DE1080108B - Process for the preparation of thionophosphonic acid ester-azides - Google Patents
Process for the preparation of thionophosphonic acid ester-azidesInfo
- Publication number
- DE1080108B DE1080108B DEF26008A DEF0026008A DE1080108B DE 1080108 B DE1080108 B DE 1080108B DE F26008 A DEF26008 A DE F26008A DE F0026008 A DEF0026008 A DE F0026008A DE 1080108 B DE1080108 B DE 1080108B
- Authority
- DE
- Germany
- Prior art keywords
- azides
- acid ester
- mol
- thionophosphonic acid
- preparation
- 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 4
- 238000002360 preparation method Methods 0.000 title description 2
- 150000001540 azides Chemical class 0.000 claims description 6
- -1 ester halides Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 241000700159 Rattus Species 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000255925 Diptera Species 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001124076 Aphididae Species 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
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000238631 Hexapoda 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
- 241000253738 Stigmaeopsis celarius Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DOLNHNMENUZESU-UHFFFAOYSA-N bis(dimethylamino) hydrogen phosphate Chemical compound CN(C)OP(O)(=O)ON(C)C DOLNHNMENUZESU-UHFFFAOYSA-N 0.000 description 1
- KFUVAAKGERCXGZ-UHFFFAOYSA-N chloromethyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)CCl KFUVAAKGERCXGZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C07F9/4465—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Verfahren zur Herstellung von Thionophosphonsäure-ester-aziden Aus der Literatur sind Thionophosphonsäure-esterchloride bekannt. Process for the preparation of thionophosphonic acid ester-acid Aus Thionophosphonic acid ester chlorides are known from the literature.
Es wurde gefunden, daß Thionophosphonsäureesterhalogenide mit Alkaliaziden in Gegenwart inerter Lösemittel so umgesetzt werden können, daß die bisher noch nicht beschriebenen Thionop.hosphonsäure-ester-azide entstehen. It has been found that thionophosphonic acid ester halides with alkali azides can be implemented in the presence of inert solvents so that the hitherto still Thionop.hosphonic acid ester-azides not described arise.
Die neuen Verbindungen werden wie andere Phosphorinsektizide angewandt, d. h. bevorzugt in Kombination mit geeigneten festen oder flüssigen Verdünnungs- oder Streckmitteln. Solche Verdünnungs- oder Streckmittel sind beispielsweise Kalk, Kaolin, Kieselgur, Kreide oder, falls es sich um flüssige Verdünnungsmittel handelt, bevorzugt Wasser in Verbindung mit geeigneten Emulgatoren sowie gegebenenfalls weitere Stabilisierungsmittel. The new compounds are used like other phosphorus insecticides, d. H. preferably in combination with suitable solid or liquid diluents or extenders. Such diluents or extenders are, for example, lime, Kaolin, kieselguhr, chalk or, in the case of liquid thinners, preferably water in conjunction with suitable emulsifiers and, if appropriate, others Stabilizers.
Die neuen Verbindungen besitzen eine insektizide Wirkung gegen eine große Anzahl von Schädlingen, wie z. B. Spinnmilben, Blattläuse, Fliegen u. dgl. The new compounds have an insecticidal effect against one large number of pests, such as B. spider mites, aphids, flies and the like.
Folgende Beispiele geben einen Überblick über das Verfahren: Beispiel 1 50g (0,25 Mol) Natriumazid werden in 250ccm wasserfreiem Aceton angeschlämmt. Unter Rühren gibt man 54 g (0,25 Mol) p-Athoxy-vinvlthionophosphonsäure-äthylesterchlorid (Kpvo 01 600 C) hinzu.The following examples give an overview of the procedure: Example 1 50 g (0.25 mol) of sodium azide are suspended in 250 cc of anhydrous acetone. 54 g (0.25 mol) of p-ethoxy-vinylthionophosphonic acid ethyl ester chloride (boiling point 01 600 C) are added with stirring.
Man rührt 20 Stunden bei 500 C, kühlt dann auf Zimmertemperatur ab und gibt das Reaktionsprodukt in 300 ccm Eiswasser. Der ölige Rückstand wird in Äther aufgenommen. Die Ätherlösung wird mit Natriumsulfat getrocknet und bei einer Badtemperatur von 300 C im Vakuum entfernt. Man erhält auf diese Weise 42 g des neuen Azides als schwachgelbes, wasserunlösliches Ö1. Ausbeute 76e/o der Theorie. An der Ratte per os zeigt das Azid eine mittlere Toxizität von 10 mg/kg.The mixture is stirred for 20 hours at 500 ° C. and then cooled to room temperature and gives the reaction product in 300 cc of ice water. The oily residue is in Ether added. The ether solution is dried with sodium sulfate and with a Bath temperature of 300 C removed in vacuo. In this way, 42 g of des new azides as a pale yellow, water-insoluble oil1. Yield 76e / o of theory. The azide showed a mean toxicity of 10 mg / kg in the rat per os.
