ingredient concentration tration II Flies ........ 0, 0101, 50010 0, 010/0 1000/0 f 1 1000 /, 0110/0 1000/0 Aphids 0, 01 "/ o00, 01" /. 100 ° /. 0.001 / 0 100% 0, ° / o 100 ° / o 0, ° / 0 100 ° / 0 Spider mites .. 0, 01 ° / 0 0 0, 01 ° / 0 100 ° / o 00, 001% 100% As can be seen from the table, the thiophosphoric acid ester according to the invention has a 100% killing effect on aphids and spider mites even in concentrations at which the known comparative compound constructed in an analogous manner already proves to be completely ineffective. When used against flies, the process product shows a significant increase in effectiveness compared to the comparison substance.

Beispiel 1 48 g O-allyl-O-methyl-thiol-phosphorsaures Natrium (0, 25 Mol) werden in 100 ccm Acetonitril gelöst. Dazu gibt man unter Rühren 40 g (0, 25 Mol) a-Chlormethylthiophenyläther. Man erwärmt 1 Stunde auf 50°C und gibt dann das Reaktionsprodukt in 300 ccm Eiswasser. Das ausgeschiedene 01 wird in 300 ccm Benzol aufgenommen, mit Wasser neutral gewaschen und anschließend mit Natriumsulfat getrocknet. Nach dem Abdestillieren des Losungsmittels erhält man 54 g des neuen Esters als wasserunlösliches, gelbes Öl. Ausbeute : 68 °/0 der Theorie.example 1 48 g of O-allyl-O-methyl-thiol-phosphoric acid sodium (0.25 mol) are dissolved in 100 cc of acetonitrile. 40 g (0.25 mol) of α-chloromethylthiophenyl ether are added with stirring. The mixture is heated to 50 ° C. for 1 hour and then the reaction product is poured into 300 cc of ice water. The precipitated oil is taken up in 300 cc of benzene, washed neutral with water and then dried with sodium sulfate. After the solvent has been distilled off, 54 g of the new ester are obtained as a water-insoluble, yellow oil. Yield: 68% of theory.

Berechnet für Mol 290... S 20, 2 °/0, P 9, 8 °/o ; gefunden.............. S 21,0%, P 10, 2%. Calculated for moles 290 ... S 20.2 ° / 0, P 9.8%; found.............. S 21.0%, P 10.2%.

Blattläuse werden noch in einer Konzentration von 0, 01% 100%ig abgetötet. DL50 Ratte per os : 5 mg/kg. Aphids are killed at a concentration of 0.01% 100%. DL50 rat orally: 5 mg / kg.

Beispiel 2 48 g (0, 25 Mol) O-allyl-O-methyl-thiol-phosphorsaures Natrium werden in 100 ccm Acetonitril gelöst.Example 2 48 g (0.25 mol) of O-allyl-O-methyl-thiol-phosphoric acid sodium are dissolved in 100 cc of acetonitrile.

Anschließend gibt man bei 75°C 35 g (0, 25 Mol) ß-[Diäthylamino]-äthylchlorid hinzu, Man hält noch 1 Stunde bei 75°C und arbeitet dann in üblicher Weise auf. Es werden 35 g des neuen Esters als wasserlösliches, schwachgelbes Ö1 erhalten. Ausbeute : 48% der Theorie.Then at 75 ° C. 35 g (0.25 mol) of β- [diethylamino] ethyl chloride are added added, it is kept at 75 ° C. for 1 hour and then worked up in the usual way. 35 g of the new ester are obtained as a water-soluble, pale yellow oil. Yield: 48% of theory.

Berechnet für Mol 267... N 7,8%, S 10,9%, P 10,7%; gefunden .............. N 6,8%, S 11,0%, P 11,0%. Calculated for Mol 267 ... N 7.8%, S 10.9%, P 10.7%; found .............. N 6.8%, S 11.0%, P 11.0%.

