Improved Richman-Atkins syntheses of cyclic polyamines particularly 1,4,7-Triazacyclononane (tacn) and 1,4,7-Triazacyclodecane (tacd), with the aid of cation-exchange in purification and isolation

Abstract

Die Tri‐N‐tosyl‐Derivate (VIa) und (VIb) der Titelverbindungen werden jeweils nach zwei Methoden dargestellt: Kondensation des Tri‐N‐tosyl‐diethylentriamins (I) mit den Ditosylaten (IIa) bzw. (IIb) und Kondensation des Bis‐(tosyloxyeth′yl)‐tosylamids (IV) mit den Di‐N‐tosyl‐alkylendi‐ aminen (Va) bzw. (Vb) [im Falle der Kondensation von (IV) mit (Va) entstehen neben (VIa) höhere Kondensationsprodukte in wechselnden Mengen].

Titanium Triamidotriamine Compounds: Syntheses, Structures and Redox Properties

“…The NMR spectra of H 3 N 3-F [9]N 3 and H 3 N 3 [11]N 3 reveal C 3v and C 2v symmetry, respectively, compatible with fast nitrogen inversion of the macrocyclic amines. On the other hand, in the proton spectra of 3 and 4 the macrocyclic resonances are split into two groups that were identified by NOE difference experiments as the protons pointing towards the SiMe 2 pendant arm groups (H syn ) and opposite to them (H anti ).…”

“…The reaction sequence used to synthesize 1,4,7- [11]N 3 ) and their sodium derivatives Na 3 N 3-F [9]N 3 (THF) 2 (3) and Na 3 N 3 [11]N 3 (THF) 2 (4) is presented in Scheme 1. H 3 N 3-F - [9]N 3 (1) and H 3 N 3 [11]N 3 (2) were obtained in quantitative yields from the corresponding triazamacrocycle trihydrochloride derivatives.…”

“…H 3 N 3-F - [9]N 3 (1) and H 3 N 3 [11]N 3 (2) were obtained in quantitative yields from the corresponding triazamacrocycle trihydrochloride derivatives. [11,12] (4) were also isolated in quantitative yields from THF from the reaction of 1 and 2 with NaH, respectively.…”

“…All titanium compounds display distorted trigonal prismatic geometries where the metal is coordinated to the six nitrogen donors. Fluxional processes that convert the conformations of the five-and six-membered metallacycles and the Δ and Λ enantiomers of [Ti{N 3 [11] placed tacn with triazacycloundecane (tacu). Although this goal has not been attained, we describe here the syntheses and characterisation of the new ligand precursors together with their sodium, Ti III and Ti IV derivatives.…”

N-Tosyl-8-azaspiro[4.5]deca-1,3-diene

“…The piperidine ring has a chair conformation. (Searle & Geue, 1984) with sodium cyclopentadienide in hexamethylene phosphoramide (Halterman, Vollhardt, Welker, B1/iser & Brse, 1987).…”