An efficient catalytic method for the Beckmann rearrangement of ketoximes to amides and aldoximes to nitriles mediated by propylphosphonic anhydride (T3P®)

N-(5-Bromopyridin-2-yl)acetamide

“…For a related structure, see: Loureiro et al (2008). For further synthetic information, see: Augustine et al (2011); Sollogoub et al (2002). Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).…”

“…(1E)-1-(5-Bromopyridin-2-yl)-N-hydroxyethanimine (2 g, 0.0093 mol) was taken in N,N dimethyl formamide (20 ml) at 25-26°C under a nitrogen atmosphere. Propylphosphonic anhydride (0.6 g, 0.00093 mol, 50% solution in ethylacetate) was added at the same temperature (Augustine et al, 2011). The reaction mixture was heated to 100°C for 5 hrs.…”

Organocatalyzed Beckmann rearrangement of cyclohexanone oxime in a microreactor: Kinetic model and product inhibition

“…For example, there are nearly 2 t of ammonium sulfate per ton of CPL produced in this process . To develop green chemistry and process intensification, much effort has been made, such as vapor‐phase Beckmann rearrangement over solid catalysts and liquid‐phase Beckmann rearrangement in solid or organic catalysts . Recently, there have been growing interests in the Beckmann rearrangement with organocatalysts because of mild reaction conditions with much safer and no by‐production of ammonium sulfate.…”

Copper immobilized on aminated ferrite nanoparticles by 2‐aminoethyl dihydrogen phosphate (Fe3O4@AEPH2‐CuII) catalyses the conversion of aldoximes to nitriles

“…Moreover, nitriles as key components of numerous natural products are industrially important for the production of agrochemicals, pharmaceuticals, polymers, dyes and pigments . There are a variety of synthetic routes to nitriles from diverse chemical precursors reported in the literature, including Sandmeyer reaction, ammoxidation of aldehydes, metal‐catalysed cyanation of aryl halides, nucleophilic substitution of alkyl halides with cyanides, oxidation of amines, hydrocyanation of alkenes, Kolbe nitrile synthesis, Rosenmund–von Braun reaction and dehydration of amides and aldoximes . Among these, the dehydration of aldoximes into nitriles is one of the most suitable candidate reactions for clean nitrile synthesis, because of the availability of starting materials and the avoidance of very toxic cyanide ion.…”