SU262730A1 - METHOD FOR PRODUCING BENZO-1,2,4-TRIAZYLENE ETHERS OF PHOSPHORIC TIOPHOSPHORIC OR THYOPHOSPHONE ACIDS - Google Patents

Description

This invention relates to a process for the preparation of new compounds of benzo-1,2,4-triazinyl esters of phosphoric, thiophosphoric or thiophoofonic acids of the general formula

OR

0-p

where R is lower alkyl;

R is lower alkyl, alkoxy or phenyl; X - oxygen or sulfur.

These compounds are obtained easily and with a good yield. Similarly known oposo; to obtain nitrogen-containing heterocyclic esters of phosphoric acid by reacting 3-hydroxy-benzo-1,2,4-triazine with phosphoric acid chlorides of the general formula

Hal

R

where R, R and X have the above value, and Hal is a halogen atom.

The reaction should preferably be carried out in a suitable inert organic solvent, for example, in gasoline, benzene, toluene, ether, alcohols, dimethylformamide, as well as in the presence of an acid acceptor, which can be used as an alkali metal salt , potassium and sodium carbonates 5 and tertiary amines.

The reaction temperature may vary in a wide range from 20 to 120 ° C, preferably from 40 to 80 ° C.

The starting materials and the acid acceptor are taken in a stoichiometric ratio. The reaction time ranges from 30 minutes to 3 hours.

The resulting 3-hydroxy-benzo-1.2,4 triazine esters of phosphoric, thiophosphoric or thio 5 phosphonic acids are isolated in the form of colorless crystals with a clear melting point or in the form of colorless or slightly yellowish oils.

The synthesized compounds show strong insecticidal and acaricidal properties. Oh, they have little phytotoxicity and very low toxicity to warm-blooded ones. Benzo-1,2,4-triazinyl esters of phosphoric, thiophosphoric, or 5 TIO-PHOSPHONE acids are superior in their properties to well-known products that are comparable in structure and are similar in action, and can be used to protect plants and combat harmful insects. Below are examples of the method.

Example 1. A mixture consisting of 45 g (0.3 mol} of 3-hydroxybenzo-1,2,4-triazine, 42 g of potassium carbonate and 750 ml of acetonitrile is slowly heated to boiling for 1 hour. Then to the reaction mixture 52 g of O, O-diethylpho / Sulfuric acid etherate are added dropwise at boiling. The mixture is heated under reflux for 3 hours, cooled and poured into water. The oily product that has formed is dissolved in benzene and washed 1N KOH solution and then several times with water.The organic layer is dried over sodium sulfate and the solvent is evaporated under reduced After recrystallization of the residue obtained from a mixture of benzene-ligroin, 76 g {90% of theory) of O, O-diethyl-0 (| benzo-1,2,4-triazinyl-3) -phosphoric acid ester was isolated, which has t. pl. from 46 to 47 ° C.

Found,%: N 14.93; R 11.19.

CiiHuNsO P mol. weight 283.2.

Calculated,%: N 14,83; R 10.96.

Example 2. In 100 ml of dimethylformamide, 44 g (0.3 mol) of 3-hydroxybenzo-1,2,4-triazine and 31 g of triethylamino are dissolved at 50-60 ° C. To the resulting solution was added 57 a of ethochloride, O, O-diethylthiophosphoric acid. After the exothermic reaction is complete. By cooling the reaction vessel outside. Maintain the temperature at 60-70 ° C and then stir at this temperature for 2 hours. The reaction mixture was worked up in the same manner as in Example 1. 64 g (75% of theory) of benzo-1,2,4-triazinyl- (3) ether 0, O-diethylthiophosphooric acid are obtained in the form of a fully solidified product, which after recrystallization from the mixture, the benzene tridol ether is melted at 56 ° C.

Found,%: N 13.65; P 10.22; S 10.44.

CnHuNsOsP mol. , weight 293.3.

Calculated,%: N 14.04; R 10.35; S 10.70.

Ex. 3. In the same manner as in Example 1, 75 g (93% of theory) of benzo-1,2,4-triazinyl-(3) methyl ethoxythiophosphonic acid ester are obtained, starting from 44 g (0.3 mol) 3 -hydroxybenzo-1,2,4-triazine, 42 g of potassium carbonate and 48 g of methyl ethoxythiophosphonic acid sulfuric acid in acetonitrile. The resulting product has a melting point of 80 ° C.

Found,%: N 15.64; R 11.67; S 11.84.

CioH aNgOaP Mol. weight 269.3.

Calculated,%: N 15.60; R 11.51; S 11.01.

Example 4. Also, as in example 1, as a result of the interaction of 44 g (0.3 mol of 3-hydroxybenzo-1,2,4-triazine and 52 g of ethyl ethoxythiophosphonic acid ether, 43 g (51% of theory) of benzo- 1,2,4triazinyl- (3) ethyl ethoxythiophosphonic acid ester. Pure .product has T.PL. (from a mixture of benzene-ligroin).

Found,%: N 14.83; P 10.90; S 11.56.

CnHiiNsOaP Mol. weight 283.3.

Calculated:%: N 14.83; P 10.94; S 11.32.

Example 5. In the same way as described in example 1, as a result of the interaction of 44 g (0.3 mol of 3-hydroxy-benzo-1,2,4-triazi.na and 66 g (0.3 mol) of ether trichloride - 65% (65% of theory) of benzo-1,2,4-triaziNyl-3- (3) phenylethoxythiophosphonic acid ester, having a refractive index of 1.6235, are obtained from the phylethoxythiophosphonic acid.

The subject of the invention. A process for the preparation of benzo-1,2,4-triazinyl esters of phosphoric, thiophosphoric or thiophosphonic acids of the general formula

where R is the lowest a l kil; R is lower alkyl, alkoxy or phenyl;

X - oxygen or sulfur,

characterized in that 3-hydroxy-benzo-1,2, 4-triazine. is subjected to interaction with halide anhydride with phosphoric, thiophosphoric or thiophosphonic acids of general formula RO. xx

/ R r / hal

where R, KiH are as defined above, and Hal is a halogen atom, in the presence of an acid binding agent, for example, triethylamine, drawing.