DE1142606B - Process for the preparation of thionophosphonic acid thiocarbimides - Google Patents
Process for the preparation of thionophosphonic acid thiocarbimidesInfo
- Publication number
- DE1142606B DE1142606B DEF30842A DEF0030842A DE1142606B DE 1142606 B DE1142606 B DE 1142606B DE F30842 A DEF30842 A DE F30842A DE F0030842 A DEF0030842 A DE F0030842A DE 1142606 B DE1142606 B DE 1142606B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- thionophosphonic acid
- thionophosphonic
- ethyl ester
- mol
- 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 9
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 13
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 claims 1
- HHWPFFRBGDKTTO-UHFFFAOYSA-J [O-]P([O-])([O-])=O.[O-]P(O)(O)=O.[Si+4].S Chemical class [O-]P([O-])([O-])=O.[O-]P(O)(O)=O.[Si+4].S HHWPFFRBGDKTTO-UHFFFAOYSA-J 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- 238000009835 boiling Methods 0.000 description 17
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 12
- 229940116357 potassium thiocyanate Drugs 0.000 description 12
- 241000700159 Rattus Species 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 phosphonyl isocyanates Chemical class 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 241001454295 Tetranychidae Species 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 241000254179 Sitophilus granarius Species 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- FHGSIFXOLKKLHA-UHFFFAOYSA-N CCOP(C(C)C)(O)=S.Cl Chemical compound CCOP(C(C)C)(O)=S.Cl FHGSIFXOLKKLHA-UHFFFAOYSA-N 0.000 description 1
- MGJNTCKRAHBWDM-UHFFFAOYSA-N CCOP(C=C(C)C)(O)=S.Cl Chemical compound CCOP(C=C(C)C)(O)=S.Cl MGJNTCKRAHBWDM-UHFFFAOYSA-N 0.000 description 1
- XPBDNTAGBLCEEN-UHFFFAOYSA-N CCOP(C=C)(O)=S Chemical compound CCOP(C=C)(O)=S XPBDNTAGBLCEEN-UHFFFAOYSA-N 0.000 description 1
- MHOWCHQNHPCPOE-UHFFFAOYSA-N CCP(O)(OC)=S.Cl Chemical compound CCP(O)(OC)=S.Cl MHOWCHQNHPCPOE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WJXGTMBHOPEHGM-UHFFFAOYSA-N Cl.CCOP(C)(O)=S Chemical compound Cl.CCOP(C)(O)=S WJXGTMBHOPEHGM-UHFFFAOYSA-N 0.000 description 1
- WXJXBKBJAKPJRN-UHFFFAOYSA-N Methanephosphonothioic acid Chemical compound CP(O)(O)=S WXJXBKBJAKPJRN-UHFFFAOYSA-N 0.000 description 1
- XXNRHOAJIUSMOQ-UHFFFAOYSA-N Methylphosphonothioic acid o-ethyl ester Chemical compound CCOP(C)(O)=S XXNRHOAJIUSMOQ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- ILRHGKSQOWBYCL-UHFFFAOYSA-N chloro-ethoxy-ethyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)CC ILRHGKSQOWBYCL-UHFFFAOYSA-N 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AIJQQTBLBLBZDI-UHFFFAOYSA-N ethoxy-ethyl-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(O)(=S)CC AIJQQTBLBLBZDI-UHFFFAOYSA-N 0.000 description 1
- HBFNIDYFNYYMOB-UHFFFAOYSA-N ethoxy-hydroxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(O)(=S)C1=CC=CC=C1 HBFNIDYFNYYMOB-UHFFFAOYSA-N 0.000 description 1
- SHHNZMWZZCIDHE-UHFFFAOYSA-N ethoxy-hydroxy-phenyl-sulfanylidene-lambda5-phosphane hydrochloride Chemical compound Cl.CCOP(O)(=S)C1=CC=CC=C1 SHHNZMWZZCIDHE-UHFFFAOYSA-N 0.000 description 1
- ZQNTVBSGZCDDBT-UHFFFAOYSA-N ethoxy-hydroxy-propan-2-yl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(O)(=S)C(C)C ZQNTVBSGZCDDBT-UHFFFAOYSA-N 0.000 description 1
- HAAYVVLTAGBXIM-UHFFFAOYSA-N ethoxy-hydroxy-propyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCP(O)(=S)OCC HAAYVVLTAGBXIM-UHFFFAOYSA-N 0.000 description 1
- IYKWJYJKZYNNFF-UHFFFAOYSA-N ethoxy-phenyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(S)(=S)C1=CC=CC=C1 IYKWJYJKZYNNFF-UHFFFAOYSA-N 0.000 description 1
