SU370212A1 - METHOD OF OBTAINING TERTIARY ARYLETHYNTHOLPHOSPHINES - Google Patents

Description

one

The invention is an improved process for the preparation of tertiary aryl ethynylphosphines of the general formula

(CeHs) pR (С С-СБН4Х)

where X is hydrogen, alkyl, chlorine or nitro;

,.12.

These compounds can be used to obtain intermediates in the synthesis of phosphorus-containing complexones, dyes or polymers.

A known method for producing tertiary submerged-phenylethylene phosphates by the interaction of phosphorus trichloride with substituted-phenylethylene magnesium bro, mid. However, in this way only symmetric phosphines can be obtained. In addition, a large amount of flammable ether, a solvent, is required for organomagnesium synthesis.

There is also known a method of producing a single phosphine, triphenylethylene phosphine, by reacting phosphorus trichloride with copper acetylide, but it is not possible to obtain substituted phenylethylene phosphines by this method, since the reaction ends with a flash.

In order to simplify and expand the range of target products, a universal method for the preparation of tertiary aryl ethynylphosphines by reacting copper arylacetylide with the corresponding chlorophosphine in a polar aprotic solvent, such as tetrahydrofuran, is proposed. The process is preferably carried out at 20-66 ° C.

To increase the yield of the target product, norodes can be performed in the presence of lithium salts. Target products are recovered by known techniques. The use of not only phosphorus trichloride, but also chlorophosphines allows us to get asymmetric tertiary phosphines along with symmetric phenylethynylphosphines, which is not described in the literature.

Example 1. To a suspension of 2.1 g of copper and nitrophenylacetylene in 30 ml of tetrahydrofuran (THF) was added at 64 ° C a solution of 2.7 g of phenyldichlorophosphine in 20 ml of THF. Mixture

boil for 1 hour and then stir at room temperature. The resulting solution is treated with 25% ammonium hydroxide, the organic products are chromatographed on alumina, 1.5 g of crystalline material are separated, which is extracted with petroleum ether. Obtain 0.82 g (yield 41%) of p-nitrophenylacetylene and 0.3 g (yield 15%) of phenylbys- (l-nitrophenylethyl) phosphine, m.p. 164.5-165 ° C. IR spectrum, cm - 1595

and 1350 (NOa); 2200 ().

Found,%: C 65.55; H 3.70; N 7.03; R 7.77. CsaHiaNaOiP

Calculated,%: C, 66.01; H 3.27; N 7.00; R 7.75.

Example 2. To a solution of 1.74 g of lithium bromide in 40 ml of THF, 2.1 g / g of copper nitrophenylacetylide and 1.35 g of phenyldichlorophosphine were added successively. The mass is stirred for 1 hour at 20 ° C and treated as indicated in Example 1. 0.71 g (yield 35%) of phenyl-bms- (p-nitrophenylethynyl) phosphine is obtained.

Example 3. To a solution of 0.85 g of lithium chloride in 20 ml of THF, 1.65 g of copper phenylacetylide and 2.2 g of diphenylchlorophosphine were added. The mass is stirred for 1 hour at 20 ° C and for another 1 hour at 66 ° C; then decompose 15% aqueous solution of ammonia. Organic products are extracted with benzene, benzene is distilled off; oily residue hardens with the addition of 2-3 drops of ethanol. Obtain 2.4 3 (yield 84%) diphenyl- (phenylethil) phosphine, so pl. 43.5-44 ° C. IR spectrum: 2175 cc-1 (). According to literary data, m. Pl. of this compound is 44 ° C.

Example 4. To a solution of 0.51 g of lithium chloride in 20 ml of THF was added successively 1.26 g of copper l-nitrophenylacetylenide and 0.3 g of phosphorus trichloride. The mass is stirred for 1 hour at 20 ° C and esh, e for 1 hour at 66 ° C, then decomposed with a 15% aqueous solution of ammonia. The organic products are extracted with benzene, the benzene is distilled off, the residue is treated with petroleum ether. Obtain 0.35 g (yield 40o / o) "-nitrophenylacetylene and 0.22 g (yield 23%) trms-C / g-nitrophenylethyl) phosphine, so pl. 190 ° C (decomposition). IR spectra, comp-1: 1595 and 1350 (NOa); 2175 ().

Found,%: N 8.82; R 6.65.

CsiHisNsOgP.

Calculated,%: N 8.95; R 6.59.

Subject invention

1. Method of producing tertiary aryl-ethynylphosphines obsh, formula

(SbH5) „Р (С С-СБН4Х) sn where X is hydrogen, alkyl, chlorine or nitro group;

P: -0, 1.2,

based on acetylide, characterized in that, in order to simplify the process and expand the range of target products, copper arylacetylide is reacted with the corresponding chlorophosphine in a polar aprotic medium (solvent, for example tetrahydrofuran, followed by isolation of the target product by known techniques.

2. Method as claimed in Claim 1, characterized in that the process is carried out in the presence of lithium salts.

3. Method according to paragraphs. 1 and 2, characterized in that the process is carried out at 20-66 ° C.