DOCSLIB.ORG

A Systematic Approach to Understanding Organic Reactivity

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

A Systematic Approach to Understanding Organic Reactivity in Ionic Liquids: Changes in Cybotacticity-Induced Solvent Heterogeneity as an Important Determinant In Reaction Outcomes of Substitution Processes This thesis is presented for the partial fulfilment of the requirements for the degree of Doctor of Philosophy in the School of Chemistry by Hon Man Yau October, 2011 PLEASE TYPE THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: Yau First name: Hon Man Other name/s: Abbreviation for degree as given in the University calendar: Ph.D. School: School of Chemistry Faculty: Science Title: A Systematic Approach to Understanding Organic Reactivity in Ionic Liquids: Changes in Cybotacticity-Induced Solvent Heterogeneity as an Important Determinant In Reaction Outcomes of Substitution Processes Abstract 350 words maximum: (PLEASE TYPE) Described herein is the initial development towards a general framework for predicting changes in organic reactivity in ionic liquids through the mechanistic studies of several representative substitution processes with well-defined mechanisms. The temperature-dependent kinetic behaviour of the ethanolysis of 1-fluoro-2,4-dinitrobenzene as a model nucleophilic aromatic substitution reaction was examined in molecular and ionic solvents. Activation parameters obtained and relevant molecular dynamics simulations performed highlight the importance of cybotactic regions characterised by anion-π interaction. Activation parameters and free energy relationships for the Menschutkin reactions between pyridine and a series of substituted benzyl bromides and unsubstituted benzyl halides in both molecular and ionic liquid solvents were investigated. The Menschutkin reaction was found to be entropically favoured in ionic liquid regardless of the leaving group involved. By systematically replacing the aromatic starting materials with non-aromatic ones, the effect of delocalised electron density in either the electrophile or the nucleophile of the aforementioned Menschtkin reaction was evaluated. Cybotacticity associated with nitrogen centre in the nucleophiles and related changes were found to be responsible for changes in reactivity observed on changing solvent to the ionic liquid and are consistent with related molecular dynamics simulations of the starting materials. Kinetic analyses were also carried out for the reaction between 1-(1-chloroethyl)-4-methoxybenzene and pyridine, which proceeds through both unimolecular and bimolecular pathways simultaneously. The results are discussed in relation to the bimolecular Menschutkin reactions presented in the early chapters of this thesis as well as previous work on a unimolecular substitution process and the potential for solvent-controlled reactivity is discussed. The Menschutkin reaction between benzyl bromide and pyridine was investigated in ionic liquids composed of either a 1,3- dialkylimidazolium cation or a 1,2,3-trialkylimidazolium cation. The generality of electrostatic interactions and the impact of charge density were examined based on the activation parameters obtained from temperature-dependent kinetics analysis. A general “one-pot” method for obtaining relative rates of reaction in complex mixtures has been established through the construction of free energy relationships for various reactions under competitive conditions. The advantages of the technique, compared to existing methods in the literature, are discussed in terms of accuracy, efficiency and applicability. Declaration relating to disposition of project thesis/dissertation I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or in part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all property rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral theses only). 21st February, 2012. .. ..... Signature Witness Date The University recognises that there may be exceptional circumstances requiring restrictions on copying or conditions on use. Requests for restriction for a period of up to 2 years must be made in writing. Requests for a longer period of restriction may be considered in exceptional circumstances and require the approval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: THIS SHEET IS TO BE GLUED TO THE INSIDE FRONT COVER OF THE THESIS COPYRIGHT STATEMENT ‘I hereby grant the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all proprietary rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstract International (this is applicable to doctoral theses only). I have either used no substantial portions of copyright material in my thesis or I have obtained permission to use copyright material; where permission has not been granted I have applied/will apply for a partial restriction of the digital copy of my thesis or dissertation.' Signed .............................................................................. Date .................................................................................. AUTHENTICITY STATEMENT ‘I certify that the Library deposit digital copy is a direct equivalent of the final officially approved version of my thesis. No emendation of content has occurred and if there are any minor variations in formatting, they are the result of the conversion to digital format.’ Signed .............................................................................. Date .................................................................................. ORIGINALITY STATEMENT ‘I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.’ Signed ................................................................. Date ..................................................................... Author’s Statement I solemnly declare that the work presented in this thesis has not previously been submitted at the University of New South Wales or any other institution for the consideration of a degree or diploma. To the best of my knowledge, none of the work reported herein has previously been published or presented by another person except where due reference is made. It should be noted that the publication of a closely related study completed during my honours year is included in Appendix 6 for reference and completeness due to the extensive discussion related to the publication in the text. Shon Glyn Jones, who is affiliated with the University of Wales, Bangor, carried out the molecular dynamics simulations presented in Chapter 1 as a result of collaboration with Dr Anna Croft. Associated analysis of the molecular dynamics simulation data and all other material presented in this thesis is the outcome of my own work, except to the extent where the conception and design of the project as well as stylistic and linguistic presentation are acknowledged. Yau, Hon Man 28th October, 2011. Dedicated to my grandmother CVIVSVIS HOMINIS EST ERRARE NVLLIVS NISI INSIPIENTIS IN ERRORE PERSEVERARE The Twelfth Philippic, M. Tullius Cicero A Systematic Approach to Understanding Organic Reactivity in Ionic Liquids: Changes in Cybotacticity-Induced Solvent Heterogeneity as an Important Determinant In Reaction Outcomes of Substitution Processes Contents Acknowledgements i Publications and Colloquia v Abstract vii Abbreviations 1 List of Compounds 3 Introduction 7 Results and Discussion, Chapter 1 24 A Nucleophilic Aromatic Substitution Process in an Ionic Liquid Results and Discussion, Chapter 2 34 Menschutkin Reactions as Model Bimolecular Nucleophilic Substitution Reactions in an Ionic Liquid Results and Discussion, Chapter 3 46 Menschutkin Reactions Revisited: Cybotacticity about Nitrogen Nucleophiles as an Important Determinant in Reaction Outcomes Results and Discussion, Chapter 4 61 Towards Solvent-Controlled Reactivity in Ionic Liquids Results and Discussion, Chapter 5 67 The Importance of Electrostatic Interactions in Determining Reaction Outcomes in Ionic Liquids Results and Discussion, Chapter 6 76 A General “One-Pot” Method for Relative Rates Analysis Conclusions 94 Experimental 97 References 167
Recommended publications
  • ITAR Category