- WSIBSROLHMRZNT-UHFFFAOYSA-N ethyl-hydroxy-methoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(O)(=S)OC WSIBSROLHMRZNT-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- CLJZCBKOLLCYLB-UHFFFAOYSA-N hydroxy-methoxy-methyl-sulfanylidene-$l^{5}-phosphane Chemical compound COP(C)(O)=S CLJZCBKOLLCYLB-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-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
- C07F9/28—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)]
- C07F9/44—Amides thereof
- C07F9/4461—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4484—Compounds containing the structure C-P(=X)(N-acyl)-X, C-P(=X)(N-heteroatom)-X or C-P(=X)(N-CN)-X (X = O, S, Se)
- C07F9/4492—Compounds containing the structure P(=X)(N-C(=X)-) (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (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 Thionophosphonsäurethiocarbimiden Es ist bekannt, Phosphortrichlorid, Phosphoroxychlorid, Phosphorsulfochlorid und Arylphosphindichlorid mit Silberrhodanid bzw. Isocyanat umzusetzen. Ferner ist es bekannt, daß man durch Umsetzung von Metallcyanaten mit Verbindungen der Formel RnP(: O)rCI3 n in der n 1 oder 2 und x 0 oder 1 bedeutet, die entsprechenden Phosphin- und Phosphonylisocyanate erhält. Über die Wirkung dieser Verbindungen auf Schadlinge ist bisher nichts bekanntgeworden. Process for the preparation of thionophosphonic acid thiocarbimides Es is known, phosphorus trichloride, phosphorus oxychloride, phosphorus sulfochloride and arylphosphine dichloride to implement with silver rhodanide or isocyanate. It is also known that one by Implementation of metal cyanates with compounds of the formula RnP (: O) rCl3 n in the n 1 or 2 and x denotes 0 or 1, the corresponding phosphine and phosphonyl isocyanates receives. So far nothing has been known about the effect of these compounds on pests.
Es ist ferner aus der deutschen Patentschrift 952085 bekannt, Thionophosphorsäureestermonochloride mit Halogencyan umzusetzen, wobei Thiophosphorsäurethiocarbimide erhalten wurden. It is also known from German patent specification 952085, Thionophosphorsäureestermonochloride to react with cyanogen halide, thiophosphoric acid thiocarbimides being obtained.
Es wurde nun gefunden, daß man zu Thionophosphorsaurethiocarbimiden mit gegenüber diesen bekannten Verbindungen erheblich gesteigerter insektizider Wirkung gelangt, wenn man Thionophosphonsäure-alkylestermonohalogenide der allgemeinen Formel in der R einen niederen Alkyl-, Chloralkyl-, Alkenyl-oder den Phenylrest bedeutet und R' für einen niederen Alkylrest steht, mit Alkalirhodaniden in Gegenwart inerter Lösungsmittel in an sich bekannter Weise zu Verbindungen der allgemeinen Formel umsetzt, wobei R und R' die weiter oben angegebene Bedeutung haben.It has now been found that thionophosphoric acid ethiocarbimides with a considerably increased insecticidal action compared to these known compounds are obtained if thionophosphonic acid alkyl ester monohalides of the general formula are used in which R denotes a lower alkyl, chloroalkyl, alkenyl or phenyl radical and R 'denotes a lower alkyl radical, with alkali metal rhodanides in the presence of inert solvents in a manner known per se to give compounds of the general formula converts, where R and R 'have the meaning given above.
Diese Reaktion wird vorteilhaft bei leicht erhöhter Temperatur durchgeführt. This reaction is advantageously carried out at a slightly elevated temperature.
