DOCSLIB.ORG

The Oxidation of Triethylamine by Thallium (III) Chloride

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Oxidation of Triethylamine by Thallium (III) Chloride AN ABSTRACT OF THE THESIS OF ROBERT LAWRENCE ARNESON for theMASTER OF SCIENCE (Name of student) (Degree) in Chemistry presented on e7 /5404,"/ (Major) Date,/ Title: THE OXIDATION OF TRIETHYLAMINE BYTHALLIUM(III) CHLORIDE Redacted for privacy Abstract approved: Dr. Yoke III The oxidation of triethylamine by the two electron oxidant thallium(III) chloride was studied and the results compared to those when triethylamine is oxidized by copper(II) halides.This study requires anhydrous conditions since in an aqueous systemthallium(III) chloride is extensively hydrolyzed and triethylamine causes precipitation of thallium(III) oxide.Most of the work was carried out in anhydrous acetonitrile.Synthesis techniques and analytical methods for thallium(III) chloride had to be developed prior to any comprehensive investigations of the oxidation-reduction reaction. The stoichiometry of the reaction was investigated using inert atmos- phere techniques and a variety of analytical techniques, including potentiometric and conductometric techniques.In addition, character- ization of the reaction products was undertaken by severalmethods. Thallium(III) chloride reacts vigorously with an excess of triethylamine to give white, solid thallium(I) chloride, triethyl- ammonium chloride,and a red-brown tarry amine oxidation product. The amine oxidation product is thought to be primarily a polymerof N, N-diethylvinylamine.This tarry solid was separated completely from the thallium salts, but always contained some chloride,possibly present as an amine hydrochloride.The physical properties of the polymer were not completely characterized. The reaction is thought to involve an initial complexformation between triethylamine and thallium(III) chloride, withrapid oxidation- reduction occuring within the complex. There is then a net transfer of two electrons, with loss of two protons and two chlorides toproduce two moles of hydrogen chloride and one mole each ofthallium(I) chloride and N, N-diethylvinylarnine.Subsequent reactions involving polymerization of the vinyl amine and protonation of this vinylamine polymer and of free triethylamine occur. No secondaryreactions between thallium(I) chloride and the polymer, free triethylamine, or triethylammonium chloride occur, but thallium(I) chloride does react with excess thallium(III) chloride to form thallium(I)tetra- chlorothallate(III).The oxidation-reduction reaction is rapid and irreversible with no prolonged secondary changes occuring in the reaction mixture upon standing.The secondary reaction of thallium(I) chloride and thallium(III) chloride makes the apparent reaction stoichiometry as determined by potentiometry and conductivity unusual, and not the expected one to one mole ratio of triethylamine to thallium(III) chloride. The reaction of triethylamine and thallium(III) chloride differs from that of triethylamine and free halogens, i.e. ,chlorine and bromine, in three aspects.First, the halogen reaction appears to occur in two stages.The initial stage is a fast reaction producing large amounts of solid products and a light yellow liquid layer, After separation of the solids, a slower reaction continues in the liquid, with the yellow liquid darkening to brown or black, and with the precipitation of more solid products.This slow reaction continues for days.Secondly, the initial reaction is much more vigorous than that of thallium(III) chloride with triethylamine,Finally, the stoichiometry of the halogen-triethylamine reaction is quite time- dependent and variable whereas thalliurn(III) chloride reacts in a single stage at a definite and reproducible mole ratio. It is uncertain from this work whether the interaction between thallium(III) trifluoroacetate and triethylamine in acetonitrile involves any oxidation-reduction. The Oxidation of Triethylamine by Thallium(III) Chloride by Robert Lawrence Arneson A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science June 1974 APPROVED: Redacted for privacy Professoof Chemistry n charge of ma Redacted for privacy Head of Department of Chemistry Redacted for privacy Dean of Graduate School Date thesis is presented Typed by Ilene Anderton for Robert Lawrence Arneson ACKNOW LEDGEMENTS I would like to extend my thanks to my research advisor, Dr. John