    ITAR Category

    Category XIV—Toxicological Agents, Including Chemical Agents, Biological Agents, and Associated Equipment *(a) Chemical agents, to include: (1) Nerve agents: (i) O-Alkyl (equal to or less than C10, including cycloalkyl) alkyl (Methyl, Ethyl, n-Propyl or Isopropyl)phosphonofluoridates, such as: Sarin (GB): O-Isopropyl methylphosphonofluoridate (CAS 107–44–8) (CWC Schedule 1A); and Soman (GD): O-Pinacolyl methylphosphonofluoridate (CAS 96–64–0) (CWC Schedule 1A); (ii) O-Alkyl (equal to or less than C10, including cycloalkyl) N,N-dialkyl (Methyl, Ethyl, n- Propyl or Isopropyl)phosphoramidocyanidates, such as: Tabun (GA): O-Ethyl N, N- dimethylphosphoramidocyanidate (CAS 77–81–6) (CWC Schedule 1A); (iii) O-Alkyl (H or equal to or less than C10, including cycloalkyl) S–2-dialkyl (Methyl, Ethyl, n- Propyl or Isopropyl)aminoethyl alkyl (Methyl, Ethyl, n-Propyl or Isopropyl)phosphonothiolates and corresponding alkylated and protonated salts, such as: VX: O-Ethyl S-2- diisopropylaminoethyl methyl phosphonothiolate (CAS 50782–69–9) (CWC Schedule 1A); (2) Amiton: O,O-Diethyl S-[2(diethylamino)ethyl] phosphorothiolate and corresponding alkylated or protonated salts (CAS 78–53–5) (CWC Schedule 2A); (3) Vesicant agents: (i) Sulfur mustards, such as: 2-Chloroethylchloromethylsulfide (CAS 2625–76–5) (CWC Schedule 1A); Bis(2-chloroethyl)sulfide (CAS 505–60–2) (CWC Schedule 1A); Bis(2- chloroethylthio)methane (CAS 63839–13–6) (CWC Schedule 1A); 1,2-bis (2- chloroethylthio)ethane (CAS 3563–36–8) (CWC Schedule 1A); 1,3-bis (2-chloroethylthio)-n- propane (CAS
  • 'Response to the Director-General's Request

