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Synthesis of Phosphoric Ethers

#K-1284


Catalytic Synthesis of Phosphoric Ethers from Low-Valence Phosphorus Derivatives

Tech Area / Field

  • CHE-SYN/Basic and Synthetic Chemistry/Chemistry

Status
8 Project completed

Registration date
20.04.2005

Completion date
20.08.2008

Senior Project Manager
Valentine M

Leading Institute
Institute of Organic Catalysis and Electrochemistry, Kazakstan, Almaty

Supporting institutes

  • JSC «Kaustic», Kazakstan, Pavlodar reg., Pavlodar

Collaborators

  • University of Illinois / Department of Natural Resources and Environmental Sciences / Illinois State Geological Survey, USA, IL, Champaign

Project summary

Aim of the project: Elaboration of direct catalytic synthesis of phosphoric ethers from red, white phosphorus, metal phosphides, alcohols and elemental sulfur.

The industrial method of valuable phosphoric ether’s production is based on the process of alkoxylation of high-valence phosphorus derivatives (PCI3, PCI5, POCI3, P2S5). The synthesis is multistep, proceeds under harsh conditions with formation of a considerable amounts of toxic and hard-utilized wastes (hydrogen- and alkyl chloride). Low-valence phosphorus derivatives: red, white phosphorus, metal phosphides (Pn, P4, Cu3P, Zn3P2), are rarely used in synthesis of organophosphorus compounds (OPC) because of their inertness in organic transformations. Some of known organic reactions with their participation pass under harsh conditions, initiating by UV- and radioactive radiation, free radicals, superbasis, halogens. Using of catalysts in organic reactions gives wide possibilities for direct, ecologically safe synthesis of valuable organophosphorus compounds from low-valence phosphorus derivatives.

The transition metal complexes have been used for the first time for activation molecules of phosphorylation agent and organic substrates in our process. The catalytic reactions of the oxidative phosphorylation of elemental phosphorus and metal phosphides flow past under mild conditions (20-80 0С, 104-105 ПА O2) with high velocity and selectivity up to di-, trialkylphosphates and dialkylphosphites. The direction of the reaction depends on the nature of reactants, oxidizer and catalyst. The oxidation by oxygen is efficient. The red phosphorus and metal phosphides are one of the most perspective phosphorylation agents from both ecological and technological point of view.

The project is of applied researches. Expected results of the project are the following:

  • Using of catalysts in oxidative functionalization of low-valence phosphorus derivatives will allow to conduct the synthesis of valuable organophosphorus compounds by a new, ecoefficient way from cheap and accessible raw materials or wastes.
  • Researching of new oxidative Р-О and Р-S coupling reaction’s will expand possibilities of choosing of synthesis optimum condition’s and range of organophosphorus compounds at Pavlodar Chemical Plant.
  • The direct catalytic oxidation of low-valence inorganic phosphorus derivatives will permit to replace an industrial method of phosphoric ethers deriving, based on using of toxic chlorine derivatives of high-valence phosphorus, for "chlorine-free technology "
  • The further application of obtained results will reduce ecological damage caused by hard-utilized wastes of organophosphorus ethers production and oil refining. Utilization of the last once to valuable thiophosphate, by direct oxidative Р-S coupling of low-valence phosphorus derivatives with sulfur, is one of the most actual problems for RK both in fundamental and applied areas.

The introduction of the project will permit the "weapon" experts of Pavlodar Chemical Plant to redirected their activity in scientific research area with further application in obtaining of valuable organophosphorus ethers, using of scientific potential of D.V.Sokolsky Institute of Organic Catalysis and Electrochemistry. The technological experience of the PCP "weapon" experts will promote integration of scientists into world scientific community.

We are planing to work out multifunctional catalysts of new oxidative Р-О and Р-S coupling reactions of red phosphorus, metal phosphide, white phosphorus with aliphatic, aromatic alcohols and elemental sulfur under support of ISTC. It will give the wide perspectives for creation of scientific bases of ecoefficient technologies of valuable OPC.

Foreign collaborator will assist in providing of necessary test supplies for the project staff, in conducting of joint workshops, in preparing of technical reports.

The new catalytic reactions will be investigated by methods of kinetics, volumetric analysis, redox potentiometry, gas chromatography. The initial reactants will be investigated by methods of X-ray powder diffraction analysis, XPE-spectroscopy, the structure of intermediate complexes – by methods of potentiometry, EPR- and UV- spectroscopy, the products will be isolated by method of high-vacuum distillation and will be identified by methods of GC-analysis, IR- and NMR 31P, 13C-spectroscopy. The optimum catalytic systems, oxidizers and phosphorylation agents will be tested on PCP by making of preparative synthesis.


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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.

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