Search results for "Protic solvent"
showing 10 items of 10 documents
Selective Extraction and Efficient Binding in a Protic Solvent of Contact Ion Triplets by Using a Thiourea-Based Bis-Calix[6]arene Receptor
2013
We report a D3h-symmetric tail-to-tail bis-calix[6]thiourea 5 that displays two divergent cavities triply connected by thiourea linkages. This calix[6]tube was efficiently synthesized through a [1+1] macrocyclization reaction and characterized by X-ray diffraction analysis. The binding properties of this heterotritopic receptor were evaluated in a protic environment (i.e., CD3OD/CDCl3) through NMR studies. Thus, bis-calix[6]thiourea 5 exhibits a remarkable ability in the cooperative complexation of an anion sandwiched between two ammonium ions, a high selectivity for ammonium sulfate salts being observed. The anion is bound through multiple hydrogen-bonding interactions at the thiourea bind…
“Water-stable boron-iodinated dicarbollide dianions [7,8-nido-C2H2B9I9]2−and [7,8-nido-C2H2B9I8H]2−”
2007
The reaction of 3,4,5,7,8,9,10,11,12-I(9)-1,2-closo-C(2)B(10)H(3) with KOH/EtOH gave a mixture of the boron periodinated [1,2,3,4,5,6,9,10,11-I(9)-7,8-nido-C(2)B(9)H(2)](2-) and the highly iodinated on boron [1,2,4,5,6,9,10,11-I(8)-7,8-nido-C(2)B(9)H(3)](2-) in approximately 50% each. Moreover, 3,4,5,6,7,8,9,10,11,12-I(10)-1,2-closo-C(2)B(10)H(2) was reacted with KOH/EtOH to purely produce [1,2,3,4,5,6,9,10,11-I(9)-7,8-nido-C(2)B(9)H(2)](2-). It is the first dinegative dicarbollide stable in water or protic solvent reported in literature.
Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory
2011
P-chirogenic, supramolecular hydrogen-bonding C1-symmetrical sulfonamido–phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the PIII and the PV tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic solvent environment. Several strategies to access the corresponding enantiopure compounds were investigated, such as diastereoselective crystallization, or enantioselective synthesis. It was possible to resolve such a class of chiral liga…
Structural features of selected protic ionic liquids based on a super-strong base
2019
Protic ionic liquids (PIL) were prepared from a super-strong base 1,7-diazabicyclo[5.4.0]undec-7-ene (DBU) and super-strong acids, trifluoromethane sulfonic acid (TfOH), and (trifluoromethanesulfonyl)-(nonafluorobutylsulfonyl)imide, (IM14H), ([DBUH][TfO] and [DBUH][IM14], respectively; the latter for the first time) and their chemical and physical properties and structural features have been explored using a synergy of experimental and computational tools. The short range order in neat DBU, as well as the long range structural correlations induced by charge correlation and hydrogen bonding interactions in the ionic liquids, have been explored under ambient conditions, where these compounds …
Effect of Polarity of Solvent on Silanization of Halloysite Nanoclay Using (3-Glycidyloxy propyl) Trimethoxy Silane
2021
Abstract: The grafting of silane groups on clay surfaces has been recently investigated in order to fabricate versatile compounds with new potential applications in materials science and ecological engineering. This work explored the influence of variety of solvents with variable polarity on the silanization of halloysite nanoclay (HNT) surface by (3-Glycidyloxy propyl) trimethoxy silane. To this purpose, the functionalization of HNT by 3-Glycidyloxypropyltrimethoxysilane (GOPTMS) has been conducted in Ethanol (polar protic solvent), Tetrahydrofuran (THF) and Acetonitrile (polar aprotic solvents), and Hexane, 1,4-Dioxane and Toluene (non polar solvents). The silane grafted materials were ch…
Phycocyanobilin in solution – a solvent triggered molecular switch
2014