    'Response to the Director-General's Request

    OPCW Scientific Advisory Board Twenty-Fifth Session SAB-25/WP.1 27 – 31 March 2017 27 March 2017 ENGLISH only RESPONSE TO THE DIRECTOR-GENERAL'S REQUEST TO THE SCIENTIFIC ADVISORY BOARD TO PROVIDE CONSIDERATION ON WHICH RIOT CONTROL AGENTS ARE SUBJECT TO DECLARATION UNDER THE CHEMICAL WEAPONS CONVENTION 1. Response to the Director-General’s Request to the Scientific Advisory Board to Consider Which Riot Control Agents are Subject to Declaration Under the Chemical Weapons Convention (hereinafter “the Convention”). Annex: Response to the Director-General’s Request to the Scientific Advisory Board to Consider Which Riot Control Agents are Subject to Declaration Under the Chemical Weapons Convention. CS-2017-0268(E) distributed 27/03/2017 *CS-2017-0268.E* SAB-25/WP.1 Annex page 2 Annex RESPONSE TO THE DIRECTOR-GENERAL’S REQUEST TO THE SCIENTIFIC ADVISORY BOARD TO CONSIDER WHICH RIOT CONTROL AGENTS ARE SUBJECT TO DECLARATION UNDER THE CHEMICAL WEAPONS CONVENTION 1. EXECUTIVE SUMMARY 1.1 This report provides advice from the Scientific Advisory Board (SAB) on which riot control agents (RCAs) would be subject to declaration under the Convention in response to a request by the Director-General at the Board’s Twentieth Session in June 2013 [1]. The request appears in Appendix 1. 1.2 The SAB considered a list of 59 chemicals that included the 14 chemicals declared as RCAs since entry into force of the Convention; chemicals identified as potential RCAs from a list of “riot control agents and old/abandoned chemical weapons” to be considered for inclusion in the OPCW Chemical Agent Database (OCAD) that had been drafted by the SAB’s Temporary Working Group (TWG) on Analytical Procedures in 2001 (Appendix 2) [2]; an initial survey conducted by the Technical Secretariat in 2013 of RCAs that have been researched or are available for purchase, beyond those that are already declared; and 12 additional chemicals recognised by the SAB as having potential RCA applications.
  • The Institute of Paper Science and Technology

    The Institute of Paper Science and Technology

    The Institute of Paper Science and Technology Atlanta, Georgia Doctor's Dissertation The Preparation, Characterization, and Condensation Reactions of Polymer-Supported Lignin Models Robert A. Barkhau June, 1989 THE PREPARATION, CHARACTERIZATION, AND CONDENSATION REACTIONS OF POLYMER-SUPPORTED LIGNIN MODELS A thesis submitted by Robert A. Barkhau B.A. 1983, Carthage College M.S. 1985, Lawrence University in partial fulfillment of the requirements of The Institute of Paper Chemistry for the degree of Doctor of Philosophy from Lawrence University Appleton, Wisconsin Publication rights reserved by The Institute of Paper Chemistry June, 1989 TABLE OF CONTENTS SUMMARY 1 INTRODUCTION 4 PERSPECTIVE 4 GENERAL OVERVIEW OF ALKALINE PULPING REACTIONS 5 LIGNIN CONDENSATION REACTIONS 9 Model Compound Studies 9 Isolated and Residual Lignin Studies 14 Lignin-Carbohydrate Condensation 17 PULPING REACTION SYSTEMS 18 Traditional Investigations 18 Polymer-supported Models 19 THESIS OBJECTIVES 23 RESULTS AND DISCUSSION 24 EXPERIMENTAL APPROACH 24 THE HETEROGENEOUS SUPPORT 25 Evaluation of Supporting Resins 25 Diffusion in the Macroporous Network 29 Theoretical Considerations 29 Activation Energy 30 ii PREPARATION AND CHARACTERIZATION OF A POLYMER- SUPPORTED PHENOL 32 The Trityl Ether Linked Model 32 Synthetic Approach 32 Preparation of Polymer-supported Trityl Chloride 33 Preparation of Polymer-supported Trityl Ether Linked Guaiacylpropanol 36 Stability of the Trityl Ether Linkage Under Alkaline Pulping Conditions 37 The Benzyl Ether Linked Model 41 Synthetic
  • 3.2.2 Table B: List of Dangerous Goods in Alphabetical Order the Following

