Synthesis of Phosphoric Ethers
Catalytic Synthesis of Phosphoric Ethers from Low-Valence Phosphorus Derivatives
Tech Area / Field
- CHE-SYN/Basic and Synthetic Chemistry/Chemistry
8 Project completed
Senior Project Manager
Genisaretskaya S V
Institute of Organic Catalysis and Electrochemistry, Kazakstan, Almaty
- JSC «Kaustic», Kazakstan, Pavlodar reg., Pavlodar
- Natural Resources Canada, Canada, Varennes\nUniversity of Illinois / Department of Natural Resources and Environmental Sciences / Illinois State Geological Survey, USA, IL, Champaign
Project summaryThe proposed project “Catalytic synthesis of phosphoric ethers from low-valence phosphorus derivatives” is aimed at developing a catalytic syntheses of phosphoric ethers from red or white phosphorus, metal phosphides, alcohols and elemental sulfur.
These ethers are a valuable organoelement compounds which are broadly employed as extractors of rare and radioactive metals, flame-retardants for plastic materials, additives for lubricants, the means for plants defence in agricultural industry, etc. The industrial methods for their production are based on the alkoxylation of high-valence phosphorus derivatives (PCI3, PCI5, POCI3, P2S5) under harsh conditions. These multistep syntheses are and accompanied by formation of a considerable amounts of a toxic and hard-utilized wastes (HCl, RCl, H2S). The low-valence phosphorus derivatives such as red and white phosphorus, metal phosphides (Pn, P4, Cu3P, Zn3P2) are rarely used in synthesis of organophosphorus compounds (OPC) because of their inertness in organic transformations. The most known organic reactions of elemental phosphorus and metal phosphides are initiated by UV- and radioactive radiation, free radicals, superbases or halogens. The scientists at the Institute of Organic Catalysis and Electrochemistry in Almaty (Kazakhstan) have first proposed an original catalytic method for the oxidative functionalisation of these phosphorylating agents under mild reaction conditions. The new catalytic protocol allows to remove most wastes, to incorporate into the process all the advantages of a homogeneous catalytic reaction, and to elaborate a new “one-pot” catalytic syntheses of a valuable organophosphorus chemicals directly from available products of the phosphorus and oil industries. Particularly, the next catalytic processes will be developed in the project:
- The oxidative Р-О coupling of elemental phosphorus or metal phosphides to alcohol to obtain dialkylphosphites P(O)H(OR)2 and trialkylphosphates P(O)(OR)3;
- The double oxidative Р-О and Р-S coupling of elemental phosphorus or metal phosphides to alcohol and sulfur to obtain trialkylthionphosphates P(S)(OR)3.
The catalytic reactions will be studied by methods of kinetics, volumetry, redox potentiometry, gas chromatography. The initial metal phosphides and red phosphorus will be investigated by methods of X-ray powder diffraction analysis and XPE-spectroscopy. The state of transition metal catalysts will be determined by methods of potentiometry, EPR- and UV- spectroscopy. Organophosphorus products will be isolated by high-vacuum distillation and identified by methods of GC-analysis, IR- and NMR 31P, 13C-spectroscopy.
The catalytic syntheses conditions will be optimized to test them in enlarged scale at JSC “Kaustik” in Pavlodar (Kazakhstan). The project will permit the "weapon" experts of JSC “Kaustik” to redirect their activity to a civil research area. Their technological experience together with scientific potential of the IOCE participants will allow to develop a new generation of innovative technologies of organoelement derivatives from a low-valence phosphorus derivatives, alcohol and sulfur.
The International Science and Technology Center (ISTC) is an intergovernmental organization connecting scientists from Kazakhstan, Armenia, Tajikistan, Kyrgyzstan, and Georgia with their peers and research organizations in the EU, Japan, Republic of Korea, Norway and the United States.
ISTC facilitates international science projects and assists the global scientific and business community to source and engage with CIS and Georgian institutes that develop or possess an excellence of scientific know-how.