We present a computational investigation of the conformational response of phycocyanobilin (PCB) to the ability of solvents to form hydrogen bonds. PCB is the chromophore of several proteins in light harvesting complexes. We determine the conformational distributions in different solvents (methanol and hexamethylphosphoramide HMPT) by means of ab initio molecular dynamics simulations and characterize them via ab initio calculations of NMR chemical shift patterns. The computed trajectories and spectroscopic fingerprints illustrate that the energy landscape is very complex and exhibits various conformations of similar energy. We elucidate the strong influence of the solvent characteristics on…
The Role of Site-Specific Hydrogen Bonding Interactions in the Solvation Dynamics of N-Acetyltryptophanamide
2012
Measurements of the ultrafast broadband UV fluorescence of N-acetyltryptophanamide (NATA) provide detailed information on its relaxation patterns in three different solvents: methanol (MeOH), water and acetonitrile (ACN). Several processes leading to excited state solvation and cooling are found to occur on different characteristic time scales and are thoroughly analyzed. Comparison between protic MeOH and aprotic ACN allows one to single out a 12 Ps component in the former, which is attributed to the rearrangement of H-bonds existing between the protic solvent and excited NATA. This significantly stabilizes the excited state and provides the molecule with an efficient cooling mechanism. Th…
Design, synthesis and spectral studies of novel bile acid-arene conjugates: Trans to cis isomerization of azobenzene core controlled by bile acid hyd…
2008
Abstract Four bile acid-arene conjugates, 1,4-bis[dimethyl(3α,7α,12α-trihydroxy-5β-cholan-24-amidoethyl)ammoniomethyl]benzene dibromide ( 1 ), 1,3,5-tris[dimethyl(3α,7α,12α-trihydroxy-5β-cholan-24-amidoethyl)ammoniomethyl]benzene tribromide ( 2 ), bis{4-[dimethyl(3α,7α,12α-trihydroxy-5β-cholan-24-amidoethyl)ammoniomethyl]phenyl}diazene dibromide ( 3 ), and bis{4-[dimethyl(3α-hydroxy-5β-cholan-24-amidoethyl)ammoniomethyl]phenyl}diazene dibromide ( 4 ), have been synthesized in good yields, and their structures have been characterized by 1 H, 13 C, 13 C DEPT-135, PFG 1 H, 13 C HMQC, PFG 1 H, 13 C HMBC, and PFG 1 H, 15 N HMBC NMR spectra. Their molecular weights and elemental compositions have…
Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution
2017
A novel eight-membered macrocycle of the hemicucurbit[n]uril family, chiral (all-R)-cyclohexanohemicucurbit[8]uril (cycHC[8]) binds anions in a purely protic solvent with remarkable selectivity. The cycHC[8] portals open and close to fully encapsulate anions in a 1 : 1 ratio, resembling a molecular Pac-Man™. Comprehensive gas, solution and solid phase studies prove that the binding is governed by the size, shape and charge distribution of the bound anion. Gas phase studies show an order of SbF6− ≈ PF6− > ReO4− > ClO4− > SCN− > BF4− > HSO4− > CF3SO3− for anion complexation strength. An extensive crystallographic study reveals the preferred orientations of the anions within the octahedral cav…
C-H Bond Arylation of Pyrazoles at the β-Position: General Conditions and Computational Elucidation for a High Regioselectivity
2021
International audience; Direct arylation of most five-membered ring heterocycles are generally easily accessible and strongly favored at the α-position using classical palladium-catalysis. Conversely, regioselective functionalization of such heterocycles at the concurrent β-position remains currently very challenging. Herein, we report general conditions for regioselective direct arylation at the β-position of pyrazoles, while C-H α-position is free. By using aryl bromides as the aryl source and a judicious choice of solvent, the arylation reaction of variously N-substituted pyrazoles simply proceeds via β-C-H bond functionalization. The β-regioselectivity is promoted by a ligand-free palla…