DOCSLIB.ORG

New Methods for the Synthesis of Organozinc and Organocopper Reagents

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
New Methods for the Synthesis of Organozinc and Organocopper Reagents Claudia Piazza New Methods for the Synthesis of Organozinc and Organocopper Reagents München 2002 Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München New Methods for the Synthesis of Organozinc and Organocopper Reagents Claudia Piazza aus Treviso, Italien München, 2002 Erklärung Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29. Januar 1998 von Professor Dr. Paul Knochel betreut. Ehrenwörtliche Versicherung Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet. München, am 30. Oktober 2002 Claudia Piazza Dissertation eingereicht am 30. Oktober 2002 1. Gutachter: Prof. Dr. Paul Knochel 2. Gutachter: Prof. Dr. em. Wolfgang Steglich Mündliche Prüfung am 4. Dezember 2002 Table of Contents Introduction 1 Overview 2 1.1 Organozinc reagents 2 1.2 Uncatalysed reactions of zinc organometallics 5 1.2.1 Aminomethylation 5 1.2.2 Fragmentation of homoallylic zinc alcoholates 6 1.2.3 Generation of benzylic zinc reagents 9 1.3 Transition metal catalysed reactions of zinc organometallics 10 1.4 Organocopper reagents 11 1.4.1 Vinylic organocuprates 13 2 Objectivies 16 Results and Discussion 1 Aminomethylation of Functionalized Organozinc Reagents and Grignard Reagents 19 1.1 Summary 23 2 Preparation of Benzylic Zinc Reagents via a Fragmentation Reaction 24 2.1 Summary 27 3 Preparation of Allylic Zinc Reagents via a Cyclization-Fragmentation Reaction 28 3.1 Attempted synthesis of functionalized allylic zinc reagents via a cyclization-fragmentation reaction 34 3.2 Summary 35 4 Preparation of Highly Functionalized Organocuprates via Halogen-Copper Exchange 36 4.1 Higher order cyanocuprates 36 4.2 Non-transferable ligands 36 4.3 Functionalized aryl cyanocuprates 38 4.4 Screening of other non-transferable groups 39 4.5 Neopentyl and neophyl group as non-transferable ligands 41 4.6 Halogen-copper exchange on functionalized arylic compounds 42 4.6.1 Reactions of lithium dineopentylcuprate 43 4.6.2 Aldehydes and ketones: reactions of neophylcuprate 46 4.7 Regioselective functionalization of polyiodinated arylic substrates 50 4.8 The role of copper cyanide 54 4.9 Substitution reactions with functionalized mixed cuprates 54 4.10 Summary 56 5 Iodine-Copper Exchange on Vinylic Substrates 57 5.1 Summary 60 6 Halogen-Copper Exchange on Heterocycles 61 6.1 Summary 65 7 Summary and Outlook 66 Experimental Section 1 General Conditions 72 2 Typical Procedures (TP) 75 TP 1 Typical procedure for the aminomethylation of functionalized organozinc and Grignard reagents 75 TP 2 Typical procedure for palladium-catalyzed deprotection of allylamines 75 TP 3 Typical procedure for the preparation of benzylic alcohols via a fragmentation reaction 75 TP 4 Typical procedure for the generation of homoallylic zinc reagents via a cyclization-fragmentation reaction 76 TP 5 Typical procedure for the halogen-copper exchange on arylic substrates 76 TP 6 Typical procedure for the iodine-copper exchange on ethyl (2Z)-3-iodo-3-phenylpropenoate 77 TP 7 Typical procedure for the bromine-copper exchange on N,N-diallyl-2-bromo-3-methyl-butenamide 77 TP 8 Typical procedure for the iodine-copper exchange on imidazole derivatives 78 3 Synthesis of Organozinc and Organocopper Reagents 79 4 Aminomethylation of Functionalized Organozinc Reagents