15795-03-6Relevant academic research and scientific papers
Structural study of a novel acetylide-thiourea derivative and its evaluation as a detector of benzene
Khairul, Wan M.,Daud, Adibah Izzati,Mohd Hanifaah, Noor Azura,Arshad, Suhana,Razak, Ibrahim Abdul,Zuki, Hafiza Mohamed,Erben, Mauricio F.
, p. 353 - 361 (2017)
The new derivative 1-hexanoyl-3-(4-p-tolylethynyl-phenyl)-thiourea (APHX) was synthesised by the addition reaction between 4[4-aminophenyl] ethynyltoluene and hexanoyl isothiocyanate in acetone. The acetylide group was incorporated by using Sonogashira cross-coupling reaction allowing for the preparation of acetylide-thiourea compound. APHX was then elucidated via single crystal X-ray crystallography analysis, spectroscopic and elemental analysis by Fourier Transform Infrared (FT-IR) spectroscopy, 1H and 13C Nuclear Magnetic Resonance (NMR), UV–visible analysis, CHNS-elemental analysis. APHX was also evaluated theoretically via density functional theory (DFT) approach. APHX was fabricated onto glass substrate via drop-cast technique prior to act as optical thin-film and its performance as volatile organic compounds (VOCs) sensor was investigated through the difference in UV–vis profile before and after exposure towards benzene. Preliminary findings revealed that APHX showed interaction towards benzene with about 48% sensitivity. According to thermogravimetric studies, APHX showed good thermal stability, without decomposition up to ca. 190?°C. Whilst, crystal structure of APHX consists in a nearly planar acylthiourea moiety with the C[dbnd]O and C[dbnd]S bonds utilizing trans position, favoring by an intramolecular N[sbnd]H?O[dbnd]C hydrogen bonds. The alkyl chain is oriented 90° with respect to acylthiourea group. The phenyls group in the 1-methyl-4-(phenylethynyl)benzene moieties are mutually planar and slightly twisted with respect to the acylthiourea plane. Centrosymmetric dimers generated by intermolecular N[sbnd]H?S[dbnd]C and C[sbnd]H?S[dbnd]C hydrogen bonds forming R22 (8) and R21(6) motifs are present in the crystals. The interaction between APHX with benzene has been modelled and calculated using density functional theory (DFT) via Gaussian 09 software package and the preferred sites of binding are located at the acylthiourea group.
A joint theoretical and experimental study of phenylene-acetylene molecular wires
Magyar,Tretiak,Gao,Wang,Shreve
, p. 149 - 156 (2005)
The excited state electronic structure of π conjugated phenylene-acetylene oligomers is calculated using time-dependent density functional theory approaches. The theoretical fluorescence spectra are analyzed in terms of Frank-Condon active nuclear normal modes and shown to compare well with experiment. Theoretical and experimental results for the optical absorption and emission spectra of these molecules indicate that the conjugation length can be significantly reduced by conformational rotations about the triple-bonded carbon links. This has serious implications on the electronic functionalities of polyphenylene-acetylene based molecular wires and their possible use as charge/energy conduits in nano-assemblies.
Magnetic chitosan-functionalized cobalt-NHC: Synthesis, characterization and catalytic activity toward Suzuki and Sonogashira cross-coupling reactions of aryl chlorides
Hajipour, Abdol R.,Malek, Shaghayegh Sadeghi
, (2021/04/23)
Aryl chlorides are one of the most stable and available electrophiles, however, their coupling with nucleophiles remains a challenge in organic synthesis. Herein, we prepared a Cobalt-NHC (N-Heterocyclic carbene) complex anchored on magnetic chitosan nanoparticles and assayed its catalytic activity for the reactions of substituted phenylboronic acid and also phenlacetylene with derivatives of aryl chlorides. These reactions are of great importance since they are employed for the synthesis of unsymmetrical diarylethynes and biphenyls, which belong to a prime class of building blocks. The synthesized nanocatalyst was found to be highly efficient in Suzuki and Sonogashira coupling in terms of their activity and recyclability in polyethylene glycol (PEG) as a green reaction media under conditions of temperatures (70 and 100 °C) and Co loading (3 and 6 mol%). To the best of our knowledge, this is the first attempt of using cobalt-NHC complex for catalyzing the abovementioned reactions. Moreover, replacing the earth-abundant Cobalt-based catalyst as an alternative to high cost palladium make this approach promising from sustainable chemistry view.
