| Autor: |
Zhai F; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States., Xin T; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States., Geeson MB; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States., Cummins CC; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
ACS central science [ACS Cent Sci] 2022 Mar 23; Vol. 8 (3), pp. 332-339. Date of Electronic Publication: 2022 Feb 14. |
| DOI: |
10.1021/acscentsci.1c01381 |
| Abstrakt: |
In pursuit of a more sustainable production of phosphorous acid (H 3 PO 3 ), a versatile chemical with phosphorus in the +3 oxidation state, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO 3 2- ). Using potassium hydride as the hydride source, sodium trimetaphosphate (Na 3 P 3 O 9 ), triphosphate (Na 5 P 3 O 10 ), pyrophosphate (Na 4 P 2 O 7 ), fluorophosphate (Na 2 PO 3 F), and polyphosphate ("(NaPO 3 ) n ") engendered phosphite in optimized yields of 44, 58, 44, 84, and 55% based on total P content, respectively. Formation of overreduced products including hypophosphite (H 2 PO 2 - ) was identified as a competing process, and mechanistic investigations revealed that hydride attack on in-situ-generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method was easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P 4 ) as a high-energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate was found to be a viable starting material for the production of phosphite. These results demonstrate the possibility of accessing reduced phosphorus compounds in a more sustainable manner and, more importantly, a means to close the modern phosphorus cycle.
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.) |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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