SU1439102A1 - Method of producing phosphorus-substituted trialcoxymethanes - Google Patents

Abstract

The invention relates to the chemistry of organophosphorus compounds, in particular to the preparation of phosphorus-substituted trialkoxymethanes of the formula X2P (0) C (OK) 3, i where X is RO, R or K g N, R and R are lower alkyls that can be used as complex-forming Pel's extractors and extractants simplify the process and expand its scope. Synthesis of lead sodium salt of the acid P (3+) of the formula XgPONa, where X is indicated above (in 5 - 10% excess of stoichiometry) and trialkoxycarbenium tetrafluoroborate of the formula: (RO) where R is the above. The process is carried out at a temperature from 0 to in the medium of ethyl ethyl ether in an inert gas atmosphere. 1 hp f-ly.3

Description

This invention relates to the chemistry of organophosphorus compounds, namely to a method for producing phosphorus-substituted methanes of the general formula

one

(OR) ,,

ABOUT

where X is R O, R or R J N, R, and R are the lowest aqs.

I These compounds include a trialkoxymethyl group in the molecule along with the phosphoryl group and can be used to synthesize new phosphorus-containing substances of linear and cyclic structure, as well as complexing agents and extractants.

The aim of the invention is to simplify the process and expand its scope.

According to the proposed method of phosphor-substituted trialkoxy-ietanes, the sodium salt of trivalent phosphorus is reacted with trialkoxycarbenium tetrafluoroborate in diethyl ether at a temperature O - 20 ° C,

The resulting compounds, stable, colorless liquids that are distilled under reduced pressure, can be injured in an inert gas atmosphere for a long time without change. The composition and structure of the target products are confirmed by elemental analysis data and NMR H, C, R.

All of the reactive and isolation of the target products was carried out in a dry argon atmosphere using absolute tieareHToB and solvents.

Example 1, 0,0-Diethyl (tri- & toxymethyl) phosphonate.

To a suspension of 0.05 mol of triethoxyarbonium tetrafluoroborate in diethyl ether, prepared from 9.6 g (0.05 mol) of etraethoxymethane and 9.5 g (5067 mol of boron trifluoride in 50 ml; with ethyl ether, with vigorous stirring and Cooling the fmиsi, quickly add rast-3 & OR 0.055 mol of sodium diethylfresfit JSO ml of diethyl ether, obtained by boiling a mixture of 7.6 g (0.055 mol 10% excess) of diethylphosphite, 1.3 (0.055 mol, 10% excess sodium) with 50 ml of diethyl ether. The mixture is stirred at 0.5 h;, then 100 ml of hexane is added, and

five

0

five

0

Q

5 Q

the dock is separated in a centrifuge, the solvent is distilled off, the residue is distilled. 8.5 g (59.9%) of the compound are obtained, t, kip, 85 ° C (1 mm Hg, Art.), N 1, 1.4252, Fragment PC: Jc 1P, 62 m, d, d, Jp, 259.7 Hz, 8.10 m, d The physicochemical constants of the compound coincide with the literary ones.

Example 2, 0,0-Diisopropyl (triisopropoxymethyl) phosphonate,

Analogously to example I, from 0.067 mol of triisopropoxycarbenium tetrafluoroborate obtained from 16.6 g (0.067 mol) of tetraisopropoxymethane and 12.7 g (0.089 mol) of boron trifluoride etherate in 100 ml of diethyl ether, and 0.07 mol (5% excess ) sodium diisopropylphosphite, obtained from 11.6 g (0.07 mol) of diisopropyl phosphate and 1.6 g (0.07 mol) of sodium in 75 ml of dimethoxyethane, at a process temperature of 20 s, 13.2 g (55 9%) of the compound, t, kip. 92 C (1 mm Hg), then silt, 45 ° C, n, - 1.4235. PC fragment: J, 112.36 ppm ,, d ,, J .., 266.12 Hz,

T

7.27 m, d

R

Found,%: C 54.21; H 0.04; P 8.50,

C, H J5 Og P

Calculated,%: C 54.22; H 9.95; P 8.74o

Example 3, 0,0-Dibutsh1 (tri-butoxymethyl) phosphonate.