and Grignard Reagent Using Immonium Trifluoroacetates 82 5 Preparation of Benzylic Zinc Reagents via a Fragmentation Reaction 91 6 Preparation of Allylic Zinc Reagents via a Cyclization-Fragmentation Reaction 101 7 Preparation of Highly Functionalized Organocuprates via Halogen-Copper Exchange 116 8 Iodine-Copper Exchange on Vinylic Substrates 133 9 Halogen-Copper Exchange on Heterocycles 140 10 Abbreviations 151 Introduction 2 1 Overview Organozinc and organocopper reagents are an indispensable part of the synthetic chemist’s knowledge. Nowadays, almost every synthesis of natural product has at least one step which involves the use of this kind of compounds. Therefore, there is a constant need for the development of new methods for a straightforward and efficient preparation of zinc and copper organometallics. In this work the attention was focused on a new approach for the preparation of benzylic and allylic organozincs, which are among the most reactive zinc species. Even if diorganozincs and organozinc halides display only moderate reactivity toward most organic electrophiles, the scope and synthetic application of these species were greatly extended when it was found that they can accommodate a wide range of functional groups. An important C-C bond forming reaction for the construction of nitrogen-containing molecules is the addition of carbon nucleophiles to iminium intermediates. For this reason, the use of zinc reagents with these highly reactive elctrophiles for the synthesis of functionalised amines will also be described. The vast majority of experimental protocols for the preparation of organocopper complexes involve the transmetalation process from other organometallic species. This places a limitation in the functional groups that can be present in the molecule, depending on the precursor of choice. The search for a method that avoids the transmetalation step, allowing the preparation of organocoppers bearing any kind of functionalities by direct halogen-copper exchange reaction, was considered to be of a remarkable synthetic utility and was therefore attempted. 1.1 Organozinc reagents With the synthesis of diethylzinc in 1849, E. Frankland lay the foundation stone for modern organometallic chemistry.1 However, organomagnesium2 and organolithium3 reagents were the first reagents to dominate this branch of organic chemistry. Although almost ignored for more than 100 years after their discovery, organozinc compounds are today one of the most useful class of organometallic reagents, due to their easy preparation and higher functional group 1 a) Frankland, E. Liebigs Ann. Chem. 1848-49, 71, 171. b) Frankland, E. J. Chem. Soc. 1848-49, 2, 263. 2 Grignard, V. Compt. Rend. 1900, 130, 1322. 3 a) Schlenk, W.; Holtz, J. Chem. Ber. 1917, 50, 262. b) Ziegler, K.; Colonius, H. Liebigs Ann. Chem. 1930, 479, 135. 3 compatibility in comparison with organolithium and Grignard reagents. Furthermore, their excellent reactivity in the presence of the appropriate catalyst makes them a very powerful tool for natural product synthesis, as illustrated in the preparation of prostaglandin intermediates 1 and 24 (Scheme 1). O O O OPiv O 1) IZnCH2OPiv CuCN 2 LiCl TBDMSO TMSCl, THF TBDMSO Pent TBDMSO 2) 1N HCl Pent Pent TBDMSO TBDMSO TBDMSO 83 % 1 O O 1) IZn CO Me 2 CO2Me TBDMSO TBDMSO CuCN 2 LiCl Pent Pent TMSCl, THF TBDMSO TBDMSO 2) L-Selectride 58 % 3) aq. HF, CH3CN 2 Scheme 1 There are three main classes of organozinc compounds:5 organozinc halides (RZnX), diorganozincs (R2Zn) and lithium or magnesium zincates. Organozinc halides are readily available by the direct insertion of zinc dust into organic halides6 (Scheme 2). 