Green Synthesis of Triaryl Phosphates with POCl3 in Water

Abstract The facile synthesis of triaryl phosphates by using POCl 3 and phenols under mild conditions is a great challenge for both chemical industry and organic chemistry. Especially for the reaction of functionalized phosphorus oxychloride in water, which has long been considered impossible due to its quickly hydrolysis, the fact that makes phosphorus oxychloride serve as a type of popular starting material commonly appeared in organic solvents. Herein, a feed‐controlled substitution reaction with POCl 3 in water was investigated and 97% isolated yield of triphenyl phosphate (TPP) was obtained on the kilogram scale. A broad scope of triaryl phosphates can be prepared in good yields under mild conditions without using any catalysts. The presence of appropriate amount of water could significantly promote the reaction efficiency.