DOCSLIB.ORG

Chapter 1. Air-Stable Chiral BINAP-Based Phosphines

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Chapter 1. Air-Stable Chiral BINAP-Based Phosphines Synthesis of Fluorescent Phosphorus Ligands and their Applications in Medical Imaging and Catalysis Jennifer Fairbairn Wallis Engineering Doctorate in Biopharmaceutical Process Development Supervisor of Research: Dr Lee J. Higham Industry Sponsor: High Force Research School of Chemical Engineering – Newcastle University June 2018 Abstract This thesis reports the synthesis of novel, air-stable, fluorescent phosphorus-containing compounds, based on a Bodipy backbone, and their applications in cell imaging and catalysis. The syntheses of all the novel target compounds reported in this thesis are via a primary phosphine, an under-utilised class of compound due to a hazardous reputation. Chapter 1 explores the stability of primary phosphines, how they can be made user-friendly and the ability to create a library of novel phosphorus compounds via the phosphorus-hydrogen bonds. The LJH group synthesised the first, air-stable, fluorescent primary phosphine and Chapter 2 explores a second generation of this type of ligand with an increased fluorescent quantum yield due to the addition of alkyne groups on the boron atom. Chapter 3 details the coordination chemistry of primary phosphines to group 6 and 8 transition metals. Interestingly, the addition of the metals had different effects on the photophysical properties, group 6 metal complexes retained high quantum yields, whereas group 8 metals quenched the fluorescence, possibly due to the heavy atom effect. Chapter 4 discusses the synthesis of fluorescent phosphonium salts which have the potential to be used as trifunctional imaging agents. The three functions within the compounds include i) a fluorophore, to provide in vitro fluorescence imaging, ii) a positive charge on the phosphorus atom to introduce organelle specificity – in this case, to the mitochondria and iii) the inclusion of an 18F radioisotope enables in vivo imaging techniques such as PET imaging. Chapter 5 shows further versatility of fluorescent primary phosphines where we report the synthesis of a novel, chiral, fluorescent phosphonite ligand that has been tested for its applications as a catalyst in asymmetric hydrogenation reactions of a benchmark substrate. The results showed full conversion and an enantiomeric excess (ee) of >99%. The final chapter discusses the importance of the aryl linker between the Bodipy core and the phosphorus atom. The compounds synthesised in this chapter show decreased fluorescence when the phosphorus atom is directly bound to the fluorophore and have potential applications as a switch. ii List of Publications L. H. Davies, J. F. Wallis, M. R. Probert and L. J. Higham, Synthesis, Efficient multigram synthesis of air-stable, fluorescent primary phosphines via palladium-catalyzed phosphonylation of aryl bromides, 2014, 46, 2622-2628. N. Fey, S. Papadouli, P. G. Pringle, A. Ficks, J. T. Fleming, L. J. Higham, J. F. Wallis, D. Carmichael, N. Mézailles and C. Müller, Phosphorus, Sulfur, and Silicon and the Related Elements, Setting P-Donor Ligands into Context: An Application of the Ligand Knowledge Base (LKB) Approach, 2015, 190, 706-714. S.Nigam, B. P. Burke, L. H. Davies, J. Domarkas, J. F. Wallis, P. G. Waddell, J. S. Waby, D. M. Benoit, A. Seymour, C. Cawthorne, L. J. Higham and S. J. Archibald, Chem.Commun., Structurally optimised Bodipy derivatives for imaging of mitochondrial dysfunction in cancer and heart cells, 2016, 52, 7114-7117. L. H. Davies, J. F. Wallis, R. W. Harrington, P. G. Waddell & L. J. Higham, J. Coord. Chem., Air- stable fluorescent primary phosphine complexes of molybdenum and tungsten, 2016, 69, 2069- 2080. iii Acknowledgements First, I would like to sincerely thank my supervisor Dr Lee J. Higham, for giving me this opportunity and taking a chance on me! I have had the best time working with him and his research group over the last few years. I have been given the chance to attend several international and national conferences which have been quite an experience! Thank you for your patience and guidance throughout this EngD course. I would like to thank the EPSRC for funding, as well as High Force Research who were my industrial sponsor. The team in the BBTC have been amazing throughout the years, so thank you for all of your help. A special thank you to Dr Laura Davies who taught me everything I know about Bodipy and all of the special tricks required to synthesise them! My time in the lab has been made significantly more entertaining and memorable by a number of people: the old school LJH group members: Dr Arne Ficks, Dr Manuel Abelairas-Edesa, Dr Connor Sibbald, Dr James Fleming, Dr Ana Cioran, the more recent LJH members: Charlotte Hepples, Antonio Sanchez-Cid and Graeme Bowling (not