T. Yoke, whose guidance was always available when it was needed.I also acknowledge my co-graduate students, the chemistry students, the faculty, and the staff of the Chemistry Department for their cooperation and help without which this work would have never been complete.In particular, the efforts of Mrs. Thelma Wade are gratefully acknowledged, If a thesis were dedicated to someone, then this thesis would be dedicated to my parents, Lawrence and Eleanor Arneson.Through- out my stay here at Oregon State University, they have encouraged and helped me in any way that they could.The moral support that my family, particularly my brother Alan, have so freelygiven is noted. My stay in Corvallis would have been less pleasant if not for the friendship and encouragement extended to me by the James Welty family.Their kindness and hospitality is greatly appreciated. Acknowledgement is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for a research assistantship and partial support ofthis work.I am grateful for the teaching assistantship given by the Chemistry Depart- ment of Oregon State University which made it possible to continue work on this degree. TABLE OF CONTENTS Chapter Page INTRODUCTION II. HISTORY 3 Thallium Chemistry 3 Introduction 3 Coordination Chemistry 5 Oxidation-Reduction Behavior 7 Thallium Chlorides 9 Acetonitrile as a Solvent 12 Oxidation of Amines 15 General 15 Oxidation by Metal Halides 16 Oxidation by Halogens 21 III. EXPERIMENTAL 24 Materials 24 Solvents 24 Acetonitrile 24 Methanol 25 Kerosene 25 Thallium Reagents 25 Thallium Metal Rod 25 Thallium(I) Chloride 25 Thallium(III) Chloride Tetrahydrate 26 Thallium(III) Trifluoroacetate 26 Amine Reagents 26 Triethylamine 26 Trie.thylammonium Chloride 27 Other Materials 27 Nitrosyl Chloride 27 Halogens 28 Analysis 28 Thallium Analysis 28 Precipitation of Thallium(III) as Thallium (III) Oxide From Ammoniaca.1 Solutions 29 Precipitation of Thallium(I) Chromate From Ammoniacal Solutions 30 Chapter Page Precipitation of Thallium(I) With Thionalide 31 Iodometric Titrations Involving the Oxida- tion of Iodide in Acid Solution by Thallium(III) and Back Titration With Standard Thiosulfate Solution 31 Addition of EDTA to a Thal lium(III) Solu- tion and Back Titration with Either Thorium(IV) or Lead(II) Nitrate 31 Oxidation Titration of Thallium(I) Using Cerium(IV) Sulfate Titrant 32 Chloride Analysis 32 Triethylamine Analysis 33 Equivalent Weight of Triethylammonium Chloride 33 Carbon, Hydrogen, and Nitrogen Analysis 33 Instrumental Methods 34 Infrared Spectra 34 Nuclear Magnetic Resonance Spectra 34 Conductivity 34 Conductivity Measurements 35 Conductometric Titrations 35 Potentiometry 37 pH Measurements 37 Thallium Potentiometry 37 Preparation of Thallium(III) Chloride 38 Thallium(III) Chloride Solutions 39 Attempted Preparation of Anhydrous Solid Thallium(III) Chloride 40 Chlorination of Solid Thallium or Thallium(I) Chloride 40 Removal of Solvent From Thallium(III) Solutions 41 Reaction of Thallium and Nitrosyl Chloride 42 Thallium(I) Chloride - Triethylamine System 43 Preliminary Experiments 43 Isothermal Pressure-Composition Studies 44 Thallium(I) Chloride - Triethylammonium Chloride System 45 Thallium(III) Chloride - Triethylamine Reaction 46 Preliminary Experiments 46 Chapter Page Experiments in Acetonitrile 48 Potentiometric Studies 48 Studies of Acid Formed in the Reaction 49 Conductometric Studies 50 Preparative Scale Studies 51 Thallium(III) Trifluoroacetate - Triethylamine System 54 Potentiometric Studies 54 Conductometric Studies 54 Titration of Excess Amine 55 Qualitative Experiments 55 Thallium(III) Trifluoroacetate - Water 55 Thallium(III) TrifluoroacetateTriethyl- amine 56 Reaction of Halogens with Triethylamine 56 Chlorine 56 Studies with No Solvent 56 Studies With Solvent 57 Potentiometry Study in Acetonitrile 58 Bromine 59 Studies of Products Formed 59 Stoichiometry Studies 60 IV. RESULTS 63 Thallium(I) Chloride -Triethylamine System 63 Thallium(I) Chloride -T riethylammonium Chloride System 63 Thallium(III) ChlorideTriethylamine Reaction 63 Preliminary Experiments 63 Potentiometric Titrations in Acetonitrile 65 Titration of Acid Formed in the Reaction 65 Conductometric Titrations 69 Oxidation Product Characterization 70 Thallium(III) TrifluoroacetateTriethylamine System 75 Conductometric and Potentiometric Titrations 75 Study of the Acid Produced 77 Chlorine - Triethylamine Reaction 79 General Observations 79 Potentiometric Titration 80 Bromine - Triethylamine Reaction 80 Chapter Page Preliminary Experiments 80 Stoichiometry Studies 81 V. DISCUSSION 83 BIBLIOGRAPHY 94 LIST OF TABLES Table Page 1. Standard solutions of thallium(III) chloride in acetonitrile. 