DE1006416B - Process for the preparation of O, O-dialkyl-thionophosphoric acid fluorides - Google Patents
Process for the preparation of O, O-dialkyl-thionophosphoric acid fluoridesInfo
- Publication number
- DE1006416B DE1006416B DEF16915A DEF0016915A DE1006416B DE 1006416 B DE1006416 B DE 1006416B DE F16915 A DEF16915 A DE F16915A DE F0016915 A DEF0016915 A DE F0016915A DE 1006416 B DE1006416 B DE 1006416B
- Authority
- DE
- Germany
- Prior art keywords
- thionophosphoric acid
- dialkyl
- ethyl
- thionophosphoric
- 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
Links
- 239000002253 acid Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 5
- 150000002222 fluorine compounds Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000126 substance Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000002917 insecticide Substances 0.000 claims description 2
- 150000004812 organic fluorine compounds Chemical class 0.000 claims 1
- 150000003018 phosphorus compounds Chemical class 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- OJZGWRZUOHSWMB-UHFFFAOYSA-N ethoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(O)(O)=S OJZGWRZUOHSWMB-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von O, O-Dialkyl-thionophosphorsäurefluoriden Es wurde gefunden, daß die leicht zugänglichen O-Alkyl-thiono-phosphorsäure-difluoride in Gegenwart eines geeigneten Säurebindemittels ein Fluoratom leicht gegen Reste von primären oder sekundären Alkoholen austauschen können. Dieser leichte Ersatz eines Fluoratoms in den O-Alkyl-thiono-phosphorsäure-difluoriden ist überraschend, da diese Fluoride stabil sind und z. B. durch Wasser nur schwer hydrolysiert werden.Process for the preparation of O, O-dialkyl-thionophosphoric acid fluorides It has been found that the easily accessible O-alkyl-thionophosphoric acid difluoride in the presence of a suitable acid-binding agent, one fluorine atom readily takes up residues of primary or secondary alcohols can exchange. This lightweight replacement of a fluorine atom in the O-alkyl-thionophosphoric acid difluorides is surprising since these fluorides are stable and e.g. B. are difficult to hydrolyze by water.
Im einfachen Falle der Reaktion von O-Äthyl-thionophosphorsäure-difluorid mit Alkohol verläuft die Reaktion nach folgendem Schema: Für diesen Austausch von Fluor gegen den Rest eines Alkohols haben sich als Säurebindemittel z. B. Triäthylamin und Pyridin bewährt. Als Lösungsmittel kommen vor allem solche in Frage, in denen sich das entstehende fluorwasserstoffsaure Salz bei der obigen Reaktion nur schwer löst. Solche geeigneten Lösungsmittel sind z. B. Benzol, Toluol, Äthyläther usw.In the simple case of the reaction of O-ethyl-thionophosphoric acid difluoride with alcohol, the reaction proceeds according to the following scheme: For this exchange of fluorine for the remainder of an alcohol, acid binders such. B. Triethylamine and pyridine proven. Suitable solvents are above all those in which the hydrofluoric acid salt formed is difficult to dissolve in the above reaction. Such suitable solvents are e.g. B. benzene, toluene, ethyl ether, etc.
Die neuen Verfahrensprodukte zeichnen sich durch gute kontaktinsektizide Wirksamkeit bei gleichzeitiger geringer toxischer Wirkung gegen Warmblüter aus. Während die aus den Berichten der Deutschen Chemischen Gesellschaft, Bd. 65 (1932), S. 1598ff., und dem Journal of the Chemical Society, 1948, S. l0lOff., bekannten Verbindungen, die durch Umsetzung von O-Alkylphosphorsäure-difluoriden mit Alkoholen erhalten werden, bei der Versprühung bei Warmblütern zu Atembeklemmungen und Asthmaanfällen führen, zeigen die erfindungsgemäß erhaltenen Verbindungen diese Eigenschaft nicht. Die folgenden Beispiele erläutern das Verfahren.The new process products are characterized by good contact insecticides Effectiveness with a simultaneous low toxic effect against warm-blooded animals. While the reports from the German Chemical Society, Vol. 65 (1932), P. 1598ff., And the Journal of the Chemical Society, 1948, p.1010ff., Known Compounds obtained by reacting O-alkyl phosphoric acid difluorides with alcohols can be obtained when sprayed in warm-blooded animals to dyspnoea and asthma attacks lead, the compounds obtained according to the invention do not show this property. The following examples illustrate the process.
