DE1129953B - Process for the preparation of dialkylthionophosphinic acid thiourea derivatives - Google Patents
Process for the preparation of dialkylthionophosphinic acid thiourea derivativesInfo
- Publication number
- DE1129953B DE1129953B DEF30338A DEF0030338A DE1129953B DE 1129953 B DE1129953 B DE 1129953B DE F30338 A DEF30338 A DE F30338A DE F0030338 A DEF0030338 A DE F0030338A DE 1129953 B DE1129953 B DE 1129953B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- dialkylthionophosphinic
- preparation
- thiourea derivatives
- general formula
- 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 11
- 238000000034 method Methods 0.000 title claims description 10
- 150000003585 thioureas Chemical class 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- -1 alkyl radical Chemical class 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000238814 Orthoptera Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BPSCHQMKSIMBFY-UHFFFAOYSA-N diethyl-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(O)(=S)CC BPSCHQMKSIMBFY-UHFFFAOYSA-N 0.000 description 2
- DQIMSUZRBYLFOT-UHFFFAOYSA-N hydroxy-dimethyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(C)(O)=S DQIMSUZRBYLFOT-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZNTCOMIEVWGPBB-UHFFFAOYSA-N (4-chlorophenoxy)-dimethyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(C)(=S)OC1=CC=C(Cl)C=C1 ZNTCOMIEVWGPBB-UHFFFAOYSA-N 0.000 description 1
- PEXKIPRKGNEQPD-UHFFFAOYSA-N 1,2-dichloro-3-(2,2,2-trichloro-1-phenylethyl)benzene Chemical compound ClC=1C(=C(C=CC=1)C(C(Cl)(Cl)Cl)C1=CC=CC=C1)Cl PEXKIPRKGNEQPD-UHFFFAOYSA-N 0.000 description 1
- 241000257161 Calliphoridae Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241000254022 Locusta migratoria Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 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)]
- C07F9/36—Amides thereof
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 Dialkylthionophosphinsäurethioharnstoffderivaten Aus der deutschen Patentschrift 952 712 ist bereits ein Verfahren zur Herstellung von am Stickstoff phosphorylierten Thioharnstoffen durch Einwirkung von Ammoniak bzw. primären oder sekundären Aminen auf Thionopho sphorsäure-O, O-dialkylester-N-thiocarbimide bekannt. Process for the preparation of dialkylthionophosphinic acid thiourea derivatives The German patent specification 952 712 already discloses a method for production of thioureas phosphorylated on nitrogen by the action of ammonia or primary or secondary amines on thionophosphoric acid-O, O-dialkyl ester-N-thiocarbimide known.
Die Umsetzung von Thionophosphorsäure-O,O-dialkylesterrhodaniden bzw. -isothiocyanaten mit primären oder sekundären Aminen wird weiterhin auch in ». obsc. Chim.«, Bd. 29, 1959, S. 1249 bis 1254, beschrieben. The implementation of thionophosphoric acid O, O-dialkyl ester rhodanides or isothiocyanates with primary or secondary amines is also used in ». obsc. Chim. ”, Vol. 29, 1959, pp. 1249-1254.
Thionophosphinsäurerhodanide können aus den nach dem Verfahren der deutschen Patentschrift 1 054453 leicht zugänglichen Thionophosphinsäurehalogeniden durch Umsetzen mit Alkalirhodaniden in an sich bekannter Weise erhalten werden. Thionophosphinic acid rhodanides can be obtained from the according to the method of German Patent 1,054,453 easily accessible thionophosphinic acid halides be obtained by reacting with Alkalirhodaniden in a manner known per se.
Es wurde nun gefunden, daß Thionophosphinsäurerhodanide mit primären oder sekundären Aminen unter Bildung der entsprechenden Thioharnstoffderivate der Formel in der R für einen niederen Alkylrest, R' und R" für Alkyl-, Aryl-, Aralkylreste oder einer der beiden Reste R' und R" für Wasserstoff steht, reagieren nach folgendem Reaktionsschema, das ein Beispiel für die Umsetzung ist: Die neuen Verbindungen der vorliegenden Erfindung werden auf prinzipiell bekannte Art und Weise angewendet. Sie werden entweder mit festen oder flüssigen Streck- oder Verdünnungsmitteln gemischt, wobei diesen Mischungen weitere Hilfsstoffe, wie z. B.It has now been found that thionophosphinic acid rhodanides with primary or secondary amines to form the corresponding thiourea derivatives of the formula in which R stands for a lower alkyl radical, R 'and R "stands for alkyl, aryl, aralkyl radicals or one of the two radicals R' and R" stands for hydrogen, react according to the following reaction scheme, which is an example of the reaction: The new compounds of the present invention are applied in a manner known in principle. They are mixed with either solid or liquid extenders or diluents, these mixtures being further auxiliaries, such as. B.
