Three types of tetraazamacrocycles (1,4,8,11‐tetraazacyclotetradecane, 1,4,8,12‐tetraazacyclopentadecane, and 1,4,8,11‐tetraazacyclotetradecane‐5,7‐dione) are grafted on the surface of phosphorus‐containing dendrimers possessing P(S)Cl2 end groups (for generations 1 and 3: this corresponds to three and twelve macrocycles, respectively) and on the model compound PhCHNN(Me)P(S)Cl2. 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 13C NMR spectra and from X‐ray diffraction studies of the reaction products (8, 9, 10) of the model compound.
Many types of tri- and tetracoordinated phosphorus derivatives
have been grafted on the surface
of dendrimers, starting from aldehyde terminal functions.
Depending on the solubility of the
resulting phosphorylated dendrimers, these experiments have been
carried out on generation 1
(six end groups) for phosphate- (4-[G1]),
phosphinite- (6-[G1]), and ylide-terminated
(11-[G1])
dendrimers and up to generation 5 (96 end groups) for aminophosphate-
(8-[G1],
8-[G5]),
aminophosphite (10-[G1],
10-[G5]), and functionalized
phosphonate-terminated
(14-[G1]−14-[G5],
15-[G1], 15-[G5],
17-[G1], 19-[G1],
19-[G5]) dendrimers. Most of the
phosphonate-terminated
dendrimers present an unexpected long-range phosphorus−phosphorus
coupling constant through
seven bonds (3.8 < 7
J
PP < 4.5
Hz).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.