Amines In Ionic Liquids Research Articles

Copper Catalyzed N‐Arylation of Amines in Ionic Liquid Using 1‐Aryltriazenes as Aryl Surrogates

AbstractServing [TMG][CH3COO] ionic liquid as solvent and promoter, a competent access to unsymmetrically substituted secondary amine is accomplished through a copper catalyzed mono arylation of aromatic/aliphatic amines with diverse 1‐aryltriazenes. No base, ligand, co‐catalyst, additional promoter or additives are necessary to drive the reaction. Varied functional group tolerance, shorter reaction time, better product yield, recycle and re‐use of ionic liquid highlight this reaction as a better eco‐friendly alternative for the conventional synthesis.

ChemInform Abstract: Exploiting the Use of Ionic Liquids to Access Phosphorodiamidites.

AbstractHighly moisture‐sensitive phosphorodiamidites (III) and (V) are selectively formed by reaction of alkoxydichlorophosphine with secondary amines in ionic liquids as reaction medium.

Phase Behaviour, Interactions, and Structural Studies of (Amines+Ionic Liquids) Binary Mixtures

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [C(n)mim] [NTf(2)] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory-Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C(2)mim] [NTf(2)]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C(2)mim][NTf(2)]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents.

ChemInform Abstract: Unprecedented Acceleration of the Domino Reaction Between Methyl 4‐Hydroxyalk‐3‐ynoates and Amines in Ionic Liquids.

AbstractThe ionic liquid (IL) acts as both solvent and promoter.

Unprecedented acceleration of the domino reaction between methyl 4-hydroxyalk-3-ynoates and amines in ionic liquids

Reaction between methyl 4-hydroxyalk-3-ynoates and amines leading to 4-aminofuran-2(5 H )-ones is significantly accelerated in ionic liquids, which can be recycled at least five times.

UV-Spectroscopic Quantitative Determination of Non-aromatic Amines in Ionic Liquids

In the last decade, ionic liquids have shown great promise in a plethora of applications. Nevertheless, little attention has been paid to the characterization of the purity of these fluids, which ultimately lead to non-reproducible data in the literature. Derivatization with carbon disulfide is used to quantitatively determine primary and secondary non-aromatic amines (detection limit: 0.2 wt%), such as 1-butylamine, morpholine or pyrrolidine, in ionic liquids. The corresponding dithiocarbamates formed are analyzed by ultraviolet spectroscopy at wavelengths between 277 and 285 nm.

Nonenzymatic Kinetic Resolution of Amines in Ionic Liquids

Ionic liquids are remarkably suitable and clean media for performing nonenzymatic kinetic resolution (KR) of amines through enantioselective N-acetylation: high levels of selectivity were obtained with a large variety of amines at room temperature (up to S = 30).

Facile ring opening of 2,3-epoxy-steroids with aromatic amines in ionic liquids

Efficient ring opening of steroidal 2,3-epoxides with stoichiometric amount of aromatic amines has been carried out using an ionic liquid ([bmim] +[BF 4] −) both as solvent and catalyst. The reactions were completely regio- and stereoselective in each case. The aminoalcohol products have chair conformations in ring A. The ionic liquid-mediated ring opening can efficiently be carried out with aliphatic amines like morpholine as well.

Microwave‐Assisted Aromatic Nucleophilic Substitution Reaction of Chloronitrobenzenes with Amines in Ionic Liquids.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Organic Reactions in Ionic Liquids: Ionic Liquid‐Promoted Efficient Synthesis of N‐Alkyl and N‐Arylphthalimides.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Some Observations on the Preparation of Amides and their Reduction to Amines in Ionic Liquids

Some Observations on the Preparation of Amides and their Reduction to Amines in Ionic Liquids

Molecular Sieves in Ionic Liquids as an Efficient and Recyclable Medium for the Synthesis of Imines.

A great variety of imines were efficiently isolated in high yields from the reaction of aldehydes and amines in ionic liquids. The ionic liquids could be recovered and reused for at least five cycles without loss in the yields being a useful alternative to dichloromethane or diethyl ether, which are the commonly used solvents for this reaction.

Synthesis of novel palladium–carbene complexes as efficient catalysts for amination of aryl chlorides in ionic liquid

The synthesis and characterization of [PdCl2(N-heterocyclic carbene)2] (2, 3), an air and moisture-stable complexes are reported. Amination of aryl halides in 1-methy-3-butyl-imidazolidinium tetrafluoroborate in the presence of palladium–carbene complexes as catalysts are described. Aryl chlorides undergo smooth nucleophilic substitution reactions with primary amines in ionic liquid to afford the corresponding arylamines in excellent yields under mild conditions.

Organic reactions in ionic liquids: Ionic liquid-promoted efficient synthesis ofN-alkyl andN-arylphthalimides

Phthalic anhydride reacts rapidly with Aromatic and aliphatic amines in ionic liquid [Bmim][PF6] or [Bmim][BF4] at 130 °C to give N-aryl and N-alkylphthalimides in excellent yields.

Aza‐Michael Reactions in Ionic Liquids. A Facile Synthesis of β‐Amino Compounds.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Molecular Sieves in Ionic Liquids as an Efficient and Recyclable Medium for the Synthesis of Imines

A great variety of imines were efficiently isolated in high yields from the reaction of aldehydes and amines in ionic liquids. The ionic liquids could be recovered and reused for at least five cycles without loss in the yields being a useful alternative to dichloromethane or diethyl ether, which are the commonly used solvents for this reaction.

Aza-Michael Reactions in Ionic Liquids. A Facile Synthesis of β-Amino Compounds

Abstract Electron-deficient olefins undergo smoothly aza-Michael reactions with a wide range of amines in ionic liquids in the absence of any acid catalyst to produce the corresponding β-amino compounds in excellent yields with high 1,4-selectivity. The recovered ionic liquids can be reused in subsequent reactions without loss of activity. Owing to the high polarity of ionic liquids, the enones show enhanced reactivity thereby reducing reaction times and improving the yields significantly.

Direct mono-N-alkylation of amines in ionic liquids: chemoselectivity and reactivityThis work was presented at the Green Solvents for Catalysis Meeting, held in Bruschal, Germany, 13–16 October 2002.

A simple method for the N-alkylation of primary amines was developed using ionic liquids as solvent in order to prepare secondary amines selectively. In ionic liquids overalkylation of the initially produced secondary amines is in general markedly reduced. Various amines, alkyl halides and sulfonates were examined. The observed selectivities between mono- and dialkylation are typically on the order of 9∶1, or higher. Only in the cases of allyl or benzyl bromides does the reaction give the corresponding tertiary amines exclusively. The relative nucleofugality of chloride, bromide, iodide and tosylate with several primary amines was also evaluated, as well as the effect of caesium hydroxide.