40 2. Pressure-composition data for the system thallium(I) chloride-triethylamine at 20°C. 45 3. NMR chemical shift data for the amine oxidation product. 53 4. Final mole ratios of the thallium(III) chloride - triethylamine reaction. 64 5. Endpoints of potentiometric titrations -- thallium(III) chloride - triethylamine in acetonitrile. 68 6. Acidity formed in the triethylaminethallium(III) chloride oxidation-reduction reaction in acetonitrile. 69 7. Endpoints of triethylaminethallium(III)
Load more

Recommended publications
  • Investigation of Condensed and Early Stage Gas Phase Hypergolic Reactions Jacob Daniel Dennis Purdue University
    Purdue University Purdue e-Pubs Open Access Dissertations Theses and Dissertations Fall 2014 Investigation of condensed and early stage gas phase hypergolic reactions Jacob Daniel Dennis Purdue University Follow this and additional works at: https://docs.lib.purdue.edu/open_access_dissertations Part of the Propulsion and Power Commons Recommended Citation Dennis, Jacob Daniel, "Investigation of condensed and early stage gas phase hypergolic reactions" (2014). Open Access Dissertations. 256. https://docs.lib.purdue.edu/open_access_dissertations/256 This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information. i INVESTIGATION OF CONDENSED AND EARLY STAGE GAS PHASE HYPERGOLIC REACTIONS A Dissertation Submitted to the Faculty of Purdue University by Jacob Daniel Dennis In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy December 2014 Purdue University West Lafayette, Indiana ii To my parents, Jay and Susan Dennis, who have always pushed me to be the person they know I am capable of being. Also to my wife, Claresta Dennis, who not only tolerated me but suffered along with me throughout graduate school. I love you and am so proud of you! iii ACKNOWLEDGEMENTS I would like to express my sincere gratitude to my advisor, Dr. Timothée Pourpoint, for guiding me over the past four years and helping me become the researcher that I am today. In addition I would like to thank the rest of my PhD Committee for the insight and guidance. I would also like to acknowledge the help provided by my fellow graduate students who spent time with me in the lab: Travis Kubal, Yair Solomon, Robb Janesheski, Jordan Forness, Jonathan Chrzanowski, Jared Willits, and Jason Gabl.
    [Show full text]
  • Analysis of Ammonia and Volatile Organic Amine Emissions in a Confined Poultry Facility
    Utah State University DigitalCommons@USU All Graduate Theses and Dissertations Graduate Studies 5-2010 Analysis of Ammonia and Volatile Organic Amine Emissions in a Confined Poultry Facility Hanh Hong Thi Dinh Utah State University Follow this and additional works at: https://digitalcommons.usu.edu/etd Part of the Analytical Chemistry Commons Recommended Citation Dinh, Hanh Hong Thi, "Analysis of Ammonia and Volatile Organic Amine Emissions in a Confined Poultry Facility" (2010). All Graduate Theses and Dissertations. 598. https://digitalcommons.usu.edu/etd/598 This Thesis is brought to you for free and open access by the Graduate Studies at DigitalCommons@USU. It has been accepted for inclusion in All Graduate Theses and Dissertations by an authorized administrator of DigitalCommons@USU. For more information, please contact [email protected]. Copyright © Hanh Hong Thi Dinh 2010 All Right Reserved iii ABSTRACT Analysis of Ammonia and Volatile Organic Amine Emissions in a Confined Poultry Facility by Hanh Hong Thi Dinh, Master of Science Utah State University, 2010 Major Professor: Dr Robert S. Brown Department: Chemistry and Biochemistry The National Air Emission Monitoring Study (NAEMS) project was funded by the Agricultural Air Research Council (AARC) to evaluate agricultural emissions nationwide. Utah State University (USU) is conducting a parallel study on agricultural emissions at a Cache Valley poultry facility. As part of this parallel study, samples of animal feed, eggs and animal waste were collected weekly from three manure barns (designated: manure barn, barn 4 - manure belt and barn 5 - high rise) from May 2008 to November 2009. These samples were analyzed to determine ammonia content, total Kjeldahl nitrogen content and ammonia emission.
