SU301336A1 - METHOD OF OBTAINING O, O-DIALKYLBENZYLPHOSPHONATE - Google Patents

Description

This invention relates to the preparation of O, Odalkylbenzylphosphonates of the general formula .R

GH2P (Y) (OR02

where R-СНз, СгНй, СНгСОСНз, R-Н, С1, СНз,, СгНй, «zo-СзНт, Hi Y - O, S.

A known method for producing O, O-dialkyl benzyl phosphonates by reacting a dialkyl phosphorous acid salt with halogenated aromatic compounds when heated.

The proposed method consists in the fact that according to the method described above, a number of new, not previously described compounds are obtained, which possess considerable fungicidal activity and can be successfully used not only to combat rice digestion, but also to control wheat stem rust. and Mu: nisty dew of cucumbers.

The essence of the method is that the salts of dialkylphosphorous or dialkylthiophosphorous acids are reacted with chloromethylated aromatic compounds when heated, for example, to 70-90 ° C, in an inert organic solvent medium.

Example 1. O, O-diethyl-1,2-methoxy-5chlorobenzylphosphonate.

3.61 g of diethylphosphorous acid are added to the suspension of 0.6 g of Na in 30 ml of absolute toluene at 25 ° C; at the end of the addition of the whole acid, the mixture is heated at

60 ° C until Na is completely dissolved, then a solution of 5 g of 2-methoxy-5-chlorobenzyl chloride in 20 ml of absolute toluene is added, heated at 80 ° C for 1 hour, cooled, the precipitate is filtered, washed with dry ether,

the organic solution is evaporated in vacuo; residue In an amount of 6.5 g is distilled. Obtain 3.42 g (51.35%) O, O-diztil- (2-methoxy5-chlorobenzyl) -phosphonate, t. Kip. 140-141 ° C (0.25 mm Hg. Art.); p 1.5150; df 1.2176.

Found, p 10.25; 10.48; C1 12.23, 12.32.

C, 2Hl8ClO4P. To a suspension of 0.6 g of metallic Na in 20 ml of absolute toluene was added dropwise 4.035 g of diethyl thiophosphorous acid, stirred at a temperature of: 70 ° C until complete dissolution of Na, then a solution of 5 g of 5-chloro-2-methoxybenzyl chloride in 20 ml of toluene, heated for 3 hours at 70-80 ° C, cooled, the precipitate is filtered off, washed with benzene, the solvent is distilled off in a vacuum, the residue in the amount of 8.3 g is distilled with 1.5362 p. Obtain 3 g of O, O-diethyl- (5-chloro-2-metho, xibe.nzil) -tiophosphonate, t. Kip. 130-140 ° C (0.25 mm Hg. Art.); 1,5365; df 1,2099. Found,%: P 10.00; 10.13; S 10.06; 10.32; C1 11.23; 11.33. CisHisClOsPS. Calculated, o / o: R 10.03; S 10.38; C1 11.48. Example 3. O, O-diethyl- (5-chloro-2-ethoxybenzyl) -tiophosphonate. Under the conditions of Example 2, from 5 g of 2-ethoxy-5-chlorobenzyl chloride, 3.75 g of diethyl thiophosphorous acid and 0.56 2 of metallic Na, 2.7 g of O, O-diethyl- (5-chloro-2-ethoxybenzyl) -tiophosphate, m.p. 136-138 ° C (0.22 mm Hg. Art.). The product is subjected to additional purification on a column of silica gel, eluted with a mixture of benzene-hexane 3: 1, get oil oil | ° 1,5300; df 1.1812. Found, o /: P 10.30; C1 10.99; 10.78; S 10.62; 10.86. CisHsoClOsPS. Calculated,%: P 9.60; C1 10.98; S 9.93. Example 4. O, O-diisopropyl- (5-chloro-2ethylthiobe-nzil) phosphonate. Under the conditions of Example 2, from 5 g of 5-chloro-2-ethylthiobenzyl chloride, 3.76 g of diisopropylphosphorous acid and 0.51 g of metallic Na in toluene, 5 g of () O, O-diisopropyl- (5-chloro-2- ethylthiobenzyl) -phosphonate, t. Kip. 142-145 ° C (0.14 mm Hg. Art.); p® 1.5050; df 1.1373. Found, P 8.79; 8.97; C1 9.72; 9.86; S 8.83; 8.81. С15Н24С1ОЗР5. Calculated,%: P 8,83; C1 10.11; S 9.14. Example 5. O, O-diisopropyl- (5-methyl-acetonyloxybenzyl) phosphonate. To a suspension of 0.54 g of Na in toluene was added 7.8 g (two-fold excess) of diisopropyl phosphorous acid, heated to complete the reduction of Na, then at 70 ° C an olol solution of 5 g of 2-acetonyloxy-5-meylbenzyl chloride was added, heated at 70 -80 ° C for 10 hours, cooled, the precipitate is filtered off with water, dried with anhydrous Na2SO4, the solvent is distilled off, to obtain 5.7 g of an oil sp ~ ° 1,4950. Found,%: P 9.41; 9.81. CirHzTOgP. Calculated, o / o: R 9.05. Similar to the described examples, other O, O-dialkyl benzyl phosphonates are obtained. The subject matter of the invention 1. Method for the preparation of O, O-dialkyl benzyl phospholates of the general formula: characterized in that the salts of dialkylphosphorous or dialkylthiophosphorous acid are reacted with chloromethylated aromatic ethers in an inert organic solvent when heated, followed by isolation of the target product by known methods. 2. Method according to claim 1, characterized in that the process is carried out at 70-90 ° C.