DOCSLIB.ORG

S/XXYXNN(\AAN (KNW 2

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
S/XXYXNN(\AAN (KNW 2 United States Patent 19 11 4,356,038 Bain et al. 45) Oct. 26, 1982 54 STABILIZATION OF CHLORINATED 3,049,571 8/1962 Brown .......................... 570/110 ALPHATIC HYDROCARBONS AND USE OF 3,238,065 3/1966 Fullhart, Jr. .......................... 34/11 STABILIZED COMPOSITION IN CLEANING 3,281,480 10/1966 Hardies ............. 252/71 X 3,549,715 12/1970 Cormany et al. ................... 570/10 ARTICLES 4,115,461 9/1978 Spencer et al. ................. 252/171 X 75 Inventors: David Bain, Sutton Leach; John E. Martin, Grappenhall; John H. Saul, FOREIGN PATENT DOCUMENTS Upton-by-Chester; Neil Winterton, 788495 6/1968 Canada. Tarvin, all of England 1435548 5/1976 United Kingdom ................ 252/17 1439970 6/1976 United Kingdom ................ 252/17 73 Assignee: Imperial Chemical Industries 2024242 1/1980 United Kingdom . Limited, London, England 2024243 1/1980 United Kingdom . 21 Appl. No.: 170,835 Primary Examiner-Richard D. Lovering 22 Filed: Jul. 16, 1980 Attorney, Agent, or Firm-Cushman, Darby & Cushman 30 Foreign Application Priority Data 57 ABSTRACT A solvent composition for cleaning metal and other Jul. 25, 1979 (GB United Kingdom ................. 792.5867 articles which comprises 1,1,1-trichloroethane having Apr. 25, 1980 GB United Kingdom ................. 8O13705 dissolved therein a stabilizing amount of a mixture of 51) Int. Cl. ......................... C1D 7/50; C23G 5/02; stabilizing components comprising (i) tertiary butanol C09K 15/16; C07C 17/42 (ii) nitromethane and (iii) 1-or 2-nitropropane or nitro 52 U.S. C. .......................................... 134/2; 134/31; ethane, in which mixture the specified stabilizing com 252/171; 252/364; 252/405; 570/110 ponents are present in the mole fraction percent ranges 58 Field of Search ....................... 252/364, 171, 405; encompassed by Contour Kin FIG. 1 of the drawings in 134/11, 2, 31; 570/110 the case where component (iii) is 1-or 2-nitropropane or by Contour A in FIG. 2 of the drawing in the case 56) References Cited where component (iii) is nitroethane. U.S. PATENT DOCUMENTS 3,000,978 9/1961 Fredenburg ........................ 570/18 13 Claims, 2 Drawing Figures KEY WIDEST SCOPE OF THE INVENTION N SX MORE PREFERRED REGION as Sy d S 2. s/XXYXNN(\AAN (KNW 2. /XXNXXNKNXNX38X\%\N X. & N 2. NX AywyswearyayawpawsQNX8.Q & TBA, MOE FRACTION / I U.S. Patent Oct. 26, 1982 Sheet 2 of 2 4,356,038 4,356,038 1. 2 TABLE STABILIZATION OF CHLORINATED ALPHATIC Tertiary 1-Nitro- Nitro HYDROCARBONS AND USE OF STABILIZED Butano propane methane COMPOSTION IN CLEANING ARTICLES Mole Mole Mole Contour fraction 2 fraction 9% fraction 2% This invention relates to the stabilisation of 1,1,1-tri K 3 to 8 3 to 50 3 to 84 chloroethane. L 20 to 83 3 to 40 7 to 77 A wide variety of organic compounds have been M 35 to 80 3 to 34 10 to 62 proposed for the stabilisation of 1,1,1-trichloroethane. O Referring now to FIG. 2 the lines I, II and III of the These include, by way of example, ethers e.g. 1,4-diox triangle represent the mole fraction percent of each of ane and 1,3-dioxolane, ketones, alkyl nitrates, amines, the three components (Dt-butanol (II) nitromethane and phenolic compounds, aliphatic alcohols e.g. tertiary (III)nitroethane. Contour A encompasses an area repre butanoi, nitroalkanes containing one to three carbon senting the broadest range of the mole fraction percent atoms, epoxides e.g. 1,2-butene, and alkyl substituted 15 of the three components which are within the scope of pyrroles. Hundreds of different mixtures of stabilisers the invention. Contour B encompasses an area repre from these and other groups of compounds have been senting a preferred range of mole fractions percent of proposed. the three components. We have now found that a surprising and improved Contour C encompasses an area representing an espe 20 cially preferred range of mole fractions percent of the effect is obtained in the