CH374649A - Process for the preparation of thiophosphoric acid esters - Google Patents
Process for the preparation of thiophosphoric acid estersInfo
- Publication number
- CH374649A CH374649A CH6349358A CH6349358A CH374649A CH 374649 A CH374649 A CH 374649A CH 6349358 A CH6349358 A CH 6349358A CH 6349358 A CH6349358 A CH 6349358A CH 374649 A CH374649 A CH 374649A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid esters
- preparation
- thiophosphoric acid
- stands
- salts
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 241000607479 Yersinia pestis Species 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 propargyl halides Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 239000004927 clay Substances 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
- 239000003995 emulsifying agent Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000020075 ouzo Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003839 salts 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
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, 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
Landscapes
- 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
Verfahren zur Herstellung von Thiophosphorsäureestern
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Thiophosphorsäureestem der Formel
EMI1.1
in welcher R für niedere Alkylreste und X für Schwefel oder Sauerstoff stehen, das dadurch gekennzeichnet ist, dass O, O-Dialkyl-thio-bzw.-dithio- phosphorsäuresalze mit Propargylhalogeniden umgesetzt werden. Geeignete Salze sind beispielsweise die Alkalisalze, besonders jedoch die leicht zugänglichen Ammoniumsalze der obengenannten Säuren.
Ferner betrifft die Erfindung die Verwendung der neuen Thiophosphorsäureester zur Schädlings- bekämpfung.
Die erfindungsgemäss erhaltenen neuen Verbindungen zeichnen sich durch eine gute Spinnmilben- und Blattläuse-Wirkung aus und besitzen zum Teil systemische Eigenschaften. Sie werden in der für andere Phosphorsäureester üblichen Art und Weise angewandt, das heisst bevorzugt als Komponente in Schädlingsbekämpfungsmitteln, welche die üblichen festen oder flüssigen Streck-bzw. Verdünnungsmit- tel enthalten. Feste Streckmittel sind z. B. Talkum, Kreide, Bentonit, Tonerde, Kaolin usw. Als flüssiges Verdünnungsmittel kommt vor allem Wasser in Frage, worin die obengenannten Verbindungen zweckmässig unter Verwendung eines Hilfslosemittels, wie Dimethylformamid oder Aceton, und eines han delsüblichen Emulgators einemulgiert werden.
Beispiel 1
EMI1.2
51 g des Ammoniumsalzes der 0, 0-Diäthyl-di- thiophosphorsäure werden in 150 cm3 Methyläthyl- keton gelöst. Bei 800 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 Ather aufgenommen und die äthe- rische Schicht zweimal mit je 50 cm3 Wasser gewaschen. Nach dem Trocknen der ätherischen Schicht mit Natriumsulfat wird der Ather abdestilliert und der Rückstand im Hochvakuum rektifiziert.
Der Ester siedet bei 0,1 mm bei 66 . Die Ausbeute beträgt 41 g = 73 ouzo der Theorie.
Beispiel 2
EMI1.3
41 g des Ammoniumsalzes der 0, 0-Diäthyl-thiol- phosphorsäure werden in 125 cm3 Athanol gelöst.
Bei 700 werden sodann 20 g Propargylchlorid zugegeben. Unter beständigem Rühren wird bei der gleichen Temperatur innerhalb einer Stunde die Re aktion vervollständigt. Es wird wie im Beispiel 1 angegeben aufgearbeitet, wobei 25 g = 49 /o der Theorie des neuen Esters der obenangegebenen Formel erhalten werden. Der Ester siedet bei 0,01 mm bei 55 . Blattläuse und Spinnmilben werden von 0,1 /oigen Lösungen 100 /aig abgetötet.
PATENTANSPRtYCHE
I. Verfahren zur Herstellung von Thiophosphor- säureestern der Formel
EMI2.1
worin R für niedere Alkylreste und X für Schwefel oder Sauerstoff stehen, dadurch gekennzeichnet, dass 0, 0-Dialkyl-thio-bzw.-dithiophosphorsäuresalze mit Propargylhalogeniden umgesetzt werden.
Process for the preparation of thiophosphoric acid esters
The present invention relates to a process for the preparation of thiophosphoric acid esters of the formula
EMI1.1
in which R stands for lower alkyl radicals and X stands for sulfur or oxygen, which is characterized in that O, O-dialkyl-thio- or -dithiophosphoric acid salts are reacted with propargyl halides. Suitable salts are, for example, the alkali metal salts, but especially the easily accessible ammonium salts of the abovementioned acids.
The invention also relates to the use of the new thiophosphoric acid esters for pest control.
The new compounds obtained according to the invention are distinguished by a good action of spider mites and aphids and some of them have systemic properties. They are used in the manner customary for other phosphoric acid esters, that is to say preferably as a component in pesticides which contain the customary solid or liquid extenders or. Contains thinner. Solid extenders are e.g. B. talc, chalk, bentonite, clay, kaolin, etc. As a liquid diluent, especially water comes into question, in which the above compounds are conveniently emulsified using an auxiliary such as dimethylformamide or acetone, and a commercial emulsifier.
example 1
EMI1.2
51 g of the ammonium salt of 0, 0-diethyl-di- thiophosphoric acid are dissolved in 150 cm3 of methyl ethyl ketone. At 800, 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 cm3 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. The yield is 41 g = 73 ouzo of theory.