forgetting adopted member Dr Tommy Winstanley) and all of the other students within the Johnston Lab. A special mention to Manuel, (we were the original Boss-Monkey team and he introduced me to Estrella Galicia and Faustino I), James and Charlotte who have all assisted me with research in the lab, but have also created the best memories outside of the lab, and hope that we will continue to meet up at our annual beer and gin festivals throughout the year! I could not have completed this work without the help of our fantastic crystallographer Dr Paul Waddell, and NMR experts Dr Corinne Wills and Prof. William Mcfarlane, they have undoubtedly helped me complete and understand this work. Another special thank you to all of the academic research collaborators involved with this research, especially Prof Steve Archibald and Dr Amy Reeve who both helped out with cell studies. I have been lucky enough to work with several Erasmus and Masters Students and I’d especially like to thank Francesca, Anna, Giorgia, Vince, Sophie, Tom and everyone else who contributed towards the Bodipy research! Finally I’d like to thank my amazing Dad for always believing in me and helping me get to where I am today, even when I doubted myself he would always guide me and tell me I could do it - my Mam would be so proud of what I have achieved. My sisters Katie and Rachael and my boyfriend Chris have also been exceptionally patient during the last 5 years. I love you all! iv Abbreviations General: β Beta particle B3LYP Becke Parameter Lee-Yang-Parr CT Computed Tomography DFT Density Functional Theory γ Gamma ray HOMO Highest Occupied Molecular Orbital HPLC High-Performance Liquid Chromatography LMCT Ligand-to-Metal Charge Transfer LUMO Lowest Unoccupied Molecular Orbital 99m Metastable isotope MLCT Metal-to-Ligand Charge Transfer MMCT Metal-to Metal Charge Transfer MRI Magnetic Resonance Imaging PET Positron Emission Tomography PeT Photoinduced electron Transfer RT Room Temperature SOMO Singly Occupied Molecular Orbital SPECT Single Photon Emission Computed Tomography TLC Thin Layer Chromatography t1/2 Half-life Chemicals: Bodipy 4,4-difluoro-4-borata-3a-azonia-4a-aza-s-indacene CDCl3 Deuterated chloroform DCM Dichloromethane DDQ 2,3-Dicyano-5,6-dichloroparabenzoquinone DMSO Dimethyl sulfoxide DPPB 1,4-Bis-(diphenylphosphino)-butane Et2O Diethyl ether v HP(O)(OEt)2 Diethyl phosphite LiAlH4 Lithium aluminium hydride MgSO4 Magnesium sulphate NEt3 Triethylamine Pd(OAc)2 Palladium(II) acetate POBr3 Phosphoryl oxybromide POCl3 Phosphoryl oxychloride TFA Trifluoroacetic acid THF Tetrahydrofuran TMSCl Chlorotrimethylsilane Units: Å Angstroms cm Centimetres ° Degrees °C Degrees Celsius eq Equivalents eV Electron Volts Hz Hertz h Hours L Litres mg Milligrams MHz Megahertz mmol Millimolar mins Minutes M Molar nm Nanometres ppm Parts per million s Seconds vi Experimental techniques terms: APCI Atmospheric-Pressure Chemical Ionisation br Broad δ Chemical shift d Doublet ε Molar Absorption Coefficient EI Electron Ionisation ESI Electrospray Ionisation FTIR Fourier Transform Infrared Spectroscopy HRMS High Resolution Mass Spectrometry I Nuclear Spin J Coupling Constant LRMS Low Resolution Mass Spectrometry NIR Near-Infrared NSI Nanospray Ionisation m Multiplet NMR Nuclear Magnetic Resonance ΦF Quantum yield q Quartet s Singlet t Triplet vii Table of Contents Abstract ............................................................................................................................................ ii List of Publications ......................................................................................................................... iii Acknowledgements ........................................................................................................................ iv Abbreviations .................................................................................................................................. v Background and Introduction .................................................................................................. 2 1.1 Organophosphorus Compounds ........................................................................................ 2 1.2 Phosphines ........................................................................................................................ 2 Steric Parameters of Phosphorus Ligands ................................................................. 2 Electronic Parameters of Phosphorus Ligands .......................................................... 3 Phosphine Ligands of Relevance ............................................................................... 4 Multifunctional Imaging Agents ............................................................................... 6 Primary Phosphines ................................................................................................