    [Show full text]
  • Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard
    Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas Juan-Carlos Lizardo-Huerta, Baptiste Sirjean, Laurent Verdier, René Fournet, Pierre-Alexandre Glaude To cite this version: Juan-Carlos Lizardo-Huerta, Baptiste Sirjean, Laurent Verdier, René Fournet, Pierre-Alexandre Glaude. Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas. Journal of Physical Chemistry A, American Chemical Society, 2017, 121 (17), pp.3254-3262. 10.1021/acs.jpca.7b01238. hal-01708219 HAL Id: hal-01708219 https://hal.archives-ouvertes.fr/hal-01708219 Submitted on 13 Feb 2018 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. Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas Juan-Carlos Lizardo-Huerta†, Baptiste Sirjean†, Laurent Verdier‡, René Fournet†, Pierre-Alexandre Glaude†,* †Laboratoire Réactions et Génie des Procédés, CNRS, Université de Lorraine, 1 rue Grandville BP 20451 54001 Nancy Cedex, France ‡DGA Maîtrise NRBC, Site du Bouchet, 5 rue Lavoisier, BP n°3, 91710 Vert le Petit, France *corresponding author: [email protected] Abstract The destruction of stockpiles or unexploded ammunitions of nitrogen mustard (tris (2- chloroethyl) amine, HN-3) requires the development of safe processes.
    [Show full text]
  • Bio-Reducible Polyamines for Sirna Delivery
    Bio-Reducible Polyamines for siRNA Delivery by James Michael Serginson of the Department of Chemistry, Imperial College London Submitted in support of the degree of Doctor of Philosophy 1 Declaration of Authorship I do solemnly vow that this thesis is my own work. Where the work of others is referenced, it is clearly cited. 2 Abstract Even though siRNA shows great promise in the treatment of genetic disease, cancer and viral infection; the lack of a suitable delivery vector remains a barrier to clinical use. Currently, viral vectors lead the field in terms of efficacy but are generally regarded as prohibitively dangerous. Synthetic alternatives such as cationic polymers could overcome this problem. Previous work in the group found that small, cationic, disulfide-containing, cyclic polyamines – despite being non-polymeric – were useful as vectors for pDNA transfection; this work focuses on adapting the material for siRNA. A branched analogue of the cyclic compounds was prepared and the synthetic procedures investigated are discussed. The suitability of both compounds for siRNA delivery was studied in depth. Characterisation of their interactions with nucleic acids under various conditions was carried out using light-scattering techniques, gel electrophoresis and fluorescent dye exclusion assays. Results from these experiments were used to allow successful use of the materials as vectors and enable understanding of the mechanism of the template-driven polymerisation. Early data concerning the efficacy of the materials as an siRNA delivery system in vitro was obtained using A549 lung carcinoma cells as a model system with siRNAs targeting the production of the enzyme GAPDH. Both compounds showed a hint of successful siRNA Delivery but the data was not overwhelmingly conclusive.
