SU854931A1 - Method of preparing tetra-substituted methylenediphosphines - Google Patents

Description

The invention relates to the chemistry of organophosphorus compounds, and in particular to a new method for producing tetra-substituted methylenediphosphines of the general formula

RBN _g P

substituted methylphosphines with chlorophosphines in an organic solvent in an inert gas atmosphere when heated to VI. This method is based on the creation of PCH ^ P fragments during synthesis [2J

The disadvantage of this method is the extreme inaccessibility of the starting compounds, as well as the need to use alkaline where R and R * are the same or different alkyl or aryl.

These compounds can be used as bidentate ligands in the preparation of various complexes with metals, and are also the basis for the synthesis of methylenediphosphorus compounds with one, one or two four-coordinated phosphorus atoms in the molecule.

A known method of producing tetra-substituted methylenediphosphines by the interaction of sodium diphenylphosphide with methylene chloride [1].

Closest to the invention in technical essence and the achieved result is a method for producing tetrasubstituted methtsyldiphosphines by the interaction of the t-element of metals. As a result of this, the real total yield of the target products in terms of the initial compound - phosphorus trichloride

5-10%.

the purpose of the invention is to simplify the process and increase the yield of the target product. The goal is achieved in that, according to the method for producing tetra-substituted methylene diphosphines of formula I, tetrachloromethylene diphosphine is reacted with an organomagnesium compound in an organic solvent in an inert gas atmosphere under cooling from -20 to 10 ° C.

The proposed method for the production of tetra-substituted methylenediphosphines is characterized by the availability of initial

compounds and allows to obtain target products with a yield of 70-96%

Example 1. Tetramethylmethylene diphosphine. To a solution of methylmagnesium iodide obtained from 12.2 g (0.5 g-atom) of magnesium and 72.2 g (0.5 mol) of methyl iodide in 250 ml of di-5 ethyl ether and cooled to -20 ° C, slowly at while stirring, a solution of 21.8 g (0.1 mol) of tetrachloromethylene diphosphine in 100 mp diethyl ether is added dropwise. The mixture 10 is heated to boiling ether and after cooling is slowly decomposed with a solution of 55 g of ammonium chloride in .250 ml of water, previously saturated with argon. The ether layer was separated, the 15 aqueous layer was extracted with ether, the ether extracts were dried with calcined sodium sulfate, the ether was distilled off, the residue was distilled in vacuo. 10.5 g (77%) of tetramethylmethylene- are obtained. 20 diphosphine, b.p. 45 ° (15 mm), 1.5120-, d ^2U 0.8934.

Found,%: C 44.05; H 10.32; P 45.67.

C ₅ H. ^ ₄ Pq. ..,

Calculated,?.: C 44.14; H 10.37;

P 45.53.

PMR spectrum; cf (CHa) 1.23 ppm (triplet), J (RSN) 1 Hz. NMR ^{3- |} P: <5p + 58 ppm

Example 2. Tetraethylmethylene-30 diphosphine. To a solution of ethyl magnesium bromide obtained from 12 g (0.45 mol) of magnesium and 54.5 g (0.5 mol) of ethyl bromide in 200 ml of diethyl ether and cooled to -10 ° C, 35 are slowly added dropwise with stirring: ^ a solution of 21.8 g (0.1 mol) of tetrachloromethylene diphosphine in 100 ml of diethyl ether. The selection of the target product is carried out analogously to example 1. Receive 17.5 g (90%) of tetraethylmethylene diphosphine, so Kip. 54 ° C (1 mm), n ^ ⁰ 1.5108; 0 ^ 0.8958.

Found,?: C 55.97; H 11.46; P 32.08.

C _a H ₂₁ P ^.

Calculated,%: C 56.23; H 11.53; P 32.24.