Load more

Recommended publications
  • The Synthesis of Molecules Containing Quaternary Stereogenic Centers Via the Intramolecular Asymmetric Heck Reaction
    The Synthesis of Molecules Containing Quaternary Stereogenic Centers via the Intramolecular Asymmetric Heck Reaction Reported by Eric P. Gillis April 19, 2007 INTRODUCTION The enantioselective synthesis of compounds containing quaternary stereocenters continues to be a challenging endeavor and is a field of intense interest and development.1,,,,2 3 4 5 From the perspective of methods development, the asymmetric synthesis of compounds containing quaternary stereocenters poses a distinct challenge due to the sterically congested environment in which C-C bonds must be formed and stereochemical information must be transferred. Existing asymmetric methods have been applied successfully in desymmetrization processes that transform prochiral quaternary centers into stereodefined quaternary centers. However, for processes in which a quaternary stereocenter is created directly via a C-C bond forming reaction, only a few asymmetric reactions have been fruitful. The diversity in the array of methods that exist for the synthesis of compounds containing quaternary stereocenters is necessitated in part because of the number of distinct quaternary stereocenter architectures that are possible (Scheme 1). The construction of acyclic quaternary stereocenters is particularly challenging due to the number of degrees of freedom associated with these structures. However, promising results for the construction of these stereocenters via allylation,6 allylic alklyation,7 and Michael addition8 have been reported recently. For the synthesis of cyclic quaternary stereocenters a number of methods have been employed successfully including the intramolecular Heck reaction,9 alkylation,10 arylation,11 and Michael addition12. Fused bicyclic quaternary stereocenters are generally accessed via the desymmetrization of a prochiral quaternary center. In this regard, theoretically any SCHEME 1.
    [Show full text]
  • Downloads/DL Praevention/Fachwissen/Gefahrstoffe/TOXIKOLOGI SCHE BEWERTUNGEN/Bewertungen/Toxbew072-L.Pdf
    Distribution Agreement In presenting this thesis or dissertation as a partial fulfillment of the requirements for an advanced degree from Emory University, I hereby grant to Emory University and its agents the non-exclusive license to archive, make accessible, and display my thesis or dissertation in whole or in part in all forms of media, now or hereafter known, including display on the world wide web. I understand that I may select some access restrictions as part of the online submission of this thesis or dissertation. I retain all ownership rights to the copyright of the thesis or dissertation. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. Signature: _____________________________ ______________ Jedidiah Samuel Snyder Date Statistical analysis of concentration-time extrapolation factors for acute inhalation exposures to hazardous substances By Jedidiah S. Snyder Master of Public Health Global Environmental Health _________________________________________ P. Barry Ryan, Ph.D. Committee Chair _________________________________________ Eugene Demchuk, Ph.D. Committee Member _________________________________________ Paige Tolbert, Ph.D. Committee Member Statistical analysis of concentration-time extrapolation factors for acute inhalation exposures to hazardous substances By Jedidiah S. Snyder Bachelor of Science in Engineering, B.S.E. The University of Iowa 2010 Thesis Committee Chair: P. Barry Ryan, Ph.D. An abstract of A thesis submitted to the Faculty of the Rollins School of Public Health of Emory University in partial fulfillment of the requirements for the degree of Master of Public Health in Global Environmental Health 2015 Abstract Statistical analysis of concentration-time extrapolation factors for acute inhalation exposures to hazardous substances By Jedidiah S.
