Metal-Free Synthesis of N-Alkyl-2,5-Unsubstituted/ Monosubstituted Fulleropyrrolidines: Reaction of [60]Fullerene with Paraformaldehyde and Amines (original) (raw)
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Synthetic approaches towards the preparation of water-soluble fulleropyrrolidines
Carbon, 2000
Fullerene derivatives have interesting biological activities that make them good candidates for applications in medicinal chemistry. However, the development of these applications is hampered by the fact that fullerene derivatives are insoluble in water and polar media. We present here a general method for the preparation of N-functionalized fulleropyrrolidines with solubilizing groups via 1,3-dipolar cycloaddition of azomethine ylides to C .
Spectroscopic Analyses of Modified Fulleropyrrolidine Derivatives
The Open Spectroscopy Journal, 2015
Fullerene (C 60) is enhanced with pyrrolidine group to produce fulleropyrrolidine which is considered as one of the most important derivatives of fullerene. Fulleropyrrolidine is further modified in order to enhance its solubility which in turn could enhance its biological applications. Accordingly this work is dedicated to modify fulleropyrrolidine carbodithioic acid as NO 2 group introduced at meta position. Quantitative structure-activity relationship models (QSAR) was utilized to evaluate the biological activates of the investigated compounds through some descriptors. Later on chalcogenide could be subtitled in order to form three derivative groups. The QSAR descriptors were compared with the QSAR of the parent compound. Results indicate that, NO 2 group enhances the biological activity.
Synthesis and characterization of novel cardanol based fulleropyrrolidines
Cardanol oil, a renewable raw material well known by product of the cashew industry, has been used as the starting material for the synthesis of novel fulleropyrrolidines cardanol based. In this work, cardanol has been used as building block for the preparation of target cardanol based precursors obtained by the way of the convenient transformation of the functional groups (aromatic ring, -OH group or the double bonds of the side chain) of the cardanolic structure. Pure 3-n-pentadecylphenol and its derivatives having homogeneous chemical composition, used as the precursor of any fulleropyrrolidines, have been prepared by hydrogenation of the un-saturated side chain and subsequent alkylation of the aromatic ring of cardanol. The reactivity of olefinic double bond present in the side-chain which can undergo easy transformation i.e. oxirane formation as well as metathesis reactions affording various interesting fulleropyrrolidines is also described.
Rapid microwave-assisted synthesis of N-benzyl fulleropyrrolidines under solvent free conditions
RSC Adv., 2015
A series of new N-benzyl fulleropyrrolidines were synthesized in a one-pot of C 60 with the dibenzylamine and aldehyde derivatives using microwave irradiation under solvent-free conditions in good yield. This method provides several advantages involving high yields and rates, decrease in the extent of decomposition of the substrates, as well as environmental friendliness compared to the conventional methods.
A large series of disubstituted fulleropyrrolidines was synthesized and analyzed by cyclic voltammetry. The three main groups of target compounds differ by a flexible N-chain, while their further diversity was achieved by the introduction of various rigid, aryl substituents at the pyrrolidine carbon. Some dialkyl analogues were also designed for comparison, A standard [3+2]cycloaddition of in situ generated azomethine ylides to C 60 afforded a variety of disubstituted fulleropyrrolidines. Furthermore, a set of dumbbell-shaped di(fulleropyrrolidine) derivatives containing rigid fumaryl or isophthaloyl diamide platform was prepared with the aim of investigating a long-range effect of the second fulleropyrrolidine moiety on their electrochemical properties. All compounds were fully characterized by comparative analysis of spectral data, while examination of electrochemical properties was performed on representative samples, distinguished by main structural subunits. All compounds expressed quite similar electron-accepting ability, lower than C 60 , but higher in comparison to structurally similar N-methylfulleropyrrolidine.
Structural and electronic properties of pyrrolidine-functionalized [60] fullerenes
We have investigated energetic, geometric, electronic, and field emission properties of three recently synthesized fulleropyrrolidines based on the density functional theory method B3LYP/6-31G(d). Fulleropyrrolidines show higher conductivity, and solubility in water, and smaller work function in comparison with the pristine C 60 fullerene. The functionalization of C 60 with different pyrrolidines containing -NH 2 , NO, or NO 2 groups transforms it to an n-type semiconductor. The functionalization can also dramatically enhance the electrophilicity of the C 60 about 23-37%. Moreover, it should be mentioned that the work function is mainly influenced by the pyrrolidine containing -NO 2 group whereas the conductivity is largely affected by the one containing -NH 2 functionality.
Synthesis of [60]fullerene–glycopyranosylaminopyrimidin-4-one conjugates
Tetrahedron, 2008
The synthesis of several C 60 derivatives containing a 6-(b-D-glycopyranosylamino)pyrimidin-4-one unit and a C 60 euridine conjugate is described. The fullerene derivatives bearing a 4-(b-D-glycopyranosylamino)pyrimidin-4-one moiety were synthesised by 1,3-dipolar cycloaddition reactions of C 60 with azomethine ylides generated in situ from the corresponding 5-formylpyrimidin-4-one derivatives and N-methylglycine. The synthesis of the C 60 euridine conjugate involved the selective protection of the 2 0-and 3 0-hydroxyl groups of uridine, esterification, cyclopropanation of C 60 and, finally, the deprotection of the hydroxyl groups. One of the fullereneeglycopyranosylaminopyrimidin-4-one conjugates was characterised by single-crystal X-ray crystallography. Differentiation between pairs of diastereoisomers, for several fullerene derivatives, was achieved through the study of their gas-phase fragmentations.
Theoretical investigation on two different mechanisms of fulleropyrrolidine formation
Theoretical Chemistry Accounts, 2016
AM1 level, and finally DFT on geometries optimized at DFT level were considered. At DFT level, GGA (PBE), hybrid (PBE0) and meta-GGA (M06-2X) were used, with a 6-31+G(d) basis set. We proved that the release of NH 3 and the ring formation step in the first mechanism require a higher energy barrier compared to the second mechanism reaction steps like tautomerization and H 2 O departure. Thus, we can conclude that the second mechanism involving in a first step the azomethine ylide formation is more favorable than the first mechanism. The interest in using in a first step a semiempirical determination of reaction paths is highlighted, and the choice of the exchange-correlation functional is discussed.
Chinese Journal of Chemistry, 2006
N-Methyl-2-(4-N,N-diphenylaminophenyl)fulleropyrrolidine and N-methyl-2-(4-dip -tolylaminophenyl)fulleropyrrolidine were synthesized via the 1,3-dipolar cycloaddition reactions under microwave irradiation. The molecular structures were identified and characterized by MS, UV-Vis, FT-IR, 1 H NMR and fluorescence spectra. Photoinduced intramolecular electron transfer process from C 60 moiety to triphenylamine moiety have been studied by nanosecond laser flash photolysis. The optimized structure and the distribution of the frontier molecular orbitals for C 60-TPA were obtained by using DFT method at B3LYP/6-31G(d) level. The results indicated that the intramolecular photoinduced electron transfer could occur in these compounds, which were in excellent agreement with the nanosecond transient absorption spectra observed experimentally in polar solvent. The electronic spectrum of the compound C 60-TPA was studied by ZINDO method on the basis of the optimized geometrics, which was essentially consistent with experimental values.