DE881194C - Process for the preparation of thiophosphoric acid esters of 3-halooxycoumarins - Google Patents
Process for the preparation of thiophosphoric acid esters of 3-halooxycoumarinsInfo
- Publication number
- DE881194C DE881194C DEF6868A DEF0006868A DE881194C DE 881194 C DE881194 C DE 881194C DE F6868 A DEF6868 A DE F6868A DE F0006868 A DEF0006868 A DE F0006868A DE 881194 C DE881194 C DE 881194C
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- halooxycoumarins
- acid
- acid esters
- thiophosphoric acid
- 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
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000003580 thiophosphoric acid esters Chemical class 0.000 title description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 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 group [H]* 0.000 claims description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 dimethylthiophosphoric acid ester Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UCQRPBLOYKRHFQ-UHFFFAOYSA-N CCOP(O)([ClH]CC)=S Chemical compound CCOP(O)([ClH]CC)=S UCQRPBLOYKRHFQ-UHFFFAOYSA-N 0.000 description 2
- 241000256113 Culicidae Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZMOGFQUYHKDQGZ-UHFFFAOYSA-N COP(O)([ClH]C)=S Chemical compound COP(O)([ClH]C)=S ZMOGFQUYHKDQGZ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010626 work up procedure Methods 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
- C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
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 Thiophosphorsäureestern der 3-Halogenoxycumarine Es wurde gefunden, daß sich 3-Halogenoxycumarin, das in 4-Stellung alkylsubstituiert sein kann, mit Dialkylthiophosphorsäuremonochloriden bei erhöhter Temperatur in Gegenwart eines säurebindenden Mittels zu Estern der Formel worin R1 und R2 für Alkylreste stehen und X Wasserstoff oder Alkyl bedeutet, umsetzt. Die Umsetzung wird zweckmäßig in einem Verdünnungsmittel vorgenommen, in dem sich die 3-Halogenoxycumarine leicht lösen. Besonders bewährt haben sich alsLösungsmittel Ketone, z. B. Aceton, Methyläthylketon, Methylpropylketon usw. Zur Beschleunigung der Reaktion kann dem Umsetzungsgemisch zweckmäßig eine kleine Menge feinverteilten Kupferpulvers zugegeben werden.Process for the preparation of thiophosphoric acid esters of 3-halooxycoumarins It has been found that 3-halooxycoumarin, which may be alkyl-substituted in the 4-position, reacts with dialkylthiophosphoric acid monochlorides at elevated temperature in the presence of an acid-binding agent to form esters of the formula in which R1 and R2 are alkyl radicals and X is hydrogen or alkyl. The reaction is expediently carried out in a diluent in which the 3-halooxycoumarins dissolve easily. Ketones, e.g. B. acetone, methyl ethyl ketone, methyl propyl ketone, etc. To accelerate the reaction, a small amount of finely divided copper powder can expediently be added to the reaction mixture.
Die so erhaltenen neuen Verbindungen sind meist gut kristallisierende, farblose Substanzen. Die neuen Produkte zeichnen sich, bei geringer Giftwirkung gegen Warmblüter, dadurch aus, daB sie eine ausgezeichnete Wirkung gegen Mückenlarven entfalten. Folgende. Tabelle gibt eine Übersicht -über die Mückenlarvenwirkung einiger Vertreter der neuen Stoffklasse: Beispiel z 849 3-Chlor-4-methyl-7-oxycumarin werden fein gepulvert und mit 40o ccm Methyläthylketon angeschlämmt. Zu der Anschlämmung gibt man 42g gesiebtes, trockenes Kaliumcarbonat und 2 g Kupferpulver. Unter Rühren läBt man dann bei 75° 66 g Dimethylthiophosphorsäuremonochlorid zulaufen und hält unter Rühren dieTemperatur noch etwa .3 Stunden. Dann kühlt man ab, filtriert die Salze ab und dampft das Filtrat ein. Der erhaltene feste Rückstand wird aus Methylalkohol umkristallisiert. Man erhält no g des Dimethylthiophosphorsäureesters des 4-Methyl-3-chlor-7-oxycumarins. Die Verbindung kristallisiert in farblosen Nadeln und hat einen Schmelzpunkt von io5°.The new compounds obtained in this way are mostly colorless substances that crystallize well. The new products are characterized by the fact that they have an excellent effect against mosquito larvae, with little toxicity against warm-blooded animals. The following. The table gives an overview of the mosquito larvae effect of some representatives of the new substance class: Example z 849 3-chloro-4-methyl-7-oxycoumarin are finely powdered and slurried with 40o cc of methyl ethyl ketone. 42 g of sieved, dry potassium carbonate and 2 g of copper powder are added to the slurry. With stirring, 66 g of dimethylthiophosphoric acid monochloride are then allowed to run in at 75 ° and the temperature is maintained for about 3 hours while stirring. It is then cooled, the salts are filtered off and the filtrate is evaporated. The solid residue obtained is recrystallized from methyl alcohol. No g of the dimethylthiophosphoric acid ester of 4-methyl-3-chloro-7-oxycoumarin is obtained. The compound crystallizes in colorless needles and has a melting point of 105 °.
