DE1116659B - Process for the production of fluorophenylmercaptomethylthiol or dithiophosphonic or phosphinic acid esters - Google Patents
Process for the production of fluorophenylmercaptomethylthiol or dithiophosphonic or phosphinic acid estersInfo
- Publication number
- DE1116659B DE1116659B DEF27055A DEF0027055A DE1116659B DE 1116659 B DE1116659 B DE 1116659B DE F27055 A DEF27055 A DE F27055A DE F0027055 A DEF0027055 A DE F0027055A DE 1116659 B DE1116659 B DE 1116659B
- Authority
- DE
- Germany
- Prior art keywords
- dithiophosphonic
- acid esters
- fluorophenylmercaptomethylthiol
- phosphinic acid
- production
- 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 4
- FLQUDUCNBDGCRI-UHFFFAOYSA-N hydroxy-sulfanyl-sulfidophosphanium Chemical compound SP(S)=O FLQUDUCNBDGCRI-UHFFFAOYSA-N 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 150000003573 thiols Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- -1 Fluorophenyl mercaptomethyl dithiophosphoric acid esters Chemical class 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 2
- 241001674044 Blattodea Species 0.000 description 2
- 241000256113 Culicidae Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QHNNVTNQSGOVKB-UHFFFAOYSA-M [K+].CP([S-])(=S)C Chemical compound [K+].CP([S-])(=S)C QHNNVTNQSGOVKB-UHFFFAOYSA-M 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- VUNPVDGCKKSVOD-UHFFFAOYSA-N ethylsulfanyl-hydroxy-methyl-sulfanylidene-lambda5-phosphane Chemical compound CCSP(C)(O)=S VUNPVDGCKKSVOD-UHFFFAOYSA-N 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 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
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 238000005406 washing Methods 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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)
Description
Verfahren zur Herstellung von Fluorphenylmercaptomethylthiol-bzw. -dithiophosphon- oder phosphinsäureestern Aus der deutschen Patentschrift 957 213 sind schon Fluorphenylmercaptomethyl - dithiophosphorsäureester bekannt. Diese Verbindungen besitzen nach den Angaben der obengenannten deutschen Patentschrift gute insektizide Eigenschaften. Process for the production of fluorophenylmercaptomethylthiol or. dithiophosphonic or phosphinic acid esters From German patent specification 957 213 Fluorophenyl mercaptomethyl dithiophosphoric acid esters are already known. These connections have good insecticides according to the information in the above-mentioned German patent Properties.
Gegenstand der Erfindung ist die Herstellung von Estern der allgemeinen Formel in der R1 einen Alkylrest und R2 einen Alkyl- oder Alkoxyrest bedeutet, und die sich also von Thiolphosphonsäuren, Dithiophosphonsäuren, Thiolphosphinsäuren oder Dithiophosphinsäuren ableiten.The invention relates to the preparation of esters of the general formula in which R1 denotes an alkyl radical and R2 denotes an alkyl or alkoxy radical, and which are thus derived from thiolphosphonic acids, dithiophosphonic acids, thiolphosphinic acids or dithiophosphinic acids.
Die neuen erfindungsgemäßen Verbindungen werden auf prinzipiell bekannte Weise durch Umsetzen von Fluorphenylmercaptomethylhalogeniden mit Salzen von Thiol- bzw. Dithiophosphonsäureestern oder Thiol- bzw. Dithiophosphinsäuren der allgemeinen Formel in der R1 und Ra die vorstehend genannte Bedeutung haben und Me ein Alkalimetall oder die NH4-Gruppe ist, erhalten. Die Umsetzung von p-Fluorphenylmercaptomethylchlorid mit dimethyldithiophosphinsaurem Kalium wird durch das Formelschema erläutert: Die neuen Ester sind hervorragende Schädlingsbekämpfungsmittel, die sich durch insektizide und akarizide Wirksamkeit auszeichnen. Die Anwendung der Ester geschieht auf prinzipiell bekannte Art und Weise, nämlich in Verbindung mit geeigneten festen oder flüssigen Streck- oder Verdünnungsmitteln. Solche sind z. B., falls es sich um feste Streckmittel handelt, Talkum, Kreide, Bentonite, Kieselgur oder vorzugsweise Wasser, im Falle eines flüssigen Verdünnungsmittels. Falls die Verbindungen in Wasser selbst nicht löslich sind, ist der Zusatz eines Lösungsvermittlers bzw. eines geeigneten handelsüblichen Emulgators empfehlenswert oder notwendig.The new compounds according to the invention are produced in a manner known in principle by reacting fluorophenyl mercaptomethyl halides with salts of thiol or dithiophosphonic esters or thiol or dithiophosphinic acids of the general formula in which R1 and Ra are as defined above and Me is an alkali metal or the NH4 group. The reaction of p-fluorophenyl mercaptomethyl chloride with potassium dimethyldithiophosphinate is illustrated by the equation: The new esters are excellent pesticides, which are characterized by insecticidal and acaricidal effectiveness. The esters are used in a manner known in principle, namely in conjunction with suitable solid or liquid extenders or diluents. Such are z. B., if it is a solid extender, talc, chalk, bentonite, kieselguhr or preferably water, in the case of a liquid diluent. If the compounds are not soluble in water, the addition of a solubilizer or a suitable commercially available emulsifier is recommended or necessary.
