26487-09-2Relevant academic research and scientific papers
Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
Reeves, Jonathan T.,Malapit, Christian A.,Buono, Frederic G.,Sidhu, Kanwar P.,Marsini, Maurice A.,Sader, C. Avery,Fandrick, Keith R.,Busacca, Carl A.,Senanayake, Chris H.
supporting information, p. 9481 - 9488 (2015/08/11)
An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. (Chemical Equation Presented).
Versatile ruthenium(ii)-catalyzed C-H cyanations of benzamides
Liu, Weiping,Ackermann, Lutz
supporting information, p. 1878 - 1881 (2014/02/14)
Direct cyanations of arenes and heteroarenes bearing only weakly coordinating amides were accomplished using a robust ruthenium(ii) catalyst. The user-friendly C(sp2)-H activation occurred with the assistance of carboxylate with high site-selectivity, excellent functional group tolerance and ample scope.
INVESTIGATIONS ON N,N-DIALKYLBENZAMIDES BY NMR SPECTROSCOPY. PART IV. COMPARISON OF BARRIERS TO ROTATION ABOUT THE AMINE C-N BOND IN ORTHO-SUBSTITUTED N,N-DIMETHYL-AND N,N-DIETHYLBENZAMIDES
Gryf-Keller, Adam,Terpinski, Jacek,Zajaczkowska-Terpinska, Ewa
, p. 429 - 434 (2007/10/02)
The barriers to rotation about the amide C-N bond in a series of ortho-substituted N,N-dimethyl and N,N-diethylbenzamides have been compared.It has been stated that for most of substituents, namely CH3, Cl, Br, I and NO2, the rates of rotation in both series of compounds are identical within the accuracy of measurement (kEt/kMe ca.1).The remaining compounds (F, CN, CH3) show a higher rate of rotation in the series of diethylbenzamides (kEt/kMe ca.1,5).An exception are the OH derivatives in which the internal H-bond is present and because of that the barrier to rotation is lowered and the kEt/kMe ratio raised up to 2.3.