    3.2.2 Table B: List of Dangerous Goods in Alphabetical Order the Following

    Copyright © United Nations, 2008 3.2.2 Table B: List of dangerous goods in alphabetical order The following Table B is an alphabetical list of the substances and articles which are listed in the UN numerical order in Table A of 3.2.1. It does not form an integral part of ADN. It has been prepared, with all necessary care by the Secretariat of the United Nations Economic Commission for Europe, in order to facilitate the consultation of Annexes A and B, but it cannot be relied upon as a substitute for the careful study and observance of the actual provisions of those annexed Regulations which, in case of conflict, are deemed to be authoritative. NOTE 1: For the purpose of determining the alphabetical order the following information has been ignored, even when it forms part of the proper shipping name: numbers; Greek letters; the abbreviations "sec" and "tert"; and the letters "N" (nitrogen), "n" (normal), "o" (ortho) "m" (meta), "p" (para) and "N.O.S." (not otherwise specified). NOTE 2: The name of a substance or article in block capital letters indicates a proper shipping name (see 3.1.2). NOTE 3: The name of a substance or article in block capital letters followed by the word "see" indicates an alternative proper shipping name or part of a proper shipping name (except for PCBs) (see 3.1.2.1). NOTE 4: An entry in lower case letters followed by the word "see" indicates that the entry is not a proper shipping name; it is a synonym. NOTE 5: Where an entry is partly in block capital letters and partly in lower case letters, the latter part is considered not to be part of the proper shipping name (see 3.1.2.1).
  • Benzopinacolate Promoted Radical Carbon-Carbon Bond Forming

    Benzopinacolate Promoted Radical Carbon-Carbon Bond Forming

    Bis(trimethylstannyl)benzopinacolate Promoted Radical Carbon-Carbon Bond Forming Reactions and Related Studies Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Franklin Lee Seely Graduate Program in Chemistry The Ohio State University 2010 Dissertation Committee: Robert S. Coleman, Co-Advisor David J. Hart, Co-Advisor T. V. RajanBabu Abstract This research has dealt primarily with the development of novel methods for radical carbon-carbon bond formation. A major focus of this research has been the hydrogen atom free generation of trialkyltin radicals. The bulk of this thesis will deal with the use of bis(trimethylstannyl)benzopinacolate 1 in mediating radical reactions. We have demonstrated that these conditions allow a wide variety of inter and intramolecular free radical addition reactions. We have given evidence that these reactions proceed via a novel non-chain free radical mechanism. ii Dedication This thesis is dedicated to Tracy Lynne Court. You have given me the courage to try again. iii Acknowledgments I would like to sincerely thank Dr. David J. Hart for all his help, the countless hours of work he put in, and for making this possible. I would like to thank Dr. Robert S. Coleman for agreeing to act as my advisor, and all the support and guidance he has given. I would like to than Dr. T. V. RajanBabu for reading my thesis and all his thoughtful suggestions. iv Vita Education 1981-1985 ………………………………………………………..B.S., The University
  • (12) United States Patent (10) Patent No.: US 6,846,946 B2 Joyce Et Al

