A method for production of alkyl(phenyl)phosphine complexes baranovich

 

(57) Abstract:

The invention relates to the chemistry of organophosphorus compounds with s-R connection, namely to obtain alkyl(phenyl)phosphine-Baranovka complex of the General formula R2PHBH3(1), where R is alkyl or phenyl, which are used as starting substances for the synthesis of water-soluble catalysts used in the production of polymers. Describes how to obtain alkyl(phenyl)phosphine-Baranovka complex interaction dialkyl(diphenyl)chlorophosphines with a complex hydride with sodium borohydride in an organic solvent is dimethyl ether of ethylene glycol, at a temperature of 10-100oWith original reagents taken in equimolar ratio with subsequent isolation of the target product known techniques. The technical result is a significant simplification and cheapening of the process and however obtaining a high quality product with a high yield of 70-90% and the content of the main substance of 95%. 2 C.p. f-crystals.

The present invention relates to the chemistry of organophosphorus compounds with C-R-communication, namely to obtain alkyl(phenyl)phosphine-Baranovich complexes of General formula

R2MVN3(1),

R - Ala is used in the production of polymers.

A method of obtaining alkyl(phenyl)phosphine-Baranovich complexes of the General formula (1) interaction dialkyl(diphenyl)chlorophosphines with lithium aluminum hydride and borane in tetrahydrofuran, the original reactants are taken in equimolar ratio, followed by separation of the target product by extraction with benzene, selected as a prototype (J. Am. Chem. Soc., 1990, 112, 5244-5252).

The disadvantage of the prototype is the use of volatile borane and explosive and quite expensive lithium aluminum hydride.

Task to be solved by the present invention is directed, is simpler and cheaper method of producing alkyl(phenyl)phosphine-Baranovich complexes.

This problem is solved by that in a method of producing alkyl(phenyl)phosphine-Baranovich complexes of the General formula (1) interaction dialkyl(diphenyl)chlorophosphines with a complex hydride in the environment of an organic solvent at equimolar ratio of the initial reagents, followed by separation of the target product, according to the invention as a complex hydride use borohydride sodium, as the organic solvent is dimethyl ether of ethylene glycol and the reaction is conducted at a temperature of 10-100

Appropriate upon receipt of the product with the highest possible output, 70-90%, the reaction of lead, essentially, when 40oC.

The invention consists in that as a complex hydride use borohydride sodium, which is also a reducing agent and a source of borane, is sustainable and relatively cheap substance, as the organic solvent used dimethyl ether of ethylene glycol, which, due to the inertia of the original reagents and good solubility therein of sodium borohydride provides the most complete transformation of the initial reagents, and conducting the reaction at a temperature of 10-100oWith until the end of the reaction. This temperature is chosen experimentally and, as shown by the experiments, is optimal from the point of view of the yield of the target product. At temperatures below 10oWith almost no reaction goes on, and at temperatures above 100oWith the decomposition of the target product and the yield is considerably reduced. The maximum possible yield of the target product 70-90% at 40oC.

The content of the basic substance in the obtained product according to NMR is 95%.

The proposed method of policemilitary sustainable, cheap enough of sodium borohydride instead of explosive and quite expensive lithium aluminum hydride and volatile borane and at the same time to get a high quality product with high yield.

These advantages enable the above-mentioned method in an enlarged scale.

Example 1. 3-necked flask equipped with stirrer and reflux condenser, inert gas load of 30 g (0,79 mol) of sodium borohydride and dimethyl ether of ethylene glycol (diglyme). With stirring to the resulting suspension was added dropwise 141 g (0.6 mol) (C-CC)2Cl of dicyclohexylphosphino and the reaction is carried out at 40oC. the Criterion for the end of the reaction is the formation of NaCl.

The resulting mass is remove the solvent and produce extraction in tetrahydrofuran (C-CC)2MVN3dicyclohexylphosphino-bananowy complex.

Get colorless crystals phosphine-Baranovka complex dicyclohexylphosphino-borane.

The yield is 88%, the content of the basic substance according to the method of NMR is 95%. Melting point 74-76oC. elemental analysis Data correspond to theory.

Example 2. Conditions of experience, as in point is mesheanii to the resulting suspension was added dropwise 126 g (0.7 mol) t-Bu2PCl di-tert-butylphosphine and the reaction is carried out at 100oC.

Get colorless crystals t-Bu2PHBH3di-tert-butylphosphino-Baranovka complex. The yield is 60%, the content of the main substance of 95%, the data of elemental analysis correspond to theory.

Example 3. Conditions of experience, as in example 1, only upload 7.2 g (to 0.19 mol) of sodium borohydride and diglyme. With stirring to the resulting suspension was added dropwise to 40 g (0.18 mol) Ph2PCl diphenylchlorophosphine in diglyme and the reaction is carried out at 30oC.

Get colorless crystals Ph2PHBH3diphenylphosphine-Baranovka complex.

The yield is 60%, the content of the main substance of 95%, the data of elemental analysis correspond to theory.

Example 4. Conditions of experience, as in example 1, except that the synthesis dicyclohexylphosphino-Baranovka complex will receive in the absence of inert gas. The yield is 83%, the content of the basic substance according to the method of NMR is 95%.

1. A method for production of alkyl(phenyl)phosphine-Baranovich complexes of General formula

where R is alkyl or phenyl,

by reacting dialkyl(diphenyl)chlorophosphines with of komplecie, with subsequent isolation of the target product, characterized in that as a complex hydride using sodium borohydride as the organic solvent is dimethyl ether of ethylene glycol, and the reaction is carried out at 10-100S.

2. The method according to p. 1, characterized in that the synthesis of lead in the atmosphere of inert gas.

3. The method according to p. 1, characterized in that the reaction are essentially at 40C.

 

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