Grafting of tetraazamacrocycles on the surface of phosphorus-containing dendrimers

Three types of tetraazamacrocycles (1,4,8,11-tetraazacyclotetradecane, 1,4, 8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane-5,7-di one) are grafted on the surface of phosphorus-containing dendrimers possess ing P(S)Cl-2 end groups (for generations 1 and 3: this corresponds to three and twelve macrocycles, respectively) and on the model compound PhCH=NN(Me )P(S)Cl-2. Depending on the nature of the macrocycle, the reaction induces the formation of five-membered rings (diazaphospholanes) or of six-membered rings (diazaphosphorinanes). The structure of the adducts is deduced from C-13 NMR spectra and from X-ray diffraction studies of the reaction product s (8, 9, 10) of the model compound.