DE1224307B - Process for the preparation of thiophosphoric acid esters - Google Patents
Process for the preparation of thiophosphoric acid estersInfo
- Publication number
- DE1224307B DE1224307B DEB72094A DEB0072094A DE1224307B DE 1224307 B DE1224307 B DE 1224307B DE B72094 A DEB72094 A DE B72094A DE B0072094 A DEB0072094 A DE B0072094A DE 1224307 B DE1224307 B DE 1224307B
- Authority
- DE
- Germany
- Prior art keywords
- acid esters
- preparation
- carbon atoms
- general formula
- thiophosphoric 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
Links
- 238000000034 method Methods 0.000 title claims description 8
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- -1 1-Ethylmercapto-2-hydroxy-2-cyano-propane Chemical compound 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- ZKDXKBIOEVBFGV-UHFFFAOYSA-N 1-ethylsulfanylpropan-2-one Chemical compound CCSCC(C)=O ZKDXKBIOEVBFGV-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- KMJJJTCKNZYTEY-UHFFFAOYSA-N chloro-diethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OCC KMJJJTCKNZYTEY-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Verfahren zur Herstellung von Thiophosphorsäureestern Die Erfindung betrifft ein Verfahren zur Herstellung von organischen Phosphorsäureestern der allgemeinen Formel In dieser Formel bedeutet R1 einen Alkyl- oder Alkoxyrest mit 1 bis 3 Kohlenstoffatomen, R2 einen Alkylrest mit 1 bis 3 Kohlenstoffatomen und Rs einen Alkylrest mit 1 bis 6 Kohlenstoffatomen.Process for the production of thiophosphoric acid esters The invention relates to a process for the production of organic phosphoric acid esters of the general formula In this formula, R1 denotes an alkyl or alkoxy radical having 1 to 3 carbon atoms, R2 an alkyl radical having 1 to 3 carbon atoms and Rs an alkyl radical having 1 to 6 carbon atoms.
Die Herstellung der Verbindungen der Formel I erfolgt nach folgendem Mehrstufenverfahren, bei dem jedoch die Zwischenprodukte nicht isoliert zu werden brauchen: Ketone der allgemeinen Formel R3-S-CH2-CO-R2 II werden mit Blausäure zu den entsprechenden Cyanhydrinverbindungen umgesetzt, welche wiederum mit Verbindungen der Formel worin R1 die oben angegebene Bedeutung hat und Hal für ein Halogenatom steht, zur Reaktion gebracht werden. Das Verfahren verläuft entsprechend dem folgenden allgemeinen Reaktionsschema: 1. R3-S-CH2-CO-R2 + HCN In den Formeln des Reaktionsschemas besitzen R1 bis R, und Hal die oben angegebene Bedeutung.The compounds of the formula I are prepared by the following multistage process, in which, however, the intermediates do not need to be isolated: Ketones of the general formula R3-S-CH2-CO-R2 II are reacted with hydrocyanic acid to give the corresponding cyanohydrin compounds, which in turn are reacted with compounds the formula in which R1 has the meaning given above and Hal stands for a halogen atom, are reacted. The procedure is according to the following general reaction scheme: 1. R3-S-CH2-CO-R2 + HCN In the formulas of the reaction scheme, R1 to R and Hal have the meanings given above.
Die bei diesem Verfahren als Ausgangsstoffe verwendeten Ketone der Formel II und Halogenderivate der Säuren und Thiosäuren des Phosphors der Formel III werden nach bekannten Verfahren hergestellt. The ketones used as starting materials in this process Formula II and halogen derivatives of the acids and thioacids of phosphorus of the formula III are produced by known processes.
Die neuen Phosphorsäureester der allgemeinen Formel I sind hochwirksame Schädlingsbekämpfungsmittel mit nur geringer Toxizität gegen Warmblüter. Insbesondere besitzen sie ausgeprägte insektizide und acarizide Eigenschaften. Hinsichtlich bekannter, strukturell verwandter Schädlingsbekämpfungsmittel weisen die Wirkstoffe eine überlegene Wirksamkeit auf. The new phosphoric acid esters of the general formula I are highly effective Pesticides with low toxicity against warm-blooded animals. In particular they have pronounced insecticidal and acaricidal properties. With regard to known, structurally related pesticides have the active ingredients a superior one Effectiveness on.
Die Anwendung der Wirkstoffe erfolgt in der für Schädlingsbekämpfungsmittel üblichen Weise. The application of the active ingredients takes place in the for pesticides usual way.
Das folgende Beispiel dient zur Erläuterung der Erfindung. The following example serves to illustrate the invention.
Beispiel O,O-Diäthyl-O-(1-äthylmercapto-2-cyano-propyl-2)-thionophosphat a) 1-Athylmercapto-2-hydroxy-2-cyano-propan 118 g Athylmercaptoaceton in 90 ccm Benzol und 98 g Natriumcyanid in 150 ccm Wasser werden zusammengegeben und unter kräftigem Rühren auf 0°C abgekühlt. Bei 0 bis +5"C werden 214 ccm konzentrierte Salzsäure langsam zugetropft. Anschließend wird der Reaktionsansatz bei +10"C 10 Stunden gerührt und dann über Nacht stehengelassen. Example O, O-diethyl-O- (1-ethylmercapto-2-cyano-propyl-2) thionophosphate a) 1-Ethylmercapto-2-hydroxy-2-cyano-propane 118 g of ethylmercaptoacetone in 90 ccm Benzene and 98 g of sodium cyanide in 150 ccm of water are combined and taken under cooled to 0 ° C with vigorous stirring. At 0 to +5 "C, 214 cc are concentrated Hydrochloric acid was slowly added dropwise. The reaction mixture is then at +10 "C 10 hours stirred and then left to stand overnight.
