Volcanic ash as reusable catalyst in the green synthesis of 3H-1,5-benzodiazepines

Abstract The volcanic ash from the Andes mountain range (Puyehue-Cordon Caulle volcanic complex situated in western South America on the Argentinean-Chilean border) was used as heterogeneous acid catalyst in the suitable synthesis of 3H-1,5-benzodiazepines. The natural ashes were classified according to their particle size to generate the different catalytic materials. The catalysts were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), vibrational spectroscopies (FT-IR and Raman), and textural properties were determined by N2 adsorption (SBET). Potentiometric titration with n-butylamine was used to determine the acidic properties of the catalytic materials. Several 3H-1,5-benzodiazepines were obtained by reaction of o-phenylenediamine and substituted 1,3-diphenyl-1,3-propanedione in solvent-free conditions, giving good to excellent yields of a variety benzodiazepines. The method was carried out in environmentally friendly conditions and it was operationally simple. The volcanic ash resulted in a safe and recyclable catalyst.

[1]  Z. Siddiqui,et al.  Nano silica-bonded N-propylsulfamic acid as an efficient and environmentally benign catalyst for the synthesis of 1,5-benzodiazepines , 2017, Monatshefte für Chemie - Chemical Monthly.

[2]  B. Török,et al.  Regioselective “hydroamination” of alk-3-ynones with non-symmetrical o-phenylenediamines. Synthesis of diversely substituted 3H-1,5-benzodiazepines via (Z)-3-amino-2-alkenones , 2016 .

[3]  M. Casella,et al.  Composites based on modified clay assembled Rh(III)–heteropolymolybdates as catalysts in the liquid-phase hydrogenation of cinnamaldehyde , 2016 .

[4]  G. Romanelli,et al.  A very simple solvent-free method for the synthesis of 2-arylchromones using KHSO4 as a recyclable catalyst , 2016 .

[5]  M. Zolfigol,et al.  Synthesis and characterization of two novel biological-based nano organo solid acids with urea moiety and their catalytic applications in the synthesis of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ol), coumarin-3-carboxylic acid and cinnamic acid derivatives under mild and green conditions , 2015 .

[6]  M. González,et al.  Pyroclasts of the First Phases of the Explosive-Effusive PCCVC Volcanic Eruption: Physicochemical Analysis , 2015 .

[7]  S. Z. Sayyed-alangi,et al.  ZnO Nanorods as an Efficient Catalyst for the Green Synthesis of Indole Derivatives Using Isatoic Anhydride , 2015, Chemistry of Heterocyclic Compounds.

[8]  S. S. Beigbaghlou,et al.  Use of a highly efficient and recyclable solid-phase catalyst based on nanocrystalline titania for the Pechmann condensation , 2014 .

[9]  G. Baronetti,et al.  Wells-Dawson type catalyst: An efficient, recoverable, and reusable solid acid catalyst for the solvent-free synthesis of benzodiazepines , 2014 .

[10]  J. Menéndez,et al.  Montmorillonite Clay-Promoted, Solvent-Free Cross-Aldol Condensations under Focused Microwave Irradiation , 2014, Molecules.

[11]  G. Romanelli,et al.  Preyssler Catalyst-Promoted Rapid, Clean, and Efficient Condensation Reactions for 3H-1,5-Benzodiazepine Synthesis in Solvent-Free Conditions. , 2014 .

[12]  K. Pitchumani,et al.  Solvent-Free Syntheses of 1,5-Benzodiazepines Using HY Zeolite as a Green Solid Acid Catalyst , 2014 .

[13]  G. Romanelli,et al.  Preyssler catalyst-promoted rapid, clean, and efficient condensation reactions for 3H-1,5-benzodiazepine synthesis in solvent-free conditions , 2013 .

[14]  M. González,et al.  Spectroscopic and Microscopic Characterization of Volcanic Ash from Puyehue-(Chile) Eruption: Preliminary Approach for the Application in the Arsenic Removal , 2013 .

[15]  Francesca M. Kerton,et al.  Alternative Solvents for Green Chemistry , 2013 .

[16]  M. Capron,et al.  Porous modified bentonite as efficient and selective catalyst in the synthesis of 1,5-benzodiazepines , 2013, Journal of Porous Materials.

