Phosphorus–nitrogen compounds. Part 55. The reactions of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazatriene with aliphatic difunctional alcohols, amines, and aminoalcohols. Proton and phosphorus-31 nuclear magnetic resonance spectroscopic studies of the products

A Regioselective Route to New Polytopic Receptors by Diaminolysis of Chlorocyclotriphosphazatriene-Containing Crown Ethers

“…We have developed a new class of functional crowns, derived from hexachlorocyclotriphosphazatriene, which combine the versatile reactivity of chlorocyclophosphazenes with the complexing properties of crown ether ligands . The presence of the polyether crown substituent in 1 enables its supramolecular interactions with the attacking nucleophile that results in a new powerful type of regiocontrol, giving ready access to species which would be very difficult to form according to the rules of classic cyclophosphazene chemistry, substitution pathways of which are dominated by steric, electronic, and thermodynamic effects. , …”

Host−Guest Complex Dependent Regioselectivity in Substitution Reactions of Chlorocyclotriphosphazene-Containing PNP-Crowns with Alkylenediamines

“…To date there have been no reports on the spontaneous formation of ansa derivatives in the reactions of diamines with chlorocyclophosphazenes having available PCl 2 sites. , Spiro-fused derivatives have been obtained exclusively by the reactions of 1,2-diaminoethane with N 3 P 3 Cl 6 and its geminal bis- tert -butylamino- and diphenyltetrachloro derivatives , and by the reactions of 1,3-diaminopropane with N 3 P 3 Cl 6 3,5 and the respective ansa-cyclosubstituted (aminoethyleneoxy) and {[bis(ethylene)oxo]diamino} derivatives. In this paper, we demonstrate that the spiro diaminolysis pattern is not generally valid for all ansa polyether-substituted chlorocyclophosphazenes and can be completely changed (especially marked at lower temperatures, e.g., −25 °C) toward regioselective attack at the chlorine atoms geminal to the ansa arch by the reactions of, for example, 1,2-diaminoethane ( 2a ) and 1,3-diaminopropane ( 2b ) with the monoansa[(oxytetraethyleneoxy]tetrachlorocyclotriphosphazene (PNP-crown, 1 ), previously reported by us …”

Phosphorus–nitrogen compounds. Part 59. Aromatic carbon‐13 NMR spectra of phenyl‐substituted cyclotriphosphazatrienes. Second‐order effects with phosphorus‐31 nuclei

“…The geminal compounds N3P,Ph,Cl,-, (n = 2, 4,6) were prepared by a modified Friedel-Crafts reaction. Experimental details of the preparation of the mono-spiro derivatives of geminal N,P,Ph,CI, are given elsewhere.6 13C NMR spectra were recorded using a JEOL JNM FX-200 spectrometer operating at 50.10 MHz under broad band decoupling conditions.…”