DE887814C

DE887814C - Process for the preparation of esters of thiophosphoric acid

Info

Publication number: DE887814C
Application number: DEF6944A
Authority: DE
Inventors: Rudolf Dr Muehlmann; Gerhard Dr Schrader
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1951-08-11
Filing date: 1951-08-11
Publication date: 1953-08-27

Description

(WiGBl. S. 175)(WiGBl. P. 175)

AUSGEGEBENAM 27. AUGUST 1953ISSUED AUGUST 27, 1953

F 6g44 IVc j 12 qF 6g44 IVc j 12 q

Es wurde gefunden, daß man neue wertvolle Ester der Thiophosphorsäure erhält, wenn man Dialkylthiophosphorsäuremonochloride mit Alkenylphenolen bei erhöhten Temperaturen in Gegenwart säurebindender Mittel umsetzt. Die Umsetzung der Dialkylthiophosphorsäuremonochloride mit den genannten Phenolen nimmt man zweckmäßigerweise in einem geeigneten Lösungsmittel vor. Als Lösungsmittel eignen sich z. B. Ketone, wie Methyläthylketon. Als säurebindende Mittel verwendet man z. B. feingepulvertes Kaliumcarbonat. Zur Steigerung der Reaktionsgeschwindigkeit kann man dem Reaktionsgemisch Kupferpulver zugeben. Als für die Umsetzung geeignete Alkenylphenole kommen Vinylphenol, Allylphenol, /^Methylvinylphenol u. a. m. in Frage; die Phenole können außer durch den Alkenylrest noch weiter substituiert sein.It has been found that new valuable esters of thiophosphoric acid are obtained if dialkylthiophosphoric acid monochlorides are used with alkenylphenols at elevated temperatures in the presence of acid-binding agents. The implementation of the Dialkylthiophosphorsäuremonochloride the phenols mentioned are expediently carried out in a suitable solvent. Suitable as a solvent z. B. ketones, such as methyl ethyl ketone. Acid-binding agents are used, for. B. finely powdered Potassium carbonate. To increase the rate of reaction, the reaction mixture can be added Add copper powder. Suitable alkenylphenols for the implementation are vinylphenol, allylphenol, / ^ Methyl vinyl phenol et al. m. in question; in addition to the alkenyl radical, the phenols can also be further substituted.

Die neuen Ester stellen in Wasser wenig oder nicht lösliche Öle oder kristalline Verbindungen dar. Sie zeichnen sich durch eine starke insekticide Wirkung, insbesondere gegen Mückenlarven, bei geringer toxischer Wirkung gegen Warmblüter aus.The new esters represent oils or crystalline compounds that are sparingly soluble or insoluble in water. They are characterized by a strong insecticidal effect, especially against mosquito larvae, with a low level of toxicity Effect against warm-blooded animals.

example 1

33)5 S o-Allylphenol werden in 120 ecm Methyläthylketon gelöst. Dazu gibt man 28 g feingepulvertes und feingesiebtes Kaliumcarbonat und 1,5 g Kupferpulver. Unter Rühren läßt man zu dieser Mischung bei 78⁰ 48 g Diäthylthiophosphorsäuremonochlorid zutropfen. Man erwärmt das Reaktionsprodukt dann noch 10 Stunden zum Sieden, kühlt ab, saugt die Salze ab und wäscht mit Methyläthylketon nach und entfernt aus dem Filtrat das Lösungsmittel. Der zurückbleibende Ester wird bei einem Druck von 2 mm und bei einer Temperatur von 100° von flüchtigen Anteilen befreit. Man erhält auf diese Weise 55 g des rohen Esters. Der Ester kann zur weiteren Reinigung unter einem Druck von 2 mm bei 145 ° destilliert werden.33) 5 S o-allylphenol are dissolved in 120 ecm methyl ethyl ketone. Add 28 g of finely powdered and finely sieved potassium carbonate and 1.5 g of copper powder. With stirring is added dropwise to this mixture dropwise at 78 ⁰ 48 g Diäthylthiophosphorsäuremonochlorid. The reaction product is then heated to boiling for a further 10 hours, cooled, the salts are filtered off with suction and washed with methyl ethyl ketone and the solvent is removed from the filtrate. The remaining ester is freed from volatile constituents at a pressure of 2 mm and at a temperature of 100 °. In this way 55 g of the crude ester are obtained. For further purification, the ester can be distilled under a pressure of 2 mm at 145 °.