In the PMR spectrum, the proton signals of PCHqP are in the region of RSNPSN signals _a . NAR ^ P: dp + 31 ppm

Example 3. Tetraieopropylmethylene diphosphine. To a solution of isopropyl magnesium chloride obtained from

24.3 g (1 g-atom) of magnesium and 78.5 g (1 mol) of isopropyl chloride in 500 ml of diethyl ether, cooled to 0 ° C, the solution is slowly added dropwise with stirring with stirring

43.6 g (0.2 mol) of tetrachloromethylene diphosphine in 100 ml of diethyl ether. The selection of the target product is carried out analogously to example 1. Get 46 g (92%) of tetraeopropylmethylene diphosphine, so Kip. 89 ° C (0.5mm) 'p ³ ® 1.5039; d 5 ° 0.8915.

Found,%: C 62.63; H, 12.20;

P 25.18.

S -13

Calculated,?: C 62.87, H 12.18, P 25.01.

1 H-NMR spectrum: sL (CH ₂ ) 1.40 ppm. (triplet); ² J (RSN) 1.5 Hz. NMR ³¹ P: <$ p + 7.8 ppm

Example 4. Tetravorbutyl ¹ tylenediphosphine. To a solution of sec-butyl magnesium chloride obtained from

12.2 g (0.5 g-atom) of magnesium and 46.3 g of sec-butyl chloride in ^ 50 ml of diethyl ether, at 5-10 ° С, a solution of 21.8 g (.0.1 is slowly added dropwise with stirring) mol) of tetrachloromethylene diphosphine in 150 mp diethyl ether. Isolation of the desired product is carried out analogously to Example 1. 29 g (95%) of tetra-butylmethylene diphosphine are obtained, b.p. 115 ° C (1 mm), n2 ° 1.5080 ;. d ^ ° 0.9067.

Found,?: C, 66.85; H, 12.50); R, 20.46.

^ 17 8 ea ^r o. ·

Calculated,?: C 67.07; H, 12.58); P, 20.35.

In the PMR spectrum, the signals of the RSH ^ P protons are in the region of the RSN (CH _E ) signals (CH ₂ CH ₃ ). NMR ³¹ P: s ^ + 12.8 ppm (wide signal, mixture of diastereomers).

Example 5. Tetraphenylmethylene diphosphine. To a solution of phenylmagnesium bromide obtained from 6.1t (0.25 g-atom) of magnesium and 40.2 g (0.25 mol) of bromobenzene in 100 mp diethyl ether, with cooling at -5-С ° С, slowly add with stirring dropwise a solution of 10.9 g (0.05 mol) of tetrachloromethylene diphosphine in 60 ml of diethyl ether. The selection of the target product is carried out analogously to example 1. Receive after reprecipitation from a mixture of diethyl ether and petroleum ether

18.4 g (96%) of tetraphenylmethylene diphosphine, mp 120 ° C.

Found,?: C, 77.89; H 5.70;

P 15.95 (-25 N Q2₽2

Calculated,?: C 78.11; H 5.77; P 16.12.

PMR spectrum: cH ^ CH ^) 3.10 ppm (triplet), dj (RSN) 2 Hz. ΗΜΡ ^3ί Ρ: <Ur + 22, b ppm

Example 6. Symmetric dimethyldiisopropylmethylene diphosphine. To a solution of 21.8 g (0.1 mol) of tetrachloromethylene diphosphine in 350 mp diethyl ether, cooled to -20 ° C, isopropyl magnesium chloride solution obtained from 5.8 g (0.24 g atom) is slowly added with stirring. magnesium and 18.9 g (0.24 mol) of isopropyl chloride in 200mp ether, and with stirring, the temperature of the reaction mixture was brought to 20 ^ 0. Then the mixture was again cooled to -20 ^ 0 and a solution of methyl magnesium iodide prepared from 4.8 g (0.2 g atom) of magnesium and 29 g (0.2 mol) of methyl iodide in 200 ml of diethyl ether was slowly added with stirring. The selection of the target product is carried out analogously to example 1. $

13.5 g (70%) of symmetric dimethyldiisopropylmethylene diphosphine are obtained, b.p. 72 ° C (2 mm), n £ ° l, 5076; d2 ° 0.9003. ^R

Found,%: C 56.05; H, 11.40; ' ^and

P 32.14.