Analogously to example 1 of 0.067 mol of tributoxycarbenium tetrafluoroborate obtained from 20.4 g (0.067 mol) of tetrabutoxymethane and 12.7 g (0.089 mol) of boron trifluoride etherate in 100 ml of diethyl ether, and 0.074 mol (10% excess) of dibutylphosphite sodium, prepared from 14.4 g (0.074 mol) of dibutiphosphite and 1.7 g (0.074 mol) of sodium in 75 ml of dimethoxyethane, gives 19.3 g (68%) of compound at process temperature 0 ° C. t, kip, 135 ° C (0.7 mmHg, st,), 1.4390, PC fragment: 111.76 m, d, d, jpc 260.01 Hz, Sf 8.24 m, d.

Found,%: C 59.90; H 0.86; P 7.27,

Cr, H jOfiP

Calculated,%: C 59.41; H 10.68;

P 7.30,

Example 4. 0.0 - Dibutyl (tri-ethoxymethyl) phosphonate.

Analogously to example 1 of 0.053 moles of triethoxycarbenium tetrafluoroborate obtained from 10.2 g (0.053 moles)

1439102 tetraethoxymethane and 10.1 g (O, 071 mol)

boron trifluoride etherate in 75 ml of diethyl ether, and 0.058 mol (10% excess) of sodium dibutyl phosphite, prepared from 1 1.2 g (0.058 mol) of dibutyl phosphite and 1.3 g (0.058 mol) of sodium in 60 ml of dimethoxyethane, with 10.7 g (59.4%) of the compound, t, kip (1 mm Hg), p 1.4295 are obtained at the process temperature. Fragment.PC: 11.82 ppm, d., Jpc 259.76 Hz, p 8.54 ppm The physicochemical constants of the compound coincide with the literary ones.

Example 5, Diisoprops1 (tri-ethoxymethyl) phosphine oxide.

Analogously to example 1 of 0.05 mol of triethoxycarbenium tetrafluoroborate.

Calculated,%: C 53.24; H 10.42; R 9.15 ..

Example 7. 0,0-Diethyl (tri-ethoxymethyl) phosphonate.

Analogously to example 1 of 0.05 mol of triethoxycarbenium tetrafluoroborate obtained from 9.6 g (0.05 mol) of tetraethoxymethane and 9.6 g (0.067 mol) 10 of boron trifluoride etherate in 50 ml of ether and 0.05 mol (no excess) of di - sodium ethyl phosphate, obtained from 6.9 g (0.05 mol) of diethyl phosphite and 1.2 g (0.05 mol) of sodium in 50 ml of diethyl ether 15, at a process temperature of 3.2 g (31.4 %) compounds whose physicochemical constants are given in Example 1.

The proposed method is different.

obtained from 9.6 g (0.05 mol) of tet-20 simplicity, does not require complex apparatus of ethoxymethane and 9.5 g (0.067 mol)

Boron trifluoride etherate in 50 ml

diethyl ether, and 0.0525 mol

(5% excess) of sodium diisopropylphosphinite prepared from 7 g

(0.0525 mol) diisopropylphosphine

acids and 0.0525 zero sodium bis (trimetsh1silyl) amide in 40 ml of diethyl

ether, at a process temperature of 15 ° C

8.2 g (58.6%) of the compound are obtained.

m.p.

104 C (1 mm Hg), p

1.4571. PC fragment: (112.53 ppm, D. Jpo 140.38 Hz, f 51.83 ppm

Found,%: C 55.5A; H 10.46; R 11.21.

C,} 0 R.