    [Show full text]
  • Design and Synthesis of Chiral Ligands and Their Applications in Transition
    The Pennsylvania State University The Graduate School Department of Chemistry DESIGN AND SYNTHESIS OF CHIRAL LIGANDS AND THEIR APPLICATIONS IN TRANSITION METAL-CATALYZED ASYMMETRIC REACTIONS A Dissertation in Chemistry by Wei Li 2012 Wei Li Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2012 The dissertation of Wei Li was reviewed and approved* by the following: Gong Chen Assistant Professor of Chemistry Dissertation Advisor Chair of Committee Tom Mallouk Evan Pugh Professor of Material Chemistry and Physics Alex Radosevich Assistant Professor of Chemistry Qing Wang Associate Professor of Material Science and Engineering Xumu Zhang Professor of Chemistry Special Member Barbara J. Garrison Shapiro Professor of Chemistry Head of the Department of Chemistry *Signatures are on file in the Graduate School iii ABSTRACT Transition metal catalyzed reactions are among the most powerful and direct approaches for the synthesis of organic molecules. During the past several decades, phosphorous-containing ligands have been extensively studied in transition metal - catalyzed transformations particularly asymmetric hydrogenations. Development of new chiral ligands and efficient catalyst systems for various prochiral unsaturated substrates in asymmetric hydrogenations are the focus of this dissertation. An important family of atropisomeric biaryl bisphosphine ligands, C3*-TunePhos and related bisaminophosphines have been designed and synthesized. The Ru catalysts of the highly modular C3*-TunePhos have been proved to be highly efficient (up to 99.8% ee, up to 1,000,000 TON) for practical asymmetric hydrogenations of a wide range of unfunctionalized ketones as well as α-, β- keto esters and N-2-substituted allylphthalimides. The synthetic utility of bisaminophosphine ligands was studied for rhodium-catalyzed asymmetric hydrogenations of α-dehydroamino acid esters, affording up to 98% ee’s.
    [Show full text]
  • Synthesis of Isothiocyanates Using DMT/NMM/Tso− As a New Desulfurization Reagent
    molecules Article Synthesis of Isothiocyanates Using DMT/NMM/TsO− as a New Desulfurization Reagent Łukasz Janczewski 1,* , Dorota Kr˛egiel 2 and Beata Kolesi ´nska 1 1 Faculty of Chemistry, Institute of Organic Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland; [email protected] 2 Department of Environmental Biotechnology, Faculty of Biotechnology and Food Sciences, Lodz University of Technology, Wolczanska 171/173, 90-924 Lodz, Poland; [email protected] * Correspondence: [email protected] Abstract: Thirty-three alkyl and aryl isothiocyanates, as well as isothiocyanate derivatives from esters of coded amino acids and from esters of unnatural amino acids (6-aminocaproic, 4-(aminomethyl)benzoic, and tranexamic acids), were synthesized with satisfactory or very good yields (25–97%). Synthesis was performed in a “one-pot”, two-step procedure, in the presence of organic base (Et3N, DBU or NMM), and carbon disulfide via dithiocarbamates, with 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4- methylmorpholinium toluene-4-sulfonate (DMT/NMM/TsO−) as a desulfurization reagent. For the synthesis of aliphatic and aromatic isothiocyanates, reactions were carried out in a microwave reactor, and selected alkyl isothiocyanates were also synthesized in aqueous medium with high yields (72–96%). Isothiocyanate derivatives of L- and D-amino acid methyl esters were synthesized, under conditions without microwave radiation assistance, with low racemization (er 99 > 1), and their absolute configuration was confirmed by circular dichroism. Isothiocyanate derivatives of natural and unnatural amino acids were evaluated for antibacterial activity on E. coli and S. aureus bacterial strains, where the Citation: Janczewski, Ł.; Kr˛egiel,D.; most active was ITC 9e.
