24949-34-6Relevant academic research and scientific papers
ON THE MECHANISM OF THE DIAZIRINE EXCHANGE REACTION WITH AZIDE ANION
Bainbridge, Kathleen E.,Dailey, William P.
, p. 4901 - 4904 (1989)
Treatment of isotopically labeled bromophenyldiazirine containing one 15N atom with azide ion produces benzonitrile which contains 50percent 15N.This suggests that N-azidodiazirines are intermediates in the reaction.Ab initio calculations predict that N-azidodiazirines will have a very low barrier to decomposition to nitrile and two molecules of nitrogen.
Oxadiazolone-Enabled Synthesis of Primary Azaaromatic Amines
Yu, Xiaolong,Chen, Kehao,Yang, Fan,Zha, Shanke,Zhu, Jin
supporting information, p. 5412 - 5415 (2016/11/06)
Despite their tremendous synthetic and pharmaceutical utility, primary azaaromatic amines remain elusive for access based on a generally applicable C-H functionalization strategy. An oxadiazolone-enabled approach is reported for convenient entry into N-unsubstituted 1-aminoisoquinolines through Co(III)-catalyzed redox-neutral, step-, atom-, and purification-economic C-H functionalization with alkynes. A 15N labeling experiment reveals the effectiveness of both oxadiazolone N atoms as directing sites. The installed primary amine can be harnessed as a synthetically useful handle for attachment of divergent appendages.
An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine
V?r?s, Attila,Mucsi, Zoltn,Ban, Zoltn,Timri, Gza,Hermecz, Istvn,Mizsey, Pter,Finta, Zoltn
, p. 8036 - 8047 (2015/01/08)
The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.
A nitridoniobium(V) reagent that effects acid chloride to organic nitrile conversion: Synthesis via heterodinuclear (Nb/Mo) dinitrogen cleavage, mechanistic insights, and recycling
Figueroa, Joshua S.,Piro, Nicholas A.,Clough, Christopher R.,Cummins, Christopher C.
, p. 940 - 950 (2007/10/03)
The transformation of acid chlorides (RC(O)Cl) to organic nitriles (RC≡N) by the terminal niobium nitride anion [N≡Nb(N[Np]Ar) 3]- ([1a-N]-, where Np = neopentyl and Ar = 3,5-Me2C6H3) via i
Zirconium-mediated conversion of amides to nitriles: A surprising additive effect
Ruck, Rebecca T.,Bergman, Robert G.
, p. 5375 - 5377 (2007/10/03)
Chloride coordination is the key: Dimethylzirconocene reacts with amides to form methylzirconium amide complexes. On heating, in the presence of a chloride source, these compounds are converted into N-acylimidozirconocene complexes that react intramolecularly to form the corresponding nitrile compounds (see scheme; Cp = C5H5). Mechanistic studies reveal that chloride coordination to zirconium is required for this transformation to occur.
