DE814297C - Process for the preparation of aromatic esters of dialkylthiophosphoric acids - Google Patents
Process for the preparation of aromatic esters of dialkylthiophosphoric acidsInfo
- Publication number
- DE814297C DE814297C DEP14587A DEP0014587A DE814297C DE 814297 C DE814297 C DE 814297C DE P14587 A DEP14587 A DE P14587A DE P0014587 A DEP0014587 A DE P0014587A DE 814297 C DE814297 C DE 814297C
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- aromatic esters
- dialkylthiophosphoric
- acids
- slurried
- 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
- 239000002253 acid Substances 0.000 title claims description 6
- 150000007513 acids Chemical class 0.000 title claims description 4
- 125000003118 aryl group Chemical group 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 4
- -1 dimethyl-p-nitrophenylthiophosphoric acid ester Chemical class 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- ZMOGFQUYHKDQGZ-UHFFFAOYSA-N COP(O)([ClH]C)=S Chemical compound COP(O)([ClH]C)=S ZMOGFQUYHKDQGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- UCQRPBLOYKRHFQ-UHFFFAOYSA-N CCOP(O)([ClH]CC)=S Chemical compound CCOP(O)([ClH]CC)=S UCQRPBLOYKRHFQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KKSSRKXFFQBTDZ-UHFFFAOYSA-N (2,3-diethyl-4-nitrophenoxy)-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical class CCC1=C(CC)C([N+]([O-])=O)=CC=C1OP(O)(O)=S KKSSRKXFFQBTDZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KMJJJTCKNZYTEY-UHFFFAOYSA-N chloro-diethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OCC KMJJJTCKNZYTEY-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
Verfahren zur Herstellung von aromatischen Estern der Dialkylthiophosphorsäuren Es wurde gefunden, daß man aromatische Ester der Dialkylthiophosphorsäuren herstellen kann, wenn man Dialkylthiophosphorsäuremonochloride auf Salze von Phenolen in Gegenwart von metallischem Kupfer bei erhöhten Temperaturen, vorzugsweise in einem indifferenten Lösungsmittel, einwirken läßt. Man erhält so die gewünschten Ester in kurzer Zeit mit guter Ausbeute und in großer Reinheit. Temperatursteigerungen auf etwa 8o bis 9o° sind in der Regel bereits ausreichend. Das zur Anwendung kommende metallische Kupfer kann in beliebiger Form vorliegen. So kann man beispielsweise der Reaktionsmischung eine kleine Menge Kupferpulver zugeben, man kann aber auch gegebenenfalls die ITmsetzung in einem kupfernen Gefäß ausführen. Die nach dem neuen Verfahren hergestellten Verbindungen eignen sich z. B. zur Insektenbekämpfung. Beispiel i 1399 p-Nitrophenol werden in einemRührkolben mit 400 ccm Chlorbenzol angeschlämmt. Dazu werden 70 g calc. Soda, 2 g metallisches Kupfer und i g Kaliumbromid gegeben. Unter Rühren gibt man bei 8o° igog Diäthylthiophosphorsäurechlorid hinzu. Es setzt sofort eine Reaktion ein, die die Temperatur des reagierenden Produktes auf go bis 95° bringt. Man rührt noch 5 Stunden bei 85 bis 9o° und arbeitet dann auf. Es werden 265 bis 2709 Diäthyl-p-nitrophenylthiophosphorsäureester erhalten. Ausbeute: 9o % d. Th. Das erhaltene Produkt ist schwach rötlichgelb gefärbt und praktisch frei von Nebenprodukten.Process for the preparation of aromatic esters of dialkylthiophosphoric acids It has been found that aromatic esters of dialkylthiophosphoric acids can be prepared if dialkylthiophosphoric acid monochlorides are allowed to act on salts of phenols in the presence of metallic copper at elevated temperatures, preferably in an inert solvent. The desired esters are thus obtained in a short time with good yield and in great purity. Temperature increases to around 8o to 9o ° are usually sufficient. The metallic copper used can be in any form. For example, a small amount of copper powder can be added to the reaction mixture, but it is also possible, if necessary, to carry out the conversion in a copper vessel. The compounds prepared by the new process are suitable, for. B. for insect control. Example i 1399 p-Nitrophenol are slurried with 400 cc of chlorobenzene in a stirred flask. For this purpose 70 g calc. Soda, 2 g metallic copper and ig potassium bromide added. Diethylthiophosphoric acid chloride is added at 80 ° C. while stirring. A reaction starts immediately, which brings the temperature of the reacting product up to 95 °. The mixture is stirred for a further 5 hours at 85 to 90 ° and then worked up. 265 to 2709 diethyl p-nitrophenylthiophosphoric acid esters are obtained. Yield: 90% of theory Th. The product obtained is pale reddish yellow in color and practically free from by-products.
