Fluorescent Aminal Linked Porous Organic Polymer for Reversible Iodine Capture and Sensing Muhammad A
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New Insights Into the Mechanism of Schiff Base Synthesis from Aromatic
A peer-reviewed version of this preprint was published in PeerJ on 15 December 2020. View the peer-reviewed version (peerj.com/articles/ochem-4), which is the preferred citable publication unless you specifically need to cite this preprint. Silva PJ. 2020. New insights into the mechanism of Schiff base synthesis from aromatic amines in the absence of acid catalyst or polar solvents. PeerJ Organic Chemistry 2:e4 https://doi.org/10.7717/peerj-ochem.4 New insights into the mechanism of Schiff base synthesis from aromatic amines in the absence of acid catalyst or polar solvents Pedro J Silva Corresp. 1 1 FP-ENAS/Fac. de Ciências da Saúde, Universidade Fernando Pessoa, Porto, Portugal Corresponding Author: Pedro J Silva Email address: [email protected] Extensive computational studies of the imine synthesis from amines and aldehydes in water have shown that the large-scale structure of water is needed to afford appropriate charge delocalisation and enable sufficient transition state stabilisation. These insights cannot, however, be applied to the understanding of the reaction pathway in apolar solvents due their inability to form extensive hidrogen-bonding networks. In this work, we perform the first computational studies of this reaction in apolar conditions. This density- functional study of the reaction of benzaldehyde with four closely related aromatic amines (aniline, o-toluidine, m-toluidine and p-toluidine) shows that an additional molecule of amine may provide enough stabilization of the first transition state even in the absence of a hydrogen bonding network. Our computations also show that the second reaction step cannot take place unless an extra proton is added to the system but, crucially, that reaction rate is so high that even picomolar amounts of protonated base are enough to achieve realistic rates. -
Synthesis and Structural Studies of a New Class of Quaternary Ammonium
Rivera et al. Chemistry Central Journal 2011, 5:55 http://journal.chemistrycentral.com/content/5/1/55 RESEARCHARTICLE Open Access Synthesis and structural studies of a new class of quaternary ammonium salts, which are derivatives of cage adamanzane type aminal 1, 3, 6, 8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) Augusto Rivera1*, John Sadat-Bernal1, Jaime Ríos-Motta1, Michal Dušek2 and Lukáš Palatinus2 Abstract Background: Novel mono N-alkyl quaternary ammonium salts (3a-f) were prepared using the Menschutkin reaction from the cage adamanzane type aminal 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) and alkyl iodides, such as methyl, ethyl, propyl, butyl, pentyl and hexyl iodide (2a-f), in dry acetonitrile at room temperature. Results: The structures of these new quaternary ammonium salts were established using various spectral and electrospray ionization mass spectrometry (ESI-MS) analyses. Compound (3b) was also analyzed using X-ray crystallography. Conclusion: It was noted that alkyl chain length did not significantly affect the reaction because all employed alkyl iodide electrophiles reacted in a similar fashion with the aminal 1 to produce the corresponding mono N- quaternary ammonium salts, which were characterized by spectroscopic and analytical techniques. Background amines with haloalkyls [7]. We found that no reaction Cage aminals of the adamanzane type are tricyclic ter- occurred when N-alkylation was attempted using alkyl tiary tetraamines, which can act as bases or as nucleo- bromides and chlorides. Compound 1 reacts with alkyl philes. The main subject of research in our laboratory iodides in dry acetonitrile at room temperature to pro- (Universidad Nacional, Bogotá) is the reactivity of these duce mono N-alkyl ammonium quaternary salts (3a-f) polyamine bases toward nucleophiles and electrophiles. -
Research Journal of Pharmaceutical, Biological and Chemical Sciences
ISSN: 0975-8585 Research Journal of Pharmaceutical, Biological and Chemical Sciences Metal Complexes of Schiff's Bases Containing Sulfonamides Nucleus: A Review. Zainab Hussain1, Majid Khalaf2, Hadeel Adil2, Dheaa Zageer2, 3, Firas Hassan2, Salam Mohammed4, and Emad Yousif1*. 1Department of Chemistry, College of Science, Misan University, Misan, Iraq . 