Die Thionophosphonsäurethiocarbimide sind farblose bis schwachgelbe,
im Vakuum destillierbare, wasserunlösliche Öle. Die neuen Verbindungen zeichnen
sich durch eine sehr starke Reaktionsfähigkeit aus. Sie sollen als Schädlingsbekämpfungsmittel
und zur Herstellung neuartiger Zwischenprodukte Verwendung finden. Die Überlegenheit
der erfindungsgemäß herstellbaren Verbindungen gegenüber den bekannten insektiziden
und strukturell ähnlich zusammengesetzten Verbindungen geht aus der folgenden Tabelle
hervor:
Dann wird das Reaktionsprodukt in 600ml Eiswasser gegossen. Das ausgeschiedene Öl wird mit 300 ml Benzol aufgenommen und mit Wasser neutral gewaschen. Die benzolische Lösung wird mit Natriumsulfat getrocknet. Anschließend wird fraktioniert.Then the reaction product is poured into 600 ml of ice water. The excreted Oil is taken up with 300 ml of benzene and washed neutral with water. The benzene Solution is dried with sodium sulfate. Then it is fractionated.
Man erhält auf diese Weise 102 g Methyl-thionophosphonsäure-O-methylesterthiocarbimid vom Kp.1 66°C. Ausbeute 610/o der Theorie. DL6o Ratte per os 500 mg/kg.In this way, 102 g of methyl thionophosphonic acid O-methyl ester thiocarbimide are obtained from bp 1 66 ° C. Yield 610 / o of theory. DL6o rat orally 500 mg / kg.
Beispiel 2 159 g (1 Mol) Methyl-thionophosphonsäure-O-äthylesterchlorid (Kp.12 60°C) gibt man unter gutem Rühren zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril. Man erwärmt das Reaktionsprodukt 4 bis 5 Stunden auf 50"C und arbeitet dann wie im Beispiel 1 auf. Auf diese Weise werden 145 g Methyl-thionophosphonsäure-O-äthylesterthiocarbimid vom Kp.o,ol 39"C erhalten. Ausbeute 80% der Theorie. DL50 Ratte per os 250 mglkg.Example 2 159 g (1 mol) of methyl thionophosphonic acid O-ethyl ester chloride (boiling point 12 60 ° C.) are added with thorough stirring to a slurry of 97 g of potassium thiocyanate in 400 ml of acetonitrile. The reaction product is heated to 50 "C for 4 to 5 hours and then worked up as in Example 1. In this way, 145 g of methylthionophosphonic acid O-ethyl ester thiocarbimide of boiling point 39" C are obtained. Yield 80% of theory. DL50 rat per os 250 mglkg.
Beispiel 3 173 g (1 Mol) Äthyl-thionophosphonsäure-O-äthylesterchlorid (Kp.i 48 cc) gibt man unter gutem Rühren zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril. Man erwärmt das Reaktionsprodukt unter gutem Rühren 5 Stunden auf 50°C und arbeitet dann wie im Beispiel 1 auf.Example 3 173 g (1 mol) of ethyl thionophosphonic acid O-ethyl ester chloride (boiling point 48 cc) are added to a suspension of 97 g of potassium thiocyanate in 400 ml of acetonitrile with thorough stirring. The reaction product is heated to 50 ° C. for 5 hours with thorough stirring and then worked up as in Example 1.
Es werden auf diese Weise 139 g Äthyl-thionophosphonsäure-O-äthylesterthiocarbimid vom Kp.0,01 46°C erhalten. Ausbeute 71010 der Theorie. DL Ratte per os 250 mg/kg.There are in this way 139 g of ethyl thionophosphonic acid O-ethyl ester thiocarbimide obtained with a boiling point of 0.01 46 ° C. Yield 71010 of theory. DL rat orally 250 mg / kg.