4 a) Miyaji, K.; Ohara, Y.; Miyauchi, Y.; Tsuruda, T.; Arai, K. Tetrahedron Lett. 1993, 34, 5597. b) Yoshino, T.; Okamoto, S.; Sato, F. J. Org. Chem. 1991, 56, 3205. c) Koga, M.; Fujii, T.; Tanaka, T. Tetrahedron 1995, 51, 5529. 5 Knochel, P.; Jones, P. Organozinc Reagents. A Practical Approach, Oxford University Press, 1999. 6 a) Berk, S. C.; Yeh, M. C. P.; Jeong, N.; Knochel, P. Organometallics 1990, 9, 3053; b) Berger, S.; Langer, F.; Lutz, C.; Knochel, P.; Mobley, A.; Reddy, C. K. Angew. Chem. 1997, 109, 1603; Angew. Chem. Int. Ed. 1997, 36, 1496. c) Rottändler, M.; Knochel, P. Tetrahedron Lett. 1997, 38, 1749. d) Zhu, L.; Wehmeyer, R. M.; Rieke, R. D. J. Org. Chem. 1991, 56, 1445. 4 Zn RX RZnX X = I, Br THF O NHBoc IZn CO Bn 2 ZnI Scheme 2 Diorganozinc reagents require different methods of preparation, like iodine-zinc and boron-zinc exchange.7 These methods are applicable to the formation of primary and secondary diorganozinc species8 (Scheme 3). Et2Zn 1) Et2BH 1 1 1 R -(CH2)2-I R (CH2)2 Zn R CuX cat. 2 2) Et2Zn Zn AcO Zn TIPSO 2 2 Scheme 3 Remarkably, by using i-Pr2Zn, configurationally defined secondary dialkylzinc reagents have been prepared7c (Scheme 4). OBn 1) Et BH (3 equiv) OBn 1) CuCN 2LiCl OBn 2 H H 50 °C, 16 h -78 °C, 30 min Ph 2 1 Ph Ph 2) i-Pr Zn (3 equiv) 2) 1-bromo-1-hexyne (5 equiv) 2 3 Zni-Pr 25 °C, 5 h -55 °C, 2 d Bu dr(1,2) = 93 : 7 dr(1,2) > 99 : 1 overall yield 47 % Scheme 4 7 a) Langer, F.; Waas, J.; Knochel, P Tetrahedron Lett. 1993, 34, 5261. b) Langer, F.; Schwink, L.; Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P. J. Org. Chem. 1996, 61, 8229. c) Boudier, A.; Hupe, E.; Knochel, P. Angew. Chem. 2000, 112, 2396; Angew. Chem. Int. Ed. 2000, 39, 2294. 8 a) Schwink, L.; Knochel, P. Tetrahedron Lett. 1994, 35, 9007. b) Devasagayaraj, A.; Schwink, L.; Knochel, P. J. Org. Chem. 1995, 60, 3311. 5 Diorganozincs display enhanced chemical reactivity compared to alkylzinc halides, but even more reactive are lithium or magnesium zincates, which are readily prepared by transmetalation reactions from the corresponding magnesium or lithium reagents and are well suited to halogen- zinc exchange reactions9 (Scheme 5). R2Zn + RM R3ZnM ZnCl2 + 3RM Br Br Br R3ZnLi R'Br Pd (0) Br Zn(L) R' Scheme 5 1.2 Uncatalysed reactions of zinc organometallics 1.2.1 Aminomethylation In contrast with organolithium and Grignard reagents, organozincs have a relatively covalent carbon-metal bond, resulting in their more moderate reactivity than that of organometallics containing a more polar carbon-metal bond. Only reactive classes of organozinc reagents like allylic zinc halides10 and zinc enolates11 efficiently undergo additions to carbonyl compounds. On the other hand, a few classes of highly reactive electrophilic reagents directly react with zinc organometallics, among them immonium salts. Iminium salts are important intermediates in organic synthesis12 and aminomethylation is a transformation which has been performed with various immonium salts13 or iminium salt precursors.14 The reaction of these intermediates with functionalised organozinc reagents was first reported by Saidi,15 who performed a three component aminoalkylation of aldehydes promoted by lithium perchlorate.