Zum Nachweis der überlegenen Eigenschaften der Verfahrensprodukte
wurde der erfindungsgemäß er hältliche Ester der Formeln
mit dem aus der deutschen Patentschrift 957 213 bekannten Ester der Formel II
bei der Anwendung gegen Blattläuse, Schaben und Mückenlarven verglichen. Aus der
folgenden Tabelle ist ersichtlich, in welcher Konzentration einer wäßrigen
Lösung
die Verbindungen I und II noch wirksam bzw nicht mehr wirksam sind.
Danach verdünnt man die Mischung mit Wasser, nimmt das ausgefallene Öl in Benzol auf und wäscht die entstandene Benzollösung mit Wasser und Natriumbicarbonat. Nach dem Trocknen der Lösung wird das Benzol abdestilliert und das zurückbleibende Öl im Vakuum destilliert. Kp.0,01 = 1100C. Man erhält 40 g eines hellgelben Öles; die Ausbeute beträgt 57,50/o.The mixture is then diluted with water and what has precipitated is taken Oil in benzene and wash the resulting benzene solution with water and sodium bicarbonate. After the solution has dried, the benzene is distilled off and what remains Oil distilled in vacuo. Bp 0.01 = 1100C. 40 g of a pale yellow oil are obtained; the yield is 57.50 / o.
Beispiel 2 Eine Mischung aus 49 g (0,3 Mol) Kaliumsalz des Methyldithiophosphonsäureäthylesters, 44 g (0,25 Mol) 4-Fluorphenylmercaptomethylchlorid und 150 com Aceton läßt man über Nacht bei Zimmertemperatur rühren und erwärmt sie am Morgen noch 1 Stunde auf 50 bis 60"C. Nach dem Erkalten der Mischung gießt man sie in Wasser und nimmt das entstandene Öl in Benzol auf. Nach dem Waschen der Benzollösung mit Wasser und Natriumbicarbonat trocknet man sie über Natriumsulfat. Das Benzol wird aus der Lösung abdestilliert und das zurückbleibende Öl im Hochvakuum destilliert. Man erhält 65 g Ester vom Kp.0,01 = 108 bis 109"C als hellgelbes, wasserunlösliches Öl. Die Ausbeute beträgt 89,2 O/o, die DL95 an der Ratte per os 10 mg/kg.Example 2 A mixture of 49 g (0.3 mol) of the potassium salt of methyldithiophosphonic acid ethyl ester, 44 g (0.25 mol) of 4-fluorophenyl mercaptomethyl chloride and 150 com of acetone is allowed to stir overnight at room temperature and is warmed to 50 to 60 "in the morning for another hour. C. After the mixture has cooled, it is poured into water and the resulting oil is taken up in benzene. After washing the benzene solution with water and sodium bicarbonate, it is dried over sodium sulfate. The benzene is distilled off from the solution and the remaining oil is distilled in a high vacuum 65 g of ester with a boiling point of 0.01 = 108 to 109 "C are obtained as a light yellow, water-insoluble oil. The yield is 89.2% and the DL95 in rats is 10 mg / kg per os.
Beispiel 3 Eine Mischung aus 50 g (0,3 Mol) dimethyldithiophosphinsaurem Kalium, 44 g (0,25 Mol) 4-Fluorphenylmercaptomethylchlorid und 150 ccm Aceton wird über Nacht gerührt. Zur Vervollständigung der Umsetzung erwärmt man die Mischung danach 1 Stunde auf 50 bis 60"C und arbeitet sie dann wie bereits beschrieben auf. Man erhält ein Öl, das rasch kristallisiert. Aus einem Lösungsmittelgemisch von Benzol und Petroläther umkristallisiert, erhält man 58 g derbe Kristalle vom Fp. = 70 bis 71"C; die Ausbeute beträgt 87,3 O/o.Example 3 A mixture of 50 g (0.3 mol) of potassium dimethyldithiophosphinate, 44 g (0.25 mol) of 4-fluorophenyl mercaptomethyl chloride and 150 cc of acetone is stirred overnight. To complete the reaction, the mixture is then heated to 50 to 60 ° C. for 1 hour and then worked up as already described. An oil is obtained which crystallizes rapidly. Recrystallized from a solvent mixture of benzene and petroleum ether, 58 g of coarse crystals are obtained of m.p. = 70 to 71 "C; the yield is 87.3%.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF27055A DE1116659B (en) | 1958-11-18 | 1958-11-18 | Process for the production of fluorophenylmercaptomethylthiol or dithiophosphonic or phosphinic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF27055A DE1116659B (en) | 1958-11-18 | 1958-11-18 | Process for the production of fluorophenylmercaptomethylthiol or dithiophosphonic or phosphinic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1116659B true DE1116659B (en) | 1961-11-09 |
Family
ID=7092272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF27055A Pending DE1116659B (en) | 1958-11-18 | 1958-11-18 | Process for the production of fluorophenylmercaptomethylthiol or dithiophosphonic or phosphinic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1116659B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE957213C (en) * | 1954-06-10 | 1957-01-31 | Geigy Ag J R | Process for the preparation of new thiolthionophosphoric acid esters |
-
1958
- 1958-11-18 DE DEF27055A patent/DE1116659B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE957213C (en) * | 1954-06-10 | 1957-01-31 | Geigy Ag J R | Process for the preparation of new thiolthionophosphoric acid esters |
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