DE963872C - Process for the preparation of thiophosphoric acid esters - Google Patents
Process for the preparation of thiophosphoric acid estersInfo
- Publication number
- DE963872C DE963872C DEF18361A DEF0018361A DE963872C DE 963872 C DE963872 C DE 963872C DE F18361 A DEF18361 A DE F18361A DE F0018361 A DEF0018361 A DE F0018361A DE 963872 C DE963872 C DE 963872C
- Authority
- DE
- Germany
- Prior art keywords
- acid esters
- thiophosphoric acid
- preparation
- acid
- melting point
- 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.)
- Expired
Links
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- WMKXMEBGSGFRMT-UHFFFAOYSA-N ethyl n-(2-chloroacetyl)carbamate Chemical compound CCOC(=O)NC(=O)CCl WMKXMEBGSGFRMT-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000700159 Rattus Species 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- ZZPSWGCEFNZCSN-UHFFFAOYSA-N [Na].COP(S)(=S)OC Chemical compound [Na].COP(S)(=S)OC ZZPSWGCEFNZCSN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 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
- 230000004071 biological effect Effects 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
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- 235000013601 eggs Nutrition 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 150000003582 thiophosphoric acids Chemical class 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
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Thiophosphorsäureestern Aus der deutschen Patentschrift 8z9 998 ist es bekannt, Phosphor- bzw. Thiophosphörsäureester durch Reaktion von dialkoxyphosphor- bzw. -thiophosphorsauren Salzen mit halogensubstituierten Säureamiden herzustellen.Process for the production of thiophosphoric acid esters From the German Patent specification 8z9 998 it is known to use phosphoric or thiophosphoric acid esters Reaction of dialkoxyphosphoric or thiophosphoric acid salts with halogen-substituted ones To produce acid amides.
Es wurde nun gefunden, daß man zu ähnlichen Verbindungen mit erheblich verbesserter biologischer Wirksamkeit gelangt, wenn man Dialkoxythiol- bzw. -thionothi,olphosphorsäuren in Form ihrer Salze oder in Gegenwart eines säurebindenden Mittels mit Halogenacylurethanen umsetzt.It has now been found that similar compounds with considerably improved biological effectiveness is achieved if dialkoxythiol or thionothi, olphosphoric acids in the form of their salts or in the presence of an acid-binding agent with haloacyl urethanes implements.
Die erfindungsgemäßen Verbindungen zeichnen sich bei niederer Toxizität durch eine gute, teilweise sogar hervorragende biologische Wirksamkeit aus. Während z. B. der Thiolthionophosphorsäureester der folgenden Formel erst bei iooo mg/kg an der Ratte per os tödlich wirkt, besitzt die bekannte Verbindung eine erheblich höhere Toxizität, sie wirkt an der Ratte per os mit 25 mg/kg tödlich.The compounds according to the invention are distinguished by a good, in some cases even excellent, biological activity with low toxicity. While z. B. the thiolthionophosphoric acid ester of the following formula The known compound only has a fatal effect on the rat per os at 1,000 mg / kg 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. Beispiel i 168 g Chloracetylu@rethan (Fp. 127°) der Formel und 186 g Diäthyldithiophosphorsäure werden in iioo ccm Alkohol gelöst. Bei einer Temperatur von 4o bis 45° werden sodann iooo ccm einer n/i-Natronlauge langsam zugetropft. Die resultierende Lösung wird durch Absaugen von geringen: Verunreinigungen befreit und darauf mit i2oo ccm Wasser verdünnt. Man läßt erkalten und saugt von den abgeschiedenen Kristallen ab.The new compounds are also characterized by an improved aphid effect. Example i 168 g of chloroacetylurethane (melting point 127 °) of the formula and 186 g of diethyldithiophosphoric acid are dissolved in 100 cc of alcohol. At a temperature of 40 to 45 °, 100 ccm 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 100 cc 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 °.
Beispiel 2 16,8 g Chloracetylurethan werden in 15o ccm Methyläthylketon gelöst. Diese Lösung läßt man bei 6o° unter Rühren zu einer Lösung von 23,5 g des Ammoniumsalzes der Diisopropyldithiophosphorsäure in 150 ccm Methyläthylketon tropfen. Man hält die Temperatur noch i Stunde bei 6j° und verdünnt dann mit viel Wasser. Beim längeren Stehen kristallisiert das Umsetzungsprodukt in farblosen Kristallen vom Fp.4o° aus. Es werden 25 g des neuen Esters erhalten.Example 2 16.8 g of chloroacetyl urethane are dissolved in 150 cc 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 cc of methyl ethyl ketone. The temperature is kept at 6 ° for an hour and then diluted with plenty of water. On prolonged standing, the reaction product crystallizes out in colorless crystals with a melting point of 40 °. 25 g of the new ester are obtained.