2Department of Chemistry, College of Science, Al-Nahrain University, Baghdad, Iraq. 3Forensic DNA Center for Research and Training, Al-Nahrain University, Baghdad, Iraq. 4College of Engineering and Architecture, University of Nizwa, Birkat Almouz, 616 Nizwa, Oman. ABSTRACT Schiff's bases are versatile ligands which are synthesized from the condensation of primary amines with carbonyl groups. Schiff's bases play an important role in Inorganic chemistry due to formation of very stable complexes with various transition and inner-Transition Metals. Transition metal complexes derived from the Schiff base ligands have widly applications. This review summarizes some metal complexes of schiff's bases derived from sulfonamide derivatives and reviewed the applications of Schiff's bases chelates in quantitative analysis. Keywords: Schiff bases, Metal complexes, Quantitative analysis. *Corresponding author September – October 2016 RJPBCS 7(5) Page No. 1008 ISSN: 0975-8585 Overview of of Schiff's bases A Schiff's base is a nitrogen analog of an aldehyde or ketone in which the C=O group is replaced by C=N-R group. It is usually formed by condensation of an aldehyde or ketone with a primary amine according to the following scheme (Scheme 1): Scheme 1: Formation of Schiff's bases. Where R, may be an alkyl or an aryl group. Schiff's bases that contain aryl substituents are substantially more stable and more readily synthesized, while those which contain alkyl substituents are relatively unstable. -
Synthesis and Characterization of Polymeric Schiff Bases
SYNTHESIS AND CHARACTERIZATION OF POLYMERIC SCHIFF BASES FROM 2,5-DIFORMYLFURAN A Thesis Present to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Master of Science Tengfei Xiang December, 2012 SYNTHESIS AND CHARACTERIZATION OF POLYMERIC SCHIFF BASES FROM 2,5-DIFORMYLFURAN Tengfei Xiang Thesis Approved: Accepted: Advisor Dean of the College Dr. Yi Pang Dr. Chand Midha Co-Advisor Dean of the Graduate School Dr. Ping Yi Dr. George R. Newkome Department Chair Date Dr. Kim C. Calvo ii ABSTRACT Furan derivatives have the potential to be an alternative resource since it can be obtained from biomass in large scale. Many monomers derived from furfural and 5-hydroxymethylfurfural (HMF), have been used in polymerization investigation in recent years. However, few studies in using 2,5-diformylfuran(DFF) as monomer has been reported, probably due to the limited availability of monmer. Polymeric Schiff bases (or polyimines) is a class of materials containing –CH=N structural unit, which exhibit good thermal stability, useful mechanical properties. In this work, the polymeric Schiff bases obtained from polycondensation of DFF and aromatic, aliphatic diamines, and more comprehensive characterization study has been carried out. FT-IR and 13C Solid NMR study of products confirmed the formation of – CH=N structural unit. And MALDI-TOF mass spectrum showed a typical polymer pattern, providing further understanding on the polymerization process. Thermal Analysis had also been carried out for both alphatic and aromatic polymeric Schiff Bases. iii DEDICATION I would like to dedicate this thesis to my mother, Yumei Jiang, for her love, patience and understanding. -
Synthesis of Monocyclic Diaziridines and Their Fused Derivatives
Special Issue Reviews and Accounts ARKIVOC 2008 (i) 128-152 Synthesis of monocyclic diaziridines and their fused derivatives Nina N. Makhova,* Vera Yu. Petukhova, and Vladimir V. Kuznetsov N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47, Leninsky prosp., 119991 Moscow, Russian Federation E-mail: [email protected] Abstract Diaziridines and their fused analogues have a wide-range potential as a test subjects for theoretical and practical application. This review covers our investigations focused on the development of optimal methods for the synthesis of monocyclic and fused diaziridine derivatives. Several approaches to the preparation of monocyclic diaziridine derivatives were developed: (1) a synthesis of 3,3-di- and 1,3,3-trialkylmono- and α,ω-bis(diaziridin-1-yl)alkanes from ketoxime O-sulfonates and ammonia, and primary aliphatic amines, respectively, as well as of practically previously inaccessible 3-monoalkyldiaziridines from ammonium salts of aldoxime O-sulfonic acids and ammonia (2) a synthesis of diaziridines from carbonyl compounds, primary aliphatic amines, and aminating reagents in water (or a water–MeOH mixture) at controlled pH of the medium, as well as from carbonyl compounds, amines and N-chloroalkylamines in aprotic solvents in the presence of K2CO3, and (3) a synthesis of 1,2,3-trialkyldiaziridines from N- chloroalkylamines without carbonyl compounds in the presence of primary aliphatic amines at high pressure. As regards fused diaziridine derivatives, general and simple methods were developed to prepare four types of these structures: 1,5-diazabicyclo[3.1.0]hexanes, 1,6- diazabicyclo[4.1.0]heptanes, 1,3,5-triazabicyclo[3.1.0] hexanes, including the parent compound and 2,4-nonsubstituted structures, and 1,3,6-triazabicyclo[3.1.0]hexanes, the latter being previously unknown. -
Derivatives of the Triaminoguanidinium Ion, 6. Aminal-Forming Reactions with Aldehydes and Ketones [9]