Beispiel 2 849 3-Chlor-4-methyl-7-oxycumarin werden in 400 ccm Methyläthylketon angeschlämmt. Dazu gibt man 42 g gepulvertes und- gesiebtes Kaliumcarbonat und 2 g Kupferpulver. Bei 75° läBt man dann unter Rühren 72 g Diäthylthiophosphor*säuremonochlorid hinzulaufen. Man hält die Temperatur unter weiterem Rühren noch 15 Stunden auf 75 bis 85°, kühlt dann ab, trennt von den Salzen, verdampft das Lösungsmittel und kristallisiert den Rückstand aus Äthylalkohol um. Man erhält Zog g des Diäthylthiophosphorsäureesters des 4-Methyl-3-chlor-7-oxycumarins vom Fp.91°. Beispiel 3 479 4-Methy1-3-brom-7-oxycumarin werden in 15o ccm Methylpropylketon gelöst. Dazu gibt man 21 g feingepulvertes Kaliumcarbonat und 1 g Kupferpulver. Dann gibt man bei 85° 36 g Diäthylthiophosphorsäuremonochlorid hinzu und hält noch 12 Stunden bei dieser Temperatur. Nach der üblichen Aufarbeitung erhält man 5o g des Diäthylthiophosphorsäureesters des 4-Methyl-3-brom-7-oxycumarins. Nach dem Umkristallisieren aus Alkohol zeigt die neue Substanz einen Schmelzpunkt von 1o5°.Example 2 849 3-chloro-4-methyl-7-oxycoumarin are suspended in 400 cc of methyl ethyl ketone. To this are added 42 g of powdered and sieved potassium carbonate and 2 g of copper powder. 72 g of diethylthiophosphoric acid monochloride are then allowed to run in at 75.degree. The temperature is kept at 75 ° to 85 ° for 15 hours with further stirring, then cooled, separated from the salts, the solvent is evaporated and the residue is recrystallized from ethyl alcohol. Zog g of diethylthiophosphoric acid ester of 4-methyl-3-chloro-7-oxycoumarins with a melting point of 91 ° are obtained. Example 3 479 4-Methy1-3-bromo-7-oxycoumarin are dissolved in 150 cc of methyl propyl ketone. Add 21 g of finely powdered potassium carbonate and 1 g of copper powder. 36 g of diethylthiophosphoric acid monochloride are then added at 85.degree. C. and the mixture is kept at this temperature for a further 12 hours. After the usual work-up, 50 g of the diethylthiophosphoric acid ester of 4-methyl-3-bromo-7-oxycoumarin are obtained. After recrystallization from alcohol, the new substance shows a melting point of 10 °.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF6868A DE881194C (en) | 1951-07-31 | 1951-07-31 | Process for the preparation of thiophosphoric acid esters of 3-halooxycoumarins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF6868A DE881194C (en) | 1951-07-31 | 1951-07-31 | Process for the preparation of thiophosphoric acid esters of 3-halooxycoumarins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE881194C true DE881194C (en) | 1953-06-29 |
Family
ID=7085175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF6868A Expired DE881194C (en) | 1951-07-31 | 1951-07-31 | Process for the preparation of thiophosphoric acid esters of 3-halooxycoumarins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE881194C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1123673B (en) * | 1955-04-14 | 1962-02-15 | Montedison Spa | Process for the preparation of phosphoric acid esters and thiophosphoric acid esters of 7-oxycoumarin derivatives |
| DE1175692B (en) * | 1955-04-14 | 1964-08-13 | Montedison Spa | Process for the preparation of phosphoric acid esters and thiophosphoric acid esters of 7-oxycoumarin derivatives |
| DE1276641B (en) * | 1961-04-26 | 1968-09-05 | Ici Ltd | Lactone derivatives of phosphorus (on) thiol acids, their production and use |
| DE1291746B (en) * | 1960-12-09 | 1969-04-03 | Cooper Mcdougall & Robertson | Phosphorus and thiophosphoric acid esters of 7-oxycoumarin derivatives and process for their preparation |
| DE1493515B1 (en) * | 1962-04-18 | 1970-06-18 | Cooper Mcdougall & Robertson | Process for the preparation of phosphoric acid esters of 7-oxycoumarin derivatives |
| DE2208618A1 (en) * | 1972-02-24 | 1973-09-06 | Bayer Ag | EECTOPARASITICIDE FORMULATIONS |
-
1951
- 1951-07-31 DE DEF6868A patent/DE881194C/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1123673B (en) * | 1955-04-14 | 1962-02-15 | Montedison Spa | Process for the preparation of phosphoric acid esters and thiophosphoric acid esters of 7-oxycoumarin derivatives |
| DE1175692B (en) * | 1955-04-14 | 1964-08-13 | Montedison Spa | Process for the preparation of phosphoric acid esters and thiophosphoric acid esters of 7-oxycoumarin derivatives |
| DE1291746B (en) * | 1960-12-09 | 1969-04-03 | Cooper Mcdougall & Robertson | Phosphorus and thiophosphoric acid esters of 7-oxycoumarin derivatives and process for their preparation |
| DE1276641B (en) * | 1961-04-26 | 1968-09-05 | Ici Ltd | Lactone derivatives of phosphorus (on) thiol acids, their production and use |
| DE1493515B1 (en) * | 1962-04-18 | 1970-06-18 | Cooper Mcdougall & Robertson | Process for the preparation of phosphoric acid esters of 7-oxycoumarin derivatives |
| DE2208618A1 (en) * | 1972-02-24 | 1973-09-06 | Bayer Ag | EECTOPARASITICIDE FORMULATIONS |
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