Patent ID: 6013793
Filing Date: 2000-01-11
Classification: C07D

Abstract:
A process for the preparation of tetraazamacrocycles of the formula: ##STR36## comprising the following steps of the following Scheme: ##STR37## wherein step (a): condensing tetraazacenaphthylene (TETA) with the glyoxal derivative of formula (IV), wherein Y is --OH (glyoxal hydrate) or [--SO.sub.3 --Na.sup.+ ] (Bertagnini's salt), in a water or in water-soluble solvent or a mixture thereof, at a temperature of 0-50.degree. C., in the presence of a stoichiometric amount or slight excess of calcium hydroxide, to give the compound of formula (VI);step (b): condensing the compound of formula (V) with an alkylating agent X--CH.sub.2 --CH.sub.2 --X, wherein X is a halogen or a sulfonic acid reactive derivative, in at least stoichiometric amounts, in the presence of at least 2 moles of a base selected from alkali or alkaline-earth metal carbonates per mol of compound (VI), at a temperature of 25-150.degree. C., to give the compound of formula (VII);step (c): oxidizing the compound of formula (VII) with an oxidizing agent, in water or in a diphasic system of water and an organic solvent, resistant to oxidation, at a temperature of 0-100.degree. C., to give a mixture of oxidated products and thereafter;step (d): hydrolyzing the product of step (c) in acid aqueous solution at a pH lower than 2 or in a basic aqueous solution at a pH higher than 12, at a temperature of 110--200.degree. C., to give the compound of formula (VIII).