DEF0018361MA - - Google Patents
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- Publication number
- DEF0018361MA DEF0018361MA DEF0018361MA DE F0018361M A DEF0018361M A DE F0018361MA DE F0018361M A DEF0018361M A DE F0018361MA
- Authority
- DE
- Germany
- Prior art keywords
- ecm
- acid
- ester
- dissolved
- solution
- 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.)
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- 239000002253 acid Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 150000003580 thiophosphoric acid esters Chemical class 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- -1 haloacyl urethanes Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 241000700159 Rattus Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 2
- YJKHTSQZSRMOSE-UHFFFAOYSA-N [ClH](CCCCCCCCCCCCCCC)NC(=O)OCC Chemical compound [ClH](CCCCCCCCCCCCCCC)NC(=O)OCC YJKHTSQZSRMOSE-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WMKXMEBGSGFRMT-UHFFFAOYSA-N ethyl N-(2-chloroacetyl)carbamate Chemical compound CCOC(=O)NC(=O)CCl WMKXMEBGSGFRMT-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N Diethyl dithiophosphoric acid Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- SZXCCXFNQHQRGF-UHFFFAOYSA-N di(propan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(S)(=S)OC(C)C SZXCCXFNQHQRGF-UHFFFAOYSA-N 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- NDBRRRXCHZEEMS-UHFFFAOYSA-M sodium;dimethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].COP([S-])(=S)OC NDBRRRXCHZEEMS-UHFFFAOYSA-M 0.000 description 1
- 150000003582 thiophosphoric acids Chemical class 0.000 description 1
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
Tag der Anmeldung: 7. September 1955 Bekanntgemacht am 29. November 1956Registration date: September 7, 1955. Advertised on November 29, 1956
DEUTSCHES PATENTAMTGERMAN PATENT OFFICE
PATENTANMELDUNGPATENT APPLICATION
KLASSE 12 ο GRUPPE 1.7 01 INTERNAT. KLASSE C07f CLASS 12 ο GROUP 1.7 01 INTERNAT. CLASS C07f
F 18361 IVb/12 οF 18361 IVb / 12 ο
Dr. Gerhard Schrader, OpladenDr. Gerhard Schrader, Opladen
ist als Erfinder genannt worden has been named as the inventor
Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk
Verfahren zur Herstellung von ThiophosphorsäureesternProcess for the preparation of thiophosphoric acid esters
■■ . Aus der deutschen Patentschrift 819 998 ist es bekannt, Phosphor- bzw. Thiophosphorsäureester durch Reaktion „yon dialkox3rphosphor- bzw. -thiophosphorsauren Salzen mit halogensubstituierten Säureamiden herzustellen.■■. From the German patent specification 819 998 it is known, phosphoric or thiophosphoric acid esters by reaction of dialkox3rphosphoric or thiophosphoric acids To produce salts with halogen-substituted acid amides.
Es wurde nun gefunden, daß man zu ähnlichen Verbindungen mit erheblich verbesserter biologischer Wirksamkeit gelangt, wenn man Dialkoxythiol- bzw. -thionothiolphosphorsäuren in Form ihrer Salze oder in Gegenwart eines säurebindenden Mittels mit Halogenacylurethanen umsetzt. It has now been found that similar compounds with significantly improved biological It becomes effective when dialkoxythiol or thionothiolphosphoric acids are used in the form of their salts or in the presence of an acid-binding agent Reacts by means of haloacyl urethanes.
Die erfindungsgemäßen Verbindungen zeichnen sich bei niederer Toxizität durch eine gute, teilweise sogar hervorragende biologische Wirksamkeit aus. 15 Während z. B. der Thiolthionophosphorsäureester der folgenden FormelThe compounds according to the invention are characterized by good, in some cases, low toxicity even has excellent biological effectiveness. 15 While z. B. the thiolthionophosphoric acid ester the following formula
(C2H5O)2P-S-CH2-CO-NH-CO-OC2H5 (C 2 H 5 O) 2 PS-CH 2 -CO-NH-CO-OC 2 H 5
erst bei iooo mg/kg an der .Ratte per os tödlich wirkt, besitzt die bekannte Verbindungonly fatal per os at 1,000 mg / kg in rats acts, has the known connection
(C2H5O)2P — S — CH2 — CO — NH — CH (CH8)2 (C 2 H 5 O) 2 P - S - CH 2 - CO - NH - CH (CH 8 ) 2
609 709M06609 709M06
F 18361 IVb/12 οF 18361 IVb / 12 ο
eine erheblich höhere Toxizität, sie wirkt an der Ratte per os mit 25 mg/kg tödlich.a considerably higher toxicity, it is fatal in rats orally at 25 mg / kg.
Die neuen Verbindungen zeichnen sich darüber hinaus noch durch eine verbesserte Blattlauswirkung aus.The new compounds are also characterized by an improved aphid effect out.
168 g Chloracetylurethan (Fp. 1270) der Formel /NH-CO-CH2Cl168 g of chloroacetyl urethane (melting point 127 0 ) of the formula / NH-CO-CH 2 Cl
OC2H5 OC 2 H 5
und i86g Diäthyldithiophosphorsäure werden in iioo ecm Alkohol gelöst. Bei einer Temperatur von 40 bis 450 werden sodann 1000 ecm einer n/i-Natronlauge langsam zugetropft. Die resultierende Lösung wird durch Absaugen von geringen Verunreinigungen befreit und darauf mit 1200 ecm Wasser verdünnt. Man läßt erkalten und saugt von den abgeschiedenen Kristallen ab.and 186 g of diethyldithiophosphoric acid are dissolved in 100% of alcohol. At a temperature of 40 to 45 0 , 1000 ecm of n / i sodium hydroxide solution are then slowly added dropwise. The resulting solution is freed from minor impurities by suction and then diluted with 1200 ecm of water. It is allowed to cool and the separated crystals are filtered off with suction.
