4257-83-4Relevant articles and documents
Rearrangement of Benzylic Trichloroacetimidates to Benzylic Trichloroacetamides
Adhikari, Arijit A.,Suzuki, Tamie,Gilbert, Reesheda T.,Linaburg, Matthew R.,Chisholm, John D.
, p. 3982 - 3989 (2017/04/11)
The rearrangement of allylic trichloroacetimidates is a well-known transformation, but the corresponding rearrangement of benzylic trichloroacetimidates has not been explored as a method for the synthesis of benzylic amines. Conditions that provide the tr
Hafnium-catalyzed direct amide formation at room temperature
Lundberg, Helena,Adolfsson, Hans
, p. 3271 - 3277 (2015/06/16)
Herein, the first example of a metal-catalyzed protocol for direct amidation of nonactivated carboxylic acids at ambient temperature (26 °C) is presented. The mild reaction conditions give rise to high yields of a range of amides in reaction times as short as 90 min, employing a commercial hafnium complex, [Hf(Cp)2Cl2], as catalyst. Amino acids are transformed into their corresponding amides without racemization, and the catalyst displays full selectivity for the amidation of carboxylic acids over esters. Electronic properties of the carboxylic acids were found to have a strong influence on the rate of the amidation reaction, and the need for a balanced amount of molecular sieves was observed to be highly important for optimal reaction outcome.
Kinetics and mechanism of aminolysis of aliphatic esters in aprotic solvents
Talvik, Agu-Tonis,Tuulmets, Ants,Vaino, Evi
, p. 747 - 750 (2007/10/03)
Kinetic studies were carried out on the aminolysis reactions of substituted aliphatic esters in a variety of aprotic solvents. The reaction rate is strongly affected by inductive and steric effects of substituents in the acyl group, rising more than 104-fold from cyanoacetate to trifluoroacetate. The quantitative treatment of solvent effects revealed a rate decrease by the polarity and π-basicity of the solvents, and also an accelerating effect of the polarizability of solvents. Cyclic transition states were assumed for both the first and second-order (in amine) reactions. Copyright