Emulgatoren oder auch andere bekannte Insektizide oder Fungizide, zugesetzt werden können. Die auf diese Weise leicht zugänglichen Dialkylthionophosphinsäurethioharnstoffe sind Mittel mit insektiziden Eigenschaften.Emulsifiers or other known insecticides or fungicides, can be added. The dialkylthionophosphinic acid thioureas easily accessible in this way are agents with insecticidal properties.
Das erfindungsbegründende Merkmal des vorliegenden Verfahrens besteht in den überlegenen, technisch nutzbaren Eigenschaften der verfahrensgemäß erhältlichen Verbindungen gegenüber analog gebauten und für den gleichen Zweck verwendbaren bekannten Produkten. Diese technische Überlegenheit der verfahrensgemäß herstellbaren Thionophosphinsäurederivate geht aus den nachfolgenden Vergleichsversuchen hervor: Es wurden die nach dem Verfahren der Erfindung erhältlichen Verbindungen 1, 3 und 4 verglichen mit dem bekannten Präparat 2, das hinsichtlich seiner kontaktinsektiziden Wirkung das Dichlordiphenyltrichlormethylmethan übertrifft, sowie mit dem als insektizides Spitzenprodukt bekannten Dimethylthionophosphinsäure-O-(4-chlor-phenyl)-ester (Verbindung 5) hinsichtlich der Wirkung 0,1°/Oiger Lösungen gegen Wanderheuschrecken, Fliegenmaden und Raupen. The inventive feature of the present method is in the superior, technically usable properties of those obtainable according to the process Compounds compared to known ones which are constructed in an analogous manner and which can be used for the same purpose Products. This technical superiority of the thionophosphinic acid derivatives which can be prepared according to the process can be seen from the following comparative tests: There were those according to the process Compounds 1, 3 and 4 obtainable according to the invention compared with the known Preparation 2, the dichlorodiphenyltrichloromethylmethane with regard to its contact insecticidal effect and with the dimethylthionophosphinic acid O- (4-chlorophenyl) ester, known as an insecticidal top product (Compound 5) with regard to the effect of 0.1% solutions against locusts, Fly maggots and caterpillars.
Die ermittelten Versuchsergebnisse sind aus der nachfolgenden Tabelle
ersichtlich:
Die folgenden Beispiele erläutern das Verfahren: Beispiel 1 38 g (0,25 Mol) Dimethylthionophosphinsäurerho danid (Kp.3 93°) werden in 100 ml wasserfreiem Äther gelöst. Anschließend gibt man bei Raumtemperatur unter Rühren 24 g Anilin zu, wodurch die Reaktionstemperatur auf 40"C steigt. Man rührt die Reaktionsmischung noch 2 Stunden bei 20"C weiter und saugt dann die gebildete Dimethylthionophosphinsäurethioharnstoffverbindung als Niederschlag ab. Man erhält auf diese Weise 57g der neuen Verbindung vom Schmelzpunkt 135"C. Ausbeute 930/o der Theorie.The following examples illustrate the procedure: Example 1 38 g (0.25 mol) of dimethylthionophosphinic acid (bp 3 93 °) are dissolved in 100 ml of anhydrous ether. 24 g of aniline are then added at room temperature with stirring, as a result of which the reaction temperature rises to 40 ° C. The reaction mixture is stirred for a further 2 hours at 20 ° C. and the dimethylthionophosphinic acid thiourea compound formed is then filtered off with suction as a precipitate. In this way, 57 g of the new compound with a melting point of 135 ° C. are obtained. Yield 930% of theory.
0,1 obige Emulsionen töten Fliegenmaden 100 zig ab.0.1 above emulsions kill fly maggots 100 zillion.
Beispiel 2 32 g p-Chloranilin werden in 100 ml Äthylmethylketon gelöst. Unter Rühren gibt man zu dieser Lösung 38 g (0,25 Mol) Dimethylthionophosphinsäurerhodanid, wodurch die Temperatur auf 40"C steigt.Example 2 32 g of p-chloroaniline are dissolved in 100 ml of ethyl methyl ketone. 38 g (0.25 mol) of dimethylthionophosphinic acid rhodanide are added to this solution with stirring, as a result of which the temperature rises to 40.degree.
