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DE1063148B - Process for the preparation of O, O-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters - Google Patents

Process for the preparation of O, O-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters

Info

Publication number
DE1063148B
DE1063148B DEF24013A DEF0024013A DE1063148B DE 1063148 B DE1063148 B DE 1063148B DE F24013 A DEF24013 A DE F24013A DE F0024013 A DEF0024013 A DE F0024013A DE 1063148 B DE1063148 B DE 1063148B
Authority
DE
Germany
Prior art keywords
propargyl
thio
dialkyl
acid esters
dithiophosphoric acid
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
DEF24013A
Other languages
German (de)
Inventor
Dr H C Gerhard Schrader Dr
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
Priority to NL103634D priority Critical patent/NL103634C/xx
Priority to BE571029D priority patent/BE571029A/xx
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF24013A priority patent/DE1063148B/en
Priority to CH6349358A priority patent/CH374649A/en
Priority to GB2848658A priority patent/GB860944A/en
Priority to FR1203242D priority patent/FR1203242A/en
Publication of DE1063148B publication Critical patent/DE1063148B/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/16Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165Esters of thiophosphoric acids
    • C07F9/173Esters of thiophosphoric acids with unsaturated acyclic alcohols
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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

DEUTSCHESGERMAN

DEUTSCHLANDGERMANY

PATENTAMTPATENT OFFICE

kl. kl.

INTBRNAT. KL.INTBRNAT. KL.

F24013IVb/12oF24013IVb / 12o

ANMELDE TA G: 24. SEPTEMBER 1957REGISTRATION DAY: SEPTEMBER 24, 1957

B EKANNTMACHUNG PER ANMELDUNG UND AUSGABE DER AUSLEGESCHRIFT:NOTICE BY REGISTRATION AND ISSUE OF THE EDITORIAL:

13. AIJ G U ST 19 S 913. AIJ G U ST 19 S 9

Die Erfindung betrifft ein Verfahren zur Herstellung von 0,0-Dialkyl-S-propargyl-thio- oder -dithiophosphorsäureestern der allgemeinen FormelThe invention relates to a process for the preparation of 0,0-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters the general formula

RORO

RORO

O (S)O (S)

Verfahren zur HerstellungMethod of manufacture

von O.O-Dialkyl-S-propargyl-thio- oder -dithiophosphorsäureesternof O.O-Dialkyl-S-propargyl-thio- or phosphorodithioic acid esters

in welcher R für bevorzugt niedere Alkylreste steht.in which R is preferably lower alkyl radicals.

Die Herstellung dieser Verbindung geschieht nach an sich bekannten Methoden durch Umsetzung von Propargylhalogeniden, insbesondere Propargylchlorid oder Propargylbromid, mit Salzen von Ο,Ο-Dialkylthio- oder -dithiophosphorsäuren. Geeignete Salze sind beispielsweise die Alkalisalze, besonders jedoch die leicht zugänglichen Ammoniumsalze der obengenannten Säuren. Die erfindungsgemäßen Verbindungen zeichnen sich durch eine gute Spinnmilben- und Blattläusewirkung aus und besitzen zum Teil svstemische Eigenschaften. Sie werden in der für andere Phosphorsäureester üblichen Art und Weise angewandt, d. h. bevorzugt in Verbindung mit den üblichen festen oder flüssigen Streck- bzw. Verdünnungsmitteln. Feste Streckmittel sind z. B. Talkum, Kreide, Bentonit, Tonerde, Kaolin. Als flüssiges Verdünnungsmittel kommt vor allem Wasser in Frage, worin die obengenannten Verbindungen zweckmäßig unter Verwendung eines Hilfslösemittels, wie Dimethylformamid oder Aceton, und eines handelsüblichen ümulgators einemulgiert werden.This compound is prepared by methods known per se by reacting propargyl halides, in particular propargyl chloride or propargyl bromide, with salts of Ο, Ο-dialkylthio- or dithiophosphoric acids. Suitable salts are, for example, the alkali metal salts, but especially the readily available ammonium salts of the abovementioned acids. The compounds according to the invention are distinguished by a good action of spider mites and aphids and some of them have synthetic properties. They are used in the manner customary for other phosphoric acid esters, ie preferably in conjunction with the customary solid or liquid extenders or diluents. Solid extenders are e.g. B. talc, chalk, bentonite, clay, kaolin. A particularly suitable liquid diluent is water, into which the abovementioned compounds are expediently emulsified using an auxiliary solvent, such as dimethylformamide or acetone, and a commercially available emulsifier.

