Search results for "ILE"
showing 10 items of 14281 documents
Effect of Superbasic Ionic Liquids on the Synthesis of Dendritic PolyaminesviaAza-Michael Addition Reaction
2017
Catalytic effect of selected superbasic ionic liquids on the yield and selectivity of aza-Michael addition of ethylenediamine and ammonia to acrylonitrile was investigated. The reactions were performed in calorimetric reactor equipped with RT-IR probe (real-time IR), where all energy changes associated with chemical reactions and physical transformations were monitored. Catalytic activity of selected superbasic ionic liquids in aza-Michael addition ethylenediamine and ammonia to acrylonitrile were determined and obtained polynitriles were then hydrogenatated to final three- and four-directional dendritic polyamines. The products were characterized by instrumental analytical methods, includi…
Functionalised diimidazolium salts: the anion effect on the catalytic ability
2016
The catalytic ability of some functionalised diimidazolium ionic liquids was tested using the Michael addition of malononitrile to t-chalcone as probe reaction. Diimidazolium salts characterized by the presence of 1-(1-imidazolylmethyl)-3,5-di-[1-(3-octylimidazolylmethyl)]benzene cation and differing in the anion structure were used. Both mono- and dianions were employed and among these some chiral anions generally used as organocatalysts were taken into account. Data collected were analysed both as function of ionic liquids structure and basicity, evaluated using the Hammett basicity function. Although the use of chiral anions did not allow performing a stereochemical control of the reacti…
Synthesis, Crystal Structure and Magnetic Properties of Heteropolynuclear Re IV M II Complexes Based on the Robust [ReCl 5 (pyzCOO)] 2– Unit (pyzCOO …
2016
The syntheses, crystal structures and magnetic properties of four rhenium(IV) compounds of formulae NBu4[ReCl5(pyzCOOH)]·H2O (1), [ReCl5(µ-pyzCOO)M(dmphen)2]·2CH3CN [M = Ni (2) and Co (3)] and {[ReCl5(µ3-pyzCOO)]2Mn2(dmphen)3}n (4) (NBu4 = tetra-n-butylammonium cation, pyzCOOH = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline) are reported herein. Compound 1 was obtained by the reaction of NBu4[ReCl5(dmf)] (dmf = dimethylformamide) with pyzCOOH in acetone, whereas the other complexes were obtained by the reaction of 1 with M(ClO4)2·6H2O [M = Ni (2), Co (3), Mn (4)] and dmphen in acetonitrile. Complex 1 is a mononuclear compound, 2 and 3 are neutral heterodinuclear compl…
Heterobimetallic Oxalate‐Bridged M II Re IV (M = Zn, Cu, Ni, Co and Mn) Complexes Incorporating Bis(3,5‐dimethylpyrazol‐1‐yl)methane: Synthesis and M…
2016
Five oxalato-bridged heterobimetallic compounds of general formula [ReCl4(ox)M(bdmpzm)2].2MeCN [ox = oxalate, bdmpzm = bis(3,5-dimethylpyrazol-1-yl)methane and M = Zn (1),Cu (2), Ni (3), Co (4) and Mn (5)] have been successfully synthesized in self-assembly reactions of the [ReCl4(ox)]2- metalloligand with the coordinatively unsaturated [M(bdmpzm)2]2+ complex generated in situ by the reaction of the suitable metal(II) salt with the bdmpzm ligand. 1-5 are isostructural compounds whose crystal structures consist of neutral heterodinuclear [ReCl4(ox)M(bdmpzm)2] units and free acetonitrile molecules. The magnetic properties of 1-5 were investigated in the temperature range 2.0-300 K. The nature…
Deprotonation of Benzoxazole and Oxazole Using Lithium Magnesates
2005
International audience; The first deprotonations of oxazole and benzoxazole using lithium magnesates are described. The reactions occurred in tetrahydrofuran at room temperature using 1/3 equiv of lithium tributylmagnesate. As 2-lithiooxazole and 2-lithiobenzoxazole, lithium tri(2-oxazolyl)magnesate and lithium tri(2-benzoxazolyl)magnesate very rapidly and completely isomerized to the more stable 2-(isocyano)enolate and 2-(isocyano)phenolate type structures, respectively, a result shown by NMR analysis. The isolation of 2-substituted oxazoles and benzoxazoles in medium to good yields after electrophilic trapping was interpreted in two ways: (1) the equilibration between the open and closed…
Electrochemical meso-functionalization of magnesium(II) porphine
2010
International audience; Regioselective meso-functionalization of the totally unsubstituted magnesium(II) porphine was performed by controlled potential electrolysis with pyridine and triphenylphosphine as nucleophiles leading to the original pyridinium and phosphonium substituted derivatives, respectively. The crystallographic structure of the latter is described as the only meso-phosphonium porphyrin reported to date.