Load more

Recommended publications
  • Studies on the Acid-Base Properties of the Znbr2nabr Molten Salt System
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Okayama University Scientific Achievement Repository Chemistry Physical & Theoretical Chemistry fields Okayama University Year 1992 Studies on the acid-base properties of the ZnBr2NaBr molten salt system Hidetaka Hayashi Kiyofumi Uno Okayama University Kyoto University Zen-ichiro Takehara Akira Katagiri Kyoto University Kyoto University This paper is posted at eScholarship@OUDIR : Okayama University Digital Information Repository. http://escholarship.lib.okayama-u.ac.jp/physical and theoretical chemistry/23 386 J. Electrochem. Soc., Vol. 140, No. 2, February 1993 The Electrochemical Society, Inc. 8. T. Yoshida, K. Okabayashi, T. Assoka, and K. Abe, Ab- ics: Materials and Devices for Transmittance Con- stract 380, p. 552, The Electrochemical Society Ex- trol, C. M. Lampert and C. G. Granqvist, Editors, tended Abstracts, Vol. 88-2, Chicago, IL, Meeting, p. 482, SPIE Optical Engineering Press, Bellingham, Oct. 9-14, 1988. WA (1990). 9. K. Honda, M. Fu]ita, H. Ishida, R. Yamamoto, and K. 21. S. Hub, A. Tranchant, and R. Messina, Electrochim. Ohgaki, This Journal, 135, 3151 (1988). Acta, 33, 997 (1988). 10. T. Kase, T. Miyamoto, T. Yoshimoto, u Ohsawa, H. 22. K. Ho, D. E. Singleton, and C. G. Greenberg, This Jour- Inaba, and K. Nakasi, in Large Area Chromogenics: nal, 137, 3858 (1990). Materials and Devices .for Transmittance Control, 23. J. P. Randin, in Large Area Chromogenics: Materials C. M. Lampert and C. G. Granqvist, Editors, p. 504, and Devices for Transmittance Control, C. M. Lain- SPIE Optical Engineering Press, Bellingham, WA pert and C.
    [Show full text]
  • Notable Reactivity of Acetonitrile Towards Li2o2/Lio2 Probed By
    Topics in Catalysis https://doi.org/10.1007/s11244-018-1072-5 ORIGINAL ARTICLE Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge Tatiana K. Zakharchenko1 · Alina I. Belova1 · Alexander S. Frolov1 · Olesya O. Kapitanova1 · Juan‑Jesus Velasco‑Velez2 · Axel Knop‑Gericke2,5 · Denis Vyalikh3,4 · Daniil M. Itkis1 · Lada V. Yashina1 © Springer Science+Business Media, LLC, part of Springer Nature 2018 Abstract One of the key factors responsible for the poor cycleability of Li–O2 batteries is a formation of byproducts from irreversible reactions between electrolyte and discharge product Li 2O2 and/or intermediate LiO2. Among many solvents that are used as electrolyte component for Li–O2 batteries, acetonitrile (MeCN) is believed to be relatively stable towards oxidation. Using near ambient pressure X-ray photoemission spectroscopy (NAP XPS), we characterized the reactivity of MeCN in the Li–O2 battery. For this purpose, we designed the model electrochemical cell assembled with solid electrolyte. We discharged it first in O2 and then exposed to MeCN vapor. Further, the discharge was carried out in O2 + MeCN mixture. We have dem- onstrated that being in contact with Li–O2 discharge products, MeCN oxidizes. This yields species that are weakly bonded to the surface and can be easily desorbed. That’s why they cannot be detected by the conventional XPS. Our results suggest that the respective chemical process most probably does not give rise to electrode passivation but can decrease considerably the Coulombic efficiency of the battery. Keywords Li–O2 battery · In situ NAP XPS · Acetonitrile · Side reactions 1 Introduction Li–O2 batteries promise extraordinary high specific energy that makes them interesting for the next generation power technologies [1, 2].
