Catalytic Synthesis of Triaryl Phosphates from White Phosphorus

Abstract

Triaryl phosphates were synthesized from white phosphorus and phenols under aerobic conditions and in the presence of iron catalysts and iodine. Full conversion to phosphates was achieved without the use of chlorine, and the reactions do not produce acid waste. Triphenyl phosphate, tritolyl phosphate and tris(2,4-di-tert-butyl)phenyl phosphate were synthesized by this method with high selectivities. Various

From rocks to bioactive compounds: a journey through the global P(v) organophosphorus industry and its sustainability

“…196,197 An interesting procedure showed that phenol derivatives react with P white under aerobic conditions, with the help of iron complexes and iodine to form arylphosphates. 198 White phosphorus can also be functionalized through a radical mechanism by acting as a radical trap: photogenerated carbon radicals can react with P white to afford alkylphosphonic acid aer hydrolysis and oxidation by hydrogen peroxide. 199 A more recent radical reaction reported is the synthesis of tertiary phosphines from alkyl halides and P white using titanium complexes as catalysts.…”

Halogenation of Diphosphorus Complexes

“…In the second step, the subsequent functionalization of this P 4 X 2 moiety was performed by the exchange of the halide substituents with organic groups using alkyl lithium reagents such as n BuLi. An additional application of the halogenation of white phosphorus is its implementation in the catalytic synthesis of triarylphosphates from P 4 and phenols under aerobic conditions and in the presence of different Fe­(III) catalysts and iodine . Here, the reaction of P 4 with I 2 leads to the formation of PI 3 , which is considered to be crucial for the sustainment of this catalytic reaction.…”

Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus

“…In 2011, an efficient Fe-catalyzed method was found by the Kilian group. With the use of Fe­(acac) 3 –I 2 as the catalysts, the air (30–45 mL/min) and white phosphorus solutions (0.34–0.78 mmol of P 4 /h) were introduced into the reaction mixture through needles, making certain the 100% conversion of white phosphorus and synthesis of (ArO) 3 PO with high selectivity (Scheme D) . To the best of our knowledge, the separation of OPCs from the mixtures containing a transition metal proved to be difficult because of their strong coordination ability.…”