    (12) United States Patent (10) Patent No.: US 6,846,946 B2 Joyce Et Al

    USOO6846946B2 (12) United States Patent (10) Patent No.: US 6,846,946 B2 Joyce et al. (45) Date of Patent: Jan. 25, 2005 (54) PROCESS FOR MAKING ORGANIC Peter Joyce, "Recovering value from byproducts using PRODUCTS AND IMPROVING THE phase-transfer catalysis,” Chemical Innovation, vol. 31, No. QUALITY OF NON-PRODUCT STREAMS 9, Sep. 2001, pp. 42-44. USING PHASE TRANSFER CATALYSIS “Using Phase Transfer Catalysis to Clean Up Waste Streams, Phase Transfer Catalysis Communications, vol. 2, (75) Inventors: Peter J. Joyce, Mullica Hill, NJ (US); Issue 3, (C) 1996 PTC Communications, Inc., pp. 40, 41, and Roman Bielski, Coopersburg, PA (US); 46. Marc Halpern, Cherry Hill, NJ (US) Jean Jacques Vanden Eynde and Isabelle Mailleux, “Qua (73) Assignee: Value Recovery, Inc., Bridgeport, NJ ternary Ammonium Salt-ASSisted Organic Reactions in Water: Alkylation of Phenols,” Synthetic Communications, (US) vol. 31, Issue 1, 2000, pp. 1-7. (*) Notice: Subject to any disclaimer, the term of this Ho-Shing Wu and Jaw-Jiun Lai, “Phenoxide Allylation in a patent is extended or adjusted under 35 Phase Transfer Catalytic Extracton System,” Ind. Eng. U.S.C. 154(b) by 0 days. Chem. Res., vol. 34, Issue 5, 1995, pp. 1536–1538. V. K. Krishnakumar and Man Mohan Sharma, “A Novel Method of Recovering Phenolic Substances from Aqueous (21) Appl. No.: 10/236,382 Alkaline Waste Streams.” Ind. Eng. Chem. Process DeS. (22) Filed: Sep. 6, 2002 Dev., vol. 23, No. 2, 1984, pp. 410–413. Narendra N. Dutta, Somiran Borthakur, and Rasna Baruah, (65) Prior Publication Data “A novel process for recovery of phenol from alkaline US 2003/0158435 A1 Aug.
  • Irritant Compounds: Military Respiratory Irritants. Part I

    Irritant Compounds: Military Respiratory Irritants. Part I

    Mil. Med. Sci. Lett. (Voj. Zdrav. Listy) 2015, vol. 84(3), p. 128-139 ISSN 0372-7025 DOI: 10.31482/mmsl.2015.014 REVIEW ARTICLE IRRITANT COMPOUNDS: MILITARY RESPIRATORY IRRITANTS. PART I. LACRIMATORS Jiri Patocka 1,3 , Kamil Kuca 2,3 1 Department of Radiology and Toxicology, Faculty of Health and Social Studies, University of South Bohemia, Ceske Budejovice, Czech Republic 2 Center of Advanced Studies, Faculty of Military Health Sciences, University of Defence, Hradec Kralove, Czech Republic 3 Biomedical Research Centre, University Hospital; Hradec Kralove, Czech Republic Received 29 th September 2014. Revised 24 th May 2015. Published 4 th September 2015. Summary World War I was a conflict where chemical warfare was first used on a massive scale. The earliest chemical attack occurred on the Western Front in October 1914 in Neuve Chapelle, but its effects were so minimal that the Allies learned about it only after the war from German documents. The attack in the Bolimow area, carried out by the Germans against the Russian army with artillery shells containing gas T (xylyl and benzyl bromides), was therefore the first attack on a massive scale recorded on the victim side. The attack, which occurred after it, made it possible to obtain some tactical success, but without a strategic breakthrough. Some of the later German attacks on the Eastern Front where chlorine was used proved to be more effective, but despite many victims there was not any major strategic success achieved. The Russians did not take attempts to use chemical weapons in the World War I. Key words: respiratory irritants; irritant gases; chemical warfare agents; riot control agents; World War I INTRODUCTION comfort to acute airway and lung injury and even death.
  • Chemical Resistance of SIGRATHERM® Foil and Sheets