Oxygen Transfer from Trimethylamine N ‐Oxide to Cu I Complexes Supported by Pentanitrogen Ligands
2020
[N,N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L1) and [N,N-bis(2-quinolylmethyl)-N-bis(2-pyridyl)methylamine] (L2) were employed to prepare CuII and CuI complexes for spectroscopic and structural characterization. [L1CuII(H2O)](NO3)2 and [L2CuII(NO3)]NO3 have Jahn–Teller distorted octahedral geometries and give rise to isotropic EPR spectra in frozen solution. [L1CuI(CH3CN)]OTf and [L2CuI(CH3CN)]OTf have distorted trigonal bipyramidal and tetrahedral solid-state structures, respectively. The N-donors display labile behavior in solution, based on variable-temperature 1H NMR studies. Addition of trimethylamine N-oxide (Me3NO) to solutions of [L1CuI(CH3CN)]OTf and [L…
Direct Difluorination–Hydroxylation, Trifluorination, and C(sp2)–H Fluorination of Enamides
2018
A direct double functionalization involving both difluorination and hydroxylation of enamides is reported. With the appropriate combination of an electrophilic fluorinating reagent and H2O, the most convenient and ecofriendly hydroxylating agent, the preparation of 3-(difluoroalkyl)-3-hydroxyisoindolin-1-ones was achieved under basic or Bronsted acidic conditions. Suitable conditions for trifluorination as well as C(sp2)–H fluorination were also identified. Subsequent asymmetric functionalization of the obtained gem-difluorinated products has also been demonstrated.
Light Induced C-C Coupling of 2-Chlorobenzazoles with Carbamates, Alcohols, and Ethers.
2016
A light induced, transition-metal-free C-C coupling reaction of 2-chlorobenzazoles with aliphatic carbamates, alcohols, and ethers is presented. Inexpensive reagents, namely sodium acetate, benzophenone, water, and acetonitrile, are employed in a simple reaction protocol using a cheap and widely available 25 W energy saving UV-A lamp at ambient temperature.
N-Cobaltocenium Amide as Reactive Nucleophilic Reagent for Donor–Acceptor Bimetallocenes
2017
Deprotonation of the aminocobaltocenium ion [Cc-NH2]+ ([H-1]+) generates the nucleophilic imine CcNH (1). Reaction of 1 with acid chlorides R–COCl (R = Ph, Fc, and Cc+) yields the reference amide [Ph-CO-NH-Cc]+ (2+) and the amide-linked hetero- and homobimetallocenes [Fc-CO-NH-Cc]+ (3+) and [Cc-CO-NH-Cc]2+ (42+), respectively. Cation–anion interactions of charged amides 2+–42+ in the solid state and in solution are probed by single crystal X-ray diffraction and NMR and IR spectroscopy. Intramolecular metal–metal interactions in donor–acceptor heterobimetallocene 3+ and in mixed-valent homobimetallocene 4+ (prepared electrochemically) are discussed within the Marcus–Hush framework aided by s…