专利号:US-6051704-A 优先权日:1996-07-22 标题:Synthesis of macrocyclic tetraamido-N ligands 发明人:GORDON-WYLIE SCOTT W; COLLINS TERRENCE J 权利人:UNIV CARNEGIE MELLON 摘要:New synthetic methods for the preparation of macrocyclic amido-N donor ligands are provided. The primary method of the present invention involves in general only two synthetic steps. In the first step, an α or β amino carboxylic acid is allowed to react with an optimal (approximately stoichiometric) amount of an activated malonate or oxalate derivative with mild heating. Upon completion of the double coupling reaction, hydrolysis of the reaction mixture yields a diamide containing intermediate (a macro linker). In the second step, stoichiometric amounts of a diamine, preferably an orthophenylene diamine, are added to the macro linker intermediate in the presence of a coupling agent and heat. This second double coupling reaction, is allowed to proceed for a period of time sufficient to produce a macrocyclic tetraamido compound. The substituent groups on the α or β amino carboxylic acid, the malonate, and the aryl diamine may all be selectively varied so that the resulting tetraamido macrocycle can be tailored to specific desired end uses. The macrocyclic tetraamide ligand may then be complexed with a metal, such as a transition metal, and preferably the middle and later transition metals, to form a robust chelate complex suitable for catalyzing oxidation reactions.
专利号:US-7060818-B2 优先权日:2003-02-21 标题:Synthesis of macrocyclic tetraamido compounds and new metal insertion process 发明人:HORWITZ COLIN P; GHOSH ANINDYA 权利人:UNIV CARNEGIE MELLON 摘要:An improved method of synthesizing a macrocyclic tetraamido compound includes protecting the amino portion of an amino carboxylic acid to form a protected amino carboxylic acid; exposing the protected amino carboxylic acid to a first solvent, preferably a hydrocarbon solvent, such as toluene or 1,2-dichloroethane, dichloromethane, dibromomethane and 1,2-dibromoethane. The carboxylic acid portion of the protected amino carboxylic acid is then converted to an activated carboxylic acid by one of esterification or acid halide formation, to form a protected amino activated carboxylic acid derivative. The protected amino activated carboxylic acid derivative is reacted with a diamine in the presence of a second solvent, such as THF or ,2-dichloroethane, dichloromethane, dibromomethane and 1,2-dibromoethane, to form a protected diamide diamine intermediate. Following deprotection, the diamide diamine intermediate is reacted with an activated diacid, such as an activated malonate, oxalate or succinate derivative to form the macrocyclic tetraamido compound. The macrocyclic tetraamido compound may further be complexed with a transition metal.
专利号:US-6011152-A 优先权日:1996-07-22 标 题 :Synthesis of macrocyclic tetraamido-N ligands
专利号:WO-2004076425-A1 优先权日:2003-02-21 标题:Improved synthesis of macrocyclic tetraamido compounds and new metal insertion process
专利号:CN-114380681-B 优先权日:2022-01-27 标 题:A kind of synthesis method of 2-(bromomethyl)-2-butylhexanoic acid