Beispiel 4 179 g (1 Mol) a-chlormethyl-thionophosphonsäure-O-methylesterchlorid (Kp.1 52DC) gibt man unter gutem Rühren zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril. Man erwärmt 4 Stunden auf 45"C und arbeitet dann in üblicher Weise auf. Man erhält so 92 g a-Chlor methyl-thionophosphonsäure-O-methylesterthiocarbimid vom Kp.o,ol 58"C. Ausbeute 460/0 der Theorie.Example 4 179 g (1 mol) of a-chloromethyl-thionophosphonic acid-O-methyl ester chloride (boiling point 52DC) are added to a suspension of 97 g of potassium thiocyanate in 400 ml of acetonitrile with thorough stirring. The mixture is heated to 45 "C for 4 hours and then worked up in the usual way. 92 g of a-chloro-methyl-thionophosphonic acid-O-methyl ester thiocarbimide with a boiling point of 58" C are obtained. Yield 460/0 of theory.
Dbo Ratte per os 500 mg/kg.Dbo rat orally 500 mg / kg.
Beispiel 5 193 g (1 Mol) α-Chlormethyl-thionophosphonsäure-O-äthylesterchlorid (Kp.l 61"C) gibt man zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril. Man hält das Reaktionsprodukt 4 Stunden bei 400 und arbeitet dann in üblicher Weise auf. Man erhält so 157 g a-Chlormethylthionophosphonsäure-O-äthylesterthiocarbimid vom Kp'oi 63"C. Ausbeute 730/oder Theorie. DLso Ratte per os 250 mg/kg.Example 5 193 g (1 mol) of α-chloromethylthionophosphonic acid O-ethyl ester chloride (boiling point 61 "C) are added to a slurry of 97 g of potassium thiocyanate in 400 ml of acetonitrile. The reaction product is kept at 400 for 4 hours and then carried out as usual This gives 157 g of a-chloromethylthionophosphonic acid O-ethyl ester thiocarbimide with a boiling point of 63 "C. Yield 730 / or theory. DLso rat orally 250 mg / kg.
Beispiel 6 199 g (1 Mol) Isobutenyl-thionophosphonsäure-O-äthylesterchlorid (Kpo,ol 50-°C) C) gibt man unter gutem Rühren zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril. Man hält 4 Stunden bei 50"C und arbeitet dann in üblicher Weise auf. Es entstehen so 167 g Isobutenyl-thionophosphonsäure-O-äthylesterthiocarbimid vom Kp.o,o1 69"C. Ausbeute 760/o der Theorie. Das Ratte per os 500 mg/kg.Example 6 199 g (1 mol) of isobutenyl-thionophosphonic acid-O-ethyl ester chloride (Kpo, ol 50- ° C) C) are added with thorough stirring to a suspension of 97 g of potassium thiocyanate in 400 ml of acetonitrile. The mixture is kept at 50 "C for 4 hours and then worked up in the usual way. 167 g of isobutenyl-thionophosphonic acid-O-ethyl ester thiocarbimide with a boiling point of 69" C are formed. Yield 760 / o of theory. The rat orally 500 mg / kg.
Beispiel 7 171 g (1 Mol) Vinyl-thionophosphonsäure-O-äthyl esterchlorid (Kp.1 48°C) läßt man unter gutem Rühren zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril zulaufen. Man hält das Reaktionsprodukt 5 Stunden bei 35"C und arbeitet dann in üblicher Weise auf. Man gewinnt so 140 g Vinyl-thionophosphonsäure-O-äthylesterthiocarbimid vom Kp.1 73"C. Ausbeute 720/0 der Theorie. DLoo Ratte per os 1000 mg/kg.Example 7 171 g (1 mol) of vinyl thionophosphonic acid O-ethyl ester chloride (boiling point 48 ° C.) are allowed to run into a slurry of 97 g of potassium thiocyanate in 400 ml of acetonitrile with thorough stirring. The reaction product is kept at 35 "C for 5 hours and then worked up in the customary manner. 140 g of vinyl thionophosphonic acid O-ethyl ester thiocarbimide of boiling point 73" C are thus obtained. Yield 720/0 of theory. DLoo rat orally 1000 mg / kg.