Rdl

Calculated,%: C 56.23; H 11.53;

P 32.24.

In the PMR spectrum of the proton signals are PCHqP 15 in the PCH signal (SN _{a) r.} NMR ³⁴ P: <L> + 33.2 ppm (wide signal, mixture of diastereomers).,

Example 7, Symmetric di-20 isopropyl diphenylmethylene diphosphyan., To a solution of 21.8 g (0.1 mol) tetrachloromethylene diphosphines. in 350 ml of diethyl ether, cooled to -20 ° C, a solution of isopropyl magnesium chloride obtained from 6.1 g (0.25 g-atom) of magnesium and 19.3 g (0.25 g mol) of chloride is added slowly with stirring 2S isopropyl in 200 ml of diethyl ether, and with stirring, the temperature of the reaction mixture was adjusted to 20 ° C. The mixture was then cooled again to 0 ° C and a phenyl magnesium bromide solution prepared from 6.1 g (0.25 'g-atom) of magnesium and 40.2 g (0.25 mol) of bromobenzene in 150 ml of ether was slowly added with stirring . The selection of the target product is carried out analogously to example 1. Receive 20.2 g (64%) of symmetric diieopropyl diphenylmethylene diphosphine, so Kip 155 C 40 (0.02 mm), n ° ° 1.5809, 1.0348.

Found,%; C 77.86; H, 8.20; P 19.60.

^C 19 ^H 2t> ^₽ 2 "

Calculated,%: C 72.09; H, 8.28} P, 19.57.

In the PMR spectrum, the proton signals of JPCHgP are in the region of proton signals of PCH (CH _d ) ₂ . NMR '' ^, P: +

16.3 ppm (wide signal, mixture of diastereomers).

Claims (2)

