2905-56-8Relevant articles and documents
The scale-up of continuous biphasic liquid/liquid reactions under super-heating conditions: Methodology and reactor design
Mandrelli, Francesca,Buco, Alessia,Piccioni, Lorenzo,Renner, Florian,Guelat, Bertrand,Martin, Benjamin,Schenkel, Berthold,Venturoni, Francesco
, p. 1425 - 1430 (2017)
Biphasic liquid/liquid reactions are commonplace, however their scale-up under super-heating conditions is not. Even more challenging efforts have to be expected in the case of a large scale continuous production process, which also includes the development at a lab scale, the selection and design of the continuous reaction equipment. However, by running chemistry above the boiling point of the solvent, the solvent selection can be widened to include green solvents and continuous processing guarantees a limited and safe footprint. Herein is reported a systematic methodology for the development and scale-up of a biphasic reaction under super-heating conditions, as well as the design of a continuous reactor column suitable for handling such conditions. Taking the alkylation of benzylamine with 1,5-dibromopentane as a model reaction, kinetic determination and fluid dynamic characterization of the biphasic media have been instrumental for a successful scale-up concept which was proven in a custom-made hastelloy reactor column.
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Paden,Adkins
, p. 2487,2493 (1935)
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Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
Bera, Jitendra K.,Pandey, Pragati
supporting information, p. 9204 - 9207 (2021/09/20)
A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
, p. 2059 - 2067 (2021/09/02)
Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
Manganese-Catalyzed Hydroborations with Broad Scope
Ghosh, Pradip,Jacobi von Wangelin, Axel
supporting information, p. 16035 - 16043 (2021/06/16)
Reductive transformations of easily available oxidized matter are at the heart of synthetic manipulation and chemical valorization. The applications of catalytic hydrofunctionalization benefit from the use of liquid reducing agents and operationally facile setups. Metal-catalyzed hydroborations provide a highly prolific platform for reductive valorizations of stable C=X electrophiles. Here, we report an especially facile, broad-scope reduction of various functions including carbonyls, carboxylates, pyridines, carbodiimides, and carbonates under very mild conditions with the inexpensive pre-catalyst Mn(hmds)2. The reaction could be successfully applied to depolymerizations.