    [Show full text]
  • Catalog 2014-2015
    RIEKE METALS, INC. Catalog 2014-2015 Founders of Rieke Metals, Inc. Dr. Reuben D. Rieke grew up in Fairfax, Minnesota. He received a Bachelor of Chemistry degree from the University of Minnesota-Minneapolis, doing undergraduate research with Professor Wayland E. Noland. He received a Ph.D. from the University of Wisconsin-Madison in 1966 under the direction of Professor Howard E. Zimmerman. He then did postgraduate work with Professor Saul Winstein at UCLA. He taught at the University of North Carolina at Chapel Hill from 1966 to 1976, at North Dakota State University in Fargo from 1976 to 1977, and at the University of Nebraska-Lincoln from 1977 to 2004. Loretta Rieke was born and raised in New York City. She earned a Bachelor of Science from Queens College and did graduate studies at the University of Wisconsin-Madison. High Quality Compounds The formula: Provide unique research reagents to the world with exceptional speed and attention to detail. Since 1991, Rieke Metals, Inc has been doing just that by supplying active metals, Grignard and organic semi-conducting polymers and monomers. Headquartered in Lincoln, Nebraska, the facility produces and supplies over 10,000 research compounds. We provide quantities from grams to kilograms, ensuring high purity and service every step of the way. High Quality Service Rieke Metals is run by scientists, and we understand that research is not simple. That’s why RMI strives to make your work easier. With thousands of compounds in stock, orders are processed immediately and shipped the same day. Material electronically provided for immediate information. Technical service is only a phone call away with Rieke Metals.
    [Show full text]
  • Zinc/Bromine Batteries
    SAND2000-0893 CHAPTER 37 ZINC/BROMINE BATTERIES Paul C. Butler, Phillip A. Eidler, Patrick G. Grimes, Sandra E. Klassen, and Ronald C. Miles 37.1 GENERAL CHARACTERISTICS The zinc/bromine battery is an attractive technology for both utility-energy storage and electric-vehicle applications. The major advantages and disadvantages of this battery technology are listed in Table 37.1. The concept of a battery based on the zinc/bromine couple was patented over 100 years ago,’ but development to a commercial battery was blocked by two inherent properties: (1) the tendency of zinc to form dendrites upon deposition and (2) the high volubility of bromine in the aqueous zinc bromide electrolyte. Dendritic zinc deposits could easily short-circuit the cell, and the high volubility of bromine allows diffusion and direct reaction with the zinc electrode, resulting in self-discharge of the cell. Development programs at Exxon and Gould in the mid-1970s to early 1980s resulted in designs which overcame these problems, however, and allowed development to proceed.’ The Gould technology was developed further by the Energy Research Corporation but a high level of activity was not maintained. s-’ In the mid-1980s Exxon licensed its TABLE 37.1 Major Advantages and Disadvantages of Zinc/Bromine Battery Technology Advantages Disadvantages Circulating electrolyte allows for ease of thermal Auxiliary systems are required for circulation management and uniformity of reactant supply to and temperature control each cell System design must ensure safety as for all Good
    [Show full text]
  • A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory
    sensors Article A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory Niraj Verma 1,† , Yunwen Tao 1,†, Wenli Zou 2, Xia Chen 3, Xin Chen 4, Marek Freindorf 1 and Elfi Kraka 1,* 1 Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275-0314, USA; [email protected] (N.V.); [email protected] (Y.T.); [email protected] (M.F.) 2 Institute of Modern Physics, Northwest University, Xi’an 710127, China; [email protected] 3 Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, China; [email protected] 4 Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China; [email protected] * Correspondence: [email protected] † These authors contributed equally to this work. Received: 20 March 2020; Accepted: 15 April 2020; Published: 21 April 2020 Abstract: Over the past two decades, the vibrational Stark effect has become an important tool to measure and analyze the in situ electric field strength in various chemical environments with infrared spectroscopy. The underlying assumption of this effect is that the normal stretching mode of a target bond such as CO or CN of a reporter molecule (termed vibrational Stark effect probe) is localized and free from mass-coupling from other internal coordinates, so that its frequency shift directly reflects the influence of the vicinal electric field. However, the validity of this essential assumption has never been assessed. Given the fact that normal modes are generally delocalized because of mass-coupling, this analysis was overdue.