Beispiel 1 In einem Rührkolben werden 30g O-Äthyl-thionophosphorsäure-difluorid (Kp."o 78°) in 50 ccm Benzol gelöst. Dazu gibt man bei 40° unter Rühren eine Lösung aus 21g Triäthylamin, 10 g 98%igem Äthylalkohol und 25 ccm Benzol. Die Reaktion ist heftig und muß durch gelegentliches Kühlen gemildert werden. Nach 20 Minuten gibt man den Kolbeninhalt in einen Scheidetrichter, wäscht zweimal mit je 30 ccm Eiswasser, trennt die Benzollösung ab und trocknet sie mit Natriumsulfat. Nach dem Abdestillieren des Lösungsmittels erhält man 25 g O, O-Diäthyl-thiono-phosphorsäurefluorid vom Kp.lo 49°.example 1 30 g of O-ethyl-thionophosphoric acid difluoride (boiling point 78 °) are dissolved in 50 cc of benzene in a stirred flask. A solution of 21 g of triethylamine, 10 g of 98% ethyl alcohol and 25 cc of benzene is added at 40 ° with stirring The reaction is violent and must be alleviated by occasional cooling. After 20 minutes, the contents of the flask are placed in a separating funnel, washed twice with 30 cc of ice water each time, the benzene solution is separated off and dried with sodium sulfate. After the solvent has been distilled off, 25 is obtained g O, O-diethyl-thionophosphoric acid fluoride with a bp of 49 °.
Zur Herstellung der gleichen Verbindung kann man auch 75 g O-Äthyl-thiono-phosphorsäure-difluorid in einem Rührkolben unter Eiskühlung (bei 10 bis 15°) mit einer aus 11,5 g Natrium hergestellten Natriumäthylatlösung versetzen. Nach dem Ausreagieren gießt man das Reaktionsprodukt in viel Wasser, nimmt in Chloroform auf, trocknet und fraktioniert. Es werden 50 g 'des O, O-Diäthyl-thiono-phosphorsäurefluorids vom Kp.lo 49 bis 50° erhalten.75 g of O-ethyl-thionophosphoric acid difluoride can also be used to prepare the same compound in a stirred flask with ice cooling (at 10 to 15 °) with one of 11.5 g of sodium add sodium ethylate solution prepared. After reacting, you pour it Reaction product in plenty of water, taken up in chloroform, dried and fractionated. There are 50 g 'of the O, O-diethyl-thionophosphoric acid fluoride with a boiling point of 49 to 50 ° obtain.
Beispiel 2 30 g O-Äthyl-thiono-phosphorsäure-difluorid werden in 50 ccm Benzol gelöst. Dazu gibt man bei 40° unter Rühren eine Lösung aus 22 g ß-Oxäthyl-thioäthyläther und 21g Triäthylamin in 25 ccm Benzol. Durch gelegentliches Kühlen hält man die Temperatur auf 40°. Man arbeitet, wie im Beispiel 1 beschrieben, auf. Man erhält 23 g des neuen Esters vom Kp.o, 4 69°.Example 2 30 g of O-ethyl-thionophosphoric acid difluoride are dissolved in 50 cc of benzene. A solution of 22 g of β-oxethyl thioethyl ether and 21 g of triethylamine in 25 cc of benzene is added at 40 ° with stirring. The temperature is kept at 40 ° by occasional cooling. You work as described in Example 1 on. 23 g of the new ester with a boiling point of 4.69 ° are obtained.
