Preparation of substituted phosphide salts

Details Preparation of substituted phosphide salts Preparation of substituted phosphide salts

2000-01-11

2001-04-10

Vollano, Jean F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Phosphorus containing

C568S008000

Reexamination Certificate

active

06215026

ABSTRACT:

The present invention relates to a process for preparing substituted sodium salts of phosphides and use of such salts in preparing phosphines.
The preparation of alkali metal diarylphosphides and their subsequent conversion to unsymmetrical triarylphosphines is well-known in the literature. Triarylphosphines are widely used as ligands to transition metals to afford useful catalysts for many different chemical reactions. Examples of these reactions, which are carried out on an industrial scale, include the hydroformylation reaction to produce aldehydes from alkenes, the reaction of aryl halides or alkenes to produce esters and the metathesis of simple alkenes to higher olefins. Although triphenylphosphine is frequently used as such a ligand, better specificity is often encountered if unsymmetrical triarylphosphines or diarylalkyl are used.
Methods which have been used to produce alkali metal diphenylphosphides are low yielding, difficult to carry out on a large scale, and/or expensive. For example, Hewertson and Watson (J. Chem. Soc. 1962. 1490) teach that sodium diphenylphosphide may be prepared in >75% yield by the cleavage of triphenylphosphine with sodium metal at −75° C. in liquid ammonia. Whilst such reactions are common place in the laboratory, large scale production is hampered by the need of special (and very expensive) plant which can work at these low temperatures. Issleib and Frohlich (Z. Naturforsch, 1959, 14b, 349) have shown that the reaction may be carried out with sodium metal in dioxane. However, in this case the yield is only 25%. Clearly such a low yield is unacceptable for industrial production. Finally, metallic sodium may be reacted with chlorodiphenylphosphine (Hewertson, ibid). However, chlorodiphenylphosphine, although commercially available, is somewhat expensive and is only used because there is little alternative.
There is thus a need for a method of preparing alkali metal diarylphosphides which is high yielding, uses inexpensive and readily available raw materials and uses what may be termed “conventional” chemical plant.
It has now been surprisingly found that these requirements may be met if a reaction is carried out between a readily available triarylphosphine, typically triphenyl phosphine, and an alkali metal, typically sodium, in either a primary aliphatic amine or diamine either alone or diluted with a co-solvent.
According to the present invention there is provided a process for preparing sodium diaryl salts of phosphides of general formula (I)
R
2
P
−
Na
+
  (I)
where R is a phenyl or substituted phenyl group, by reaction of a triarylphosphine with sodium in an aliphatic amine or diamine as solvent or co-solvent.
The sodium used in the process of the invention is preferably finely dispersed in a carrier liquid. The liquid carrier may be an inert organic solvent whose boiling point is above the melting point of sodium such as, for example, toluene, xylene and petroleum ethers. Alternatively, the carrier liquid may be a mineral oil such as, for example, selected from the Shell Ordina or BP Enerpar range of high grande mineral oils.
The dispersion of sodium may be prepared by melting sodium metal in the carrier liquid and stirring rapidly. The sodium in the dispersion preferably has an average particle size in the range of 0.1 to 1000 microns, especially 0.1 to 20 microns. The sodium is preferably dispersed in an amount of 1 g of sodium per 0.1 to 100 cm
3
, especially 0.1 to 5 cm
3
of liquid carrier.
A preferred solvent is ethylenediamine. A preferred co-solvent when used is selected from hydrocarbons and ethers. The hydrocarbon co-solvent may be aromatic or aliphatic. Toluene is an example of a suitable aromatic hydrocarbon co-solvent and hexane is an example of a suitable aliphatic hydrocarbon co-solvent. Examples of suitable ether co-solvents for use in the process of the invention include tetrahydrofuran, methy′-butyl ether and glyme ethers.
The reaction may be carried out in the temperature range of about 0° C. to about 120° C., preferably in the range of 50-70° C.
The sodium diaryl of phosphides prepared according to the invention may be further treated by reaction with a compound of the general formula R
1
X, where R
1
is selected from hydrogen, phenyl or substituted phenyl (aryl) groups, naphthyl or substituted naphthyl groups, heterocyclic rings, C
1-10
carbon chains optionally containing branches or unsaturated linkages, or —(CR
1
R
1
)
n
PRR where n=1 to 10 and X is a suitable leaving group, such as halide, methoxide or nitro, to produce phosphines of the general formula.
The reaction temperature for producing unsymmetrical phosphines is preferably in the range of 0-120° C., especially 20-30° C.
The by-product from this cleavage is phenyl sodium which is a very strong base. Since this strong base may interfere with subsequent reactions, it is preferable to destroy this reagent before further chemistry is carried out. This has been carried out in the literature by the addition of ammonium salts such as ammonium chloride. In our case this is not convenient since such ammonium salts are insoluble in the reaction medium. A more convenient method of destruction is by the addition of an alcohol, such as n-butanol. Although this procedure produces sodium alkoxides and benzene these by-products do not appear to interfere with subsequent reactions.
The use of ethylenediamine has a further benefit in the subsequent reaction of the sodium diarylphosphide with a suitable electrophile in that it is an excellent solvent for conducting such reactions. Thus, the reaction may be brought about by adding the relevant alkyl or activated aryl halide, either alone or in a suitable co-solvent, to the reaction mixture and heating for an appropriate time to complete the reaction. Work-up of the final product is particularly easy by the cautious addition of water to the reaction medium. The solvent, ethylenediamine, and the inorganic by-products are soluble in water and the product simply precipitates from solution. The product may be isolated in a high degree of purity by simple filtration, washing and drying.
A particular advantage of the process of the invention is that cryogenic plant is not required and the process is easily operable in standard chemical plant on a large scale. The invention is particularly useful for preparing sodium salts of diarylphosphides, especially sodium diphenylphosphides, and then further treatment to produce unsymmetrical triarylphosphides. An advantage of the invention in relation to sodium salts is that sodium diphenylphosphide is soluble in the ethylenediamine solvent and so is tractable in subsequent reactions to give the corresponding unsymmetrical phosphine.


REFERENCES:
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patent: 5354894 (1994-10-01), Devon
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patent: 5777169 (1998-07-01), Layman, Jr. et al.
patent: 5866720 (1999-02-01), Layman, Jr. et al.
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J. Org Chem by Ashby et al 58 pp 5832-5837, Oct. 1993.*
Aldrich Chem Catalogue pp 1324-1325, 1996.

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