Aus der USA.-Patentschrift 2 693 483 sind Thionophosphorsäureester bekannt, die neben einem sauerstoffgebundenen Propargylesterrest einen Trichlorphenylesterrest im Molekül enthalten. Während die erfindungsgemäß erhältlichen Verbindungen eine ausgezeichnete insektizide Wirkung gegen Kartoffelkäfer, Fliegen, Blattläuse, Spinnmilben und Mttckenlarven besitzen, kommt diese breite insektizide Wirkung den aus der LJSA.-Patentschrift 2 693 483 bekannten Verbindungen nicht zu. Darüber hinaus besitzen die erfindungsgemäß erhältlichen Verbindungen eine systemische Wirksamkeit, d. h., sie vermögen aus dem Pflanzensystem heraus fressende Insekten abzutöten, wenn wäßrige Emulsionen der erfindungsgemäß erhältKchen Verbindungen über die Wurzeln von den zu schützenden Pflanzen aufgenommen werden. Eine solche Wirksamkeit geht den Verbindungen der obengenannten USA.-Patentschrift ab.US Pat. No. 2,693,483 discloses thionophosphoric acid esters which, in addition to an oxygen-bound propargyl ester residue, contain a trichlorophenyl ester residue in the molecule. While the compounds obtainable according to the invention have an excellent insecticidal effect against potato beetles, flies, aphids, spider mites and mosquito larvae, the compounds known from LJSA. Patent 2,693,483 do not have this broad insecticidal effect. In addition, the compounds obtainable according to the invention have a systemic activity, ie they are able to kill insects eating out of the plant system if aqueous emulsions of the compounds obtained according to the invention are taken up via the roots of the plants to be protected. The compounds of the above-mentioned USA patent specification lack such effectiveness.

Anmelder:Applicant:

Farbenfabriken Bayer Aktiengesellsdiaft, Leverkusen-BayerwerkFarbenfabriken Bayer Aktiengesellsdiaft, Leverkusen-Bayerwerk

Dr. Dr. h. c. Gerhard Schrader, Wuppertal-Cronenberg, ist als Erfinder genannt wordenDr. Dr. H. c. Gerhard Schrader, Wuppertal-Cronenberg, has been named as the inventor

»5 Sl g des Ammoniumsalzes der Ο,Ο-Diäthyldithiophosphorsäure werden in 150 ecm Methyläthylketon gelöst. Bei 800C werden 19 g Propargylchlorid zugetropft. Die Temperatur wird 1 Stunde beibehalten, wobei die Reaktion unter ständigem Rühren beendet wird. Nach Absaugen vom gebildeten Ammoniumchlorid wird das Lösemittel abdestilliert, der Rückstand in Äther aufgenommen und die ätherische Schicht zweimal mit je SO ecm Wasser gewaschen. Nach dem Trocknen der ätherischen Schicht mit Natriumsulfat wird der Äther abdestilliert und der Rückstand im Hochvakuum rektifiziert. Der Ester siedet bei 0,1 mm bei 660C. Die Ausbeute beträgt 4Ig = 73°/„ der Theorie.»5 Sl g of the ammonium salt of Ο, Ο-diethyldithiophosphoric acid are dissolved in 150 ecm of methyl ethyl ketone. At 80 ° C., 19 g of propargyl chloride are added dropwise. The temperature is maintained for 1 hour, the reaction being terminated with constant stirring. After the ammonium chloride formed has been filtered off with suction, the solvent is distilled off, the residue is taken up in ether and the ethereal layer is washed twice with 50% of water each time. After the ethereal layer has been dried with sodium sulfate, the ether is distilled off and the residue is rectified in a high vacuum. The ester boils at 0.1 mm at 66 0 C. The yield is 4Ig = 73 ° / "of the theoretical.

Beispiel 2Example 2

C2H8O,C 2 H 8 O,

P — S — CH2 — C = CHP - S - CH 2 - C = CH

C2H6O1 C 2 H 6 O 1

C2H8O'C 2 H 8 O '

Beispiel 1example 1

P-S-CH2-C=CH C2H6O'PS-CH 2 -C = CH C 2 H 6 O '

41 g des Ammoniumsalzes der O.O-Diäthylthiolphosphorsäure werden in 125 ecm Äthanol gelöst. Bei 70° C werden sodann 20 g Propargylchlorid zugegeben. Unter beständigem Rühren wird bei der gleichen Temperatur innerhalb einer Stunde die Reaktion vervollständigt.41 g of the ammonium salt of O.O-diethylthiolphosphoric acid are dissolved in 125 ecm of ethanol. At 70 ° C., 20 g of propargyl chloride are then added. Under constant stirring, the reaction is completed within one hour at the same temperature.

Es wird, wie im Beispiel 1 angegeben, aufgearbeitet, wobei 25 g = 49% der Theorie des neuen Esters der oben angegebenen Formel erhalten werden. Der Ester siedet bei 0,01 mm bei 550C. Blattläuse und Spinnmilben werden von 0,l%igen Lösungen 100%ig abgetötet.It is worked up as indicated in Example 1, 25 g = 49% of the theory of the new ester of the formula given above being obtained. The ester boils at 0.01 mm at 55 ° C. Aphids and spider mites are 100% killed by 0.1% solutions.

