63207-50-1Relevant academic research and scientific papers
Phosphorus in organic synthesis. The tanigawa reaction revisited as a method for converting alcohols to tertiary amines
Froyen, Paul,Skramstad, Jan
, p. 6387 - 6390 (2007/10/03)
Contrary to earlier observations, N-methyl-N- phenylaminotriphenylphosphonium iodide 1 (the Murahashi reagent) does not react with alcohols and primary or secondary amines under mild conditions (80°) to give secondary or tertiary amines. However the reaction can be successfully performed at higher temperatures. A mechanistic scheme implying initial amine exchange between 1 and the added amine leading to the N,N- dimethyl analog 5 is suggested. An improved synthesis where the reactive intermediate 5 is formed in situ from triphenylphosphine, carbon tetrachloride and HNR3R4 is described.
Group Transfer Reactions. - Tetracarbonylferrates from Orthoformic Acid Derivatives and Pentacarbonyliron
Daub, Joerg,Hasenhuendl, Adelheid,Krenkler, Karl P.,Schmetzer, Johannes
, p. 997 - 1015 (2007/10/02)
The nucleophilic leaving group X is transferred from orthoformic acid derivatives HC(NR2)X (X= NR2, OR, CN) to Fe(CO)5.No such reactions were observed between 4 and amide acetals (HCX2NR2) or ortho ester derivatives HCX3 (X= OR, SR).The structures of the transition metal-acyl complexes obtained have been determined by IR and NMR spectra.In the case of the reaction of tris(dimethylamino)methane (3a) with 4 the equilibrium between the resulting amidinium-carbamoyltetracarbonylferrate complex 5a and the starting materials was investigated.The equilibrium is shifted completely in favor of the ionic compound 5a.However, 3a could be isolated by extraction of this solution with an apolar solvent.Alkylation of 5a with triethyloxonium tetrafluoroborate leads to the tetracarbonyliron-carbene complex 13.Reaction of 5a with acrylonitrile or methyl acrylate by addition of both the nucleophile "NR2-" and the electrophile + and subsequent eliminations gives the β-dimethylamino substitution product 18 and 21, respectively.In contrast 3a induces polymerisation of acrylonitrile.
