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Review
. 2020 Jun 24;6(6):848-860.
doi: 10.1021/acscentsci.0c00332. Epub 2020 May 18.

Let's Make White Phosphorus Obsolete

Michael B Geeson  1 , Christopher C Cummins  1
Affiliations
Review

Let's Make White Phosphorus Obsolete

Michael B Geeson et al. ACS Cent Sci. .

Abstract

Industrial and laboratory methods for incorporating phosphorus atoms into molecules within the framework of Green Chemistry are in their infancy. Current practice requires large inputs of energy, involves toxic intermediates, and generates substantial waste. Furthermore, a negligible fraction of phosphorus-containing waste is recycled which in turn contributes to negative environmental impacts, such as eutrophication. Methods that begin to address some of these drawbacks are reviewed, and some key opportunities to be realized by pursuing organophosphorus chemistry under the principles of Green Chemistry are highlighted. Methods used by nature, or in the chemistry of other elements such as silicon, are discussed as model processes for the future of phosphorus in chemical synthesis.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Summary of the synthesis of some key phosphorus-containing compounds and their formal oxidation states. Compounds in the green box are “redox-neutral” products derived from the wet process. Compounds in the red box are derived from P4 and the thermal process. Orange phosphorus atoms are in the +3 oxidation state and are useful intermediates in chemical synthesis.
Figure 2
Figure 2
Procedures for converting alcohols into monophosphate esters using phosphoric acid. NMP, N-methyl-2-pyrrolidone; DMF, N,N-dimethylformamide.
Figure 3
Figure 3
(A) Procedure for triphosphorylation of nucleoside bases using [TBA]3[P3O9]. TBA, tetra-n-butylammonium; MstCl, 2-mesitylenesulfonyl chloride; DABCO, 1,4-diaza-bicyclo-[2.2.2]-oct-ane; PyAOP, see text. (B) Isolation of a triphosphorylating reagent and subsequent reaction with C-, N-, and O-based nucleophiles.
Figure 4
Figure 4
(A) Preparation of formula image from [TBA]3[P3O9] and trichlorosilane and subsequent conversion to phosphorus-containing products. (B) One-pot synthesis of n-octylphosphine from n-octyl chloride and phosphoric acid.
Figure 5
Figure 5
Sankey diagram depicting the global flows of phosphorus in 2011. Numbers refer to phosphorus flows in Mt/year. The values shown are adapted from the work of Scholz which should be consulted for a detailed discussion of assumptions and errors. The numbers have uncertainties of approximately a factor of 2, and up to 5. Thus, the diagram should be treated semiqualitatively.
Scheme 1
Scheme 1. Preparation of PH3, NaH2PO2, and Na2HPO3 (Minor Byproduct)
Scheme 2
Scheme 2. Thermal Disproportionation of Phosphorous Acid to Phosphine and Phosphoric Acid
In brackets: tautomerization of phosphorous acid between the pentavalent and trivalent isomers.
Scheme 3
Scheme 3. Stoichiometric Reductions of Triphenylphosphine Oxide to Triphenylphosphine
Scheme 4
Scheme 4. Biosynthesis of Phosphorus–Carbon Bonds (See Text for Abbreviations)
Scheme 5
Scheme 5. Examples of Redox-Neutral Reactions Using Silicon(IV) Compounds
Scheme 6
Scheme 6. Chlorine-Free Protocol for Processing Germanium; Adapted with permission from AAAS.
See this image and copyright information in PMC

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