Al2O3/CuI/PANI nanocomposite catalyzed green synthesis of biologically active 2-substituted benzimidazole derivatives.

This work is generally focused on the synthesis of an efficient, reusable and novel heterogeneous Al2O3/CuI/PANI nanocatalyst, which has been well synthesized by a simple self-assembly approach where aniline is oxidized into PANI and aniline in the presence of KI also acts as a reductant. The nanocatalyst was well characterized by XRD, FTIR, SEM, EDX, TEM, BET and XPS techniques. In this study, the fabricated material was employed for the catalytic one-pot synthesis of 2-substituted benzimidazoles via condensation between o-phenylenediamine and aldehydes in ethanol as a green solvent. The present method is facile and offers several advantages such as high % yield, less reaction time, and no use of additive/bases. Also, the catalyst showed better values of green metrics including low E-factor: 0.17, high reaction mass efficiency: 85.34%, high carbon efficiency: 94%, and high process mass intensity: 1.17.

[1]  P. Chaudhary,et al.  tert-Butyl nitrite catalyzed synthesis of benzimidazoles from o-phenylenediamine and aldehydes at room temperature , 2020 .

[2]  Hong-yu Zhang,et al.  A one-pot synthesis of benzimidazoles via aerobic oxidative condensation of benzyl alcohols with o-phenylenediamines catalyzed by [MIMPs]+Cl-/NaNO2/TEMPO , 2020 .

[3]  G. Moradi,et al.  Dry Reforming of Methane over Ni-Cu/Al2O3 Catalyst Coatings in a Microchannel Reactor: Modeling and Optimization Using Design of Experiments , 2019, Energy & Fuels.

[4]  D. Rawat,et al.  CuI@Al2O3 catalyzed synthesis of 2-aminonicotinonitrile derivatives under solvent free condition , 2019, Tetrahedron Letters.

[5]  Jianxin Mao,et al.  Preparation of size-controlled Pt supported on Al2O3 nanocatalysts for deep catalytic oxidation of benzene at lower temperature , 2019, Applied Surface Science.

[6]  P. Suresh,et al.  Brønsted acidic reduced graphene oxide as a sustainable carbocatalyst: a selective method for the synthesis of C-2-substituted benzimidazole , 2018 .

[7]  K. Bahrami,et al.  Mesoporous Titania-Alumina Mixed Oxide: A Heterogeneous Nanocatalyst for the Synthesis of 2-Substituted Benzimidazoles, Benzothiazoles and Benzoxazoles , 2018, ChemistrySelect.

[8]  K. Lokesh,et al.  Synthesis and electropolymerization of tetra-[β-(2-benzimidazole)] and tetra-[β-(2-(1-(4- aminophenyl))benzimidazole)] embedded cobalt phthalocyanine and their supercapacitance behaviour , 2018 .

[9]  K. Jayamoorthy,et al.  Switch-on fluorescence of 5-amino-2-mercapto benzimidazole by Mn3O4 nanoparticles: Experimental and theoretical approach , 2018, Journal of Luminescence.

[10]  M. Sheykhan,et al.  Copper-incorporated fluorapatite encapsulated iron oxide nanocatalyst for synthesis of benzimidazoles , 2017, Journal of Nanostructure in Chemistry.

[11]  M. Shingare,et al.  Synthesis of 2-aryl-1-arylmethyl-1H-benzimidazoles using chlorosulfonic acid at room temperature , 2016 .

[12]  Xiaonian Li,et al.  Cu–Pd/γ-Al2O3 catalyzed the coupling of multi-step reactions: direct synthesis of benzimidazole derivatives , 2016 .

[13]  D. Rawat,et al.  CuI nanoparticles mediated expeditious synthesis of 2-substituted benzimidazoles using molecular oxygen as the oxidant , 2016 .

[14]  A. Kokalj,et al.  Effect of Mercapto and Methyl Groups on the Efficiency of Imidazole and Benzimidazole-based Inhibitors of Iron Corrosion. , 2016, Acta chimica Slovenica.

