The known methods for the preparation of acylphosphine oxides and polyfluorobenzene-substituted triarylphosphines need to utilize PCl_(3),while the chlorine-free methods are not reported.In this work,we report a chlor...The known methods for the preparation of acylphosphine oxides and polyfluorobenzene-substituted triarylphosphines need to utilize PCl_(3),while the chlorine-free methods are not reported.In this work,we report a chlorine-free method by one-pot three-component reaction of white phosphorus(P_(4)),dilithio reagents,and acyl chlorines or polyfluorobenzenes for the synthesis of biphenyl-based acylphosphine oxides and phosphines.This reaction is green and environmentally friendly compared with the traditional method,because it avoids the use of Cl_(2) and the discharge of a large amount of waste gas and waste acid.These two products have potential applications as photoinitiators in photopolymerization or as organophosphorus ligands in catalytic reactions.展开更多
Reversible Addition Fragmentation chain Transfer(RAFT)polymerization has become a highly versatile technique for the controlled/“living”radical polymerization of a wide range of monomers under various conditions.The...Reversible Addition Fragmentation chain Transfer(RAFT)polymerization has become a highly versatile technique for the controlled/“living”radical polymerization of a wide range of monomers under various conditions.The RAFT polymerization was carried out using a dithiocarboxylate or trithiocarbonate as a Chain Transfer Agent(CTA),which mediates the growing chain radicals via an equilibrium.From both academic and industrial standpoints,it is clearly desirable to develop a RAFT process under mild conditions.Rizzardo,et al and McCormick's group have respectively reported RAFT polymerization using conventional radical initiators at ambient temperature by adjusting the structure of CTA.The RAFT Polymerization initiated byγ-radiation has also reported recently.Quinn,et al have reported the RAFT polymerization under UV radiation using CTA as the source of primary radicals at 42℃,which was well controlled at low conversions(below 20%)but less controlled at higher conversions(over 20%)due to the photolysis of CTA residues under UV radiation.展开更多
基金This work was supported by the Natural Science Foundation of China(Nos.22131001,21725201 and 21890721)the National Key R&D Program of China(No.2021YFF0701600).We thank Prof.Dr.Zhenfeng Xi of Peking University for useful discussions on the manuscript.
文摘The known methods for the preparation of acylphosphine oxides and polyfluorobenzene-substituted triarylphosphines need to utilize PCl_(3),while the chlorine-free methods are not reported.In this work,we report a chlorine-free method by one-pot three-component reaction of white phosphorus(P_(4)),dilithio reagents,and acyl chlorines or polyfluorobenzenes for the synthesis of biphenyl-based acylphosphine oxides and phosphines.This reaction is green and environmentally friendly compared with the traditional method,because it avoids the use of Cl_(2) and the discharge of a large amount of waste gas and waste acid.These two products have potential applications as photoinitiators in photopolymerization or as organophosphorus ligands in catalytic reactions.
文摘Reversible Addition Fragmentation chain Transfer(RAFT)polymerization has become a highly versatile technique for the controlled/“living”radical polymerization of a wide range of monomers under various conditions.The RAFT polymerization was carried out using a dithiocarboxylate or trithiocarbonate as a Chain Transfer Agent(CTA),which mediates the growing chain radicals via an equilibrium.From both academic and industrial standpoints,it is clearly desirable to develop a RAFT process under mild conditions.Rizzardo,et al and McCormick's group have respectively reported RAFT polymerization using conventional radical initiators at ambient temperature by adjusting the structure of CTA.The RAFT Polymerization initiated byγ-radiation has also reported recently.Quinn,et al have reported the RAFT polymerization under UV radiation using CTA as the source of primary radicals at 42℃,which was well controlled at low conversions(below 20%)but less controlled at higher conversions(over 20%)due to the photolysis of CTA residues under UV radiation.