Agro waste derived nanosilica supported Pd(ll) complex: A protocol for copper free Sonogashira reaction in water
Gogoi, Rajjyoti,Saikia, Rituraj,Borah, Geetika
, p. 80 - 88 (2019/07/04)
A palladium (II) complex immobilized onto nanosilica(Pd-imine@nanoSiO2) has been developed and evaluated as a highly efficient, retrievable catalyst for carbon-carbon triple bond activation reactions between aryl halides and terminal alkynes. Nanosilica has been derived from rice husk by simple and eco-compatible methodology. The catalyst has been extensively characterized by techniques such as FT-IR, UV–vis, powder XRD, XPS, SEM-EDX, thermogravimetric analysis, BET surface area measurement. The catalyst can be reused for five consecutive runs without compromising much with the activity. Easy preparation, its long shelf life, air-stability, wide substrate scope, ‘in water’ reactions, easy separability and good recyclability make it an ideal system for Sonogashira cross-coupling reaction. Moreover, various alkyne substrates were efficiently cross-coupled with a broad range of aryl iodides and aryl bromides to afford diaryl alkynes, providing improved yields with low catalyst loading in water. This protocol is also suitable for aliphatic alkynes.
A Merrifield resin supported Pd-NHC complex with a spacer(Pd-NHC@SP-PS) for the Sonogashira coupling reaction under copper- and solvent-free conditions
Jadhav, Sanjay N.,Kumbhar, Arjun S.,Mali, Sawanta S.,Hong, Chang Kook,Salunkhe, Rajashri S.
, p. 2333 - 2341 (2015/03/18)
Synthetic applications of a polymer supported air-stable palladium NHC complex with a spacer (catalyst 6, Pd-NHC@SP-PS) and without a spacer (catalyst 7, Pd-NHC@PS) have been studied for the Sonogashira cross-coupling reaction. The catalysts were prepared
Aerobic synthetic approach and characterisation of some acetylide-thiourea derivatives for the detection of carbon monoxide (CO) gas
Daud, Adibah Izzati,Khairul, Wan M.,Mohamed Zuki, Hafiza,Kubulat
, p. 172 - 178 (2015/04/22)
Novel acetylide-thiourea systems (PAT, EBT, and ETT), that possess both withdrawing and donating system properties were successfully synthesised with good yield (64-72%) and were characterised via several spectroscopic and analytical techniques. In turn,
An efficient zinc-catalyzed cross-coupling reaction of aryl iodides with terminal aromatic alkynes
Thankachan, Amrutha P.,Sindhu,Krishnan, K. Keerthi,Anilkumar, Gopinathan
supporting information, p. 5525 - 5528 (2015/09/21)
The first Zn-catalyzed protocol for C(sp2)-C(sp) cross-coupling reactions for the synthesis of disubstituted alkynes is described. A broad spectrum of functional groups is tolerated during the catalysis and successfully afforded a variety of di
Copper-catalyzed decarboxylative cross-coupling of alkynyl carboxylic acids with aryl halides
Zhao, Dongbing,Gao, Chao,Su, Xiaoyu,He, Yunqing,You, Jingsong,Xue, Ying
supporting information; experimental part, p. 9049 - 9051 (2011/02/17)
The copper-catalyzed decarboxylative reactions of alkynyl carboxylic acids with aryl halides were performed under relatively mild reaction conditions. Benzofurans could be further prepared smoothly by a one-pot domino protocol on the basis of decarboxylative cross-coupling of 2-iodophenol.