Beispiel 3 30g O-Äthyl-thiono-phosphorsäure-difluorid löst man in 50 ccm Benzol. Dazu gibt man unter Rühren bei 30° eine Lösung von 22 g Triäthylamin in 30 g Trichloräthylalkohol. Die heftige Reaktion wird durch gelegentliches Kühlen gemildert. Man lälit 1 Stunde bei 30° weiterrühren und arbeitet dann in der üblichen Weise auf. Es werden 31 g des neuen Esters vom Kp.3 75° erhalten. Beispiel 4 In ähnlicher Weise, wie im Beispie13 beschrieben, erhält man aus 30 g O-Äthyl-thiono-phosphorsäure-difluorid, 12 g Isopropylalkohol und 22 g Triäthylamin 25 g des Esters der folgenden Formel: vom Kp." 68°.Example 3 30 g of O-ethyl-thionophosphoric acid difluoride are dissolved in 50 cc of benzene. A solution of 22 g of triethylamine in 30 g of trichloroethyl alcohol is added with stirring at 30 °. Occasional cooling will moderate the violent reaction. The mixture is stirred for a further 1 hour at 30 ° and then worked up in the usual way. 31 g of the new ester with a boiling point of 75 ° are obtained. Example 4 In a manner similar to that described in Example 13, 25 g of the ester of the following formula are obtained from 30 g of O-ethyl-thionophosphoric acid difluoride, 12 g of isopropyl alcohol and 22 g of triethylamine: from Kp. "68 °.
Beispiel 5 Aus 30 g O-Äthyl-thiono-phosphorsäure-difluorid, 15 g sekundärem Butylalkohol und 22 g Triäthylamin erhält man auf gleiche Weise, wie im Beispiel 3 beschrieben, 33 g des Esters der folgenden Formel: vom Kp." 81 bis 82°.Example 5 From 30 g of O-ethyl-thionophosphoric acid difluoride, 15 g of secondary butyl alcohol and 22 g of triethylamine, 33 g of the ester of the following formula are obtained in the same manner as described in Example 3: from Kp. "81 to 82 °.
Beispiel 6 Aus 30g O-Äthyl-thiono-phosphorsäure-difluorid,18,5g Hexylalkohol und 22g Triäthylamin erhält man nach Beispiel 335 g des Esters der folgenden Formel: vom Kp.3 90 bis 92°. Beispiel 7 Aus 30 g 0-Äthyl-tbiono-phosphorsäure-difluorid, 18 g Glykolmonoäthyläther und 22 g Triäthylamin erhält man nach Beispiel 333 g des Esters der folgenden Formel: vom Kp.lo 95°.Example 6 From 30 g of O-ethyl-thionophosphoric acid difluoride, 18.5 g of hexyl alcohol and 22 g of triethylamine, 335 g of the ester of the following formula are obtained according to Example: from head 3 90 to 92 °. Example 7 From 30 g of 0-ethyl-tbionophosphoric acid difluoride, 18 g of glycol monoethyl ether and 22 g of triethylamine, 333 g of the ester of the following formula are obtained according to Example: from Kp.lo 95 °.
Beispiel 8 Aus 30 g O-Äthyl-thiono-phosphorsäure-difluorid, 21 g Pinacolinalkohol und 22 g Triäthylamin erhält man nach den Angaben des Beispiels 320 g des Esters der folgenden Formel: vom Kp.4 65°.Example 8 From 30 g of O-ethyl-thionophosphoric acid difluoride, 21 g of pinacoline alcohol and 22 g of triethylamine, 320 g of the ester of the following formula are obtained according to the data in Example: from Kp.4 65 °.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF16915A DE1006416B (en) | 1955-02-25 | 1955-02-25 | Process for the preparation of O, O-dialkyl-thionophosphoric acid fluorides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF16915A DE1006416B (en) | 1955-02-25 | 1955-02-25 | Process for the preparation of O, O-dialkyl-thionophosphoric acid fluorides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1006416B true DE1006416B (en) | 1957-04-18 |
Family
ID=7088392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF16915A Pending DE1006416B (en) | 1955-02-25 | 1955-02-25 | Process for the preparation of O, O-dialkyl-thionophosphoric acid fluorides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1006416B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1146882B (en) * | 1960-07-07 | 1963-04-11 | Bayer Ag | Process for the production of phosphonic acid ester fluorides and amide fluorides |
-
1955
- 1955-02-25 DE DEF16915A patent/DE1006416B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1146882B (en) * | 1960-07-07 | 1963-04-11 | Bayer Ag | Process for the production of phosphonic acid ester fluorides and amide fluorides |
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