Beispiel 3 48 g (0, 25 Mol) O-allyl-O-methyl-thiol-phosphorsaures Natrium werden in 100 ccm Acetonitril gelöst.Example 3 48 g (0.25 mol) of O-allyl-O-methyl-thiol-phosphoric acid sodium are dissolved in 100 cc of acetonitrile.

Bei 40°C gibt man unter Rühren 49 g a-Chlormethyl-(4-chlor-phenyl)-thioäther (0, 25 Mol) hinzu. Man läßt 1 Stunde bei 50° C rühren und arbeitet dann in üblicher Weise auf. Es werden 50 g des neuen Esters als wasserunlösliches, schwachgelbes 01 erhalten. Ausbeute : 59"/odeur Theorie.At 40 ° C., 49 g of α-chloromethyl (4-chlorophenyl) thioether are added with stirring (0.25 moles). The mixture is stirred for 1 hour at 50.degree. C. and then carried out in a conventional manner Way up. There are 50 g of the new ester as a water-insoluble, pale yellow 01 received. Yield: 59 "/ or theory.

Berechnet für Mol 325... S 18, 2°/os P 9, 4°/0, Cl 12, 10/0 ; gefunden .............. S 19,2%, P 9,6%, Cl 1 1, 8 °/0. Calculated for moles 325 ... S 18.2 ° / os P 9.4 ° / 0, Cl 12, 10/0; found .............. S 19.2%, P 9.6%, Cl 1 1.8 ° / 0.

DL50 Ratte per os : 25 mg/kg. Blattläuse werden in einer Konzentration von 0, 001 °/o noch 100°/oig abgetötet. DL50 rat orally: 25 mg / kg. Aphids are in a concentration of 0.001% still 100% killed.

Claims (1)

PATENTANSPRUCH : Verfahren zur Herstellung von O-Allyl-O-alkylthiol-phosphorsäureestern der allgemeinen Formel in welcher R für einen niederen Alkyl-und R' für einen gegebenenfalls substituierten Alkylrest steht, dadurch gekennzeichnet, daß O-allyl-O -alkyl-thiol-phosphorsaure Salze mit gegebenenfalls substituierten Alkylchloriden umgesetzt werden.PATENT CLAIM: Process for the preparation of O-allyl-O-alkylthiol-phosphoric acid esters of the general formula in which R stands for a lower alkyl and R 'stands for an optionally substituted alkyl radical, characterized in that O-allyl-O-alkyl-thiol-phosphoric acid salts are reacted with optionally substituted alkyl chlorides. In Betracht gezogene Druckschriften : Deutsche Auslegeschrift Nr. 1 056 117; britische Patentschrift Nr. 785 030. Documents considered: German Auslegeschrift No. 1,056,117; British Patent No. 785 030. In Betracht gezogene ältere Patente : Deutsches Patent Nr. 1 062 237. Older patents considered: German Patent No. 1 062 237.
DEF28805A 1959-06-27 1959-06-27 Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters Pending DE1119849B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF28805A DE1119849B (en) 1959-06-27 1959-06-27 Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF28805A DE1119849B (en) 1959-06-27 1959-06-27 Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters

Publications (1)

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DE1119849B true DE1119849B (en) 1961-12-21

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Application Number Title Priority Date Filing Date
DEF28805A Pending DE1119849B (en) 1959-06-27 1959-06-27 Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB785030A (en) * 1954-07-12 1957-10-23 Fisons Pest Control Ltd Process for the production of sulphinyl ethyl thiophosphates
DE1056117B (en) * 1957-01-05 1959-04-30 Bayer Ag Process for the preparation of O, O-dialkylthiolphosphoric acid and -thiolthionophosphoric acid-S-gamma-cyanallyl esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB785030A (en) * 1954-07-12 1957-10-23 Fisons Pest Control Ltd Process for the production of sulphinyl ethyl thiophosphates
DE1056117B (en) * 1957-01-05 1959-04-30 Bayer Ag Process for the preparation of O, O-dialkylthiolphosphoric acid and -thiolthionophosphoric acid-S-gamma-cyanallyl esters

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