Example 2
EMI1.3
41 g of the ammonium salt of 0, 0-diethyl-thiol-phosphoric acid are dissolved in 125 cm3 of ethanol.
At 700, 20 g of propargyl chloride are then added. With constant stirring, the reaction is completed within one hour at the same temperature. It is worked up as indicated in Example 1, with 25 g = 49 / o of the theory of the new ester of the formula given above. The ester boils at 55 at 0.01 mm. Aphids and spider mites are killed by 0.1% solutions of 100%.
PATENT APPLICATION
I. Process for the preparation of thiophosphoric acid esters of the formula
EMI2.1
in which R stands for lower alkyl radicals and X stands for sulfur or oxygen, characterized in that 0, 0-dialkyl-thio- or dithiophosphoric acid salts are reacted with propargyl halides.
Claims (1)
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 |
|---|---|
| CH374649A true CH374649A (en) | 1964-01-31 |
Family
ID=7091072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH6349358A CH374649A (en) | 1957-09-24 | 1958-09-01 | Process for the preparation of thiophosphoric 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL256593A (en) * | 1959-10-07 | |||
| 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 |
| FR1310086A (en) | 1960-11-08 | 1963-03-04 | ||
| DE2727479A1 (en) * | 1977-06-18 | 1979-01-04 | Bayer Ag | INSECTICIDES AND ACARICIDES |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2693483A (en) * | 1952-03-06 | 1954-11-02 | Dow Chemical Co | Propynyl phosphate compounds |
-
0
- NL NL103634D patent/NL103634C/xx active
- BE BE571029D patent/BE571029A/xx unknown
-
1957
- 1957-09-24 DE DEF24013A patent/DE1063148B/en active Pending
-
1958
- 1958-09-01 CH CH6349358A patent/CH374649A/en unknown
- 1958-09-04 GB GB2848658A patent/GB860944A/en not_active Expired
- 1958-09-08 FR FR1203242D patent/FR1203242A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BE571029A (en) | |
| DE1063148B (en) | 1959-08-13 |
| NL103634C (en) | |
| GB860944A (en) | 1961-02-15 |
| FR1203242A (en) | 1960-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE917668C (en) | Process for the preparation of neutral esters of dithiophosphoric acid | |
| DE1139117B (en) | Process for the preparation of thiophosphorus, thiophosphonic and thiophosphinic acid esters | |
| DE836349C (en) | Process for the preparation of neutral esters of thiophosphoric acid | |
| DE949231C (en) | Process for the preparation of chlorinated benzyl esters of thiol or thionothiol phosphoric acids | |
| CH374649A (en) | Process for the preparation of thiophosphoric acid esters | |
| DE933627C (en) | Process for the preparation of thiophosphoric acid esters | |
| DE927092C (en) | Process for the preparation of thiophosphoric acid esters | |
| DE1071696B (en) | Process for the preparation of thiophosphoric acid esters | |
| DE1109680B (en) | Process for the preparation of alkylphosphonic acid-O-alkyl-thiolesters | |
| DE1078117B (en) | Process for the preparation of thiophosphoric acid esters | |
| DE1224307B (en) | Process for the preparation of thiophosphoric acid esters | |
| AT205983B (en) | Process for the production of new methylene bis (thionothiolphosphoric acid esters) | |
| DE1063155B (en) | Process for the preparation of thiophosphoric acid esters | |
| DE1793188C3 (en) | O-alkyl-0-phenyl-thiolphosphoric acid ester, process for their preparation and compositions containing them | |
| AT221534B (en) | Process for the production of new dithiolphosphonic acid esters | |
| DE1015794B (en) | Process for the preparation of chloromethylated O, O-dialkylthiophosphoric acid esters | |
| DE1151794B (en) | Process for the preparation of the monosodium salt of phospho-enolpyruvic acid | |
| DE1071701B (en) | Process for the production of new dithiophosphonic acid esters | |
| AT226248B (en) | Process for the preparation of new thionothiolphosphinic acid esters | |
| DE947366C (en) | Process for the preparation of monothionopyrophosphoric acid-0,0,0,0-tetraalkyl esters | |
| DE1059444B (en) | Process for the preparation of thionophosphoric acid esters | |
| DE1116223B (en) | Process for the preparation of cyclohexylphosphonic acid-O-ethylthiol esters | |
| DE1092464B (en) | Process for the preparation of O, S-dialkylthiophosphoric acid chlorides | |
| DE1026323B (en) | Process for the preparation of insecticidally active O, O-dialkyl-S-phenyl-thionothiolphosphoric acid esters | |
| DE1238014B (en) | Process for the production of phosphoric acid esters |