    [Show full text]
  • Itetall IC BROMIDES AS CATALYSTS in THE
    QUANTITATIVE COMPARISON OF ;itETALL IC BROMIDES AS CATALYSTS IN THE FRIED.liL-CRAFTS KETONE SYNTHESIS i QUANTITATIVE COMPARISON OF MET ALLIC BROMIDES AS CATAL YSTS IN THE FRIEDEL-CRAFTS KETONE SYNTHESIS By Peter Taketoshi M,, ori Bachelor of .Arts Park College Parkville, Missouri 1945 Submitted to the Department of Chemistry Oklahoma Agricultural and Mechanical College In partial fulfillment of the r equirement for t he Degree of Master of Science 194'~ ii \ APPROVED BY: Chairman, Thesis Committee Head of the Department ~he~ ( ~uate~~ School 2174~10 iii ACKNOWLEDGEMENT The author wis hes to express his s i neere gr atitude to Dr . O. C. Dermer under whose guidance t his work has been accomplished . He also wi s hes to express hi s a ppreciation to the Chemi stry Department for t he s uppl y of chemicals used. iv TABLE OF CONTENTS "P age Introduction • • l Historical • • • • 2 Experimental • • • • 5 Procadure • • • • • • • • 9 Table of results . • • • • • • • 12 Discussion of results • .. • • • • • • 15 Summary • • • • • • • • 22 Bibliography • • • • • • • • • • 23 Biography • • • • • • • • • • • 25 1 I NTRODCCT ION T~lis is a continuation of the s t udy of catalystf for the Friedel­ Crafts ketone synt hesis star ted by Wilson ( .38 ), a nd continued by Suguj.­ tan (34), Johnson (17), and Billme ier (4). Ma ny metallic chlorides have been used in t his reacti on, but metallic bromides, as cat alyst s, have been rather neelected . It is the purpose of this work to study the ef fectiveness of some of the metallic bromides by following essentially the experimental pro­ cedure of Billmeier (4). 2 HISTORICAL In 1877, the French chemist Friedel and his American colleague Crafts (12) discovered the f amous Friedel-Crafts reaction, which now has s uch great industrial a pplication (7 , 13, 18, 35).
    [Show full text]
  • Safety Review of Bromine- Based Electrolytes for Energy Storage Applications
    PP127316 Safety Review of Bromine- Based Electrolytes for Energy Storage Applications ICL Industrial Products Report No.: 1, Rev. 1 Date: February 26, 2016 Project name: PP127316 DNV USA, Inc. Report title: Safety Review of Bromine-Based Electrolytes for 5777 Frantz Rd Energy Storage Applications Dublin, OH 43017 Customer: ICL Industrial Products, Tel: +1-614-761-1214 Address Contact person: Sharona Atlas and David Murphy Date of issue: February 26, 2016 Project No.: PP127316 Organization unit: OAPUS304 Report No.: 1, 1 Document No.: No Task and objective: Create/Propose a Safety Testing Plan. To review Con Edison’s existing safety related materials and identify gaps by cross checking with relevant standards in the industry. Assess the risk and consequences of potential hazards that may occur to the TESS. Recommend the approach and relevant testing in order to fill the identified gaps. Davion M. Hill Prepared by: Verified by: Approved by: [Davion Hill, Ph.D.] William Kovacs III, P.E. [Name] [Group Leader, Energy & Materials] Senior Engineer – Oil & Gas Fatigue and [title] Fracture Rev. No. Date Reason for Issue Prepared by Verified by Approved by Table of contents 1 EXECUTIVE SUMMARY ..................................................................................................... 2 2 APPROACH ..................................................................................................................... 1 3 BOWTIE MODEL .............................................................................................................
