90109-25-4Relevant academic research and scientific papers
(2-Ethylhexyl)sodium: A Hexane-Soluble Reagent for Br/Na-Exchanges and Directed Metalations in Continuous Flow
Annapureddy, Rajasekar Reddy,Harenberg, Johannes H.,Hoefer, Carla A.,Knochel, Paul,Weidmann, Niels,Wiegand, Alexander J.
, p. 14296 - 14301 (2021)
We report the on-demand generation of hexane-soluble (2-ethylhexyl)sodium (1) from 3-(chloromethyl)heptane (2) using a sodium-packed-bed reactor under continuous flow conditions. Thus, the resulting solution of 1 is free of elemental sodium and therefore suited for a range of synthetic applications. This new procedure avoids the storage of an alkylsodium and limits the handling of metallic sodium to a minimum. (2-Ethylhexyl)sodium (1) proved to be a very useful reagent and undergoes in-line Br/Na-exchanges as well as directed sodiations. The resulting arylsodium intermediates are subsequently trapped in batch with various electrophiles such as ketones, aldehydes, Weinreb-amides, imines, allyl bromides, disulfides and alkyl iodides. A reaction scale-up of the Br/Na-exchange using an in-line electrophile quench was also reported.
Preparation of Functionalized Aryl, Heteroaryl, and Benzylic Potassium Organometallics Using Potassium Diisopropylamide in Continuous Flow
Harenberg, Johannes H.,Knochel, Paul,Weidmann, Niels
supporting information, p. 12321 - 12325 (2020/05/04)
We report the preparation of lithium-salt-free KDA (potassium diisopropylamide; 0.6 m in hexane) complexed with TMEDA (N,N,N′,N′-tetramethylethylenediamine) and its use for the flow-metalation of (hetero)arenes between ?78 °C and 25 °C with reaction times between 0.2 s and 24 s and a combined flow rate of 10 mL min?1 using a commercial flow setup. The resulting potassium organometallics react instantaneously with various electrophiles, such as ketones, aldehydes, alkyl and allylic halides, disulfides, Weinreb amides, and Me3SiCl, affording functionalized (hetero)arenes in high yields. This flow procedure is successfully extended to the lateral metalation of methyl-substituted arenes and heteroaromatics, resulting in the formation of various benzylic potassium organometallics. A metalation scale-up was possible without further optimization.
Sulfur Analogues of Psychotomimetic Agents. 3. Ethyl Homologues of Mescaline and Their Monothio Analogues
Jacob, Peyton,Shulgin, Alexander T.
, p. 881 - 888 (2007/10/02)
All possible monothio analogues of the mono-, di-, and triethoxy homologues of mescaline have been synthesized and pharmacologically evaluated in man.Modifications at the ring position para to the ethylamine chain, either with a sulfur atom, a longer alkyl chain, or both, lead to compounds of high central nervous system activity.The 4-n-propoxy and 4-n-butoxy homologues and their corresponding 4-thio analogues were also synthesized and pharmacologically evaluated.The propyl homologues retain high potency, but a butyl group (either with or without a sulfur atom) leads to a decrease in activity.The m-ethyl or m-thio analogues retain some central action but the diethoxy and especially the triethoxy homologues are relatively inactive as psychotomimetic drugs.
