20799-93-3Relevant academic research and scientific papers
Two isostructural URJC-4 materials: From hydrogen physisorption to heterogeneous reductive amination through hydrogen molecule activation at low pressure
Montes-Andrés, Helena,Leo, Pedro,Mu?oz, Antonio,Rodríguez-Diéguez, Antonio,Orcajo, Gisela,Choquesillo-Lazarte, Duane,Martos, Carmen,Martínez, Fernando,Botas, Juan A.,Calleja, Guillermo
, p. 15733 - 15740 (2020)
Herein, two novel isostructural metal-organic frameworks (MOFs) M-URJC-4 (M = Co, Ni; URJC = "Universidad Rey Juan Carlos") with open metal sites, permanent microposity, and large surface areas and pore volumes have been developed. These novel MOFs, with polyhedral morphology, crystallize in the monoclinic P21/c space group, exhibiting a three-dimensional structure with microporous channels along the c axis. Initially, they were fully characterized and tested in hydrogen (H2) adsorption at different conditions of temperature and pressure. The physisorption capacities of both materials surpassed the gravimetric H2 uptake shown by most MOF materials under the same conditions. On the basis of the outstanding adsorption properties, the Ni-URJC-4 material was used as a catalyst in a one-pot reductive amination reaction using various carbonyl compounds and primary amines. A possible chemical pathway to obtain secondary amines was proposed via imine formation, and remarkable performances were accomplished. This work evidences the dual ability of M-URJC-4 materials to be used as a H2 adsorbent and a catalyst in reductive amination reactions, activating molecular H2 at low pressures for the reduction of C=N double bonds and providing reference structural features for the design of new versatile heterogeneous materials for industrial application.
Benzhydrylamine: An effective aminating agent for the synthesis of primary amines
Sun, Quan-Wei,Xing, Jun-De,Qin, Yu-Hong,Yin, Xu-Wen,Zhou, Yi
, p. 181 - 183 (2018/05/26)
Aldehydes, ketones, alkyl toluene-p-sulfonates and halides are converted into the corresponding primary amines with benzhydrylamine as a valuable ammonia synthon in moderate to excellent yields.
Visible-Light-Mediated Umpolung Reactivity of Imines: Ketimine Reductions with Cy2NMe and Water
Wang, Rui,Ma, Mengyue,Gong, Xu,Panetti, Grace B.,Fan, Xinyuan,Walsh, Patrick J.
supporting information, p. 2433 - 2436 (2018/04/27)
A novel carbanionic reactivity of imines mediated by photoredox catalysis is demonstrated. The umpolung imine reactivity is exemplified by proton abstraction from water as a key step in the reduction of benzophenone ketimines to amines (up to 98% yield). Deuterium is introduced into amines efficiently using D2O as an inexpensive deuterium source (≥95% D ratio). The mechanism of this unusual transformation is probed.
Polymer-supported hantzsch 1,4-dihydropyridine ester: An efficient biomimetic hydrogen source for the reduction of ketimines and electron-withdrawing group conjugated olefins
Che, Jun,Lam, Yulin
experimental part, p. 1752 - 1758 (2010/09/11)
A polymer-supported Hantzsch 1,4-dihydropyridine ester was observed to be a useful selective reducing agent for the reduction of ketimines and electron-withdrawing conjugated olefins. The rate of the reduction of electron-withdrawing conjugated olefins is dependent on the nature of the conjugated substituents and could be enhanced by microwave irradiation. The reduction of (Z)-α-cyano-β-bromomethylcinnamates to cyclopropane derivatives using polymer-supported Hantzsch 1,4-dihydropyridine ester was found to proceed stereoselectively and in good yields.
Synthesis of amides and lactams in supercritical carbon dioxide
Mak, Xiao Yin,Ciccolini, Rocco P.,Robinson, Julia M.,Tester, Jefferson W.,Danheiser, Rick L.
supporting information; experimental part, p. 9381 - 9387 (2010/03/04)
(Chemical Equation Presented) Supercritical carbon dioxide can be employed as an environmentally friendly alternative to conventional organic solvents for the synthesis of a variety of carboxylic amides. The addition of amines to ketenes generated in situ via the retro-ene reaction of alkynyl ethers provides amides in good yield, in many cases with ethylene or isobutylene as the only byproducts of the reaction. Reactions with ethoxy alkynes are performed at 120-130°C, whereas tert-butoxy derivatives undergo the retro-ene reaction at 90°C. With the exception of primary, unbranched amines, potential side reactions involving addition of the amines to carbon dioxide are not competitive with the desired C-N bond-forming reaction. The amide synthesis is applicable to the preparation of β-hydroxy and β-amino amide derivatives, as well as amides bearing isolated carbon-carbon double bonds. Preliminary experiments aimed at developing an intramolecular variant of this process to afford macrolactams suggest that the application of CO2/co-solvent mixtures may offer advantages for the synthesis of large-ring compounds.
?-Allyl palladium methodology for selective deprotection of allylamines. Practical synthesis of secondary amines
Lemarie-Audoire, Sandrine,Savignac, Monique,Dupuis, Christophe,Genet, Jean Pierre
, p. 1157 - 1166 (2007/10/03)
The palladium-promoted deallylation of allylamines derived from primary and secondary amines is achieved with high to quantitative yield in the presence of 2-mercaptobenzoic acid as an allyl scavenger.This method was used for the sequential cleavage of diallylamines.A synthetic application of this procedure is presented in the preparation of secondary amines from diallylamines. - Keywords: allylamine; deallylation; sequential deprotection; ?-allyl palladium complexes; 2-mercaptobenzoic acid; substitution of amines
UNEXPECTED PRODUCTS IN A KABACHNIK-FIELDS SYNTHESIS OF AMINOPHOSPHONATES
Gancarz, Roman
, p. 59 - 64 (2007/10/02)
In a Kabachnik-Fields synthesis of aminophosphonates derived from aromatic ketones the formation of hydroxyphosphonates, their rearrangement to corresponding phosphates and amine promoted decomposition of the last, leads to a number of unexpected products, which in some cases could be the only products of reaction.Key words: 1-Aminophosphonates; 1-hydroxyphosphonates; Kabachnik-Fields reaction; phosphonate-phosphate rearrangement.
Reaction of Diphenylcarbene with Amines and the Question of Triplet-Singlet Equilibration
Nazran, A. S.,Griller, D.
, p. 4613 - 4615 (2007/10/02)
The optical absorption spectrum of triplet diphenylcarbene in solution is quenched by substrates such as methanol and amines to give the respective O-H and N-H insertion products.Is this a direct reaction of the triplet carbene with the substrates which runs counter to the rules of spin selection, or does it involve thermal population of the singlet state of the carbene which then reacts with the substrates? These Questions are addressed through kinetic, isotopic, and product studies of the reaction between diphenylcarbene and butylamines.
Sodium Borohydride Induced Deamination of Diarylimines
Sharma, Indra,Ray, Suprabhat
, p. 59 - 61 (2007/10/02)
Sodium borohydride reduction of diarylimines (I) in ethanol at room temperature affords the corresponding diarylamines (II) and/or diarylmethanes (III) depending on the nature of substituent in the diaryl moiety of the imines. o-Hydroxydiarylimines, beari