    [Show full text]
  • Synthesis of C2-Symmetric P-Chiral Bis(Phosphine Borane)
    Synthesis of C2-symmetric P-chiral bis(phosphine borane)s and their application in rhodium(I) catalyzed asymmetric transformation by Holly Ann Heath A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Montana State University © Copyright by Holly Ann Heath (2001) Abstract: A new development for the synthesis C2-Synnnetric P-Chiral Bis(phosphine borane) ligands is reported, These ligands are based on the asymmetric induction of prochiral phosphine ligands with organolithium/chiral diamine complexes. These ligands have been evaluated in asymmetric rhodium(I) catalyzed hydrogenation and [4 + 2] cycloisomerization reactions. Enantiomeric excesses as high as 99% were obtained for ene-diene cycloadditions. Synthesis of C2-Symmetric P-Chiral Bis(phosphine borane)s and Their Application in Rhodium(I) Catalyzed Asymmetric Transformation by Holly Ann Heath A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Montana State University Bozeman, Montana March 2001 ii APPROVAL of a dissertation submitted by Holly Ann Heath This dissertation has been read by each member of the dissertation committee and has been found to be satisfactory regarding content, English usage, format, citations, bibliographic style, and consistency, and is ready for submission to the College of Graduate Studies. Dr. Thomas Livinghouse < Chairperson, Graduate Committee Date Approved for the Department of Chemistry Dr. Paul A. Grieco Department Head Approved for the College of Graduate Studies Dr. Bruce R. McLeod Graduate Dean Date iii STATEMENT OF PERMISSION TO USE In presenting this dissertation .in partial fulfillment of the requirements for a doctoral degree at Montana State University-Bozeman, I agree that the Library shall make it available to borrowers under rules of the Library.
    [Show full text]
  • Argonne Report.Pdf
    CONTENTS NOTATION ........................................................................................................................... xi ABSTRACT ........................................................................................................................... 1 1 INTRODUCTION ........................................................................................................... 5 1.1 Overview of the Emergency Response Guidebook ................................................ 5 1.2 Organization of this Report ..................................................................................... 7 2 GENERAL METHODOLOGY ....................................................................................... 9 2.1 TIH List ................................................................................................................... 10 2.1.1 Background ................................................................................................. 10 2.1.2 Changes in the TIH List for the ERG2012 ................................................. 11 2.2 Shipment and Release Scenarios ............................................................................ 11 2.2.1 Shipment Profiles ........................................................................................ 12 2.2.2 Treatment of Chemical Agents ................................................................... 14 2.3 Generics, Mixtures, and Solutions .......................................................................... 17 2.4 Analysis of Water-Reactive
    [Show full text]
  • NAC/AEGL Committee Meeting Minutes, December 2007
    National Advisory Committee (NAC) for Acute Exposure Guideline Levels (AEGLs) for Hazardous Substances December 5-7, 2007 Meeting-44 Highlights Orlando World Center Marriott 8701 World Center Drive Orlando, FL INTRODUCTION Ernest Falke distributed a CD containing the most recent Technical Support Documents for all AEGL program chemicals that are proposed, interim, or final status. Dr. Falke also stated that the Prepublication Copy of NAS Volume 6 was released in September, 2007, and that the published volume should be available for distribution by the March meeting. Paul Tobin informed the group that the NAC/AEGL committee was recognized by the FACA awards program twice (last year and this year). There are 27 EPA FACAs, and only the NAC/AEGL was recognized twice; a total of only 3 EPA FACAs were recognized. Specifically, the NAC/AEGL was recognized for timeliness of Federal Register notices, transparency of the process, public input (both via the meeting and the Federal Register), and international impact. The draft NAC/AEGL-43 meeting highlights were reviewed. Due to a rounding error, the 30-minute AEGL-3 value for dichlorosilanes should be 110 ppm, not 105 ppm. A motion was made by Bob Benson and seconded by John Hinz to accept the minutes as proposed with the aforementioned correction. The motion passed unanimously by a show of hands (Appendix A). The Final NAC/AEGL-43 meeting highlights are attached (Appendix B). The highlights of the NAC/AEGL-44 meeting are summarized below along with the Meeting Agenda (Attachment 1) and the Attendee List (Attachment 2). The subject categories of the highlights do not necessarily follow the order listed in the NAC/AEGL-44 Agenda.
