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New "chlorine free" technology of organophosphorus compounds based on catalytic reaction of elemental phosphorus


Foreseen Results

To develop a chlorine free technology for the synthesis of organophosphorus compounds based on catalytic activation and functionalization of white phosphorus in the presence of organic substrates.
White phosphorus is widely used precursor for the synthesis of many useful organophosphorus compounds. In most instances, this important multistep synthesis requires at its initial stage the conversion of elemental phosphorus to phosphorus chlorides. The technology which is currently used in the industrial plants of the EU, CCE and NIS countries, for the synthesis of these chemicals, is largely based on the direct oxidation of white phosphorus by chlorine, followed by phosphorylation of the phosphorus chloride by the appropriate organic substrate. Evolution of hydrogen chloride accompanies this latter reaction. The present methods of air purification employed in the industrial plants based on this technology to produce organophosphorus derivatives, do not secure the complete removal of both chlorine and hydrogen chloride from the productive cycle.
As a consequence, this latter step causes the emission of a large amount of hydrogen chloride (and chlorine) into the atmosphere with consequent serious environmental problems.
Our project is aimed to develop a new generation of organophosphorus derivatives which could be synthesized through an innovative and environmentally acceptable "chlorine free" technology based on the catalytic synthesis of the organophosphorus compounds from white phosphorus and organic substrates mediated by transition metal complexes.
The milestone of this project stands on the recent discovery from the Kazakh partner of the project of the feasibility of the catalytic oxidative phosphorylation of alcohols and amines by elemental phosphorus. The development of the joint project will lead this "chlorine free" approach to the synthesis of several organophosphorus derivatives, such as symmetric and asymmetric trialkylphosphates, dialkylphosphites, trioxyalkylphosphinoxides, triamidophosphazoalkanes etc. Most of these compounds are broadly employed in different technological areas (extractors of rare and radioactive elements,inhibitors of metal corrosion and polymer burning, additives to combustible-lubricating materials, brake-liquids, bioactive substances for further elaboration in pharmaceutical and agricultural industries, etc), and are produced in tons amount in industrial plants in both EU and CCE/NIS countries.
Clearly, the elimination of chlorine from the manufacturing processes employed in the synthesis of such organophosphorus chemicals would simplify not only the production processes, but more importantly, would allow one to achieve a cleaner technology with a reduced environmental impact.
The latter question is of outmost interest for all the country participating to the proposal and is of paramount importance for Kazakhstan which is the world largest producer of elemental phosphorus, a raw chemical which is so far used only for the production of phosphorus chlorides and oxides.

Funding Scheme

CSC - Cost-sharing contracts


Via Jacopo Nardi 39
50132 Firenze

Participants (3)

Route De Narbonne 205
31077 Toulouse
Institute of Organic Catalysis and Electrochemistry
142,Kunaev Street 142
480100 Almaty
Institute of Theoretical Physics and Astronomy - Lithuanian Academy of Sciences
12,A. Gostauto 12
2600 Vilnius