    [Show full text]
  • List of Lists
    United States Office of Solid Waste EPA 550-B-10-001 Environmental Protection and Emergency Response May 2010 Agency www.epa.gov/emergencies LIST OF LISTS Consolidated List of Chemicals Subject to the Emergency Planning and Community Right- To-Know Act (EPCRA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the Clean Air Act • EPCRA Section 302 Extremely Hazardous Substances • CERCLA Hazardous Substances • EPCRA Section 313 Toxic Chemicals • CAA 112(r) Regulated Chemicals For Accidental Release Prevention Office of Emergency Management This page intentionally left blank. TABLE OF CONTENTS Page Introduction................................................................................................................................................ i List of Lists – Conslidated List of Chemicals (by CAS #) Subject to the Emergency Planning and Community Right-to-Know Act (EPCRA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the Clean Air Act ................................................. 1 Appendix A: Alphabetical Listing of Consolidated List ..................................................................... A-1 Appendix B: Radionuclides Listed Under CERCLA .......................................................................... B-1 Appendix C: RCRA Waste Streams and Unlisted Hazardous Wastes................................................ C-1 This page intentionally left blank. LIST OF LISTS Consolidated List of Chemicals
    [Show full text]
  • Selection of Catalyst for Group Transfer Polymerization of 1-Butadienyloxytrimethylsilane
    Polymer Journal, Vol. 24, No. 7, pp 669-677 (1992) Selection of Catalyst for Group Transfer Polymerization of 1-Butadienyloxytrimethylsilane Hiroshi SuMI, Tadamichi HIRABAYASHI, Yoshihito INAI, and Kenji YoKOTA Department of Materials Science & Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466, Japan (Received November 19, 1991) ABSTRACT: Catalytic activity of various Lewis acids in the group transfer polymerization (GTP) of 1-butadienyloxytrimethylsilane (BdTMS) initiated with benzaldehyde was investigated. Among the Lewis acids studied, three zinc halides (ZnBr2 , Znl2 , ZnC1 2) and HgBr2 gave soluble polymers with narrow molecular weight distributions in quantitative yields. The polymerizations proceeded apparently on the insoluble solid catalyst. The other soluble Lewis acid catalysts, including (C2H 5),A1Cl, A1Cl 3 , SnC14 , SnBr4 , and TiBr4 , gave polymers in moderate to poor yields and often gelled polymers. Through 1 H NMR monitoring of the polymerization, time vs. monomer and initiator consumption curves were obtained, and then initiation and propagation rates were estimated from slopes of the curves. Both rates were enhanced in an order of ZnBr2 >Znl2 >ZnC12 . This order is consistent with that of chemical shifts of formyl carbon of equimolar mixture of ZnX2 with benzaldehyde, as well as crotonaldehyde which is a model for a polymer end, in chloroform-d. This order was also compatible with the decreasing order in MwiM. values of the resulting polymers. Thus, use of ZnBr2 as the catalyst resulted
    [Show full text]
  • Chemical Names and CAS Numbers Final