    [Show full text]
  • Determination of Dimethylamine and Triethylamine in Hydrochloride
    Short Communications Determination of Dimethylamine and Triethylamine in Hydrochloride Salts of Drug Substances by Headspace Gas Chromatography using Dimethyl Sulphoxide- imidazole as Diluent J. GOPALAKRISHNAN* AND S. ASHA DEVI1 Piramal Enterprises Limited, Analytical Development Laboratory, 1, Nirlon complex, Off Western expressway, Goregaon (E), Mumbai-400 101, 1School of Biosciences and Technology, VIT University, Vellore-632 014, India Gopalakrishnan and Asha Devi: Determination of Amines in Drug by Headspace Gas Chromatography A simple, rapid, accurate and precise analytical method for determination of secondary and tertiary amines in hydrochloride salt form of drug substances in non-aqueous medium, which does not require any derivatization, was developed by headspace gas chromatography. Dimethylamine hydrochloride and triethylamine hydrochloride were analyzed in metformin hydrochloride. The sample was dissolved in a vial containing dimethyl sulphoxide and imidazole. The vials were incubated at 100°, for 20 min. The syringe temperature was maintained at 110°. DB624 column with 30 m×0.32 mm i.d., 1.8 µm film thickness was used. The injector and detector temperature were 200° and 250°, respectively. The analytical program used was carrier gas (nitrogen) flow rate: 1 ml/min; injected gas volume: 1.0 ml; split ratio: 1:10; oven temperature program: 40° for 10 min, followed by an increase up to 240° at 40°/min. The analytical method was validated with respect to precision, recovery, limit of detection and quantification and linearity. Key words: Aliphatic amines, dimethylamine, triethylamine, metformin hydrochloride, DMSO, imidazole, headspace gas chromatography Organic solvents are used in the synthesis of limit for unspecified impurities is 0.10%, i.e., 1000 pharmaceutical compounds and they must be controlled ppm[4].
    [Show full text]
  • Chemical Resistance Guide CHEMICAL RESISTANCE GUIDE
    Chemical Resistance Guide CHEMICAL RESISTANCE GUIDE This Chemical Resistance Guide incorporates three (800) 430-4110. North also offers ezGuide™,an Key to Degradation and Permeation Ratings types of information: interactive software program which is designed to electronically help you select the proper glove for E - Excellent Exposure has little or no effect. The glove retains its properties after extended exposure • Degradation (D) is a deleterious change in one use against specific chemicals. This "user friendly" G - Good Exposure has minor effect with long term exposure. Short term exposure has little or no effect or more of the glove’s physical properties. The guide walks you step-by-step through the process most obvious forms of degradation are the loss to determine what type of glove to wear and its F - Fair Exposure causes moderate degradation of the glove. Glove is still useful after short term of the glove’s strength and excessive swelling. permeation resistance to the selected contaminant. exposure but caution should be exercised with extended exposure Several published degradation lists (primarily Product features, benefits and ordering information P - Poor Short term exposure will result in moderate degradation to complete destruction “The General Chemical Resistance of Various of the suggested products also are included in the Elastomers” by the Los Angeles Rubber Group, program. ezGuide can be accessed from the North N/D Permeation was not detected during the test Inc.) were used to determine degradation. web site, www.northsafety.com or ordered I/D Insufficient data to make a recommendation • Breakthrough time (BT) is defined as the elapsed by e-mailing us at [email protected].
    [Show full text]
  • Verification of Methods for Selected Chemical Warfare Agents (Cwas)
    EPA/600/R-12/653 | January 2013 | www.epa.gov/ord Verifi cation of Methods for Selected Chemical Warfare Agents (CWAs) Offi ce of Research and Development National Homeland Security Research Center Disclaimer This document was prepared as an account of work sponsored by an agency of the United States government. U.S. Environmental Protection Agency (EPA) funded and collaborated in this research under Interagency Agreement DW-89-92328201 with the U. S. Department of Energy (DOE). It has been reviewed by EPA but does not necessarily reflect EPA’s views. Neither the United States government nor Lawrence Livermore National Security, LLC, nor any of their employees makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not constitute or imply its endorsement, recommendation, or favoring by the United States government or Lawrence Livermore National Security, LLC. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or Lawrence Livermore National Security, LLC, and shall not be used for advertising or product endorsement purposes. Auspices Statement This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344; the Lawrence Livermore National Laboratory report number is LLNL-TR-583012. The research team was comprised of Heather Mulcahy, Roald Leif, Edmund Salazar, and Carolyn Koester.