    [Show full text]
  • Diphosphine Complexes on Alpo4-Sepiolite Supports
    catalysts Article Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO4-Sepiolite Supports Verónica Caballero 1, Rafael Estevez 1, Diego Luna 1,* , Felipa M. Bautista 1 , Antonio A. Romero 1 , Laura Aguado-Deblas 1 , Jesús Hidalgo-Carrillo 1 and Isabel Romero 2 1 Departamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, Spain; [email protected] (V.C.); [email protected] (R.E.); [email protected] (F.M.B.); [email protected] (A.A.R.); [email protected] (L.A.-D.); [email protected] (J.H.-C.) 2 Departament de Química and Serveis Tècnics de Recerca, Universitat de Girona, C/M. Aurèlia Campmany, 69, E-17003 Girona, Spain; [email protected] * Correspondence: [email protected]; Tel.: +34-957212065 Abstract: In this work, the covalent immobilization of two ruthenium(II) complexes, II II i.e., [Ru Cl (bpea){(S)(-)(BINAP)}](BF4), 1, and [Ru Cl(bpea)(DPPE)](BF4), 2, where BINAP = 2,2’- bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO4-Sepiolite@1 and AlPO4-Sepiolite@2) by using a N-tridentate ligand N,N-bis-(2- pyridylmethyl)ethylamine (bpea), linked to an amorphous AlPO4-Sepiolite (20/80) inorganic support. Citation: Caballero, V.; Estevez, R.; This AlPO4-sepiolite support is able to immobilize the double amount of ruthenium complex (1.65%) Luna, D.; Bautista, F.M.; Romero, than the amorphous AlPO4 (0.89%). Both heterogenized complexes have been assessed as catalysts A.A.; Aguado-Deblas, L.; in the liquid phase hydrogenation of several substrates with carbonyl and/or olefinic double bonds Hidalgo-Carrillo, J.; Romero, I.
    [Show full text]
  • Recent Advances of BINAP Chemistry in the Industrial Aspects
    NEW TOOLS IN SYNTHESIS 1055 Recent Advances of BINAP Chemistry in the Industrial Aspects Hidenori Kumobayashi, Takashi Miura,* Noboru Sayo, Takao Saito, Xiaoyong Zhang Central Research Laboratory, Takasago International Corporation, 1-4-11 Nishi-yawata, Hiratsuka, Kanagawa 254-0073, Japan Fax (0463)25-2084; E-mail: [email protected] Received 24 April 2001 and ketones such as a-(acylamino)acrylic acids,6 enam- Abstract: New efficient synthetic methods of optically active BI- 7 8 ides, a,b-unsaturated carboxylic acids, allylic and ho- NAP [BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] and 9 10 its variants are described. Application of these BINAP variants in moallylic alcohols, alkylidene lactones, alkenyl 10 11 12 asymmetric catalytic hydrogenation of prochiral ketones and olefins ethers, b-keto esters, b-hydroxyketones, and b-ami- to various industrially important compounds is discussed. noketones.12 Key words: BINAP ligands, ruthenium and iridium catalysts, Starting with the development of l-menthol process using asymmetric hydrogenation, ketones, unsaturated carboxylic acids BINAP–Rh catalyzed asymmetric isomerization of allyl- amines,5a we have been investigating catalytic asymmet- ric synthesis mainly based on BINAP chemistry for two Introduction decades and have developed various asymmetric synthet- ic processes. All of these results are based on the success Enantioselective syntheses have been gaining more and of the marvelous abilities of the BINAP ligands. Recently more importance in a wide range of fields such as pharma- the targets of asymmetric synthesis have become varied ceuticals, agrochemicals, food additives, aromachemicals and complicated, while BINAP sometimes shows its lim- and functional materials because the biological activities itation.
    [Show full text]
  • 2020 Emergency Response Guidebook
    2020 A guidebook intended for use by first responders A guidebook intended for use by first responders during the initial phase of a transportation incident during the initial phase of a transportation incident involving hazardous materials/dangerous goods involving hazardous materials/dangerous goods EMERGENCY RESPONSE GUIDEBOOK THIS DOCUMENT SHOULD NOT BE USED TO DETERMINE COMPLIANCE WITH THE HAZARDOUS MATERIALS/ DANGEROUS GOODS REGULATIONS OR 2020 TO CREATE WORKER SAFETY DOCUMENTS EMERGENCY RESPONSE FOR SPECIFIC CHEMICALS GUIDEBOOK NOT FOR SALE This document is intended for distribution free of charge to Public Safety Organizations by the US Department of Transportation and Transport Canada. This copy may not be resold by commercial distributors. https://www.phmsa.dot.gov/hazmat https://www.tc.gc.ca/TDG http://www.sct.gob.mx SHIPPING PAPERS (DOCUMENTS) 24-HOUR EMERGENCY RESPONSE TELEPHONE NUMBERS For the purpose of this guidebook, shipping documents and shipping papers are synonymous. CANADA Shipping papers provide vital information regarding the hazardous materials/dangerous goods to 1. CANUTEC initiate protective actions. A consolidated version of the information found on shipping papers may 1-888-CANUTEC (226-8832) or 613-996-6666 * be found as follows: *666 (STAR 666) cellular (in Canada only) • Road – kept in the cab of a motor vehicle • Rail – kept in possession of a crew member UNITED STATES • Aviation – kept in possession of the pilot or aircraft employees • Marine – kept in a holder on the bridge of a vessel 1. CHEMTREC 1-800-424-9300 Information provided: (in the U.S., Canada and the U.S. Virgin Islands) • 4-digit identification number, UN or NA (go to yellow pages) For calls originating elsewhere: 703-527-3887 * • Proper shipping name (go to blue pages) • Hazard class or division number of material 2.
