10024-89-2Relevant articles and documents
Selenoxide elimination triggers enamine hydrolysis to primary and secondary amines: A combined experimental and theoretical investigation
Bortoli, Marco,Gianoncelli, Alessandra,Ongaro, Alberto,Orian, Laura,Oselladore, Erika,Ribaudo, Giovanni,Zagotto, Giuseppe
, (2021)
We discuss a novel selenium-based reaction mechanism consisting in a selenoxide elimination-triggered enamine hydrolysis. This one-pot model reaction was studied for a set of substrates. Under oxidative conditions, we observed and characterized the formation of primary and secondary amines as elimination products of such compounds, paving the way for a novel strategy to selectively release bioactive molecules. The underlying mechanism was investigated using NMR, mass spectrometry and density functional theory (DFT).
A New Reagent for the Selective, High-Yield N-Dealkylation of Tertiary Amines: Improved Syntheses of Naltrexone and Nalbuphine
Olofson, R. A.,Martz, Jonathan T.,Senet, Jean-Pierre,Piteau, Marc,Malfroot, Thierry
, p. 2081 - 2082 (1984)
Secondary amine hydrochlorides are obtained in high yield by reaction of tertiary amines with α-chloroethyl chloroformate followed by warming the intermediate carbamate in methanol.
Metal-Free Synthesis of Heteroaryl Amines or Their Hydrochlorides via an External-Base-Free and Solvent-Free C-N Coupling Protocol
Fan, Guang-Gao,Jiang, Bo-Wen,Sang, Wei,Cheng, Hua,Zhang, Rui,Yu, Bao-Yi,Yuan, Ye,Chen, Cheng,Verpoort, Francis
, p. 14627 - 14639 (2021/11/01)
Herein, a metal-free and solvent-free protocol was developed for the C-N coupling of heteroaryl halides and amines, which afforded numerous heteroaryl amines or their hydrochlorides without any external base. Further investigations elucidated that the basicity of amines and specific interactions derived from the X-ray crystallography analysis of 3j′·HCl played pivotal roles in the reactions. Moreover, this protocol was scalable to gram scales and applicable to drug molecules, which demonstrated its practical value for further applications.
Metal – organic hybrids of tin(IV) with tuneable band gap: Synthesis, spectral, single crystal X-ray structural, BVS and CSM analysis of morpholinium hexahalostannate(IV)
Rajaraman, Thangarasu,Ramalingam, Kuppukkannu
, (2020/05/29)
Self assembled organic - inorganic hybrid materials such as morpholinium hexachlorostannate(IV) (3) and morpholinium hexabromostannate(IV) (4) have been synthesised from morpholinium chloride (1) and morpholinium bromide (2) at room temperature. The hybrids were characterized by elemental analysis, IR, NMR, TG-DTA, DRS and PL spectroscopy and single crystal X-ray diffraction. IR and NMR spectral data of (3) and (4) show very little changes compared to their parent compounds (1) and (2). However, the = NH2 + proton signal of the bromide hybrid (4), shows a relatively lower δ value due to extensive hydrogen bonding compared to its chloride analogue (3). Thermal analysis confirmed the proposed formulae of the compounds. Optical absorption measurements showed 3.80 and 2.60 eV as band gaps for (3) and (4) respectively at room temperature implying that the band gaps can be easily tuned by altering the halide ion. Single crystal X-ray structures of compounds (3) and (4) revealed extensive hydrogen bonded interactions between the morpholinium cation and the SnCl6 2? and SnBr6 2? anions in (3) and (4). In (4), two molecules of morpholinium bromide co-crystallized with the hybrid. BVS calculations performed on SnCl6 2? and SnBr6 2? anions (3) and (4) resulted in 4.10 and 4.13 respectively, which clearly established the formal oxidation state of tin in the compounds as 4+. CSM calculation on SnBr6 2? yielded a value of 0.006 signifying a near perfect octahedral geometry of the anion.