    [Show full text]
  • Nicolet Vapor Phase
    Nicolet Vapor Phase Library Listing – 8,654 spectra This library is one the most comprehensive collections of vapor phase FT-IR spectra. It is an invaluable tool for scientist involved in investigations on gas phase materials. The Nicolet Vapor Phase Library contains 8654 FT-IR spectra of compounds measured in gas phase. Most spectra were acquired by the Sigma-Aldrich Co. using product samples. Additional spectra were collected by Hannover University, University of Wurzburg and Thermo Fisher Scientific applications scientists. Spectra were collected using sampling techniques including heated or room temperature gas cell or a heated light-pipe connected to the outlet of a gas chromatograph. Nicolet Vapor Phase Index Compound Name Index Compound Name 8402 ((1- 5457 (-)-8-Phenylmenthol; (-)-(1R,2S,5R)-5- Ethoxycyclopropyl)oxy)trimethylsilane Methyl-2-(2-phenyl-2-propyl)cyc 4408 (+)-1,3-Diphenylbutane 1095 (-)-Carveol, mixture of isomers; p- 4861 (+)-1-Bromo-2,4-diphenylbutane Mentha-6,8-dien-2-ol 2406 (+)-3-(Heptafluorobutyryl)camphor 3628 (-)-Diisopropyl D-tartrate 2405 (+)-3-(Trifluoroacetyl)camphor 1427 (-)-Limonene oxide, cis + trans; (-)-1,2- 281 (+)-3R-Isolimonene, trans-; (1R,4R)- Epoxy-4-isopropenyl-1-methyl (+)-p-Mentha-2,8-diene 1084 (-)-Menthol; [1R-(1a,2b,5a)]-(-)-2- 289 (+)-Camphene; 2,2-Dimethyl-3- Isopropyl-5-methylcyclohexanol methylenebicyclo[2.2.1]heptane 2750 (-)-Menthoxyacetic acid 3627 (+)-Diisopropyl L-tartrate 1096 (-)-Myrtanol, cis-; (1S,2R)-6,6- 2398 (+)-Fenchone; (+)-1,3,3- Dimethylbicyclo[3.1.1]heptane-2-metha
    [Show full text]
  • (Ndma) in Natural Waters
    FORMATION STUDIES ON N-NITROSODIMETHYLAMINE (NDMA) IN NATURAL WATERS ___________________________________________________________ A Dissertation presented to the Faculty of the Graduate School University of Missouri-Columbia ____________________________________________________________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy ____________________________________________________________ by XIANGHUA LUO Dr. Thomas E. Clevenger, Dissertation Supervisor DECEMBER 2006 The undersigned appointed by the Dean of the Graduate School, have examined the dissertation entitled FORMATION STUDIES ON N-NITROSODIMETHYLAMINE (NDMA) IN NATURAL WATERS Presented by Xianghua Luo A candidate for the degree of Doctor of Philosophy in Environmental Engineering And hereby certify that in their opinion it is worthy of acceptance. ________________________________________________ Thomas E. Clevenger, Chair ________________________________________________ Allen Thompson, outside member ________________________________________________ Shankha K. Banerji ________________________________________________ John J. Bowders ________________________________________________ Kathleen Trauth DEDICATIONS This dissertation is dedicated to my husband Xiancheng Fang, my son Roger Hongbo Fang, my parents Xianbao Luo and Lizhen Jiang, for their love and support. ACKNOLOGEMENTS I would like to express my sincere appreciation to my advisor and mentor, Dr. Thomas E. Clevenger, for his intelligence, insight, generosity and guiding me through my research
    [Show full text]
  • Chapter 6 Amines and Amides
    Chapter 6 Amines and Amides Chapter 6 Amines and Amides Chapter Objectives: • Learn to recognize the amine and amide functional groups. • Learn the IUPAC system for naming amines and amides. • Learn the important physical properties of the amines and amides. • Learn the major chemical reactions of amines and amides, and learn how to predict the products of amide synthesis and hydrolysis reactions. • Learn some of the important properties of condensation polymers, especially the polyamides. Mr. Kevin A. Boudreaux Angelo State University CHEM 2353 Fundamentals of Organic Chemistry Organic and Biochemistry for Today (Seager & Slabaugh) www.angelo.edu/faculty/kboudrea Nitrogen-Containing Functional Groups • Nitrogen is in Group V of the periodic table, and in most of its compounds, it has three single bonds and one lone pair: N • In this chapter, we will take a look at two functional groups which contain nitrogen atoms connected to carbons: the amines and the amides. O RR''N RCN R' R' R" Amine Amide 2 Chapter 6 Amines and Amides Classification and Nomenclature of Amines 3 Amines • Amines and amides are abundant in nature. They are a major component of proteins and enzymes, nucleic acids, alkaloid drugs, etc. (Alkaloids are N- containing, weakly basic organic compounds; thousands of these substances are known.) • Amines are organic derivatives of ammonia, NH3, in which one or more of the three H’s is replaced by a carbon group. • Amines are classified as primary (1°), secondary (2°), or tertiary (3°), depending on how many carbon groups are connected to the nitrogen atom. HHN RHN RHN RR''N H H R' R' Ammonia 1° Amine 2° Amine 3° Amine 4 Chapter 6 Amines and Amides Examples: Classifying Amines • Classify the following amines as primary (1°), secondary (2°), or tertiary (3°).
