SU1439103A1 - Method of producing 0,0-dialkyl(trialcoxymethyl) phosphonates - Google Patents

Abstract

This invention relates to the chemistry of organophosphorus compounds, in particular to the creep of 0,0-dialkyl (trialkoxymethyl) phosphonates of the formula (iRO) 2P (0) C (OR,) j, where R and R are lower alkyls that are used as complexing agents and extractants . The goal is to simplify the process, expand the scope, use it and increase the yield of the target products. Synthesis is carried out from tetraalkyl pyrophosphite of formula (R0) 2 POP (OR), where R is indicated above, and methane tetraalkoxyt in a diethyl ether medium in an inert gas atmosphere. The process is carried out in the presence of a boron trifluoride etherate catalyst (1-3 mol.% Of stoichiometry) at room temperature, followed by treatment of the resulting reaction mixture with sodium dialkyl phosphite (5-10 mol.% Of stoichiometry). 1-zp f-ly. &

Description

The invention relates to the chemistry of organophosphorus compounds, namely to a process for the preparation of 0,0-dialkyl (trialkoxymethyl) phosphonates of the general formula

ly

(RO) aPC (OR,) O

where R and R, are lower alkyls.

These compounds include a trialkoxymethyl group in the molecule along with a dialkoxyphosphoryl group and can be used as semi-products of organophosphorus synthesis, as well as complexing agents and extractants.

The aim of the invention is to simplify the process, expand its scope and increase the yield of target products.

According to the proposed method for the preparation of 0,0-dialkyl (trialkoxy-methyl) phosphonates, tetraalkylpyrophosphite is reacted with tetraalkoxymethane in diethyl ether medium in the presence of boron trifluoride etherate catalyst, at room temperature, followed by formation of the reaction mixture with dialkyl phosphite.

The resulting compounds are stable colorless liquids, distilled under reduced pressure, and can be stored in an inert gas (argon) atmosphere for a long time without change. The composition and strontium target products confirmed by elemental analysis and NMR

H, C, R.

All reactions and allocation of the desired products are carried out in a dry argon atmosphere using absolute reagents and solvents. J

Example I, 0,0-Diethyl (triethoxymethyl) phosphonate.

To a solution of 6.8 g (0.026 mol) of tetraethyl pyrophosphite, 5 g (0.026 mol of tetraethoxymethane in 10 ml of diethyl ether, 0.074 g (0.00052 mol, 2t) of boron trifluoride etherate were added with vigorous stirring. The reaction mixture was mixed with

temperature until the signal of tetraethyl pyrophosphite disappears in

s

NMR P of the reaction mixture (128 ppm) then after 3 hours the mixture is treated with

0

five

0

50

50

d

five

0.0026 mol (10 mol.%) Of sodium diethylphosphate, prepared from 0.36 g (0.0026 mol) of diethyl phosphite and 0.06 g (0.0026 mol) of sodium in 5 ml of diethyl ether. The precipitate formed is separated in a centrifuge, the solvent is distilled off, the residue is distilled. 6 g (80%) of the compound are obtained, mp 85.degree. C. (I mm Hg) and 1.4252. Fragment PC: 5c 111.62 ppm, d., 259.7 Hz, op 8.1 ppm The physicochemical constants of the compound coincide with the literature data.

PRI mme R 2. 0,0-Diisopropyl (triethoxymethyl) phosphonate.

Analogously to example 1 of 8.8 g (0.028 mol) of tetraisopropyl pyrophosphite, 5.4 g (0.028 mol) of tetraethoxymethane and 0.04 g (0.00028 mol, 1 mol.%) Of boron trifluoride etherate in 10 ml of diethyl ether after treatment of the reaction mixture, 0.0017 mol (6 mol.%) of sodium diisopropyl phosphite, prepared from 0.28 g (0.0017 mol) of diisopropyl phosphite and 0.039 g (0.0017 mol) of sodium in 5 ml of ether, 5.8 g are obtained (66.7%) compounds bp. 83 ° C (1 mm Hg), p 1.4220, 7.15 ppm The physicochemical constants of the compound coincide with the literary ones.

PRI me R 3. Oh, 0-Dibutyl (triethoxymethyl) phosphonate.