    Chemical Resistance of SIGRATHERM® Foil and Sheets

    Chemical resistance of SIGRATHERM® foil and sheets This technical information is valid for SIGRATHERM flexible graphite foil and sheets, including SIGRATHERM L (lightweight graphite board), which are ● manufactured from expanded natural graphite ● free from additives, e.g. PCM's (Phase Change Material). Chemical properties Graphite is insoluble and infusible. It counts as one of the most chemically resistant materials. Organic chemistry Graphite is resistant to virtually all media in the field of organic chemistry. These typically include, for example, the intermedi- ate and/or final products of the following industries: ● Petrochemistry ● Coal conversion ● Synthetics ● Varnish and paint ● Cosmetics ● Food and stimulants industry ● Photochemicals ● Cooling agents ● Anti-freezing agents Inorganic chemistry Graphite is resistant to almost all inorganic media as well, for example to many acids and bases, as well as probably all ↑ SIGRATHERM flexible graphite foil aqueous salt solutions and to most technical gases. The following media resistance list shall provide an overview. individual cases. It should be noted, that mixtures can be For media which are not included it is generally advised to partly more critical than pure media or vice versa. confer with SGL Carbon. Four different cases can be distinguished: 1. resistant The resistance data apply to operating temperatures of the 2. not resistant medium mentioned which are known to us. However for media 3. limited resistance being operated at above 400 °C or 752 °F, we generally ask for 4. insufficient data – consultation. The third case depends on the stability of operation, operating The information is based on experience, laboratory tests and is temperatures or the concentration.
  • New York City Department of Environmental Protection Community Right-To-Know: List of Hazardous Substances

    New York City Department of Environmental Protection Community Right-To-Know: List of Hazardous Substances

    New York City Department of Environmental Protection Community Right-to-Know: List of Hazardous Substances Updated: 12/2015 Definitions SARA = The federal Superfund Amendments and Reauthorization Act (enacted in 1986). Title III of SARA, known as the Emergency Planning and Community Right-to-Act, sets requirements for hazardous chemicals, improves the public’s access to information on chemical hazards in their community, and establishes reporting responsibilities for facilities that store, use, and/or release hazardous chemicals. RQ = Reportable Quantity. An amount entered in this column indicates the substance may be reportable under §304 of SARA Title III. Amount is in pounds, a "K" represents 1,000 pounds. An asterisk following the Reporting Quantity (i.e. 5000*) will indicate that reporting of releases is not required if the diameter of the pieces of the solid metal released is equal to or exceeds 100 micrometers (0.004 inches). TPQ = Threshold Planning Quantity. An amount entered in this column reads in pounds and indicates the substance is an Extremely Hazardous Substance (EHS), and may require reporting under sections 302, 304 & 312 of SARA Title III. A TPQ with a slash (/) indicates a "split" TPQ. The number to the left of the slash is the substance's TPQ only if the substance is present in the form of a fine powder (particle size less than 100 microns), molten or in solution, or reacts with water (NFPA rating = 2, 3 or 4). The TPQ is 10,000 lb if the substance is present in other forms. A star (*) in the 313 column= The substance is reportable under §313 of SARA Title III.
  • Catalytic Challenges and Strategies for the Carbonylation of Σ-Bonds Tawfiq Nasr Allah, Louise Ponsard, Emmanuel Nicolas, Thibault Cantat

    Catalytic Challenges and Strategies for the Carbonylation of Σ-Bonds Tawfiq Nasr Allah, Louise Ponsard, Emmanuel Nicolas, Thibault Cantat

    Catalytic challenges and strategies for the carbonylation of σ-bonds Tawfiq Nasr Allah, Louise Ponsard, Emmanuel Nicolas, Thibault Cantat To cite this version: Tawfiq Nasr Allah, Louise Ponsard, Emmanuel Nicolas, Thibault Cantat. Catalytic challenges and strategies for the carbonylation of σ-bonds. Green Chemistry, Royal Society of Chemistry, In press, 23, pp.723-739. 10.1039/d0gc02343d. cea-03096007 HAL Id: cea-03096007 https://hal-cea.archives-ouvertes.fr/cea-03096007 Submitted on 4 Jan 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Catalytic challenges and strategies for the carbonylation of σ-bonds Tawfiq Nasr Allah†, Louise Ponsard†, Emmanuel Nicolas and Thibault Cantat*a The carbene character of carbon monoxide offers the possibility to utilize this C1-building block for the carbonylation of a variety of organic substrates by insertion of CO into σ-bonds. Although presenting an ideal atom economy this route requires the design and utilization of reactive catalysts able to activate strong C–O, C–N, and C–H bonds in the presence of carbon monoxide. This perspective article adresses, in the context of sustainable chemistry, the challenges and strategies facing the catalytic carbonylation of σ-bonds and presents the key advances in the field over the last decades, for the carbonylation polar and apolar substrates, such as the conversion of alcohols to formates and esters and the carbonylation of amines to amides.
  • Emergency Response Guidebook (ERG2000) Was Developed Jointly by Transport Canada (TC), the U.S

