The method of obtaining 2-chloroethylphosphonic acid

 

(57) Abstract:

The inventive product 2-chloro-ethylphosphonate acid. Reagent 1: CH2-CHCl. Reagent 2: (CH3O2P(O)H. the reaction Conditions: as of reagent 2 use technical dimethylphosphite, containing 85 to 95 wt.% dimethylphosphite and 5 to 15 wt.% monomethylether, and the process is conducted in the presence of a peroxide initiator, a mixture of ditretbutilfenol and tert-butylbenzaldehyde, taken in a mass ratio of 1 : 4 - 12, with subsequent hydrolysis of the resulting reaction mixture, and processing the products of hydrolysis of 25 - 35% aqueous hydrogen peroxide solution, taken in an amount of 1 wt.the share of 20 - 50 wt. share the products of hydrolysis. 1 C. p. F.-ly.

The invention relates to the field of chemistry of organophosphorus compounds, and in particular to an improved method for producing a 2-chloroethylphosphonic acid, which can be used in agriculture as a plant growth regulator, and as an intermediate for various biologically active substances, such as a drug, which is a 50% aqueous solution, known under the names: atrel, computan, ethephon etc.

Known methods for producing 2-chloroethylphosphonic three-(2-chloroethyl)phosphite in di-(2-chloroethyl)new ester 2-chloroethylphosphonic acid, which is then hydrolized in an acidic medium to 2-chloroethylphosphonic acid. Different implementations of this scheme are presented in the patent literature [1] However, the methods based on isomerization, have high stability, based on scarce raw materials and do not provide a high yield of the desired product of sufficient purity.

An alternative method of obtaining 2-chloroethylphosphonic acid based on the reactions of addition of dialkylphosphites to vinyl chloride in the presence of peroxide initiators, followed by acid hydrolysis of the resulting esters [2]

The closest technical solution is the method of obtaining 2-chloroethylphosphonic acid, which consists in the interaction of dimethylphosphite with vinyl chloride at a molar ratio of 2:1-1,3 and heated to 150-160aboutWith the presence of high-temperature and high-boiling peroxide with subsequent hydrolysis of pre-distilled dimethyl-2-chloroethylphosphonic chloride hydrogen [3]

The disadvantages of this method is not a high yield of the target product due to losses caused by the formation when heated during the synthesis of the original dimethylphosphite not less than 5-15% monomethyl etilfosfonova acid. Specified onomatology ether when the hydrolysis can give the target 2-chloroethylphosphonic acid, however, according to the prototype, due to high boiling point, it is not transferred and remaining as residue along with the telomeric products creates additional obstacles distilled dimethyl ether 2-chloroethylphosphonic acid, increasing its loss. The overall decrease output 2-chlorinethylphosphine aside for these reasons, it may be in terms of industrial production up to 20-25%

The aim of the invention is to increase the yield of 2-chloroethylphosphonic acid and the simplification of its receipt.

The objective is achieved by the use of hydrolysis nepereshagnuli product accession technical 85-95% of dimethylphosphite to vinyl chloride in which the maintenance of telomeres is reduced to 1-5% as a result of the selection of the initiator mixture, consisting of dicret.-butylperoxide and tert.-butylbenzaldehyde mass ratio of 1:4-12. In this case, 2,7-4,1 molar excess dimethylphosphite by increasing the process of chain transfer on dimethylphosphite the maintenance of telomeres is reduced to 1-5% with a slight increase in the content nanometrology ether 2-chloroethylphosphonic acids is the notes and after distillation of the excess dimethylphosphite leads to a mixture of the following composition, wt. Dimethyl-2-chloroethyl - phosphonate 80-95 Monomethyl-2-chloroethyl - phosphonate 2-12 Dimethylphosphite and mono - methylphosphate 2-3 Telomeres, needent - truth impurities 1-5

Further acid hydrolysis of this mixture of gaseous hydrogen chloride or concentrated hydrochloric acid better under pressure from di - and nanometrology ether 2-chloroethylphosphonic acid target product in the form of 88-96% of water or 50 2% aqueous solution (preparative form), telomeres lead to higher phosphonic acids with a content of carbon atoms in the chain from 4 to 12, and residual mono - and dimethylphosphite go into phosphorous acid. Subsequent treatment of the products of hydrolysis of 25-35% aqueous solution of hydrogen peroxide translates phosphorous acid phosphorous. Simultaneously, oxidation of various resins and unsaturated telomeres, which allows to obtain the target product as a white crystalline mass containing at least 88-96% 2-chloroethylphosphonic acid and not more than 2-3% orthophosphoric acid, does not interfere with the effect of growth regulator and capable of performing the function of phosphate fertilizers. Being part of the final product of the highest phosphonic acids have surface activity and contribute to zmajeva operativnoy form.

It is known that in industrial output 2-chloroethylphosphonic acid on isomerization method contains at least 8-9 by-products, including oxyethylation, vinylphosphonate, phosphorous and phosphoric acids and the number of dimers [4] During storage of the product admixture

ClCH2-CH2-OCH2-CH2Cl

(acidic ether) is hydrolyzed with the formation of highly toxic ethylenchlorhydrine.

In this regard, the quality of the product according to the proposed method is significantly higher because it does not contain toxic compounds.