Man rührt das Reaktionsgemisch noch 2 Stunden bei 20°C und saugt dann das entstandene feste Reaktionsprodukt ab. Es werden auf diese Weise 57 g des Dimethylthlonophosphinsäurethioharnstoffderivates erhalten. Schmelzpunkt 153"C. Ausbeute 82 01o der Theorie. 0,1°/Oige Emulsionen töten Raupen 100%ig ab.The reaction mixture is stirred for a further 2 hours at 20 ° C. and then suctioned the resulting solid reaction product from. In this way, 57 g of the dimethylthlonophosphinic acid thiourea derivative are obtained obtain. Melting point 153 "C. Yield 82,010 of theory. 0.1% emulsions kill caterpillars 100%.
Beispiel 3 36 g (0,2 Mol) Diäthylthionophosphinsäurerhodanid (Kp.0,01 650 C) werden in 100 ml wasserfreiem Äther gelöst. Dazu gibt man unter Rühren 19 g Anilin, wodurch die Reaktionstemperatur auf 500 C steigt.Example 3 36 g (0.2 mol) of diethylthionophosphinic acid rhodanide (boiling point 0.01 650 C) are dissolved in 100 ml of anhydrous ether. 19 g of aniline are added with stirring, as a result of which the reaction temperature rises to 500.degree.
Man erwärmt die Reaktionsmischung noch V2 Stunde auf 50"C und kühlt sie dann auf Normaltemperatur ab. Es werden auf diese Weise 38 g des Diäthylthionophosphinsäurethioharnstoffderivates erhalten. Schmelzpunkt 96"C. Ausbeute 700/o der Theorie. Die Verbindung wirkt bei blow flies in einer Menge von 200 ppm tödlich.The reaction mixture is heated to 50 ° C. for another half an hour and cooled then down to normal temperature. In this way, 38 g of the diethylthionophosphinic acid thiourea derivative are obtained obtain. Melting point 96 "C. Yield 700 / o of theory. The compound contributes blow flies fatally at 200 ppm.
Beispiel 4 Zu einer Lösung von 26 g p-Chloranilin in 100 ml Äthylmethylketon gibt man unter Rühren 36 g (0,2 Mol) Diäthylthionophosphinsäurerhodanid. Man erwärmt das Umsetzungsgemisch noch 1 Stunde auf 70"C und kühlt es dann auf Normaltemperatur ab. Es werden auf diese Weise 40 g des Diäthylthionophosphinsäurethioharnstoffderivates erhalten. Schmelzpunkt 121"C, Ausbeute 66°/o der Theorie. 0,1°/Oige Emulsionen töten Raupen 100 0/0ig ab.Example 4 36 g (0.2 mol) of diethylthionophosphinic acid rhodanide are added to a solution of 26 g of p-chloroaniline in 100 ml of ethyl methyl ketone with stirring. The reaction mixture is heated to 70 ° C. for a further hour and then cooled to normal temperature. In this way 40 g of the diethylthionophosphinic acid thiourea derivative are obtained. Melting point 121 ° C., yield 66% of theory. 0.1% emulsions kill caterpillars 100%.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF30338A DE1129953B (en) | 1960-01-19 | 1960-01-19 | Process for the preparation of dialkylthionophosphinic acid thiourea derivatives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF30338A DE1129953B (en) | 1960-01-19 | 1960-01-19 | Process for the preparation of dialkylthionophosphinic acid thiourea derivatives |
Publications (1)
Publication Number | Publication Date |
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DE1129953B true DE1129953B (en) | 1962-05-24 |
Family
ID=7093728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DEF30338A Pending DE1129953B (en) | 1960-01-19 | 1960-01-19 | Process for the preparation of dialkylthionophosphinic acid thiourea derivatives |
Country Status (1)
Country | Link |
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DE (1) | DE1129953B (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE952712C (en) * | 1955-01-28 | 1956-11-22 | Bayer Ag | Process for the production of phosphorus-containing thioureas |
-
1960
- 1960-01-19 DE DEF30338A patent/DE1129953B/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE952712C (en) * | 1955-01-28 | 1956-11-22 | Bayer Ag | Process for the production of phosphorus-containing thioureas |
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