0000000000483758
AUTHOR
Hazi Ahmad Beejapur
Thiazolium salts as catalysts for etherification reaction
Thiazolium-based catalysts for the etherification reaction of benzylic alcohols under solvent-free condition
Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction me…
Sistemi TEMPO-C60 come Catalizzatori Riciclabili Attivi nell’Ossidazione di Alcoli
Organocatalytic Alcohol Oxidation Catalyzed by Recyclable TEMPO-functionalized [60]fullerene
Thiazolium-‐based catalysts for the etherification of benzylic alcohols under solvent-free conditions
In this work, thiazolium and imidazolium hybrid materials (SBA-15-Thia and SBA-15-Imi) were prepared by grafting the bis-vinylthiazolium or imidazolium salts onto thiol functionalized SBA-15 mesostructured silica. The catalytic activity was tested for the etherification of 1-phenylethanol, in heterogeneous conditions. The reactions were performed under different gas phases and reaction times. The SBA-15-Thia displayed an excellent catalytic performance, also with others benzyl alcohols. This material was successfully used in seven consecutive runs. Further studies were carried out in homogenous conditions. The results obtained allow proving that oxygen play an active role in the reaction pr…
Fullerene as a Platform for Recyclable TEMPO Organocatalysts for the Oxidation of Alcohols
[60]Fullerene has been employed successfully as a molecular platform to anchor 12 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties. Such an octahedrally substituted C60-derivative has been employed as an organocatalyst for the oxidation of primary and secondary alcohols using the Anelli protocol. The reaction showed a general applicability to various alcohols, and the catalyst was recovered easily and could be recycled for at least seven cycles with no loss in catalytic activity. EPR spectroscopy studies revealed that the amount of radicals decreases during the catalytic cycles, even if the recovered material still displays unchanged catalytic activity. This new approach paves the way …
Catalytic Synergism in a C60IL10TEMPO2 Hybrid in the Efficient Oxidation of Alcohols
A novel fullerene (5:1)hexakisadduct bearing two 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals and ten 1-propyl-3-methylimida- zolium bromide moieties has been synthesized and characterized. Such an C60IL10TEMPO2 hybrid has been successfully employed as a catalyst in the se- lective oxidation of a wide series of alcohols and is highly active at just 0.1 mol% loading. Moreover, it can be easily recovered by adsorption onto a multi- layered covalently-linked SILP phase (mlc-SILP) through a "release and catch" approach and reused for up to 12 cycles without loss in efficiency. Inter- estingly, a catalytic synergistic effect of TEMPO and imidazolium bromide moieties combined in the same…
A Simple Procedure for Oxidation of Alcohols using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl Acetate
Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.
Recyclable Catalyst Reservoir: Oxidation of Alcohols Mediated by Noncovalently Supported Bis(imidazolium)-Tagged 2,2,6,6-Tetramethylpiperidine 1-Oxyl
Bis(imidazolium)-tagged 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) catalysts were adsorbed on different supports such as silica gel, silica gel modified with highly cross-linked polymeric imidazolium networks, and highly cross-linked polymeric imidazolium networks entrapping magnetic particles. These systems provided a convenient tool for the oxidation of both primary and secondary alcohols working as recyclable reservoirs for the bis(imidazolium)-tagged TEMPO catalysts. By using EPR spectroscopy it was demonstrated that the catalyst was released as the corresponding oxoammonium salt in the solution during the recycling step, thus promoting the oxidative process in a homogeneous fashion. …
IONIC LIQUIDS MODIFIED CATALYSTS: SYNTHESIS, IMMOBILIZATION AND USES.
Synthesis, catalytic activity and recovery of Ionic liquid modified and un-modified catalysts have mainly been focused in this thesis. Particularly, our attention has been given to 2,2,6,6-Tetramethyl-piperidine-N-oxyl (TEMPO) catalyst for its unique redox behavior in alcohol oxidation to carbonyl compounds. In order to tag appropriate number of IL moieties, [60]Fullerene as well as benzylic linker units were employed as a molecular support. However, covalently supported catalysts were recovered by a short silica pad while, ionic liquid-tagged TEMPO catalysts were recovered by a non-covalent “Release and Catch” approach using silica grafted polymeric multilayered covalently supported ionic …
ChemInform Abstract: A Simple Procedure for the Oxidation of Alcohols Using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl Acetate.
Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.