Calculated,%: C 55.70; H 10.43; Р И, 05 „

Example 6. Tetraethyldiamido (triethoxymethyl) phosphonate.

Analogously to example 1 of 0.05 mol of triethoxycarbenium tetrafluoroborate obtained from 9.6 g (0.05 mol) of tetraethoxymethane and 9.5 g (0.067 mol) of boron trifluoride etherate in 50 ml of diethyl ether, and 0544 mol (8% excess ) tetraethyldiamidophosphite sodium, prepared from 10.4 g (0.054 mol) of tetraethyl diamidophosphite and 0.054 mol of sodium bis (trimethylsilyl) amide in 75 ml of diethyl ether, at a process temperature of 5 ° C, 6.9 g (40.8%) of the compound are obtained, m.p. 106 ° C (1 mm Hg), 1.4615. PC fragment: S (. 112.315 ppm, d.

Field decoration and, if necessary, can be easily extended to phosphate-substituted trialkoxymethanes of various structures — important products of organophosphorus synthesis.

The method is the first example of the use of the interaction of alkoxycarbenium ion with a phosphorus-containing anion in order to create a new phosphorus-carbon bond.

Claims (1)

1. A method for producing phosphorus-substituted trialkoxymethanes of the general formula X2PC (OR) j, 40 where X is R O, R W1I R N, R and R are lower alkyls, using a phosphorus-containing reagent and carrying out the process in an organic medium 45 of the solvent in an inert gas atmosphere, characterized in that, in order to simplify the process and to expand its field of use, as a phosphorus-containing reagent 50 take sodium salt of salt three-carb Jpc 219.72 Hz, 5 p 18.65 ppm Found,%: P, 9.38. C, C 53.19; H 10.27; phosphorus of the general formula XgPONa, where X has the indicated values, which is reacted with a trialkoxycarbonium tetrafluoroborate of the general formula (RO) C BF, where R has the indicated values, at a temperature from 0 to 20 ° C and in Ka4jBCTBe organic solvent - use diethyl ether. 2 Calculated,%: C 53.24; H 10.42; R 9.15 .. Example 7. 0,0-Diethyl (tri-ethoxymethyl) phosphonate. Analogously to example 1, from 0.05 mol of triethoxycarbenium tetrafluoroborate obtained from 9.6 g (0.05 mol) of tetraethoxymethane and 9.6 g (0.067 mol) of boron trifluoride etherate in 50 ml of ether and 0.05 mol (no excess) of di- sodium ethylphosphite prepared from 6.9 g (0.05 mol) diethyl phosphite and 1.2 g (0.05 mol) sodium in 50 ml diethyl ether; at a process temperature, 3.2 g (31.4%) are obtained compounds whose physicochemical constants are given in Example 1. The proposed method is different. Field decoration and, if necessary, can be easily extended to phosphate-substituted trialkoxymethanes of various structures — important products of organophosphorus synthesis. The method is the first example of the use of the interaction of alkoxycarbenium ion with a phosphorus-containing anion in order to create a new phosphorus-carbon bond. Invention Formula 1. A method for producing phosphorus-substituted trialkoxymethanes of the general formula X2PC (OR) j, where X is R O, R W1I R N, R and R are lower alkyls, using a phosphorus-containing reagent and carrying out the process in an organic medium solvent in an inert gas atmosphere, characterized in that, in order to simplify the process and expand its scope, as a phosphorus-containing reagent take the sodium salt of trivalent phosphorus acid of the general formula XgPONa, where X has the indicated values, which is reacted with trialkoxycarbonium tetrafluoroborate of the general formula (RO) C BF, where R has the values indicated, at a temperature from 0 ° C to 20 ° C and in Ka4jBCTBe organic solvent - use diethyl ether. 5U391026 2 "The method according to p. 1, about tl and h - is used in a 5-10% excess of stoichi y and with the fact that sodium geometry. salt of tripartite phosphorus acid