Ausbeute: 210 g = 70% der Theorie vom Fp. 73°.Yield: 210 g = 70% of theory with a melting point of 73 °.
16,8 g Chloracetylurethan werden in 150 ecm
Methyläthylketon gelöst. Diese Lösung läßt man bei 6o° unter Rühren zu einer Lösung von 23,5 g
des Ammoniumsalzes der Diisopropyldithiophosphorsäure in 150 ecm Methyläthylketon, tropfen.
Man hält die Temperatur noch 1 Stunde bei 6o° und verdünnt dann mit viel Wasser. Beim längeren
Stehen kristallisiert das Umsetzungsprodukt in farblosen Kristallen vom Fp. 400 aus. Es werden
25 g des neuen Esters erhalten.
Ausbeute: 65% der Theorie.16.8 g of chloroacetyl urethane are dissolved in 150 ecm of methyl ethyl ketone. This solution is allowed to drop at 60 ° with stirring to a solution of 23.5 g of the ammonium salt of diisopropyldithiophosphoric acid in 150 ecm of methyl ethyl ketone. The temperature is kept at 60 ° for a further hour and then diluted with plenty of water. On prolonged standing, the reaction product crystallizes as colorless crystals of mp. 40 0 out. 25 g of the new ester are obtained.
Yield: 65% of theory.
B e i s ρ i e 1 3B e i s ρ i e 1 3
167 g Chloracetylurethan (Fp. 1270) werden in 350 ecm Methylalkohol gelöst. Zu dieser Lösung gibt man unter Rühren eine Auflösung von 180 g dimethyldithiophosphorsaurem Natrium in 300 ecm Wasser. Man hält unter Rühren noch 1 Stunde bei 8o° und gibt dann 500 ecm kaltes Wasser zu. Es fällt ein Öl aus, das abgetrennt und in 400 ecm Benzol aufgenommen wird. Nach dem Trocknen des Benzols mit Natriumsulfat wird das Lösungsmittel abdestilliert. Es hinterbleiben 160 g des neuen Esters der Formel167 g Chloracetylurethan (mp. 127 0) are dissolved in 350 cc of methyl alcohol. A solution of 180 g of sodium dimethyldithiophosphate in 300 ecm of water is added to this solution with stirring. The mixture is kept at 80 ° for 1 hour while stirring and then 500 ecm of cold water is added. An oil precipitates, which is separated off and taken up in 400 ecm of benzene. After the benzene has been dried with sodium sulfate, the solvent is distilled off. 160 g of the new ester of the formula remain
CH,0.CH, 0.
CH3OCH 3 O
P-S-CHo-CO-NH-CO-OC9H,PS-CHo-CO-NH-CO-OC 9 H,
C9H, O,C 9 H, O,
C2H5O'C 2 H 5 O '
P-S-CH2-CO-NH-CO-OC2H5 PS-CH 2 -CO-NH-CO-OC 2 H 5
die nach eintägigem Stehen zu einer weißen, kristallinen Masse erstarrt sind. Schmelzpunkt 45°.which solidified to a white, crystalline mass after standing for one day. Melting point 45 °.
An der Ratte per os zeigt der neue Ester bei 100 mg/kg noch keine toxischen Symptome.In the rat per os, the new ester does not yet show any toxic symptoms at 100 mg / kg.
76 g diäthylthiolphosphorsaures Ammonium werden in 200 ecm Methyläthylketon gelöst. Dazu gibt man bei 75° 66 g Chloracetylurethan (Fp. 1270), gelöst in 200 ecm Methyläthylketon. Man hält das Reaktionsprodukt 1V2 Stunde bei 750, kühlt dann auf Zimmertemperatur ab und saugt das entstandene Ammoniumchlorid ab. Das Lösungsmittel wird im Vakuum entfernt, der Rückstand in Chloroform aufgenommen, mit Wasser gewaschen, getrennt und mit Natriumsulfat getrocknet. Nach dem Abdestillieren des Lösungsmittels bleiben 75 g des rohen Esters -zurück. Ausbeute 83 °/o. Nach kurzem Stehen erstarrt der ölige Rückstand zu einer weißen, kristallinen Masse. Schmelzpunkt 440.76 g of diethylthiolphosphoric acid ammonium are dissolved in 200 ecm of methyl ethyl ketone. To this are added at 75 ° Chloracetylurethan 66 g (mp. 127 0) dissolved in 200 cc of methyl ethyl ketone. The reaction product is maintained 1V2 hours at 75 0, then cooled to room temperature and filtered off the resulting ammonium chloride. The solvent is removed in vacuo, the residue is taken up in chloroform, washed with water, separated and dried with sodium sulfate. After the solvent has been distilled off, 75 g of the crude ester remain behind. Yield 83%. After standing for a short time, the oily residue solidifies to a white, crystalline mass. Melting point 44 0 .
o,oi°/oige wäßrige Suspensionen des neuen Esters der Formelo, oi% aqueous suspensions of the new ester of the formula
töten Blattläuse zu ioo°/o ab. Das Präparat ist auch gegen die Eier der Roten Spinne in einer Konzentration von 0,1 °/o sicher wirksam. Der go Ester entfaltet ausgesprochene systemische Wirkungen bei lebenden Pflanzen.kill aphids to 100 per cent. The preparation is also effective against the eggs of the red spider in a concentration of 0.1 per cent. The go Ester has pronounced systemic effects on living plants.
Claims (1)
Family
ID=
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