One-Pot Synthesis of Tetraazamacrocyclic Complexes from the Arnold Salt

Abstract

We present an improved synthesis of bis(hexafluorophosphate) Arnold salt, which is a synthon of triformylmethane. The salt is shown to be a substrate for the one-pot, aqueous synthesis of macro­cyclic tetraiminato complexes of copper(II) and nickel(II). The synthesis of complexes is a major improvement over the original stepwise procedure, and is characterized by short reaction time, ease of product separation, scalability, and high yields.

Monosulfonated dibenzo-24-crown-8 and its properties

“…Macrocyclic complex 1 was synthesized from the Arnold salt according to a known one-pot procedure. 63 Acetonitrile (ACN) and dichloromethane (DCM) were dried over P 2 O 5 and distilled. Other materials were used as received: dibenzo-24-crown-8 (>98%, TCI Chemicals), tetrabutylammonium methoxide in methanol 20% w/w (Sigma-Aldrich), methyl trifluoromethanesulfonate (≥98%, Sigma-Aldrich), dibutylamine (>99.0%, TCI Chemicals), 4-amino-1-butanol (>98%, TCI Chemicals), ammonium hexafluorophosphate (99.8%, Apollo Scientific), 3,5-bis(trifluoromethyl)phenyl isocyanate (98%, Sigma-Aldrich), and silica gel 60 silanized for column chromatography (0.063–0.200 mm, Merck).…”

“…Dialdehyde 1 63 (1.03 g, 3.38 mmol) was suspended in DCM (100 ml). Methyl triflate (1.10 g, 2.0 eq.)…”