    [Show full text]
  • EXPOSURE and INTERACTION the Potential Health Impacts of Using Multiple Pesticides
    EXPOSURE AND INTERACTION The Potential Health Impacts of Using Multiple Pesticides Virginia Zaunbrecher, J.D. Dale Hattis, Ph.D. Ron Melnick, Ph.D. Susan Kegley, Ph.D. Timothy Malloy, J.D. John Froines, Ph.D. Authors Virginia Zaunbrecher, J.D., UCLA Sustainable Technology & Policy Program Dale Hattis, Ph.D., Clark University Ron Melnick, Ph.D., Ron Melnick Consulting Susan Kegley, Ph.D., Pesticide Research Institute Timothy Malloy, J.D., UCLA Sustainable Technology & Policy Program John Froines, Ph.D., UCLA Sustainable Technology & Policy Program Contributors Lindsey Sears, M.A. Timothy J. Brown, Ph.D. Camille Sears Christina Batteate, M.P.H., UCLA Sustainable Technology & Policy Program Charlene Nguyen, UCLA Sustainable Technology & Policy Program UCLA Sustainable Technology & Policy Program The Sustainable Technology & Policy Program, a joint undertaking of the UCLA School of Law and the Fielding School of Public Health, is an interdisciplinary research and education program. Its mission is to advance public health and environmental protection by integrating science, law, and engineering to promote prevention in public and private decision making. Acknowledgements This research was made possible by generous support from the Clarence E. Heller Charitable Foundation. The Center for Occupational and Environmental Health (COEH) at UCLA provided additional support. The authors bear responsibility for any factual errors. Recommendations and views expressed are those of the authors and do not necessarily represent those of the funder or of the University of California. Appendices and Supplementary Materials All appendices and supplementary materials mentioned in this report are available at: http://www.stpp.ucla.edu/node/586 KEY TERMS AND DEFINITIONS Combined exposure to a single stressor (e.g.
    [Show full text]
  • Chemfile Vol.6 No 8
    2006 VOLUME 6 NUMBER 8 Privileged Ligands DUPHOS AND BPE PHOSPHOLANE LIGANDS DSM MONOPHOS™ FAMILY CHIRALQUEST PHOSPHINE LIGANDS SOLVIAS® FERROLceNYL-BASed LIGANDS (S)-MonoPhosTM: a powerful ligand for asymmetric synthesis. sigma-aldrich.com Introduction Chemists are continually searching for novel, efficient chiral transition metal catalysts to effect ever more difficult transformations. Highly effective asymmetric catalytic systems Vol. 6 No. 8 offer the possibility of synthesizing either desired enantiomer pure from simple achiral Aldrich Chemical Co., Inc. starting materials, with the chiral products then being directly employed in natural 1 Sigma-Aldrich Corporation product synthesis. Research groups have spent much well-earned effort in designing 6000 N. Teutonia Ave. high performance ligand platforms2 that exhibit the following general characteristics: Milwaukee, WI 53209, USA 1) the synthesis should be economically viable and allow for systematic variations in the architecture; 2) most (if not all) members of the ligand family should be readily produced from milligram to kilogram scale; and 3) the ligands should bind strongly to the metal center as well as generate a highly active and selective catalyst system. To Place Orders Chiral salens,3 bisoxazolines,4 tartrate ligands,5 and cinchona alkaloids6 represent the Telephone 800-325-3010 (USA) original “privileged ligands” classes that effect a wide variety of transformations under FAX 800-325-5052 (USA) exceptional enantiocontrol and with high productivity. Impressively, R&D groups
    [Show full text]