Beispiel 8 221 g (1 Mol) Phenyl-thionophosphonsäure-O-äthylesterchlorid (Kp.oo1 75"C) gibt man unter gutem Rühren zu einer Anschlämmung von 97 g Kaliumrhodanid in 400 ml Acetonitril. Man erwärmt 5 bis 6 Stunden auf 35"C und arbeitet dann in üblicher Weise auf. Man erhält so 218 g Phenyl-thionophosphonsäure-O-äthylesterthiocarbimid als wasserunlösliches, farbloses 01. Ausbeute 900/0 der Theorie.Example 8 221 g (1 mol) of phenyl-thionophosphonic acid-O-ethyl ester chloride (boiling point 75 "C) are added with thorough stirring to a slurry of 97 g of potassium thiocyanate in 400 ml of acetonitrile. The mixture is heated to 35" C for 5 to 6 hours and the process is carried out then in the usual way. This gives 218 g of phenyl-thionophosphonic acid-O-ethyl ester thiocarbimide as a water-insoluble, colorless 01. Yield 900/0 of theory.
Dieselbe Verbindung wird auf folgendem Wege erhalten: 184 g (1 Mol) Phenyl-dithiophosphonsäure-O-äthylester und 101 g Triäthylamin werden in 250 ml Benzol gelöst. Man läßt 106 g Bromcyan, gelöst in 250 ccm Benzol, bei etwa 40 bis 45"C langsam zulaufen. Man hält das Gemisch 1 Stunde bei dieser Temperatur. Das Reaktionsprodukt wird in Eiswasser gegossen und die Benzolschicht abgetrennt, getrocknet und das Lösemittel darauf im Vakuum abdestilliert. Es hinterbleiben 202 g der obigen Verbindung. The same compound is obtained in the following way: 184 g (1 mol) Phenyl-dithiophosphonic acid-O-ethyl ester and 101 g of triethylamine are in 250 ml Benzene dissolved. One leaves 106 g of cyanogen bromide, dissolved in 250 cc of benzene, at about 40 to 45 "C. The mixture is kept at this temperature for 1 hour The reaction product is poured into ice water and the benzene layer is separated off and dried and the solvent is then distilled off in vacuo. There remains 202 g of the above Link.
Beispiel 9
Beispiel 10 Man tropft 159 g (1 Mol) Äthyl-thionophosphonsäure-O-methylesterchlorid (Kp.1 44"C) unter Rühren bei 40"C zu einer Lösung von 97 g (1 Mol) Kaliumrhodanid in 500 ccm Acetonitril, rührt die Mischung danach noch 8 Stunden bei der angegebenen Temperatur und gießt sie dann in 500 ccm Wasser.Example 10 159 g (1 mol) of ethyl thionophosphonic acid O-methyl ester chloride (boiling point 44 "C) are added dropwise with stirring at 40" C to a solution of 97 g (1 mol) of potassium thiocyanate in 500 cc of acetonitrile, and the mixture is then stirred 8 hours at the specified temperature and then pour it into 500 cc of water.
Das ausgeschiedene Öl wird in 300 ccm Benzol aufgenommen, die benzolische Lösung bis zur neutralen Reaktion mit Wasser gewaschen, über Natriumsulfat getrocknet und fraktioniert destilliert. Man erhält auf diese Weise 135 g (750/0 der Theorie) Äthylthionophosphonsäure-O-methylesterthiocarbimid vom Kp.1 66"C. An der Ratte per os zeigt die Verbindung eine mittlere Toxizität von 250 mg je Kilogramm Tier.The separated oil is taken up in 300 cc of benzene, the benzene Solution washed with water until neutral, dried over sodium sulfate and fractionally distilled. This gives 135 g (750/0 of theory) Ethylthionophosphonic acid O-methyl ester thiocarbimide with a boiling point of 66 "C. On the rat per os the compound shows an average toxicity of 250 mg per kilogram of animal.