(54) METHOD FOR OBTAINING TETRAY-SUBSTITUTED METHYLENEDIPHOSPHINES The invention relates to the chemistry of organophosphorus compounds, namely to a new method of preparing tetrasubstituted methylene diphosphines of the general formula RHENR where R and R are the same or different alkyl or aryl. These compounds can be used as bidentate ligands in the preparation of various complexes with metals, and also form the basis for the synthesis of methylenediphosphorus-containing compounds with one or two tetra-coordinating phosphorus atoms in the molecule. A known method for the preparation of tetra-substituted methylene diphosphines by the interaction of sodium diphenylphosphide with methylene chloride tl. The closest to the invention in technical essence and the achieved result is a method for producing tetra-substituted carbonaceous and phosphine compounds by interaction of methyl substituted methylphosphines with chlorophosphines in an organic solvent medium under an inert gas atmosphere when heated to. This method is based on the creation of G21 fragments during the synthesis. The disadvantage of this method is the extremely inaccessibility of the initial compounds, as well as the need to use alkali metals. As a result, the real total yield of the target products in terms of the starting compound is phosphorus trichloride 5-10%. The purpose of the invention is to simplify the process and increase the yield of the target product. This goal is achieved by the fact that according to the method for preparing tetra-substituted methylene diphosphines of formula I, tetrachloromethylene diphosphine is reacted with an organomagnesium compound in an organic solvent medium under an inert gas atmosphere with cooling from -20 to. The proposed method for the preparation of tetrasubstituted methylenediphosphines (characterized by the availability of similar compounds) and allows to obtain whole products with a yield of 70-96%. Example 1. Tetramethylmethylenediphosphine. To a solution of methyl magnesium iodide, prepared from 12.2 v (0.5 g-atom) of magnesium and 72.2 g (0.5. Mol) of methyl iodide in 250 ml of diethyl ether and cooled to -20 s, is added dropwise with stirring. a solution of 21.8 g (0.1 mol) of tetrachloromethylenediphosphate in 100 ml of diethyl ether. The mixture is heated to the boiling point of ether and, after cooling, slowly decompose with a solution of 55 g of ammonium chloride in -250 ml of water, previously saturated with argon. The ether layer is separated, the aqueous layer is extracted with ether, the ether extract is dried with calcined sodium sulphate, the ether is distilled off and the residue is distilled in vacuum. 10.5 g (77%) of tetramethylmethyl diphosphine are obtained, b.p. 45 (15 NM), 1.5120, O, 8934. Found,%: C 44.05; H 10.32; R 45.67. C5H. ,, Ra. Calculated,%: C 44.14; H 10.37; R 45.53. PMR spectrum; ((SS) 1.23 ppm (triplet), J (PCH) 1- Hz. 58 ppm. Example 2. Tetraethylmethyl diphosphine. To a solution of ethylmagnesium bromide prepared from 12 g (0.45 mol) of magnesium and 54.5 g (0.5 mol) of ethyl bromide in 200 ml of diethyl ether and OhlanshanEyum are slowly added dropwise with stirring while stirring 1 1 solution of 21.8 g (0.1 mol) of tetrachloromethylenediphosphine in 100 ml of diethyl ether. analogs are carried out in Example 1. 17.5 g (90% of tetraethylmethylenediphosphine, bp 54C (1 mm), n2 ° 1.5108; d50.8958. Found: C 55.97; H 11, 46; R 32.08. CoHo, jP ,,. Calculated,%: C 56.23, - H 11.53; R 32.24. In the PMR spectrum with PCH2P protons are in the PCHnCHj signal area. 31 ppm Example 3 Tetraisopropylmethylene diphosphine. To a solution of isopropyl magnesium chloride, Hoivty is obtained from 24.3 g (1 g atom) of magnesium and 78.5 g (1 mol) of iopropyl chloride in 500 ml of diethyl ether, cooled until, slowly a solution of 43.6 g (0.2 mol) of tetrachloromethylene diphosphine in 100 ml of diethyl ether pa is added dropwise with stirring. The depletion of the desired product is carried out analogously to Example 1. 