909 607/413909 607/413

Claims (1)

3 43 4 PATENTANSPRUCH:. .. ; worin R Alkylreste, vorzugsweise niedermolekulare,PATENT CLAIM :. ..; wherein R is alkyl radicals, preferably low molecular weight, Verfahren zur Herstellung von Ο,Ο-Dialkyl-S-prö- bedeutet, dadurch gekennzeichnet, daß 0,0-Dialkyl·Process for the preparation of Ο, Ο-dialkyl-S-prö- means, characterized in that 0,0-dialkyl pargyl-thio- oder dithiophosphorsäureestem der allge- thio- oder -dithiophosphorsäuresalze mit Propargyl-pargyl-thio- or dithiophosphoric acid esters of the general thio- or -dithiophosphoric acid salts with propargylic meinen Formel halogeniden umgesetzt werden.my formula halides are implemented. ' : - RO' : - RO /''""^ C^2 — C = CH In Betracht gezogene Druckschriften:/ ''"" ^ C ^ 2 - C = CH I n Publications considered: RO USA.-Patentschrift Nr. 2 693 483. R O U.S. Patent No. 2,693,483. ®> 909 607/413 8.59®> 909 607/413 8.59
DEF24013A 1957-09-24 1957-09-24 Process for the preparation of O, O-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters Pending DE1063148B (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL103634D NL103634C (en) 1957-09-24
BE571029D BE571029A (en) 1957-09-24
DEF24013A DE1063148B (en) 1957-09-24 1957-09-24 Process for the preparation of O, O-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters
CH6349358A CH374649A (en) 1957-09-24 1958-09-01 Process for the preparation of thiophosphoric acid esters
GB2848658A GB860944A (en) 1957-09-24 1958-09-04 Thiophosphoric acid esters
FR1203242D FR1203242A (en) 1957-09-24 1958-09-08 Process for preparing thiophosphoric esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF24013A DE1063148B (en) 1957-09-24 1957-09-24 Process for the preparation of O, O-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters

Publications (1)

Publication Number Publication Date
DE1063148B true DE1063148B (en) 1959-08-13

Family

ID=7091072

Family Applications (1)

Application Number Title Priority Date Filing Date
DEF24013A Pending DE1063148B (en) 1957-09-24 1957-09-24 Process for the preparation of O, O-dialkyl-S-propargyl-thio- or -dithiophosphoric acid esters

Country Status (6)

Country Link
BE (1) BE571029A (en)
CH (1) CH374649A (en)
DE (1) DE1063148B (en)
FR (1) FR1203242A (en)
GB (1) GB860944A (en)
NL (1) NL103634C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3019159A (en) * 1960-05-11 1962-01-30 American Cyanamid Co Novel phosphorodithioates and methods for preparing the same
DE1173723B (en) * 1960-09-21 1964-07-09 Basf Ag Preparations for the control of insects
DE1175938B (en) * 1959-10-07 1964-08-13 Montedison Spa Insecticidal and acaricidal agents
DE1221627B (en) 1960-11-08 1966-07-28 Monsanto Co Process for the preparation of carbamoylmethylthiophosphoric acid esters
CN112010894A (en) * 2020-08-17 2020-12-01 湖州师范学院 Sulfur phosphate compound, nonaqueous lithium ion battery electrolyte containing sulfur phosphate compound and lithium ion battery

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2727479A1 (en) * 1977-06-18 1979-01-04 Bayer Ag INSECTICIDES AND ACARICIDES

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2693483A (en) * 1952-03-06 1954-11-02 Dow Chemical Co Propynyl phosphate compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2693483A (en) * 1952-03-06 1954-11-02 Dow Chemical Co Propynyl phosphate compounds

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1175938B (en) * 1959-10-07 1964-08-13 Montedison Spa Insecticidal and acaricidal agents
US3019159A (en) * 1960-05-11 1962-01-30 American Cyanamid Co Novel phosphorodithioates and methods for preparing the same
DE1173723B (en) * 1960-09-21 1964-07-09 Basf Ag Preparations for the control of insects
DE1221627B (en) 1960-11-08 1966-07-28 Monsanto Co Process for the preparation of carbamoylmethylthiophosphoric acid esters
CN112010894A (en) * 2020-08-17 2020-12-01 湖州师范学院 Sulfur phosphate compound, nonaqueous lithium ion battery electrolyte containing sulfur phosphate compound and lithium ion battery
CN112010894B (en) * 2020-08-17 2023-08-11 湖州师范学院 A kind of phosphoric acid ester compound, non-aqueous lithium-ion battery electrolyte containing it and lithium-ion battery

Also Published As

Publication number Publication date
CH374649A (en) 1964-01-31
NL103634C (en)
GB860944A (en) 1961-02-15
BE571029A (en)
FR1203242A (en) 1960-01-15

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