Beispiel e 278g p-Nitrophenol werden in 8oo ccm Chlorbenzol aasgeschlämmt. Dazu gibt man 1509 calc. Soda, 3 g Kupferpulver und 2 g Kaliumbromid. Bei 8o° werden in 5 Minuten 330 g Dimethylthiophosphorsäuremonochlorid eingerührt. Es setzt eine Reaktion ein, die die Innentemperatur auf 9o bis 95° steigen läßt. Es wird noch 5 Stunden bei 85 bis 9o° nachgerührt und dann wie üblich aufgearbeitet. Es werden 450g Dimethyl-p-nitrophenylthiophosphorsäureester vom KPE 158° erhalten, Ausbeute: 85,5 % d. Th.Example e 278 g of p-nitrophenol are slurried in 8oo ccm of chlorobenzene. Add 1509 calc. Soda, 3 g copper powder and 2 g potassium bromide. 330 g of dimethylthiophosphoric acid monochloride are stirred in at 80 ° in 5 minutes. A reaction begins which causes the internal temperature to rise to 90 ° to 95 °. The mixture is stirred for a further 5 hours at 85 to 90 ° and then worked up as usual. 450 g of dimethyl-p-nitrophenylthiophosphoric acid ester from KPE 158 ° are obtained, yield: 85.5 % of theory . Th.
Beispiel 3 88 g ß-Methylumbelliferon werden in 1200 ccm Chlorbenzol aasgeschlämmt. Dazu gibt man 5o g Pottasche, 2 g Kupferpulver und i g Kaliumbromid. Unter Rühren werden bei 80° 95 g Diäthylthiophosphorsäuremonochlorid zugegeben. Man hält die Temperatur noch 9 Stunden auf 95 bis ioo° und arbeitet dann in der üblichen Weise auf. Es werden ioo g Ester vom F. 38° erhalten, entsprechend einer Ausbeute von 72 %.Example 3 88 g of β-methylumbelliferone are slurried in 1200 ccm of chlorobenzene. Add 50 g of potash, 2 g of copper powder and ig potassium bromide. With stirring, 95 g of diethylthiophosphoric acid monochloride are added at 80 °. The temperature is kept at 95 to 100 ° for a further 9 hours and then worked up in the usual way. 100 g of ester with a melting point of 38 ° are obtained, corresponding to a yield of 72%.
Beispiel 4 176 g ß-Methylumbelliferon werden in 1200 ccm Chlorbenzol aasgeschlämmt. Dazu gibt man i io g Kaliumcarbonat (trocken) und 7 g Kupferpulver. Bei 8o° läßt man unter Rühren 175g Dimethylthiophosphorsäuremonochlorid zulaufen. Man hält unter Rühren die Temperatur 6 Stunden auf 9o°. Nach dem Absaugen der Salze und dem Abdestillieren des Lösungsmittels hinterbleibt ein Rückstand, der schnell kristallinisch erstarrt. Man erhält 250g des Reaktionsproduktes entsprechend einer Ausbeute von 83 % d. Th. Die neue Verbindung kristallisiert aus Methanol in farblosen Prismen vom Schmelzpunkt 77°.Example 4 176 g of β-methylumbelliferone are slurried in 1200 cc of chlorobenzene. Add 10 g of potassium carbonate (dry) and 7 g of copper powder. At 80 °, 175 g of dimethylthiophosphoric acid monochloride are run in with stirring. The temperature is kept at 90 ° for 6 hours while stirring. After the salts have been filtered off with suction and the solvent has been distilled off, a residue remains which quickly solidifies in a crystalline manner. 250 g of the reaction product are obtained, corresponding to a yield of 83% of theory. Th. The new compound crystallizes from methanol in colorless prisms with a melting point of 77 °.