Dann wird die wäßrige Schicht abgetrennt, die benzolische Lösung getrocknet und das Lösungsmittel abdestilliert. Die Ausbeute an 1 -Athyl-mercapto-2-hydroxy-2-cyano-propan beträgt 120 g, entsprechend 830/o der Theorie.The aqueous layer is then separated off and the benzene solution is dried and the solvent is distilled off. The yield of 1-ethyl-mercapto-2-hydroxy-2-cyano-propane is 120 g, corresponding to 830 / o of theory.
Analyse: Stickstoff berechnet 9,65010, gefunden 9,450/0. b) O,O-Diäthyl-O-(1-äthylmercapto-2-cyanopropyl-2)-thionophosphat 14,5 g l-Athylmercapto-2-hydroxy-2-cyano-propan werden mit 50 ccm Toluol und 10,1 g Triäthylamin auf 65"C erhitzt und 20 g O,O-Diäthyl-thiophosphorylchlorid langsam zugetropft. Nach 4 Stunden bei 70 bis 80"C wird abgekühlt, vom gebildeten Triäthylaminhydrochlorid abgesaugt und das Lösungsmittel abdestilliert. Der Rückstand wird in 50 ccm Methylenchlorid gelöst, die Lösungen mit 10 ccm Wasser geschüttelt und sodann nach Abtrennen des Wassers getrocknet. Nach Abdestillieren des Lösungsmittels werden die restlichen flüchtigen Bestandteile auf dem kochenden Wasserbad an der Olpumpe abgesaugt. O,O-Diäthyl-O-(1-äthylmercapto-2-cyanopropyl-2)-thionophosphat wird in einer Ausbeute von 19 g entsprechend 640/0 der Theorie erhalten.Analysis: nitrogen calculated 9.65010, found 9.450 / 0. b) O, O-diethyl O- (1-ethylmercapto-2-cyanopropyl-2) thionophosphate 14.5 g of l-ethylmercapto-2-hydroxy-2-cyano-propane are mixed with 50 cc of toluene and 10.1 g of triethylamine heated to 65 "C and 20 g of O, O-diethyl thiophosphoryl chloride slowly added dropwise. After 4 hours at 70 to 80 ° C., the triethylamine hydrochloride formed is cooled suctioned off and the solvent was distilled off. The residue is dissolved in 50 cc of methylene chloride dissolved, shaken the solutions with 10 ccm of water and then after separating the Water dried. After the solvent has been distilled off, the remaining volatile components sucked off on the boiling water bath at the oil pump. O, O-diethyl O- (1-ethylmercapto-2-cyanopropyl-2) thionophosphate is obtained in a yield of 19 g corresponding to 640/0 of theory.
Analyse: Stickstoff berechnet 4,700/0, gefunden 4,950/0.Analysis: nitrogen calculated 4,700 / 0, found 4,950 / 0.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB72094A DE1224307B (en) | 1963-05-29 | 1963-05-29 | Process for the preparation of thiophosphoric acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB72094A DE1224307B (en) | 1963-05-29 | 1963-05-29 | Process for the preparation of thiophosphoric acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1224307B true DE1224307B (en) | 1966-09-08 |
Family
ID=6977296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB72094A Pending DE1224307B (en) | 1963-05-29 | 1963-05-29 | Process for the preparation of thiophosphoric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1224307B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0060984A2 (en) * | 1981-02-21 | 1982-09-29 | Bayer Ag | Process for the preparation of acid chlorides from cyanoalkyl esters of phosphoric acids |
| US4496493A (en) * | 1980-07-16 | 1985-01-29 | Union Carbide Corporation | Phosphorous esters of cyanohydrins |
| US4567168A (en) * | 1981-02-21 | 1986-01-28 | Bayer Aktiengesellschaft | Cyanohydrin phosphonates as pesticides |
| US4780458A (en) * | 1980-07-16 | 1988-10-25 | Rhone-Poulenc Nederlands B.V. | Phosphorous esters of cyanohydrins |
-
1963
- 1963-05-29 DE DEB72094A patent/DE1224307B/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4496493A (en) * | 1980-07-16 | 1985-01-29 | Union Carbide Corporation | Phosphorous esters of cyanohydrins |
| US4780458A (en) * | 1980-07-16 | 1988-10-25 | Rhone-Poulenc Nederlands B.V. | Phosphorous esters of cyanohydrins |
| EP0060984A2 (en) * | 1981-02-21 | 1982-09-29 | Bayer Ag | Process for the preparation of acid chlorides from cyanoalkyl esters of phosphoric acids |
| EP0060984A3 (en) * | 1981-02-21 | 1983-11-09 | Bayer Ag | Acid chlorides from cyanoalkyl esters of phosphoric acids, and process for their preparation |
| US4567168A (en) * | 1981-02-21 | 1986-01-28 | Bayer Aktiengesellschaft | Cyanohydrin phosphonates as pesticides |
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