Abstract: | The 2, 2'‐dihydroxybiphenyl derivatives 1d‐f react with phosphorus pentachloride to give the dioxaphosphepinium hexachlorophosphates 3a, 3b , and 17 . The trichloro‐dioxaphosphepins 8a, 8b , and 21 were discussed as intermediates, which were obtained by chlorination of the 6‐chloro‐dioxaphosphepins 7a, 7b , and 20 . The hydrolysis of the dioxaphosphepins leads to the stable, cyclic phosphates 4a, 4b, 9a, 9b, 11a, 11b, 19a, and 19b . The crystal struc‐ture of 4a was determined; two different molecules was observed in the asymmetric unit. |