SYNTHESIS OF NEW PHOSPHORUS CONTAINING MACROCYLES

Abstract

The reaction of 1,2,2,6,6-tetramethylpiperidin-4-ol 1 with PCl₃ gives the phosphorous acid monoester dichloride 2. This compound forms the macrocycles 4 and 6, respectively, in a (2 + 2) cyclocondensation with the bisphenols 3 and 5. Macrocycle 6 could be oxidized to the phosphate macrocycle 7. In the reaction of 6 with sulfur the thiophosphate macrocycle 8 was obtained. A multi-step one-pot reaction of bisphenol 5 with PCl₃, leads to the phosphorus containing out, out-cryptand 9 and in, out-cryptand 10. The in-phosphorus in cryptand 10 showed an approximately 3000 times lower oxidation rate than the out-phosphorus in the reaction with cumenehydroperoxide.

Key Words:

• Macrocycles
• cryptands
• phosphates
• phosphates
• thiophosphates
• piperidines