SU1439105A1 - Method of producing di- or trialcoxymethyl (dialkyl) phosphines - Google Patents

Description

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The invention relates to the chemistry of organophosphorus compounds, namely to a method for producing di- or trialkoxymethyl (dialkyl) phosphines of the general formula

(R), PCH (OR,) ,,

where R and R are lower alkyls, and one of them has iso structure; n - O or 1.

These compounds include a three-coordinated phosphorus atom in the molecule along with a di- or trialkoxy-methyl group and can be used as ligands in complexes with metal compounds, for the synthesis of new complexing agents and extractants, as well as intermediates in organo-chemical nical synthesis.

The aim of the invention is to increase the yield of products and expand the scope of application of the process.

According to the proposed method for producing di- or trialkoxymethyl (dialkyl) phosphines, lithium dialkyl phosphide is reacted with a di- or trialkoxycarbenium tetrafluoroborate in diethyl ether at (-30) - (-10) C.

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

 H,,

All the reactions and the selection of the target: products are carried out in a dry argon atmosphere using a6coj: ao reagents and solvents.

Example 1, DiethoxymethylCd-isopropyl) phosphine,

To a suspension of 0.08 mol of diethoxycarbenium tetrafluoroborate, obtained from 11.8 g (0.08 mol) of triethoxymethane and 15.1 g (0.1 mol) of etherate of three boric fluoride, in -20 mD of diethyl ether at -20 C, with vigorous stirring, a solution of 0.08 mol of diisopropylphosphide lithium, prepared from 9.5 g (0.08 mol) di

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isopropyl phosphine in 100 ml of tetrahydrofuran (THF). and 0.08 mol of butyl lithium (57 ml of a 1.4 N solution in penta-c). The mixture is stirred for 0.5 hours at -30 ° C. The temperature of the mixture is adjusted to room temperature. The solvent is distilled off, 150 ml of hexane is added to the residue, the oily residue is separated on

10 centrifuge, Hexane is distilled off, the residue is distilled. 10.7 g of compound are obtained, yield 60.5%, tons, bales, (2 mmHg, Art.), P 1.4568, Fragment PCH: and 5.00 ppm, D., -J 3 Hz;

15 06.38 m, d., D., Jp 3.1 Hz,

p 7.22 m, d. The physicochemical constants of the compound coincide with the literature data,

PRI me R 2, Diethoxymethyl (di-.

20 tert-butyl) phosphine,

Analogously to example 1, from 0.051 mol of diethoxycarbenium tetrafluoroborate obtained from 7.6 g (0.05 mol) of three ethoxymethane and 9.6 g of zifirata of three 25 boron fluoride in 75 ml of diethyl ether and 0.051 mol of di-tert-butyl phosphite of lithium obtained from 7 , 4 g (0.051 mol) di-tert-butylphosphine and 0.051 mol butyl lithium (36 ml

30 1.42 N solution in pentane) in 50 ml of THF, at -20 ° C, 6.5 g of compound are obtained, yield 51.6%, t, Kip, 67 ° C (1 mm Hg, Art.), Fragu; RSN: (Hz

35

4.97 ppm, d ,, LRN 1 Hz, S

106.73 m, d., D ,, j

pc

15.87 Hz

S 20.16 m, d.

Found,%: C 63.01; H 1, 69; P 2.68,

C 13 29 ° aP 40Calculated,%: C 62.87; H 11.77;

R 12.47.

PRI me R 3, Dibutoxymethyl (ditert-butyl) phosphine, I

45 Analogously to the example from 0.073 mol of dibutoxycarbenium tetrafluoroborate, obtained from 16.9 g (0.073 mol) of tributoxymethane and 13.8 g (0.097 mol) of boron trifluoride, in 80 ml

rrj diethyl ether and 0.073 mol of di-tert-butylphosphite lithium, prepared from 10.7 g of di-tert-butylphosphine and 0.073 mol of butyl lithium (52 ml, 4 N solution in pentane) in 75 ml of THF, with

"-20 ° C." 0.9 g of compound are obtained,. th.kip, (1 mm Hg), yield 48.9%, PCH Fragment: (C 4.92 m, d, d, d, dp 12. Gp, s. 107.51 m, d, d., JPC 18.31 Hz, p 22 m, d

Found,%: R 9.89,

C ,, N „Og.R,

C, 67.18; H 12.21;

C, 67.07; H 12.25;

Calculated, R 10,17.

PRI me R 4. Triethoxymethyl Cd-t-butyl) phosphine.

Analogously to example 1, from 0.057 mol of triethoxycarbenium tetrafluoroborate obtained from 10.9 g (0.057 mol) of tetraethoxymethane and 10.8 g (0.076 mol) of boron trifluoride etherate in 100 ml of diethyl ether and 0577 mol of di-tert-butylphosphite lithium obtained from 8 , 3 g (0.057 mol) of di-tert-butyl phosphine and 0.057 mol of butyl lithium (40.1 ml of a 1.42 N solution in pentane) in 75 ml of THF, 9.5 g of compound are obtained at -10 ° C, yield 57.2%. t kip. 83 C (1 mm Hg). PC fragment: & 120.72 ppm, 40.39 ppm

 Found,%: C 61.87; H 11.29; R 10.35.

 pc

10.98 Hz

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Calculated,%: C 64.64; H 11.75; R 9.26.

The proposed method is characterized by - g simplicity, does not require complex hardware design, and if necessary -. bridges can be extended to target products of various structures - important key substances in organophosphorus synthesis 10,

The method allows to obtain the target products with good yields under mild conditions, is the first example of using the interaction of 15 alkoxycarbenium ion with a phosphide anion to create a phosphorus-carbon bond.

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Claims (1)

Invention Formula The method of obtaining di - or trialkoxymethyl (dialkyl) phosphines of the general formula (R) PCH, (OR), C, jHj30jP. C 61.62; .H 11.38; (G 121,35 MD, e. (5p6.59 ppm) Found,%: P 9.47. 1v 39 Jp 4.89 Hz C, 64.48; H 11, 69; Calculated,%: R 10,59. Limer 5. Triisopropoxymethyl (butyl) phosphine. Analogously to example 1 of 0.047 mol of triisopropoxycarbenium tetrafluoroborate obtained from 11.7 g (0.4 mol of tetraisopropoxymethane and 8.9 g (0.067 mol) of boron trifluoride etherate in 75 ml of diethyl ether, and 0.047 mol of dibutyl phosphite lithium obtained from 6 , 8 g (0.047 mol) of dibutylphosphine and O, .047 mol of butyl lithium (33.6 ml of a 1.4 N solution in pentamine) in 50 ml of THF, 9.2 g of compound are obtained, yield 59%, bp 93 C (1 mm Hg). PC fragment: where R and R are lower alkyls, and one of them has isostroenie, p - O or 1, using a phosphorus-containing reagent and carrying out the process in an inert gas atmosphere, characterized in that increasing the yield of products and expanding the field of application of the process, the corresponding lithium dialkyl phosphide is used as a phosphorus-containing reagent, which is subjected to interaction with di- or trialkoxycarbenium tetrafluoroborate of the general formula + (K, 0) j., 45 where R and p have the indicated meanings, in the environment of diethyl ether at a temperature of from minus 30 to minus 10 C.