Z. Naturforsch. 2020; 75(3)b: 317–326 Jan Szabo and Gerhard Maas* Derivatives of the triaminoguanidinium ion, 6. Aminal-forming reactions with aldehydes and ketones https://doi.org/10.1515/znb-2019-0216 [9]. Some years ago, we started to study the chemistry of Received December 5, 2019; accepted January 19, 2020 salts 3, which in particular were expected to undergo mul- tiple functionalization based on the nucleophilicity of the Abstract: Cyclic aminals (N,N-acetals) could be prepared benzyl-NH nitrogen atom. Thus, 3-Cl was found to undergo by the reaction of N,N′,N″-triaminoguanidinium sul- threefold N-carbamoylation with various arylisocyanates fate, N,N′,N″-tris(benzylamino)guanidinium chloride or and thiocarbamoylation (leading to thiourea derivatives) N,N′,N″-tris(benzylamino)guanidine with formaldehyde with arylisothiocyanates [10]. In a similar manner, triple or acetone. In all cases, 1,2,4,5-tetrazinane derivatives N-acylation with acid chlorides produced N,N′,N″-tris(N- were obtained, which were structurally confirmed by X-ray acyl-N-benzylamino)guanidines, which under the action crystal structure determinations. In two cases, 1:1 cocrys- of aqueous NaOH could be transformed into mesoionic tals of two different tetrazinane products were isolated. On 1,2,4-triazolium-3-aminides [11]. Reactions of salts 3 with the other hand, the reaction of N,N′,N″-tris(benzylamino) aldehydes or ketones have not been reported so far. guanidinium chloride with benzaldehyde yielded a The presence of three amino groups in the cations of 3-(2-benzylidenehydrazin-1-yl)-1H-1,2,4-triazole. -
New Insights Into the Mechanism of Schiff Base Synthesis from Aromatic Amines in the Absence of Acid Catalyst Or Polar Solvents
New insights into the mechanism of Schiff base synthesis from aromatic amines in the absence of acid catalyst or polar solvents Pedro J. Silva1,2 1 FP-ENAS/Fac. de Ciências da Saúde, Universidade Fernando Pessoa, Porto, Portugal 2 UCIBIO@REQUIMTE, BioSIM, Departamento de Biomedicina, Faculdade de Medicina, Universidade do Porto, Porto, Portugal ABSTRACT Extensive computational studies of the imine synthesis from amines and aldehydes in water have shown that the large-scale structure of water is needed to afford appropriate charge delocalization and enable sufficient transition state stabilization. These insights cannot, however, be applied to the understanding of the reaction pathway in apolar solvents due their inability to form extensive hydrogen-bonding networks. In this work, we perform the first computational studies of this reaction in nonpolar conditions. This density-functional study of the reaction of benzaldehyde with four closely related aromatic amines (aniline, o-toluidine, m-toluidine and p-toluidine) shows that, although an additional molecule of amine may provide some stabilization of the first transition state even in the absence of a hydrogen bonding network, this is insufficient to achieve high reaction rates. Our computations also show that when an extra proton is added to the spectator amine, the activation energies become so low that even picomolar amounts of protonated base are enough to achieve realistic rates. Additional computations show that those minute amounts of protonated base may be obtained under reaction conditions without the addition of extraneous acid through the auto-protolysis of the amines themselves. To our knowledge, this is the first report of a role for the auto-protolysis of anilines in their extensive reactional repertoire. -
Mannich Reaction
1. Introduction 1.1- Mannich Reaction The Mannich reaction is three component condensation in which a compound containing an active hydrogen atom is allowed to react with formaldehyde and an NH-amine derivative . Secondary amines rather than primary amines and ammonia are employed , the resulting product (Mannich Base ) is an amine compound having the N atom linked to the R substrate through a methylene group 1,2. The aminoalkylation of CH-acidic compounds was described by several authors as early as the 19th. century. However, it was Carl Mannich who was the first to recognize the enormous significance of this reaction , and it was he who extended the chemistry into a broad based synthetic methodology through systematic research. Since then this reaction that now carries his name has developed into one of the most important C-C bond-forming reactions in organic chemistry3,4. The Mannich reaction is a classical method for the preparation of β -aminoketones and aldehydes (Mannich bases) and, as such, is one of the most important basic reaction types in organic chemistry. It is the key step in the synthesis of numerous pharmaceuticals and natural products3,4. 1 The Mannich reaction can be presented by the following equation: The essential feature of the reaction is the replacement of the active hydrogen atom by an aminomethyl or substituted aminomethyl group. The symbolizes the active hydrogen component which includes ketones, aldehydes, acids, esters, phenols, acetylenes, picolines, nitroalkanes and quinolines1,2. 1.2- Mechanism of the Mannich reaction The mechanism of the Mannich reaction has been well investigated, the condensation reaction occurs in two steps: first, the amine reacts with formaldehyde to give condensation product (5 ), (6), ( 7) (step I) which then attacks the substrate R-H (step II) .The reaction does not normally follow the other possible route (step III and IV) ; however, some successful reaction between hydroxymethyl derivatives (8) and alkylamines to give Mannich bases (9) should be mentioned . -