    Chemical Abstract Chemical Formula Chemical Name Service (CAS) Number C3H8O 1‐propanol C4H7BrO2 2‐bromobutyric acid 80‐58‐0 GeH3COOH 2‐germaacetic acid C4H10 2‐methylpropane 75‐28‐5 C3H8O 2‐propanol 67‐63‐0 C6H10O3 4‐acetylbutyric acid 448671 C4H7BrO2 4‐bromobutyric acid 2623‐87‐2 CH3CHO acetaldehyde CH3CONH2 acetamide C8H9NO2 acetaminophen 103‐90‐2 − C2H3O2 acetate ion − CH3COO acetate ion C2H4O2 acetic acid 64‐19‐7 CH3COOH acetic acid (CH3)2CO acetone CH3COCl acetyl chloride C2H2 acetylene 74‐86‐2 HCCH acetylene C9H8O4 acetylsalicylic acid 50‐78‐2 H2C(CH)CN acrylonitrile C3H7NO2 Ala C3H7NO2 alanine 56‐41‐7 NaAlSi3O3 albite AlSb aluminium antimonide 25152‐52‐7 AlAs aluminium arsenide 22831‐42‐1 AlBO2 aluminium borate 61279‐70‐7 AlBO aluminium boron oxide 12041‐48‐4 AlBr3 aluminium bromide 7727‐15‐3 AlBr3•6H2O aluminium bromide hexahydrate 2149397 AlCl4Cs aluminium caesium tetrachloride 17992‐03‐9 AlCl3 aluminium chloride (anhydrous) 7446‐70‐0 AlCl3•6H2O aluminium chloride hexahydrate 7784‐13‐6 AlClO aluminium chloride oxide 13596‐11‐7 AlB2 aluminium diboride 12041‐50‐8 AlF2 aluminium difluoride 13569‐23‐8 AlF2O aluminium difluoride oxide 38344‐66‐0 AlB12 aluminium dodecaboride 12041‐54‐2 Al2F6 aluminium fluoride 17949‐86‐9 AlF3 aluminium fluoride 7784‐18‐1 Al(CHO2)3 aluminium formate 7360‐53‐4 1 of 75 Chemical Abstract Chemical Formula Chemical Name Service (CAS) Number Al(OH)3 aluminium hydroxide 21645‐51‐2 Al2I6 aluminium iodide 18898‐35‐6 AlI3 aluminium iodide 7784‐23‐8 AlBr aluminium monobromide 22359‐97‐3 AlCl aluminium monochloride
    [Show full text]
  • Chemical Compatibility Chart
    Chemical Compatibility Chart www.topworx.com Rating Guide: A Good B Fair C Questionable D Poor Blank Insuffi cient Data Epoxy Polycarbonate PBT Brass 316 S.S. 304 S.S. 400 S.S. Aluminum Viton Buna N Neoprene EPDM Silicone Acetaldehyde A A A B D D C A A Acetamide A A B B A B A B Acetate Solvent B A A A A D C D A C Acetic Acid, Glacial A D A C D A D C D B B Acetic Acid, 20% C B D D A B D A B B A A B Acetic Acid, 80% C B D D A C D A B C C A B Acetic Acid A B D D A C D A B C C A C Acetic Anhydride D A A D A D D A B C Acetone A D B A A A B A D D C A B Acetyl Bromide Acetyl Chloride (dry) A A A A A A D D C Acetylene A A A A A A A A A B A B Acrylonitrile A A A B D D C D D Alcohols: Amyl D A A A A B B B A A D Benzyl A A A B A A C B Butyl A B A A A B A A A B B Diacetone A A A A D D D A D Ethyl A B A A A A A B A C A A B Hexyl A A A A C A A C B Isobutyl A A A B A B A A A Isopropyl A A A B A B B A A Methyl B A A A B A A A A Octyl A A A B A B B B A B Propyl A A A A A A A A A A Chemical Compatibility Chart (cont.) www.topworx.com Epoxy Polycarbonate PBT Brass 316 S.S.
    [Show full text]
  • Synthesis and Properties of Diorganomagnesium Compounds
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-1967 Synthesis and Properties of Diorganomagnesium Compounds Conrad William Kamienski University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss., University of Tennessee, 1967. https://trace.tennessee.edu/utk_graddiss/3077 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: Bruce M. Anderson, George K. Schwitzer, David A. Shirley Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Novemb er 27, 1967 To the Graduate Council: I am submitting herewith a dissertation written by Conrad Wiliiam Kamienski entitled "Synthesis and Properties of Diorgano­ magnesium Compounds." I recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a maj or in Chemistry .
    [Show full text]