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).
Catalytic Transfer Hydrodebenzylation with Low Palladium Loading
Yakukhnov, Sergey A.,Ananikov, Valentine P.
, p. 4781 - 4789 (2019)
A highly-efficient catalytic system for hydrodebenzylation reaction is described. The cleavage of O-benzyl and N-benzyl protecting groups was performed using an uncommonly low palladium loading (0.02–0.3 mol%; TON up to 5000) in a relatively short reaction time. The approach was used for a variety of substrates including pharmaceutically important precursors, and gram-scale deprotection reaction was shown. Transfer conditions together with easy-to-make Pd/C catalyst are the key features of this debenzylation scheme. (Figure presented.).
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.
Synthesis, spectroscopic studies, and single crystal X-ray diffraction analysis of a lead(II) based hybrid perovskite: Morpholinium trichloroplumbate(II)
Ramalingam, Kuppukkannu,Rizzoli, Corrado,Rajaraman, Thangarasu,Prabu, Manikandan
, p. 175 - 181 (2016)
Morpholinium trichloroplumbate(II), [cyclo-O(CH2CH2)2NH]PbCl3 (1), has been synthesized and characterized by elemental analysis, FTIR and 1H and 13C NMR spectroscopy, thermogravimetric analysis (TGA), diffuse reflectance spectra, and single-crystal X-ray diffraction analysis. An FTIR spectrum showed a shift of 100 cm-1 in the NH2 stretching due to the protonated nitrogen of the morpholinium ion. 1H NMR spectrum of the compound showed significant high-frequency shift of the resonance for the CH2 protons due to the presence of cationic charge on the adjacent nitrogen and hydrogen bonded interactions. Contrary to 1H NMR, the 13C NMR signals showed a lowering of 'δ' in the hybrid material. A diffuse reflectance spectrum (DRS) illustrated intense charge transfer in the compound. The observed band gap value for the compound is 3.23 eV based on the DRS data. TG-DT analysis showed the compound to be stable up to 241°C. Single crystal X-ray diffraction analysis of the hybrid material showed the Pb2+ ion being surrounded by six chloride anions in a distorted octahedral geometry. In addition to the six chloride anions, the oxygen atom of the morpholinium cation is also in short contact with the lead cation. Bond valence sum (BVS) calculation confirmed the formal oxidation state of lead to be +2. Continuous symmetry measure (CSM) calculations indicated the PbCl6 to be a distorted octahedron with a magnitude of 5.246 clearly far away from the trigonal prismatic geometry.
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.
Photoredox-Catalyzed Addition of Carbamoyl Radicals to Olefins: A 1,4-Dihydropyridine Approach
Cardinale, Luana,Konev, Mikhail O.,Jacobi von Wangelin, Axel
supporting information, p. 8239 - 8243 (2020/06/20)
Functionalization with C1-building blocks are key synthetic methods in organic synthesis. The low reactivity of the most abundant C1-molecule, carbon dioxide, makes alternative carboxylation reactions with CO2-surrogates especially important. We report a photoredox-catalyzed protocol for alkene carbamoylations. Readily accessible 4-carboxamido-Hantzsch esters serve as convenient starting materials that generate carbamoyl radicals upon visible light-mediated single-electron transfer. Addition to various alkenes proceeded with high levels of regio- and chemoselectivity.
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.
Synthetic method of moroxydine hydrochlofide
-
Paragraph 0053; 0054; 0055, (2016/10/10)
The invention discloses a synthetic method of moroxydine hydrochlofide. The method comprises the following steps: adding diglycol, dicyandiamide, ammonium chloride and an aqueous sulfuric acid solution with the mass concentration of 20-30% to a high pressure reaction kettle according to amass ratio of (4-6):(4-6):(2-4):(1-2), heating the obtained solution in a sealed and stirring state to 120-130DEG C, reacting under a reaction kettle pressure of 0.3-0.5MPa for 1-2h, and cooling the obtained solution to room temperature to obtain a white milk; and transferring the white milk to a reaction kettle, adding 95% ethanol according to a volume ratio of the 95% ethanol to diglycol of (7-9):1, carrying out a heating refluxing reaction for 30min to obtain a mixed solution, carrying out hot filtration on the mixed solution through a filter cylinder to a crystallization kettle, cooling the obtained filtrate in the crystallization kettle to room temperature to precipitate white crystals, centrifuging and separating the white crystals, and drying the separated white crystals in a hot wind oven at 80-85DEG C to obtain moroxydine hydrochlofide.. Moroxydine hydrochlofide is obtained through a direct reaction of dicyandiamide and morpholine hydrochloride generated through in situ reaction of diglycol and ammonium chloride under the action of sulfuric acid, so the synthetic method is simplified, side reactions are reduced, the yield is improved, and environment is protected.
Direct Preparation of Amides from Amine Hydrochloride Salts and Orthoesters: A Synthetic and Mechanistic Perspective
Di Grandi, Martin J.,Bennett, Caitlin,Cagino, Kristen,Muccini, Arnold,Suraci, Corey,Saba, Shahrokh
supporting information, p. 2601 - 2607 (2015/11/28)
The conversion of a wide range of primary and secondary aliphatic and a few arylamine hydrochloride salts to their corresponding acetamides with trimethyl orthoacetate is described. Mechanistic studies using NMR and gas chromatography-mass spectrometry techniques indicate these reactions proceed via an O-methylimidate intermediate that undergoes in situ demethylation by chloride, affording the corresponding acetamides. Synthetically, this reaction represents a practical, high-yielding protocol with a simple workup for the rapid conversion of amine hydrochloride salts to acetamides.
Nucleophilic substitution reaction at the nitrogen of arylsulfonamides with phosphide anion
Yoshida, Suguru,Igawa, Kazunobu,Tomooka, Katsuhiko
supporting information, p. 19358 - 19361 (2013/02/22)
A novel nucleophilic substitution reaction at the nitrogen of arylsulfonamides by means of phosphide anions has been described. This reaction allows for the efficient transformation of arylsulfonamides into synthetically valuable phosphamides, amines, and a variety of protected amines.