Beispiel 2 50g (0,25 Mol) Natriumazid werden in 250 ccm wasserfreiem Aceton angeschlämmt. Unter Rühren gibt man 50 g (0,25 Mol) Isobutenylthionophosphon- säure-äthylesterchlorid (Kp.0,01 500 C) hinzu. Man hält 20 Stunden auf 55°C, kühlt dann auf Zimmertemperatur ab und gibt das Reaktionsprodukt in 300 ccm Eiswasser. Der ölige Rückstand wird in 200 ccm Methylenchlorid aufgenommen. Die Aufarbeitung geschieht wie im Beispiel 1. Man erhält 45 g des neuen Esters als gelbes, wasserunlösliches Ö1. Ausbeute 870/0 der Theorie.Example 2 50 g (0.25 mol) of sodium azide are suspended in 250 cc of anhydrous acetone. 50 g (0.25 mol) of isobutenylthionophosphonic acid ethyl ester chloride (boiling point 0.01 500 ° C.) are added with stirring. The mixture is kept at 55 ° C. for 20 hours, then cooled to room temperature and the reaction product is poured into 300 cc of ice water. The oily residue is taken up in 200 cc of methylene chloride. Working up is carried out as in Example 1. 45 g of the new ester are obtained as a yellow, water-insoluble oil. Yield 870/0 of theory.
Beispiel 3 50g (0,25 Mol) Natriumazid werden in 250ccm wasserfreiem Aceton angeschlämmt. Unter Rühren gibt man 62 g (0,25 Mol) Styrylthionophosphonsäureäthylesterchlorid (Kpo,OL 970 C) hinzu. Man hält 20 Stunden auf 600 C und arbeitet dann wie im Beispiel 1 auf. Es werden 57 g des neuen Esters als farbe loses, wasserunlösliches 01 erhalten. Ausbeute 90o der Theorie.Example 3 50 g (0.25 mol) of sodium azide are suspended in 250 cc of anhydrous acetone. 62 g (0.25 mol) of ethyl styrylthionophosphonate chloride (Kpo, OL 970 C) are added with stirring. It is kept at 600 ° C. for 20 hours and then worked up as in Example 1. 57 g of the new ester are obtained as colorless, water-insoluble 01. Yield 90o of theory.
An der Ratte per os zeigt der Ester eine mittlere Toxizität von 250 mg/kg. The ester showed a mean toxicity of 250 in the rat per os mg / kg.
Beispiel 4 50g (0,25 Mol) Natriumazid werden in 250ccm wasserfreiem Aceton angeschlämmt. Unter Rühren gibt man 58 g (0,25 Mol) fi-Äthyl-thiovinyl-thionophosphonsäure -äthylesterchlorid (Kp.0,01 680 C) hinzu.Example 4 50 g (0.25 mol) of sodium azide are suspended in 250 cc of anhydrous acetone. 58 g (0.25 mol) of fi-ethyl-thiovinyl-thionophosphonic acid ethyl ester chloride (boiling point 0.01 680 ° C.) are added with stirring.
Man hält 20 Stunden bei 600 C und arbeitet dann wie im Beispiel 2 auf. Es werden 45 g des neuen Esters als schwachgelbes, wasserunlösliches Öl erhalten.It is held at 600 ° C. for 20 hours and then worked as in Example 2 on. 45 g of the new ester are obtained as a pale yellow, water-insoluble oil.
Ausbeute 76e/o der Theorie.Yield 76e / o of theory.
An der Ratte per os zeigt das Azid eine mittlere Toxizität von 100 mg/kg. The azide showed a mean toxicity of 100 in rats per os mg / kg.