Analogously to example 1 of 9.9 g (0.027 mol) of tetrabutyl pyrophosphite, 5.2 g (0.027 mol) of tetraethoxymethane and 0.077 g (0.00054 mol, 2 mol.%) Of boron trifluoride etherate in 10 ml of diethyl ether after treatment of the reaction mixture 0 , 0027 mol (10 mol%) of sodium dibutyl phosphite, obtained from 0.52 g (0.0027 mol) of dibutyl phosphite and 0.062 g (0.0027 mol of sodium in 5 ml of diethyl ether, are 5.6 g (61.5 %) of the compound

bp 111 C (1 mm Hg)

H)

five

., 4295, (p 8.54 ppm. The physicochemical constants of the compound coincide with the literature ones.

PRI me R 4. 0,0-Dipropyl (tri-propoxymethyl) phosphonate.

Analogously to example 1 of 9.8 g (0.031 mol) of tetrapropyl pyrophosphite, 7.7 g (0.031 mol) of tetrapropoximethane and 0.044 g (0.00031 mol, 1 mol.%) Of boron trifluoride etherate in I5 ml of diethyl ether after processing reaction mixture 0,0025 mol

(8 mol) sodium dipropylphosphite, prepared from 0.42 g (0.0025 mol dipropyl phosphite and 0.056 g (0.0025 mol sodium in 5 ml diethyl ether), gives 6.8 g (61.8%) of a joint; boiling point 112 ° C (1 mm Hg) p 1.4335. Fragment PC: J. 1 1 1.77 m j

d., d, Joe 260.62 Hz, (9p8.36 ppm

Found,%: C 54.38; H 10.10; R 8.58.

C.b. and b.V.calculated,%: C 54.22; H 9.95;

R 8.74.

EXAMPLE 5. O, 0-Dibutyl (tributoxymethyl) phosphonate.

Analogously to Example 1 of 1I g (0.03 mol) of tetrabutyl pyrophosphite, 9.1 (0.03 mol) of tetrabutoxymethane and 0.13 g (0.0009 mol, 3 mol%) of boron trifluoride ether in 15 ml of diethyl ether after treating the reaction mixture with 0.003 mol (10 mol.%) of sodium dibutyl phosphite, prepared from 0.58 g (0.003 mol) of dibutyl phosphite and 0.069 g (0.003 mol of sodium in 5 ml of diethyl ether, 8 g (63.5%) of the compound, t Boil 135 ° C (0.7 mm Hg), 1.4390 Fragment PC: S, 7e ppm

d., jpc 260.01 Hz,

 8.24 ppm C, 59.90; H 10.86;

Found,%; R 7.27.

.

Calculated.%: C 59.41; H 10.68; R 7.30.

Thus, the proposed method of obtaining the desired products allows these compounds to be obtained in good yields under mild conditions.

The proposed method is simple, does not require complex hardware design and, if necessary, can be easily distributed 45

0

five

0

five

0

five

0

five

03

for 0,0-dialkyl (TRI.alkoxymethyl) various-structure phosphores are important organophosphorus intermediates of synthesis.

The method is the first example of the use of the reaction of tetraalkylpyrophosphites with tetraalkoxymethanes under conditions of catalysis by boron trifluoride etherate in order to create a new bond of phospho-carbon.

Claims (2)

1. A method for the preparation of 0,0-dialkyl (trialkoxymethyl) phosphonates of the general formula (RO) PC (OR) j, where R and R, ABOUT lower alkyls, by reacting the phosphorus-containing reactant with tetraalkoxymethane in an organic solvent medium in an inert gas atmosphere, characterized in that, in order to simplify the process, expand its range of application and increase the yield of the target products, tetraalkylpyrophosphite of the general formula RO) POP (OR), where R has the indicated values as an organic solvent — diethyl ether, and the process is carried out in the presence of a catalyst — boron trifluoride etherate, taken in The amount is from 1 to 3 molar percent of stoichiometry at room temperature, followed by treatment of the resulting reaction mixture with dialkyl phosphite of sodium. 2. Method pop. 1, which differs from the fact that sodium dialkylphosphite is used in combination with 5 to 10 molar percent of stoichiometry.