Beispiel s 149 7-Oxyc,umarin werden in Zoo ccm Chlorbenzol aasgeschlämmt. Dazu gibt man bei 70° 12 g Kaliumcarbonat und ioo mg Kupferpulver und läßt unter Rühren bei ioo° igg@Diäthylthiophosphorsäuremonochlorid zufließen. Nach 8 Stunden arbeitet man das Reaktionsprodukt in der üblichen Weise auf. Man erhält 12 g des Diäthylthiophosphorsäureesters des 7-Oxycumarins vom F. 46°. Beispiel 6 88 g 6-Oxy-4-methylcumarin werden in 6oo ccm Chlorbenzol aasgeschlämmt. Dazu gibt man bei 70° 55 g Kaliumcarbonat und i g Kupferpulver. Dann läßt man unterRühren 88gDimethylthiophosphorsäuremonochlorid bei gobis ioo° zulaufen und hält die Temperatur noch 6 Stunden. Beim üblichen Aufarbeiten erhält man 6ogDimethylthiophosphorsäureester des 6-Oxy-4-methylcumarins. Die neue Verbindung ist ein dickflüssiges Öl.Example s 149 7-Oxyc, umarin are slurried in zoo cc of chlorobenzene. To this are added at 70 ° 12 g of potassium carbonate and 100 mg of copper powder and left under Stir at 100 ° igg @ diethylthiophosphoric acid monochloride. After 8 hours the reaction product is worked up in the usual manner. 12 g of des are obtained Diethylthiophosphoric acid ester of 7-oxycoumarin with a melting point of 46 °. Example 6 88 g of 6-oxy-4-methylcoumarin are slurried in 6oo ccm of chlorobenzene. To this are added 55 g of potassium carbonate at 70 ° and i g of copper powder. Then 88 g of dimethylthiophosphoric acid monochloride are left with stirring run in at gobis 100 ° and hold the temperature for another 6 hours. During the usual work-up 6o dimethylthiophosphoric acid ester of 6-oxy-4-methylcoumarin is obtained. The new Compound is a thick oil.
Beispiel? 18 g 6-Oxy-4-methylcumarin werden in 300 ccm Chlorbenzol aasgeschlämmt. Dazu gibt man bei 8o° 15 g Kaliumcarbonat und 3 g Kupferpulver. Dann. läßt man bei ioo° unter Rühren i9 g Diäthylthiophosphorsäuremonochlorid einlaufen. Die Temperatur wird nun noch io Stunden bei io5° gehalten. Nach dem Aufarbeiten werden 21 g des Diäthylthiophosphorsäureesters des 6-Oxy-4-methylcumarins erhalten. Das Produkt ist ein viskoses Öl.Example? 18 g of 6-oxy-4-methylcoumarin are slurried in 300 cc of chlorobenzene. Add 15 g of potassium carbonate and 3 g of copper powder at 80 °. Then. 19 g of diethylthiophosphoric acid monochloride are allowed to run in at 100 ° with stirring. The temperature is now held at 10 ° for a further 10 hours. After working up, 21 g of the diethylthiophosphoric acid ester of 6-oxy-4-methylcoumarin are obtained. The product is a viscous oil.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH814297X | 1948-04-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE814297C true DE814297C (en) | 1951-09-20 |
Family
ID=4538803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP14587A Expired DE814297C (en) | 1948-04-07 | 1948-10-02 | Process for the preparation of aromatic esters of dialkylthiophosphoric acids |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE814297C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1119589B (en) * | 1955-04-14 | 1961-12-14 | Montedison Spa | Preparations for combating flies |
| DE1166790B (en) * | 1959-09-03 | 1964-04-02 | Sumitomo Chemical Co | Process for the preparation of insecticidally active O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -thionophosphoric acid ester |
| 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 |
-
1948
- 1948-10-02 DE DEP14587A patent/DE814297C/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1119589B (en) * | 1955-04-14 | 1961-12-14 | Montedison Spa | Preparations for combating flies |
| 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 |
| DE1166790B (en) * | 1959-09-03 | 1964-04-02 | Sumitomo Chemical Co | Process for the preparation of insecticidally active O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -thionophosphoric acid ester |
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