[17]  Waheed Ahmad Khanday,et al.  Synthesis of 1,5-Benzodiazepine and Its Derivatives by Condensation Reaction Using H-MCM-22 as Catalyst , 2012, Journal of biomedicine & biotechnology.

[18]  N. Kaur,et al.  Montmorillonite : An efficient , heterogeneous and green catalyst for organic synthesis , 2012 .

[19]  M. Swaminathan,et al.  Solvent free synthesis of quinoxalines, dipyridophenazines and chalcones under microwave irradiation with sulfated Degussa titania as a novel solid acid catalyst , 2011 .

[20]  G. Nagendrappa.  Organic synthesis using clay and clay-supported catalysts , 2011 .

[21]  M. Himaja,et al.  GREEN TECHNIQUE-SOLVENT FREE SYNTHESIS AND ITS ADVANTAGES , 2011 .

[22]  Benjamin Willy,et al.  Three-Component Synthesis of Cryofluorescent 2,4-Disubstituted 3H-1,5-Benzodiazepines – Conformational Control of ­Emission Properties , 2008 .

[23]  J. Stephanidou-Stephanatou,et al.  An experimental and theoretical study on the regioselectivity of successive bromination sites of 7,8-dimethyl-2,4-diphenyl-3H-1,5-benzodiazepine. Efficient microwave assisted solventless synthesis of 4-phenyl-3H-1,5-benzodiazepines , 2008 .

[24]  I. Mohammadpoor‐Baltork,et al.  Efficient synthesis of 1,5-benzodiazepines catalyzed by silica supported 12-tungstophosphoric acid , 2008 .

[25]  Christian Capello,et al.  What is a green solvent? A comprehensive framework for the environmental assessment of solvents , 2007 .

[26]  D. Jung,et al.  Synthesis of 1H-1,5-Benzodiazepine Derivatives and Pyridinylquinoxalines with Heterocyclic Ketones , 2007 .

[27]  Ramu Enugala,et al.  Zinc montmorillonite as a reusable heterogeneous catalyst for the synthesis of 2,3-dihydro-1H-1,5-benzodiazepine derivatives , 2006 .

[28]  .. M.A.Pasha,et al.  An Expeditious Synthesis of 1,5-Benzodiazepine Derivatives Catalysed by p-toluenesulfonic Acid , 2006 .

[29]  K. Nagaiah,et al.  Indium(III) Bromide: A Novel and Efficient Reagent for the Rapid Synthesis of 1,5-Benzodiazepines under Solvent-Free Conditions. , 2005 .

[30]  B. Insuasty,et al.  Preparation of some light-sensitive 2-nitrophenyl-2,3-dihydro-1H-benzodiazepines , 2004 .

[31]  B. M. Reddy,et al.  An efficient synthesis of 1,5-benzodiazepine derivatives catalyzed by a solid superacid sulfated zirconia , 2003 .

[32]  P. Vázquez,et al.  Equilibrium adsorption of molybdosilicic acid solutions on carbon and silica: basic studies for the preparation of ecofriendly acidic catalysts. , 2002, Journal of colloid and interface science.

[33]  J. Stephanidou-Stephanatou,et al.  An Efficient Method for the Synthesis of 1,5‐Benzodiazepine Derivatives under Microwave Irradiation Without Solvent. , 2002 .

[34]  James H. Clark,et al.  Solid acids for green chemistry. , 2002, Accounts of chemical research.

[35]  J. Stephanidou-Stephanatou,et al.  An efficient method for the synthesis of 1,5-benzodiazepine derivatives under microwave irradiation without solvent , 2002 .

[36]  Raju Jannapu Reddy,et al.  Synthesis of 4,6‐Bis(2′‐substituted‐2′,3′‐dihydro‐1,5‐benzothiazepin‐4′ ‐yl)resorcinols as Potential Antifeedants. , 1993 .

[37]  K. Jadhav,et al.  SYNTHESIS OF 2,4-DIARYL-2,3-DIHYDRO-1,5-BENZOTHIAZEPINES AND THEIR 1,1-DIOXIDES AS ANTIBACTERIAL AGENTS , 1983 .