P R I m e R 1. In a cylindrical glass reactor with a jacket and a height of 25 cm and an inner diameter of 3 cm, is provided in the upper part of the reflux condenser, thermometer and drip funnel, and the lower part of the gas inlet with a glass spray bars and U-shaped outlet for the reaction products, are placed 600 ml of technical dimethylphosphite, containing 85 dimethylphosphite and 15 wt. monomethylether, and heated to a temperature of 155-160aboutWith by passing nitrogen. Inert gas block and in the lower part of the reactor serves gaseous vinyl chloride with a flow rate of 0.5-1.0 l/min, and in the upper part of the reactor continuously add a solution of peroxides in technicare rises to 170-172aboutC and after 15 min is set to fixed mode. In stationary mode through the reactor for 3 h skipped a solution of 24.0 g (0.12 mol) of tert.-butylbenzaldehyde and 6.0 g (0.04 mol) dicret. -butylperoxide 3.0 l (33,1 mol) technical 85% of dimethylphosphite and 180 l (8.0 mol) of vinyl chloride. The molar ratio of the vinyl chloride: phosphites are: peroxides 1,0:4,1:0,02. From the resulting reaction mass is distilled off in vacuum at a residual pressure of 15-20 mm RT.article in a boiling water bath, the excess of phosphites and get the rest of 1381 light yellow liquid, containing according to GC and PMR spectroscopy 80% dimethyl ether 2-chloroethylphosphonic acid, 12% nanometrology ether 2-chloroethylphosphonic acid, 3% of a mixture of dimethylphosphite and monomyelocytic, 5% of telomeres and unidentified impurities. This mixture is treated at a temperature of 150-160aboutC for 2 h gaseous hydrogen chloride, passing it into the reaction mass at a speed of 5 l/min, or concentrated hydrochloric acid in the amount of 1550 g at a temperature of 95-110aboutC, the mixture is then cooled to a temperature of 80-90aboutWith add 50 g 25-35% aqueous hydrogen peroxide, and stirred for 5 min and get after cooling or 1222 g of white water soderjashie. The total yield of 2-chloroethylphosphonic acid used vinyl chloride 93.1% of

P R I m m e R 2. Analogously to example 1, but in a stationary mode passed through the reactor solution to 36.0 g (to 0.19 mol) of tert.-butylbenzaldehyde and 3.0 g (0.02 mol) dicret.-butylperoxide 3.0 l (32,6 mol) technical 95% dimethylphosphite containing 5% monomethylester and 270 l (to 12.0 mol) of vinyl chloride. The molar ratio of the vinyl chloride:phosphites are: peroxides 1,0:2,7: 0,03. Obtained after distillation of the excess of phosphites 2034 grams of a mixture containing 95% dimethyl ether 2-chloroethylphosphonic acid, 2% nanometrology ether 2-chloroethylphosphonic acid, 2% of a mixture of dimethylphosphite and monomyelocytic and 1% of telomeres and unidentified impurities. Hydrolysis of this mixture, followed by processing 20 g 25-35% aqueous solution of hydrogen peroxide gives 1729 white water containing 96% 2-chloroethylphosphonic acid, 2% phosphoric acid, 1% of telomeres and 2% water, or 3275 g preparative form. The total yield of 2-chloroethylphosphonic acid used vinyl chloride 95,1%

P R I m e R 3. Analogously to example 1, but in a stationary mode passed through the reactor a solution of 32.0 g (0.16 mol) of tert.-butylbenzaldehyde and 4.0 g (0.03 mol) of ditretbutilfenol 3.0 l (32,9 mol) t is the solution of the vinyl chloride:phosphites are: peroxides 1,0:3,7: 0,02. Obtained after distillation of the excess of phosphites 1537 mixture containing 92% dimethyl ether 2-chloroethylphosphonic acid, 3% nanometrology ether 2-chloroethylphosphonic acid, 3% of a mixture of dimethylphosphite and monomyelocytic, 2% of telomeres and unidentified impurities. Hydrolysis of this mixture followed by treatment with 30 g of 25% to 35% aqueous hydrogen peroxide gives 1293 white water containing 94% 2-chloroethylphosphonic acid, 2% phosphoric acid, 2% of telomeres and 2% water, or 2466 g preparative form. The total yield of 2-chloroethylphosphonic acid used vinyl chloride 94,6%

Analysis of the reaction mixture was carried out by GLC on a chromatograph Color-100 ionization-flame detector, column 1 m x 3 mm, 5% SE-30 on chromaton N-AW-DMCS, the temperature of the column 75-175aboutC (the speed of temperature rise 15aboutC/min).

The PMR spectra were recorded on a spectrometer "Tesla DS-567 A (100 MHz) mode FT, using 15-20% solutions of samples of the reaction mass in deuterium chloroform, internal standard GDMS.

Thus, the proposed method of obtaining 2-chloroethylphosphonic acid allows to synthesize the target product with the release of 93-95% with a significant simplification of the acquisition and allocation, -CHLOROETHYLPHOSPHONIC ACID by the interaction of vinyl chloride and an excess of dimethylphosphite in the presence of a peroxide initiator in an atmosphere of inert gas at 150 160oWith, distillation of the excess dimethylphosphite with subsequent hydrolysis of the resulting reaction mixture by heating in an acidic medium, characterized in that as dimethylphosphite use technical dimethylphosphite, containing 85 to 95 wt. dimethylphosphite and 5 to 15 wt. monomethylester, as the peroxide initiator mixture of di-tert-butylperoxide and tert-butylbenzaldehyde, taken in the mass ratio 1 4 12, and the resulting hydrolysis products handle 25 of 35% aqueous hydrogen peroxide solution, taken in an amount of 1 wt.D. 20 50 wt.D. product of the hydrolysate.

2. The method according to p. 1, characterized in that the hydrolysis is subjected to the reaction mixture of the following composition, wt.

Dimethyl-2-chloroethylphosphonic 80 95

Monomethyl-2-chloroethylphosphonic 2 12

Dimethylphosphite or monomethylester 2 3

Telomeres and unidentified impurities 1 5

 

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