[15]  Xiufang Wang,et al.  Facile fabrication of reduced graphene oxide/CuI/PANI nanocomposites with enhanced visible-light photocatalytic activity , 2016 .

[16]  P. Puthiaraj,et al.  Synthesis of copper nanoparticles supported on a microporous covalent triazine polymer: an efficient and reusable catalyst for O-arylation reaction , 2016 .

[17]  Rajender S Varma,et al.  Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis. , 2016, Chemical reviews.

[18]  J. Azizian,et al.  Synthesis of benzimidazoles and benzoxazoles using TiCl3OTf in ethanol at room temperature , 2016 .

[19]  F. Shirini,et al.  Synthesis of benzimidazole and quinoxaline derivatives using reusable sulfonated rice husk ash (RHA-SO3H) as a green and efficient solid acid catalyst , 2016, Research on Chemical Intermediates.

[20]  Y. Xu,et al.  Catalytic oxidation of gaseous benzene with ozone over zeolite-supported metal oxide nanoparticles at room temperature , 2015 .

[21]  F. Alonso,et al.  Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite , 2015 .

[22]  D. Rawat,et al.  Cu(0)@Al2O3/SiO2 NPs: an efficient reusable catalyst for the cross coupling reactions of aryl chlorides with amines and anilines , 2015 .

[23]  H. García,et al.  Copper Nanoparticles Stabilized in a Porous Chitosan Aerogel as a Heterogeneous Catalyst for C−S Cross‐coupling , 2015 .

[24]  F. Alonso,et al.  Copper Nanoparticles in Click Chemistry. , 2015, Accounts of chemical research.

[25]  S. H. Siddiki,et al.  Acceptorless dehydrogenative synthesis of benzothiazoles and benzimidazoles from alcohols or aldehydes by heterogeneous Pt catalysts under neutral conditions , 2015 .

[26]  F. Alonso,et al.  Direct synthesis of β-ketophosphonates and vinyl phosphonates from alkenes or alkynes catalyzed by CuNPs/ZnO , 2015 .

[27]  P. D. de Jongh,et al.  Recent developments in the synthesis of supported catalysts. , 2015, Chemical reviews.

[28]  F. Alonso,et al.  Synthetic and Mechanistic Studies on the Solvent-Dependent Copper-Catalyzed Formation of Indolizines and Chalcones , 2015 .

[29]  A. Violi,et al.  Size-and phase-dependent structure of copper(II) oxide nanoparticles , 2015 .

[30]  Yanli Zhao,et al.  Cu0 Nanoparticles Deposited on Nanoporous Polymers: A Recyclable Heterogeneous Nanocatalyst for Ullmann Coupling of Aryl Halides with Amines in Water , 2015, Scientific Reports.

[31]  O. Stéphan,et al.  Direct Evidence of Surface Oxidation of Cobalt Nanoparticles in Alumina-Supported Catalysts for Fischer–Tropsch Synthesis , 2014 .

[32]  A. Hajipour,et al.  C–N cross‐coupling reaction catalysed by efficient and reusable CuO/SiO2 nanoparticles under ligand‐free conditions , 2014 .

[33]  O. Silakari,et al.  Benzimidazoles: an ideal privileged drug scaffold for the design of multitargeted anti-inflammatory ligands. , 2014, Mini reviews in medicinal chemistry.

[34]  J. You,et al.  Magnetically recoverable and reusable CuFe2O4 nanoparticle-catalyzed synthesis of benzoxazoles, benzothiazoles and benzimidazoles using dioxygen as oxidant , 2014 .

[35]  Mahboube Ghahramaninezhad,et al.  Reusable α-MoO3 nanobelts catalyzes the green and heterogeneous condensation of 1,2-diamines with carbonyl compounds , 2013 .

[36]  K. V. Mohan,et al.  Monodispersed and Stable Nano Copper(0) from Copper‐ Aluminium Hydrotalcite: Importance in CC Couplings of Deactivated Aryl Chlorides , 2013 .