    [Show full text]
  • Triethylamine (Casrn 121-44-8) Administered by Inhalation to F344/N Rats and B6c3f1/N Mice
    NTP TECHNICAL REPORT ON THE OXICITY TUDIES OF T S TRIETHYLAMINE (CASRN 121-44-8) ADMINISTERED BY INHALATION TO F344/N RATS AND B6C3F1/N MICE NTP TOX 78 MARCH 2018 NTP Technical Report on the Toxicity Studies of Triethylamine (CASRN 121-44-8) Administered by Inhalation to F344/N Rats and B6C3F1/N Mice Toxicity Report 78 March 2018 National Toxicology Program Public Health Service U.S. Department of Health and Human Services ISSN: 2378-8992 Research Triangle Park, North Carolina, USA NOT FOR Review Draft Triethylamine, NTP TOX 78 Foreword The National Toxicology Program (NTP) is an interagency program within the Public Health Service (PHS) of the Department of Health and Human Services (HHS) and is headquartered at the National Institute of Environmental Health Sciences of the National Institutes of Health (NIEHS/NIH). Three agencies contribute resources to the program: NIEHS/NIH, the National Institute for Occupational Safety and Health of the Centers for Disease Control and Prevention (NIOSH/CDC), and the National Center for Toxicological Research of the Food and Drug Administration (NCTR/FDA). Established in 1978, the NTP is charged with coordinating toxicological testing activities, strengthening the science base in toxicology, developing and validating improved testing methods, and providing information about potentially toxic substances to health regulatory and research agencies, scientific and medical communities, and the public. The Toxicity Study Report series began in 1991. The studies described in the Toxicity Study Report series are designed and conducted to characterize and evaluate the toxicologic potential of selected substances in laboratory animals (usually two species, rats and mice).
    [Show full text]
  • Summer Scholar Report an Investigation of the Synthesis and Transmetalation Chemistry of Tris(Aryl)Tren Ligands by Diego R
    Summer Scholar Report An investigation of the synthesis and transmetalation chemistry of tris(aryl)tren ligands By Diego R. Javier-Jimenez and David R. Manke, Department of Chemistry and Biochemistry, University of Massachusetts Dartmouth, North Dartmouth, MA Introduction Tripodal ligands based on the tris(2-aminoethyl)amine (TREN) backbone have been used for more than 25 years to support a wide variety of interesting coordination compounds.1 When fully deprotonated, the ligand is trianioinic, possessing three amido coordination sites and one amino coordination site, providing a tetradentate metal binding pocket. The ligand is able to stabilize metals in the +3 oxidation state, and favors a C3 symmetric coordination environment, leaving an open coordination site on the metal at an axial position of a trigonal bipyramid (Figure 1). These ligands have been used to stabilize molybdenum compounds able to reduce dinitrogen,2 zirconium compounds able to catalyze insertion reactions,3 and novel actinide complexes.4 Figure 1. The generic structure of the TREN ligand set, showing a metal bound in the tetradentate, tripodal tris(amido)amine binding pocket. To date, all TREN ligands possess a symmetric substitution pattern, with the same group on each of the three amido nitrogens of the ligand. A search of the Cambridge Structural Database reveals 436 metal complexes of TREN ligands. The vast majority of these complexes are tris(silyl)trens, where each amido nitrogen possesses trialkyl- or triaryl- silyl group. The synthesis of these ligands begins with the parent tris(2-aminoethyl)amine followed by a condensation with a chlorosilane.1 Less common, but still studied, are tris(aryl)tren ligands (81 of 436 structures).
    [Show full text]