1111241-70-3Relevant articles and documents
METHOD FOR CONTINUOUSLY PRODUCING α,β-UNSATURATED CARBOXYLIC ACID SALT
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Paragraph 0061-0062, (2021/04/02)
To provide a means for producing an α,β-unsaturated carboxylic acid salt with excellent reaction efficiency.SOLUTION: A method for continuously producing an α,β-unsaturated carboxylic acid salt includes: a step (1) to obtain a metal lactone compound by continuously circulating a transition metal complex through a first reactor, continuously supplying an alkene and carbon dioxide to the first reactor, and making the transition metal complex, the alkene, and the carbon dioxide react with one another; and a step (2) to make a base act on the metal lactone compound by continuously supplying the metal lactone compound continuously drawn out from the first reactor and the base to a second reactor set on the downstream of the first reactor, in which a ratio (A) of a supply amount of the carbon dioxide (mmol/minute) to a supply amount of the transition metal complex (mmol/minute) in the step (1) is 1 or less.SELECTED DRAWING: Figure 1
An efficient method for the selective iridium-catalyzed monoalkylation of (hetero)aromatic amines with primary alcohols
Blank, Benoit,Madalska, Martyna,Kempe, Rhett
supporting information; experimental part, p. 749 - 758 (2009/04/10)
An efficient multi-gram scale synthesis protocol of a variety of P,N ligands is described. The synthesis is achieved in a two-step reaction. First, the amine is deprotonated and subsequently the chlorophosphine is added to yield the corresponding P,N ligand. Deprotonation of the amine is normally achieved with n-BuLi at low temperature, but for the preparation of ligands with a 2,2′-dipyridylamino backbone and phosphines with a high steric demand KH has to be employed in combination with reaction temperatures of 110°C for the salt metathesis step. The reaction of two equivalents of a selected P,N ligand with one equivalent of the iridium complex [IrCl(cod)]2 (cod=1,5-cyclooctadiene) affords P,N ligand-coordinated iridium complexes in quantitative yield. X-Ray single crystal structure analysis of one of these complexes reveals a monomeric five-coordinated structure in the solid state. The iridium complexes were used to form catalysts for the N-alkylation of aromatic amines with alcohols. The catalyst system was optimized by studying 8 different P,N ligands, 9 different solvents and 14 different bases. Systematic variation of the substrate to base and the amine to alcohol ratios as well as the catalyst loading led to optimized catalytic reaction conditions. The substrate scope of the developed catalytic protocol was shown by synthesizing 20 different amines of which 12 could be obtained in isolated yields higher than 90%. A new efficient catalyst system for the selective monoalkylation of primary aromatic and heteroaromatic amines with primary aromatic, heteroaromatic as well as aliphatic alcohols has been established. The reaction proceeds with rather moderate catalyst loadings.
