
TY  - JOUR
A1  - Byrne, LT 
A1  - Harrowfield, JM 
A1  - Hockless, DCR 
A1  - Peachey, BJ 
A1  - Skelton, BW 
A1  - White, AH 
T1  - Calixarene Phosphorylation: Cation Control of Reaction Pathways
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1993
VL  - 46
IS  - 11
SP  - 1673
EP  - 1683
KW  - 
UR  - https://doi.org/10.1071/CH9931673 
N2  - The hydroxide ion catalysed phosphorylation of p-t- butylcalix [4] arene by diethyl chlorophosphate under heterogeneous conditions shows a marked sensitivity to the nature of the phase transfer catalyst used. Thus, substitution of tetraethylammonium bromide for the tetrabutylammonium bromide prescribed for the synthesis of the calixarene tetraphosphate leads to a major reaction product becoming a bis (phosphate) in which the calixarene binds as a unidentate  ligand to one phosphorus and as a bidentate ligand to the other. An X-ray crystal structure analysis on this new compound shows the calixarene to adopt a somewhat distorted 'cone' conformation with an unusual orientation of one of the t-butyl substituents into the cone cavity. It also reveals that a significant diastereoselectivity must operate in the formation reaction. The only other reaction product detected in this system appears to be the calixarene  tetraphosphate in a partial cone conformation. 
ER  -