Beispiel 11 Zu einer Lösung von 97 g (1 Mol) Kaliumrhodanid in 600 ccm Acetonitril tropft man bei 500 unter Rühren 187 g (1 Mol) n-Propyl-thionophosphonsäure-O-äthylesterchlorid (Kp.147"C), erhitzt das Reaktionsgemisch anschließend noch 3 Stunden auf 80"C und gießt es dann in 400 ccm Wasser. Das ausgeschiedene Öl wird in 300 ccm Benzol aufgenommen, die benzolische Lösung mit Wasser bis zur neutralen Reaktion gewaschen und über Natriumsulfat getrocknet. Bei der nachfolgenden fraktionierten Destillation erhalt man 150 g (720/0 der Theorie) n - Propyl - thionophosphonsäure - O - äthylesterthiocarbimid vom Kpo,ol 56"C. Die mittlere Toxizität (DLoo) der Verbindung beträgt 250 mg je Kilogramm Ratte bei oraler Applikation.Example 11 To a solution of 97 g (1 mol) of potassium thiocyanate in 600 cc of acetonitrile, 187 g (1 mol) of n-propyl-thionophosphonic acid O-ethyl ester chloride (boiling point 147 "C) are added dropwise at 500 ml with stirring Hours at 80 "C and then pour it into 400 cc of water. The oil which has separated out is taken up in 300 cc of benzene, the benzene solution is washed with water until it reacts neutral and dried over sodium sulfate. The subsequent fractional distillation gives 150 g (720/0 of theory) of n-propyl-thionophosphonic acid-O-ethyl ester thiocarbimide from Kpo, ol 56 "C. The mean toxicity (DLoo) of the compound is 250 mg per kilogram of rat when administered orally .
Beispiel 12 Zu einer Lösung von 97 g (1 Mol) Kaliumrhodanid in 500 ccm Acetonitril fügt man bei 30 bis 40"C 201 g (1 Mol) sec. Butyl-thionophosphonsäure-O-äthylesterchlorid, rührt die Mischung danach noch 12 Stunden bei 40"C und gießt sie dann in 400 ccm Wasser. Das ausgeschiedene Öl wird in Benzol aufgenommen, die Benzollösung mit Wasser bis zur neutralen Reaktion gewaschen und über Natriumsulfat getrocknet. Bei der anschließenden fraktionierten Destillation erhält man nach Abdampfen des Lösungsmittels 148 g (60°/o der Theorie) sec. Butylthionophosphonsäure-O-äthylesterthiocarbimid vom Kp.o.ol52"C. Die mittlere Toxizität (Das) der Verbindung beträgt 500 mg je Kilogramm Ratte bei oraler Applikation.Example 12 201 g (1 mol) of sec. Butyl-thionophosphonic acid O-ethyl ester chloride are added to a solution of 97 g (1 mol) of potassium thiocyanate in 500 cc of acetonitrile at 30 to 40 "C. The mixture is then stirred at 40" C. for a further 12 hours and then pour it into 400 cc of water. The oil which has separated out is taken up in benzene, the benzene solution is washed with water until it reacts neutral and dried over sodium sulfate. In the subsequent fractional distillation, after evaporation of the solvent, 148 g (60% of theory) of sec. Butylthionophosphonic acid O-ethyl ester thiocarbimide with a boiling point of 52 "C. The average toxicity (Das) of the compound is 500 mg per kilogram Oral application to rats.
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| Application Number | Priority Date | Filing Date | Title |
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| DEF30842A DE1142606B (en) | 1960-03-26 | 1960-03-26 | Process for the preparation of thionophosphonic acid thiocarbimides |
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| Application Number | Priority Date | Filing Date | Title |
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| DEF30842A DE1142606B (en) | 1960-03-26 | 1960-03-26 | Process for the preparation of thionophosphonic acid thiocarbimides |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342583A (en) * | 1964-01-23 | 1967-09-19 | Chemagro Corp | Method of controlling the growth of undesirable plants |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE952085C (en) * | 1955-01-27 | 1956-11-08 | Bayer Ag | Process for the preparation of thionophosphoric acid thiocarbimides |
| US2835652A (en) * | 1954-04-16 | 1958-05-20 | Du Pont | Organic phosphorus containing isocyanates and polymers |
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1960
- 1960-03-26 DE DEF30842A patent/DE1142606B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2835652A (en) * | 1954-04-16 | 1958-05-20 | Du Pont | Organic phosphorus containing isocyanates and polymers |
| DE952085C (en) * | 1955-01-27 | 1956-11-08 | Bayer Ag | Process for the preparation of thionophosphoric acid thiocarbimides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342583A (en) * | 1964-01-23 | 1967-09-19 | Chemagro Corp | Method of controlling the growth of undesirable plants |
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