Organophosphorus compounds, from elemental phosphorus

The present effort is intended to provide an update of the earlier edition, bringing to the chemist in concise form advances in the approaches to C-P bond formation previously discussed, as well as several other aspects of C-P bond formation. These latter aspects include the generation of organophosphorus compounds from elemental phosphorus (of particular industrial interest for purposes of cost containment) advances in the preparation of phosphoranes, including the use of transient oxophosphoranes as intermediates in organophosphorus compound syntheses and new approaches toward the preparation of compounds with aromatic and vinylic carbon-phosphorus bonds. 

Synthesis of organophosphorus compounds from elemental phosphorus... 

In this chapter, we first review the nature of the several forms of elemental phosphorus and then proceed to consider their uses for specific types of syntheses of compounds containing the carbon-phosphorus bond. Prior reviews have also been concerned with these topics.1 2 Our purpose here is to update these presentations and provide fundamentals for the practicing chemist venturing into the use of elemental phosphorus. We limit this discussion to the more-or-less direct syntheses of organophosphorus compounds from elemental phosphorus. We will consider reactions that generate monophosphorus species without C-P bonds as critical intermediates, pro-... 

Rauhut, M.M., Synthesis of organophosphorus compounds from elemental phosphorus, Top. Phosphorus Chem., 1, 1, 1964. 

Although black phosphorus is generally inert, red phosphorus and particularly white phosphorus are capable of undergoing reactions to generate organophosphorus compounds. Several different sets of conditions may be used to form C-P bonds from elemental phosphorus. These will be discussed in the following sections. 

Many attempts have been made to synthesise organophosphorus compounds directly from the element with varying degrees of success.i In general mixtures of products are obtained, and the yields are frequently low and variable. The main difficulty is the insolubility of phosphorus in organic liquids and consequently the reactions are heterogeneous with the attendant problems of diffusion and local concentration differences. 

The use of the term organophosphorus compound has generally been limited to those materials that contain a direct carbon-phosphorus covalent bond. We continue this restriction in the present discussion. As a result, we will omit from this discussion the chemistry and nature of materials, while containing both carbon and phosphorus, that lack the direct covalent connection of the two elements. Other sources provide significant information on such materials as simple esters of phosphoric and phosphorous acid. ... 

A particularly attractive route for the preparation of organophosphorus compounds would be direct from either red or white elemental phosphorus. However, the low reactivity with various reagents has precluded a more widespread use of this substance. Yields from these reactions tend to be rather low, and experimental conditions often necessitate high temperatures/ pressures.2... 

Carbanions arising from other organometallic compounds also react with phosphorus with the formation of organophosphorus compounds. Heating tetraphen-yltin with elemental phosphorus (1 2) for 16 h to 320 oC produced triphenyl-phosphine in 85% yield 5) ppoof for the intermediate formation of tin-phos-... 

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