Beispiel 5 50g (0,25 Mol) Natriumazid werden in 250 ccm wasserfreiem Aceton angeschlämmt. Bei 600 C gibt man 64 g Diisobutenyl-thionophosphonsäure-äthylesterchlorid (Kp.0,01 700 C) hinzu. Man erwärmt 20 Stunden auf 600 C und arbeitet dann wie im Beispiel 1 auf. Es werden 53 g des neuen Esters als farbe loses, wasserunlösliches öl erhalten. Ausbeute 82% der Theorie.Example 5 50 g (0.25 mol) of sodium azide are suspended in 250 cc of anhydrous acetone. At 600 ° C., 64 g of diisobutenyl-thionophosphonic acid ethyl ester chloride (boiling point 0.01 700 ° C.) are added. The mixture is heated to 600 ° C. for 20 hours and then worked up as in Example 1. 53 g of the new ester are obtained as a colorless, water-insoluble oil. Yield 82% of theory.
Ratte per os D L50 25 mg/kg. Rat per os D L50 25 mg / kg.
Beispiel 6 50g Natriumazid (0,25 Mol) werden in 250 ccm wasserfreiem Aceton angeschlämmt. Unter Rühren gibt man 48 g (0,25 Mol) Chlormethyl-thionophosphonsäure-äthvlesterchlorid (Kp. 610 C) hinzu. Man rührt 20 Stunden bei 55 bis 600 C und arbeitet dann in üblicher Weise auf. Es werden 41 g des neuen Azides als gelbes, wasserunlösliches öl erhalten. Ausbeute 82°/o der Theorie.Example 6 50 g of sodium azide (0.25 mol) are suspended in 250 cc of anhydrous acetone. 48 g (0.25 mol) of chloromethylthionophosphonic acid ether chloride (boiling point 610 ° C.) are added with stirring. The mixture is stirred for 20 hours at 55 to 600 ° C. and then worked up in the usual way. 41 g of the new azide are obtained as a yellow, water-insoluble oil. Yield 82% of theory.
Die neuen Verbindungen sind überraschenderweise stabil, so daß sie gefahrlos gehandhabt werden können. The new compounds are surprisingly stable, so that they can be handled safely.
Die Überlegenheit der Verbindungen gegeniiber bekannten phosphorhaltigen Insektiziden geht aus den folgenden Versuchen hervor: Verglichen wurde das aus der österreichischen Patentschrift 178 908 bekannte Bis-(dimethylamino)-phosphorsäure-azid der nachfolgenden Formel mit den Verbindungen der Beispiele 1 bis 6. Aus der nachfolgenden Gegenüberstellung geht hervor, daß die erfindungsgemäß erhältlichen Verbindungen in einer Konzentration von 0,1 0,1°/o noch sicher gegen fressende Insekten (Raupen) wirksam sind, während die aus der österreichischen Patentschrift 178 908 bekannte Verbindung I bei dieser Konzentration unwirksam ist.The superiority of the compounds over known phosphorus-containing insecticides can be seen from the following experiments: The bis (dimethylamino) phosphoric acid azide of the following formula, known from Austrian patent specification 178 908, was compared with the compounds of Examples 1 to 6. The comparison below shows that the compounds obtainable according to the invention in a concentration of 0.1 0.1% are still effective against eating insects (caterpillars), while those from the Austrian Patent specification 178 908 known compound I is ineffective at this concentration.
Noch markanter sind die Unterschiede in der Wirkung gegen Stechmücken
(vom Typ der Malaria-Überträger). Hier sind die erfindungsgemäßen Verbindungen alle
noch in Zehnerpotenzen geringeren Konzentrationen als entsprechende Verbindungen
der österreichischen Patentschrift 178 908 voll wirksam.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF26008A DE1080108B (en) | 1958-06-21 | 1958-06-21 | Process for the preparation of thionophosphonic acid ester-azides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF26008A DE1080108B (en) | 1958-06-21 | 1958-06-21 | Process for the preparation of thionophosphonic acid ester-azides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1080108B true DE1080108B (en) | 1960-04-21 |
Family
ID=7091850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF26008A Pending DE1080108B (en) | 1958-06-21 | 1958-06-21 | Process for the preparation of thionophosphonic acid ester-azides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1080108B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3358004A (en) * | 1965-10-21 | 1967-12-12 | Olin Mathieson | Bifunctional phosphorus-containing azides |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT178908B (en) * | 1951-05-29 | 1954-06-25 | Pest Control Ltd | Process for the production of new phosphorus compounds |
-
1958
- 1958-06-21 DE DEF26008A patent/DE1080108B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT178908B (en) * | 1951-05-29 | 1954-06-25 | Pest Control Ltd | Process for the production of new phosphorus compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3358004A (en) * | 1965-10-21 | 1967-12-12 | Olin Mathieson | Bifunctional phosphorus-containing azides |
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