[37]  S. Mandal,et al.  CuO nano-particles supported on silica, a new catalyst for facile synthesis of benzimidazoles, benzothiazoles and benzoxazoles , 2013 .

[38]  Yoshinori Yamamoto,et al.  Click Chemistry of Alkyne–Azide Cycloaddition using Nanostructured Copper Catalysts , 2012 .

[39]  Li-Ping Hao,et al.  Design, synthesis and biological evaluation of 6-substituted aminocarbonyl benzimidazole derivatives as nonpeptidic angiotensin II AT1 receptor antagonists. , 2012, European journal of medicinal chemistry.

[40]  Yuhua Shen,et al.  Novel structure CuI/PANI nanocomposites with bifunctions: superhydrophobicity and photocatalytic activity , 2011 .

[41]  M. Yus,et al.  Homocoupling of Terminal Alkynes Catalysed by Ultrafine Copper Nanoparticles on Titania , 2011 .

[42]  Hengshan Wang,et al.  Synthesis of a Dehydroabietyl Derivative Bearing a 2-(2′-Hydroxyphenyl)Benzimidazole Unit and Its Selective Cu2+ Chemosensing , 2010, Molecules.

[43]  Cheng‐He Zhou,et al.  Synthesis and biological activities of novel amine-derived bis-azoles as potential antibacterial and antifungal agents. , 2010, European journal of medicinal chemistry.

[44]  Michael I. Hall,et al.  Synthesis of benzazoles by hydrogen-transfer catalysis. , 2009, Organic letters.

[45]  Diego Luna,et al.  Sustainable preparation of supported metal nanoparticles and their applications in catalysis. , 2009, ChemSusChem.

[46]  G. Evano,et al.  Copper-mediated coupling reactions and their applications in natural products and designed biomolecules synthesis. , 2008, Chemical reviews.

[47]  Mira Josowicz,et al.  Composites of intrinsically conducting polymers as sensing nanomaterials. , 2008, Chemical reviews.

[48]  K. Bahrami,et al.  A Simple and Efficient One-Pot Synthesis of 2-Substituted Benzimidazoles , 2007 .

[49]  M. Curini,et al.  Ytterbium Triflate Promoted Synthesis of Benzimidazole Derivatives , 2004 .

[50]  H. Altenbach,et al.  Synthesis and resolution of 2-(2-diphenylphosphinyl-naphthalen-1-yl)-1-isopropyl-1H-benzoimidazole; a new atropisomeric P,N-chelating ligand for asymmetric catalysis , 2002 .

[51]  K. Janda,et al.  Traceless solid-phase synthesis of 5-benzoylbenzimidazoles , 2001 .

[52]  P. Kirsch,et al.  Chemical and thermal reduction of thin films of copper (II) oxide and copper (I) oxide , 2001 .

[53]  J. Iqbal,et al.  Polyaniline-Supported Cobalt Catalyst: A Three-Component Condensation Route to beta-Amino Acid Derivatives. , 1999, The Journal of organic chemistry.

[54]  W. Denny,et al.  Potential antitumor agents. 59. Structure-activity relationships for 2-phenylbenzimidazole-4-carboxamides, a new class of "minimal" DNA-intercalating agents which may not act via topoisomerase II. , 1990, Journal of medicinal chemistry.

[55]  A. Brambilla,et al.  Anti-secretory and anti-ulcer activities of some new 2-(2-pyridylmethyl-sulfinyl)-benzimidazoles , 1987 .

[56]  P. N. Preston,et al.  Synthesis, reactions, and spectroscopic properties of benzimidazoles , 1974 .

[57]  F. Gualtieri,et al.  Antiviral agents. 2. Analogs of 2-(.alpha.-hydroxybenzyl)benzimidazole , 1972 .

[58]  J. B. Wright.  The chemistry of the benzimidazoles. , 1951, Chemical reviews.