Ausbeute: 65% der Theorie. Beispiel 3 167 g Chloracetylurethan (Fp. 127°) werden in 350 ccm Methylalkohol gelöst. Zu dieser Lösung gibt man unter Rühren eine Auflösung von i 8o g dimethyldithiophosphorsaur-em Natrium in 300 ccm Wasser. Man hält unter Rühren noch i Stunde bei 8o° und gibt dann Soo ccm kaltes Wasser zu. Es fällt ein Öl aus, das abgetrennt und in 400 ccm Benzol aufgenommen wird. Nach dem Trocknen des Benzols mit Natriumsulfat wird das Lösungsmittel abdestilliert. Es hinterbleiben r6o g des neuen Esters der Formel die nach eintägigem Stehen zu einer weißen, kristallinen Masse erstarrt sind. Schmelzpunkt 45°.Yield: 65% of theory. Example 3 167 g of chloroacetyl urethane (melting point 127 °) are dissolved in 350 cc of methyl alcohol. A solution of 18o g of sodium dimethyldithiophosphoric acid in 300 cc of water is added to this solution with stirring. The mixture is kept at 80 ° for an hour, with stirring, and so cc of cold water is then added. An oil precipitates which is separated off and taken up in 400 cc of benzene. After the benzene has been dried with sodium sulfate, the solvent is distilled off. About 60 g of the new ester of the formula remain 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 ioo mg/kg noch keine toxischen Symptome. Beispiel 4 76 g diäthylthiolphosphorsaures Ammonium «-erden in 200 ccm Methyläthylketon gelöst. Dazu gibt man bei 75° 66g Chloracetylurethan (Fp. 127°), gelöst in Zoo ccm Methyläthylketon. Man hält das Reaktionsprodukt i1/2 Stunde bei 75o. 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 83d/o.-1"Tach kurzem Stehen erstarrt der ölige Rückstand zu einer weißen, kristallinen Masse. Schmelzpunkt 44°.In the rat per os, the new ester does not yet show any at 100 mg / kg toxic symptoms. Example 4 76 g of diethylthiolphosphoric ammonium earths dissolved in 200 cc of methyl ethyl ketone. 66 g of chloroacetyl urethane are added at 75 ° (Mp. 127 °), dissolved in zoo cc methyl ethyl ketone. The reaction product is kept i1 / 2 Hour at 75o. then cools down to room temperature and sucks the ammonium chloride formed away. The solvent is removed in vacuo, the residue is taken up in chloroform, washed with water, separated and dried with sodium sulfate. After distilling off of the solvent, 75 g of the crude ester remain. Yield 83d / o.-1 "Tach standing for a short time, the oily residue solidifies to a white, crystalline mass. Melting point 44 °.
o,oi0/0ige wäßrige Suspensionen des neuen Esters der Formel töten Blattläuse zu ioo% ab. Das Präparat ist auch gegen die Eier der Roten Spinne in einer Konzeniratichn von o, i % sicher wirksam. Der Ester entfaltet ausgesprochene systemische Wirkungen bei lebenden Pflanzen.0.010 / 0 aqueous suspensions of the new ester of the formula kill aphids by 100%. The preparation is also reliably effective against the eggs of the red spider in a concentration of 0.1%. The ester has pronounced systemic effects on living plants.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF18361A DE963872C (en) | 1955-09-08 | 1955-09-08 | Process for the preparation of thiophosphoric acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF18361A DE963872C (en) | 1955-09-08 | 1955-09-08 | Process for the preparation of thiophosphoric acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE963872C true DE963872C (en) | 1957-05-16 |
Family
ID=7088925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF18361A Expired DE963872C (en) | 1955-09-08 | 1955-09-08 | Process for the preparation of thiophosphoric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE963872C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1096671B (en) * | 1957-05-10 | 1961-01-05 | Bayer Ag | Pest repellants |
| DE1137429B (en) * | 1959-04-21 | 1962-10-04 | Dr Friedrich Cramer | Process for the preparation of carbamyl phosphates |
| DE1143052B (en) * | 1957-05-21 | 1963-01-31 | Murphy Chemical Company Ltd | Pest repellent with insecticidal and acaricidal effects |
| DE1173889B (en) * | 1959-04-30 | 1964-07-16 | Sandoz Ag | Process for the production of carbamic acid esters |
-
1955
- 1955-09-08 DE DEF18361A patent/DE963872C/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1096671B (en) * | 1957-05-10 | 1961-01-05 | Bayer Ag | Pest repellants |
| DE1143052B (en) * | 1957-05-21 | 1963-01-31 | Murphy Chemical Company Ltd | Pest repellent with insecticidal and acaricidal effects |
| DE1137429B (en) * | 1959-04-21 | 1962-10-04 | Dr Friedrich Cramer | Process for the preparation of carbamyl phosphates |
| DE1173889B (en) * | 1959-04-30 | 1964-07-16 | Sandoz Ag | Process for the production of carbamic acid esters |
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