Catalytic Synthesis of the Esters of Phosphorus Acids from White Phosphorus and Aliphatic or Aromatic Alcohols

Abstract

<p>The various esters of the phosphoric and phosphorous acids have been obtained directly from white phosphorus and aliphatic (or aromatic) alcohols under aerobic atmosphere in the presence of the CuX<sub>2</sub> or FeX<sub>3</sub> (X = Cl, NO<sub>3</sub>, C<sub>3</sub>H<sub>7</sub>CO<sub>2</sub>) salts. Irrespective of the variable nature of the used alcohols and catalysts, trialkyl(aryl) phosphates and dialkyl phosphites are a major products, whereas trialkyl(aryl) phosphites and dialkyl phosphates are a minor products of the phosphorylation process. Thanks to the presence of catalysts, the possible side reaction route of the radical chain oxidation of white phosphorus by oxygen to phosphorus oxides has been precluded. A comparison between the catalytic properties of CuX<sub>2</sub> and FeX<sub>3</sub> has been done. Although both of them have been found an efficient catalysts for the syntheses, the Cu(II) salts are active at 50-65 °C, whereas the Fe(III) based catalytic systems become competitive in terms of catalytic efficiency when reaction is carried out at 70-90 °C. Aromatic alcohols are characterised by less reactivity in this catalytic reaction as compared with an aliphatic ones. The same coordinative redox mechanism of the oxidative P-O coupling of P<sub>4 </sub>to ROH in the presence of both Cu(II) and Fe(III) catalysts has been proposed. Relevant steps of the catalytic cycle including the complexation of both white phosphorus and alcohol molecules to metal ion, the reduction of catalyst by white phosphorus, and the oxidation of reduced form of catalyst by oxygen have been also considered.</p>

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

“…9 In 2005, the Abdreimova group reported the FeCl 3 −I 2catalyzed reaction of phenol with P 4 to produce (PhO) 3 PO with some interesting results (Scheme 1C). 10 In 2011, an efficient Fe-catalyzed method was found by the Kilian group.…”

“…In 1992, Budnikova investigated the phosphorylation of ArOH with P 4 by an electrochemical method to give triphenyl phosphate in 82% yield (Scheme B) . In 2005, the Abdreimova group reported the FeCl 3 –I 2 -catalyzed reaction of phenol with P 4 to produce (PhO) 3 PO with some interesting results (Scheme C) . In 2011, an efficient Fe-catalyzed method was found by the Kilian group.…”

Direct Synthesis of Dialkylphosphites from White Phosphorus

“…With the use of PdCl 2 as a catalyst and NaNO 2 as an oxidant, they prepared ( n ‐BuO) 2 P(O)H in 52% yield by oxidative P−O coupling of P 4 with n‐butanol in 2000 [14] . In 2002, they used FeCl 3 as a catalyst and oxygen bubbling to produce ( n ‐BuO) 2 P(O)H in 35% yield [15] . It's a pity that all the methods mentioned above gave DAPIs in very low yields.…”

“…[13] Abdreimova et al had studied on the direct transformation of P 4 into DAPIs for many years. [14][15][16] With the use of PdCl 2 as a catalyst and NaNO 2 as an oxidant, they prepared (n-BuO) 2 P(O)H in 52% yield by oxidative PÀ O coupling of P 4 with n-butanol in 2000. [14] In 2002, they used FeCl 3 as a catalyst and oxygen bubbling to produce (n-BuO) 2 P(O)H in 35% yield.…”

“…[14] In 2002, they used FeCl 3 as a catalyst and oxygen bubbling to produce (n-BuO) 2 P(O)H in 35% yield. [15] It's a pity that all the methods mentioned above gave DAPIs in very low yields. In 2007, Abdreimova reported an improved Cucatalyzed method for the synthesis of DAPIs.…”