46 g {92%) of tetraisopropylmethylene diphosphine are obtained, b.p. 89 ° C (0.5, 5039; 0.8915. Found: C 62.63; H 12.20; P 25.18. C-ge oPaCalculated,%: C 62.87, H 12.18 , P 25.01. PMR spectrum: cL (CH) 1.40 ppm, (triplet); 2) (pcn) 1.5 Hz. NMR31r: fp + 7.8 ppm Example 4. Tetravorobutylmethylenediphosphine. To the solution of sec-butyl magnesium chloride, obtained from 12.2 g (0.5 g-atom) of magnesium and 46.3 g of chloride of secondary scrambler in 50 ml of diethyl ether, at 5-10 ° C, a solution is added dropwise with stirring , 8 g (0.1 mol) of tetrachloromethylene diphosphine in 150 ml of diethyl ether. The selection of the desired product was carried out analogously to example 1. 29 g (95%) of tetravorobutylmethylene diphosphine were obtained, b.p. 115 ° С (1 mm), p201.5080; , 9067. Found,%: C, 66.85; H 12.50 R 20.46. 17 per abCalculated,%: C 67.07; H 12.58; R 20.35. In the PMR spectrum, the PCHrj P protons are in the PCH (CHj) signal area (). NMR P: + 12.8 ppm (broad signal, a mixture of diastereomers). Example 5. Tetraphenylmethyl diphosphine. To a solution of phenylmagnesium bromide prepared by 6.1 tons (0.25 g-atom) of magnesium and 40.2 g (0.25 mol) of bromobenzene in 100 ml of diethyl ether, while cooling -5-C-s, slowly with stirring a solution of 10.9 g (0.05 mol) of tetrachloromethylene diphosphine in 60 ml of diethyl ether is added dropwise. The selection of the desired product is carried out analogously to Example 1. After re-precipitating from a mixture of diethyl ether and petroleum ether, 18.4 g (96%) of tetraphenylmethylene diphosphine, m.p. 120C. Found,%: C 77.89; H 5.70; R 15.95 C jHa / jP Calculated,%: C 78.11; H 5.77; R 16,12. PMR spectrum:) ZDO ppm (triplet), uj (pGH) 2 Hz. 22.6 ppm Example 6. Symmetric dimethylesisisopropylmethylene diphosphine To a solution of 21.8 g (0.1 mol) of tetrachloromethylene diphosphine in 350 ml of diethyl ether, cooled to -20 ° C, isopropylmagnesium chloride solution prepared from 5.8 g (0.24 g-atom) of magnesium and 18 , 9 g (0.24 mol) of isopropyl chloride in 200 ml of ether, and with stirring the temperature of the reaction mixture is brought to 20 s. The mixture is then cooled again and a solution of methylmagnesium iodide, prepared from 4.8 g (0.2 g-atom) of magnesium and 29 g (mol) of methyl iodide in 200 ml of diethyl ether, is added slowly with stirring. The selection of the desired product is carried out analogously to an example. 13.5 g (70%) of symmetrical dimethyldiisopropylmethylenediphosphine are obtained. Bp. (2 mm),; 5076; 0,9003. . Found,%: C 56.05; H ll, 40j P 32,14. . Calculated,%: C, 56.23; H 11.53; R 32.24. In the PMR spectrum, the PCNoP protons signals are in the PCH {C.Hj) 2 .. NMR: Ap + 33.2 ppm signal area. (broad signal, a mixture of diasteoeomers) .. Example 7. Symmetric diisopropyl diphenylmethylene diphosphone. To a solution of 21.8 g (0.1 mol) tetrachloromethylene diphosphine. in 350 ml of diethyl ether, cooled before, slowly with stirring is added a solution of isopropyl magnesium chloride, obtained from 6.1 g (0.25 g-atom) of magnesium and 19.3 g (0.25 g-mol of isopropyl chloride in 200 ml diethyl The reaction mixture was brought to 20 ° C with stirring. The mixture was then cooled again and a solution of phenylmagnesium bromide prepared from 6D g (0.25 g-atom) of magnesium and 40.2 mg was slowly added with stirring. g (0.25 mol) of bromobenzene in 150 ml of ether. The target product is isolated in the same way as Example 1. 20.2 g (64%) of symmetry are obtained diisopropyl diphenylmethylenediphosphine, bp 155 C (0.02 mm), p 20 1.5809-, d 1.0348. Found,%: C 77.8b H 8.20; P 19.60. - (. 2 Calculated ,%; C, 72.09; I, 8.28; P, 19.57. In the PMR spectrum, the JPCH2P proton signals are in the region of the PCH (SNd) protons, NMR 9 - P1 1. 16.3 ppm ( broad signal, mixture of diastereomers.) Claim method of producing tetrazammethaned methylene diphosphines of general formula X PtfRtPC "where R and R are the same or different alkyl or aryl, using phosphine in an organic solvent medium in an inert gas atmosphere, characterized in that The use of tetrachloromethane diphosphine, which is reacted with an organomagnesium compound, and the process is carried out while cooling to a temperature of minus 20 ° C to plus 1 ° C. Sources of information taken into account during the examination 1.K. Jsslelb, D. MCner, DarsteJlung ditert. Phosphin, Chero. Ber., 1959, 92, S.3175. 2.P.Appeb K. Geller, H-F.Shehe-. ler. Uber ein neues Oarstel ungserfahren und ungewohnlfche spaltung. er Me bis (dForganylphosp hae) durch AlkaIimetaPe, Chem, Ber., 979, 112, s. 648-653.