    Emergency Response Guidebook (ERG2000) Was Developed Jointly by Transport Canada (TC), the U.S

    SHIPPING DOCUMENTS (PAPERS)* The shipping document provides vital information when responding to a hazardous materials/dangerous goods** incident. The shipping document contains information needed to identify the materials involved. Use this infor- mation to initiate protective actions for your own safety and the safety of the public. The shipping document contains the proper shipping name (see blue- bordered pages), the hazard class or division of the material(s), ID number (see yellow-bordered pages), and, where appropriate, the Packing Group. In addition, there must be information available that describes the hazards of the material which can be used in the mitigation of an incident. The informa- tion must be entered on or be with the shipping document. This requirement may be satisfied by attaching a guide from the ERG2000 to the shipping doc- ument, or by having the entire guidebook available for ready reference. Shipping documents are required for most dangerous goods in transporta- tion. Shipping documents are kept in • the cab of the motor vehicle, • the possession of the train crew member, • a holder on the bridge of a vessel, or • an aircraft pilot’s possession. EMERGENCY CONTACT EXAMPLE OF EMERGENCY 1-000-000-0000 RESPONSE TELEPHONE NUMBER HAZARD CLASS NO. & TYPE DESCRIPTION OF OR DIVISION NO. OF PACKAGES ARTICLES QUANTITY 1 TANK TRUCK ISOPROPANOL 3 UN1219 II 3,000 LITERS SHIPPING NAME ID NUMBER PACKING GROUP EXAMPLE OF PLACARD AND PANEL WITH ID NUMBER The 4-digit ID Number may be shown on the diamond-shaped placard or on an adjacent orange panel displayed on the ends and sides of a cargo tank, vehicle or rail car.
  • As a Protection Against Chemical Warfare Agents (Cwas)

    As a Protection Against Chemical Warfare Agents (Cwas)

    University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations Dissertations and Theses October 2019 Self-Exfoliating and Reactive Polymer (SERP) as A Protection Against Chemical Warfare Agents (CWAs) SOEUN KIM University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_2 Part of the Polymer and Organic Materials Commons Recommended Citation KIM, SOEUN, "Self-Exfoliating and Reactive Polymer (SERP) as A Protection Against Chemical Warfare Agents (CWAs)" (2019). Doctoral Dissertations. 1720. https://doi.org/10.7275/15094338 https://scholarworks.umass.edu/dissertations_2/1720 This Open Access Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. SELF-EXFOLIATING AND REACTIVE POLYMER (SERP) AS A PROTECTION AGAINST CHEMICAL WARFARE AGENTS (CWAs) A Dissertation Presented By SOEUN KIM Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY September 2019 Department of Polymer Science and Engineering © Copyright by Soeun Kim 2019 All Rights Reserved SELF-EXFOLIATING AND REACTIVE POLYMER (SERP) AS A PROTECTION AGAINST CHEMICAL WARFARE AGENTS (CWAs) A Dissertation presented By SOEUN KIM Approved as to style and content by: ___________________________________________ Kenneth R. Carter, Chair ___________________________________________ Ryan C. Hayward, Member ___________________________________________ Dhandapani Venkataraman, Member ___________________________________________ E. Bryan Coughlin, Department Head Department of Polymer Science and Engineering ACKNOWLEDGMENTS I would like to acknowledge all those who have supported me during my graduate study and who have contributed to this thesis.