SU464595A1 - Method for producing 1,2,3-tris (dialkylphosphorous) propanes - Google Patents

Description

The invention relates to the chemistry of organophosphorus compounds, namely the preparation of new 1,2,3-gryce (dialkylphosphono) propanes, which can be used as polydentate ligands, extractants, surfactants, plasticizers. A known method for producing 1,2-bis (dialkylphosphono) propanes by reacting allyl bromide with dialkylphosphorous sodium. However, the described method does not result in 1,2,3-t /) iso (dialkylphosphono) propanes. Describes a method for producing 2,3-tris (dialkylphosphono) propanes of the general formula: OO 4,, F-CH-CH-CH2-FR 0 PR, where R is alkoxy, alkyl, aryl, which consists in the interaction of epihalohydrins of the general formula C, - cn-cn.-x where X is C1, Br, with sodium derivatives of the partial esters of phosphorus acids of the general formula R2PHO (3), the value of R in formula (3) is the same as in formula (1) in the medium of organic solvent , for example, benzene. The first stage of the reaction is the formation of E, 7 - epoxyphosphonate, which then interacts with the partial esters of phosphorus acids with the opening of the oxide cycle. The resulting hydroxy derivatives of phosphonic acids during the reaction process are dehydrated to unsaturated phosphonic esters, which attach a second partial ester molecule in the multiple C С bond. However, regardless of the nature of the opening of the oxide cycle, 1,2, (dialkylphosphono) propanes of the formula (1) are uniquely formed. The structure of the compounds obtained is confirmed by the data of elementary analysis, PC, CR and P -speckers. Purity was monitored by thin layer chromatography. Example 1. Getting 1,2, (diethylphosphono) propane. In a three-necked flask equipped with a reflux condenser, a dropping funnel and a mechanical stirrer, 2.3 g (0.1 ga) of sodium are placed in 100 ml of dry benzene, and 41.4 g (0 , 3 mol) of fietenphosphite.

After the total amount of sodium is dissolved, 9.25 g (0.1 lgolb) of epichlorohydrin is added dropwise to the reaction mixture, then the mixture is heated under boiling and stirring for 3-5 hours. The cooled neutral comfort mixture is equimolarly with glacial acetic acid, washed with 50 L of water, the benzene solution is dried over anhydrous magnesium sulfate and, after removal of the solvent, the residue is fractionated in vacuo. 27.6 g (65%) of 1,2,3-gryce (diethylphosphono) propane were recovered. T. Kip. 187-189 ° С / 2 лш рт. Art. p-1.4521, df 1.1747, MNB found 104.09; calculated 104.07.

Found,%: C 39.61; H 7.69; P 20.31

S.bNzzzOERz.

Calculated,%: C 39.82; H 7.74; R 20,54.

In the NMR spectra, one signal of three equivalent phosphorus atoms with -21 ppm of R / 0.46 is observed (on UV 254 UV, the eluent is a mixture of STaHOvia and acetone 1: 1).

Example 2. Getting 1,2,3-g "c (di-npropylphosphono) propane.

In a three-necked flask, equipped with a condenser, a dropping funnel and a mechanical stirrer, 2.3 g (0.1 ga) of sodium are placed in 100 ml of dry benzene, and 49.8 g (0, 3 mol) di-n-propyl phosphite. After the total amount of sodium has been dissolved, 9.25 g (0.1 mol) of epichlorohydrin is added dropwise to the reaction mixture, and after the exothermic effect is finished, the reaction mixture is heated at boiling and stirring for 3-5 hours. acid, washed with 50 ml of water, the benzene solution is dried over

About anhydrous magnesium sulfate and after removal of the solvent, the residue was fractionated in vacuo. 32.1 g (60%) 1,2,3-gr of c (di-propiylphosphono) prospa, i.p. 213- 214 ° C / 2 mm Hg. Art. L 1.4570; thick colorless liquid.

Found,%: C 47.15; H 8.65; P 17.50

C21H4709Rz.

Calculated,%: C 47.01; H 8.76; R 17.35. R / 0.73 (on UV 254 silufol, 0% eluent: 1: 1 mixture of ethanol and acetone).

Subject and reference about the and “

The method was obtained: and 1,2,3-GuOis (dialkylphosphono) propium, characterized in that the epihalohydrins are reacted with sodium derivatives of the partial esters of phosphorus acids in the medium of an organic solvent, followed by isolation of the target product by known uses.