Synthesis and Characterization of Some Novel Mannich Base Compounds
Synthesis and Characterization of Some Novel Mannich Base Compounds Dr. P. Sounthari Dr. P. R. Sivakumar Dr. P. Sounthari Dr. P.R. Sivakumar Assistant Professor, PG & Research Department of Department of Chemistry, Chemistry, PSG College of Arts and Government Arts Science, Coimbatore- College (Autonomous), 641 014. Coimbatore - 641 018, Tamil Nadu, India. ISBN 978-93-89631-02-9 ISBN 978-93-89631-04-3 (eBook) https://doi.org/10.34256/ioriip196 © IOR INTERNATIONAL PRESS. This book is an open access publication. Open Access This book is licensed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license and indicate if changes were made. The images or other third party material in this book are included in the book’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the book’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. -
Synthesis and Characterization of Covalent Adaptable Networks
Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 3-19-2018 Synthesis and Characterization of Covalent Adaptable Networks Comprised of Dynamic Imine and Aminal Covalent Bonds Albert Chao Louisiana State University and Agricultural and Mechanical College, [email protected] Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Organic Chemistry Commons, and the Polymer Chemistry Commons Recommended Citation Chao, Albert, "Synthesis and Characterization of Covalent Adaptable Networks Comprised of Dynamic Imine and Aminal Covalent Bonds" (2018). LSU Doctoral Dissertations. 4506. https://digitalcommons.lsu.edu/gradschool_dissertations/4506 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. SYNTHESIS AND CHARACTERIZATION OF COVALENT ADAPTABLE NETWORKS COMPRISED OF DYNAMIC IMINE AND AMINAL COVALENT BONDS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Albert Chao B.A., University of Cincinnati, 2010 May 2018 Acknowledgements I would like to thank my advisor Prof. Donghui Zhang for her guidance, mentorship, and financial support on the projects I have worked on during the past 5 years in graduate school at Louisiana State University. Prof. Donghui Zhang allowed me to think independently and develop projects from the beginning to the end. When I lost interest on each project, her patience and encouragement always turned failure into success. -
The Preparation and Use of Metal Salen Complexes Derived from Cyclobutane Diamine
THE PREPARATION AND USE OF METAL SALEN COMPLEXES DERIVED FROM CYCLOBUTANE DIAMINE by SMITA S. PATIL B. Tech., University of Mumbai, 2005 M. Tech., University of Mumbai, 2007 AN ABSTRACT OF A DISSERTATION Submitted in partial fulfillment of the requirements for the degree DOCTOR OF PHILOSOPHY Department of Chemistry College of Arts and Sciences KANSAS STATE UNIVERSITY Manhattan, Kansas 2014 Abstract The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. -
Exploiting Intramolecularity: Exploring Aldehyde-Catalyzed Intermolecular Hydroaminations and Mixed Aminal Chemistry by Didier A
Exploiting Intramolecularity: Exploring Aldehyde-Catalyzed Intermolecular Hydroaminations and Mixed Aminal Chemistry By Didier Alexandre Bilodeau Thesis submitted to the Faculty of Graduate and Postdoctoral Studies University of Ottawa In partial fulfillment of the requirements for the M.Sc. degree in the Ottawa-Carleton Chemistry Institute University of Ottawa Candidate Supervisor Didier Alexandre Bilodeau Dr. André M. Beauchemin © Didier Alexandre Bilodeau, Ottawa, Canada, 2018 Abstract Hydroamination reactions are very attractive to form new C-N bonds, though broadly applicable synthetic methods do not exist. The hydroamination of unactivated alkenes is especially difficult to accomplish given its negative reaction entropy, as well as potentially being a thermodynamically unfavourable transformation with some substrates. Thus, previously reported systems have often consisted of biased intramolecular systems or metal-catalyzed intermolecular variations operating at low temperatures. Recently, our group discovered that intermolecular Cope-type hydroamination of unactivated alkenes is achievable through the use of aldehydes as catalysts. These organocatalysts act solely through promoting the pre-association of reacting partners, hydroxylamines and allyl amines, in order to induce temporary intramolecularity; thus allowing for very mild reaction conditions and access to important 1,2-Diamine motifs. Aldehyde Catalyzed Intermolecular Cope-Type Hydroamination Catalysis through Temporary Intramolecularity This thesis presents studies expanding upon initial reports of aldehyde-catalyzed Cope-type intermolecular hydroamination. In the scope of these studies standard conditions were developed to compare aldehyde catalytic activity. These evaluations led to further strengthening our understanding of hypothesized trends in aldehydes’ catalytic efficiencies, ii notably the impact of electronic, steric and solvent effects. Furthermore, the possibility of using a catalytic precursor species for hydroamination was evaluated.