3667-90-1Relevant academic research and scientific papers
Synthesis of Trialkylamines with Extreme Steric Hindrance and Their Decay by a Hofmann-like Elimination Reaction
Banert, Klaus,Hagedorn, Manfred,Heck, Manuel,Hertel, Raphael,Ihle, Andreas,Müller, Ioana,Pester, Tom,Shoker, Tharallah,Rablen, Paul R.
, p. 13630 - 13643 (2020/11/13)
A number of amines with three bulky alkyl groups at the nitrogen, which surpass the steric crowding of triisopropylamine considerably, were prepared by using different synthetic methods. It turned out that treatment of N-chlorodialkylamines with organometallic compounds, for example, Grignard reagents, in the presence of a major excess of tetramethylenediamine offered the most effective access to the target compounds. The limits of this method were also tested. The trialkylamines underwent a dealkylation reaction, depending on the degree of steric stress, even at ambient temperature. Because olefins were formed in this transformation, it showed some similarity with the Hofmann elimination. However, the thermal decay of sterically overcrowded tertiary amines was not promoted by bases. Instead, this reaction was strongly accelerated by protic conditions and even by trace amounts of water. Reaction mechanisms, which were analyzed with the help of quantum chemical calculations, are suggested to explain the experimental results.
PROCESS FOR PREPARING SECONDARY AMINES IN THE LIQUID PHASE
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Paragraph 0102; 0103; 0104, (2013/07/19)
The present application relates to a process for preparing secondary amines by aminating excess primary or secondary alcohols with primary amines in the liquid phase in the presence of copper-comprising catalysts.