Claims

The new -Ester is a colorless oil, hardly soluble in water, with a pleasant, aromatic odor. Emulsions of this ester are sure to kill off at a concentration of 1: 1,000,000 Mosquito larvae.

Example 2

In a similar way, from 62 g of p-allylphenol, 56 g of potassium carbonate, 2 g of copper powder, 90 g of diethylthiophosphoric acid monochloride and 130 ecm of methyl ethyl ketone, the diethylthiophosphoric acid ester of p-allylphenol (112 g) with a boiling point of ₂ 146 ^{0 is obtained} . In a concentration of 1: 100000, this ester has a safe killing effect against mosquito larvae.

Example 3

45 g of 4-nitro-2-allylphenol are dissolved together with 30 g of powdered potassium carbonate and 1.5 g of copper powder in 200 ecm of methyl ethyl ketone. At 78 °, 50 g of diethylthiophosphoric acid monochloride are added to this mixture with stirring. Then allowed to continue stirring for 16 hours at 78 ⁰ and then worked up in the usual way. 70 g of a pale yellow, water-insoluble oil are obtained which cannot be distilled without decomposition, even in a high vacuum. This works in a dilution of 1: 1000. Ester reliably kills mosquito larvae.

Example 4

50 g of 4-AÜyl-2-methoxyphenol (eugenol) are dissolved in 200 ecm of methyl ethyl ketone. Add 35 g finely powdered potassium carbonate and 1.5 g copper powder. At 85 ° it is then added dropwise to this mixture 58 g of diethylthiophosphoric acid monochloride and holds this temperature for a further 12 hours. According to the usual Working up, 82 g of the new ester are obtained as a pale yellow, hardly water-soluble oil. To further Purification, the ester can be distilled under a pressure of 2 mm at 173 °. In one concentration from 1: 10,000 this compound kills mosquito larvae.

Example 5

67 g of 0- (^ -Methyl-vinyl) -phenol are dissolved in 100 ecm of methyl ethyl ketone. Add 56 g of potassium carbonate and 2 g of copper powder. 96 g of diethylthiophosphoric acid monochloride are then added dropwise at 78 °. The temperature of 78 ° is held for a further 10 hours. After the usual work-up, 112 g of the new ester are obtained. The ester has a boiling point of 139 ^degrees at 2 mm. In a concentration of ι: 10,000, the compound is sure to kill mosquito larvae.

Example 6

54 g of 4-methyl-8-allyl-7-oxycoumarin are dissolved in 500 ecm of methyl ethyl ketone. 28 g of potassium carbonate and 2 g of copper powder are added to this solution. At 78 ⁰ is added dropwise with stirring to this mixture, 48 g Diäthylthiophosphorsäuremonochlorid and the mixture is kept for another 1.5 hours at the boil. After the usual work-up, 50 g of the new ester are obtained. The ester crystallizes from ligroin in colorless needles with a melting point of 46 ^° .

Example 7

50 g of 4-chloro-2-aU.ylph.enol are dissolved in 200 ecm of methyl ethyl ketone. To this are added 35 g of potassium carbonate and 1.5 g of copper powder. At 78 ⁰ are added dropwise to this mixture, with stirring, 60 g Diäthylthiophosphorsäuremonochlorid. The temperature is held for a further 12 hours and then worked up in the usual way. 73 g of the new ester are obtained. The ester boils under a pressure of 3 mm at 161 °. In a concentration of 1: 100, this ester has a sure kill effect against mosquito larvae.

Patentans ρ R uc H. Process for the production of esters of thiophosphoric acid, characterized in that alkenylphenols with dialkylthiophosphoric acid monochlorides be reacted at elevated temperatures in the presence of acid binders.

I 5361 8.53