stabilisation of 1,1,1-trichloroe three components. The ranges represented by the con thane by incorporating in the solvent (i) tertiary buta tours are given for convenience in the following Table nol, (ii) nitro-methane and (iii) 1- or 2-nitropropane or II. The total mole fraction percent of the three stabilis nitroethane. Mixtures of 1-nitropropane and/or 2-nitro ing components when added together is necessarily 100 propane and nitroethane may be used. 25 percent. We have found, surprisingly, that by adding specific molar proportions of said nitroalkanes and tertiary buta TABLE I Mole Mole Mole nol to 1,1,1-trichloroethane, the stability of the solvent Fraction Fraction Fraction is significantly greater than that conferred on the sol 30 % % % vent by adding the same total molar concentration of Contour Tertiary Butanol Nitromethane Nitroethane any one of said nitroalkanes alone, any mixture of said A 15 to 90 1 to 84 to 74 nitroalkanes, or tertiary butanol. By incorporating all B 35 to 90 1 to 59 1 to 56 three of the stabilising components (i) (ii) and (iii) in the C 45 to 90 1 to 54 to 49 35 solvent, a synergistic or interelated stabilising effect is One outstanding effect of the present invention is that obtained which is entirely unexpected. 1,1,1-trichloroethane stabilised with a mixture of the The molar proportions of the three stabilising compo three components in the mole fraction percent ranges nents, namely tertiary butanol, nitromethane and nitro within the area encompassed by Contour K or Contour propane or nitroethane which are within the scope of 40 A is highly effective against the corrosive effect of light the present invention are illustrated in the triangular metals, especially aluminium. For greatest effectiveness diagrams shown in the drawings accompanying the of the mixtures of this respect we prefer mixtures within specification. the area encompassed by Contour L or Contour B and especially mixtures within the area encompassed by BRIEF DESCRIPTION OF ORAWINGS 45 Contour M or Contour C. The effectiveness of the FIG. relates to a stabilizer mixture using nitropro stabiliser against the corrosive effect of light metals can pane as component (iii). be determined by the colour developed (in Hazen units) FIG. 2 relates to a mixture containing nitroethane as in the presence of aluminium, as more particularly de component (iii). scribed hereinafter. 50 Contour K, L and Mshown in the triangular diagram Referring to FIG. 1 of the drawings, the lines I,II and of FIG. the figures quoted in Table I and Contours A, III of the triangular diagram represent the mole fraction B and C shown in the triangular diagram of FIG. 2 and percent of each of the three components (I) t-butanol, the figures quoted in Table II are based on results ob (II) nitromethane and (III) nitropropane (the nitropro tained using stabilised 1,1,1-trichloroethane in which pane illustrated is 1-nitropropane). Contour K encom 55 the total molar concentration of the three components passes an area representing the broadest range of the was 0.8 moles/liter. However these mole fractions per mole fraction percent of the three components which cent ranges apply to 1,1,1-trichloroethane having any are within the scope of the invention. Contour L en total molar concentration of the components, i.e. the compasses an area representing a preferred range of percentage ranges are independent of the total molar mole fractions percent of the three components. Con 60 concentration of the stabilizing components. tour M encompasses an area representing an especially The actual molar concentrations chosen of the stabi lisers within the defined ranges will depend on several preferred range of mole fractions percent of the three factors, including for example, cost and availability of components. the individual stabilisers and the degree of stability The ranges represented by the Contours are given for 65 required in the stabilised solvent. The latter may depend convenience in Table I; the total mole fraction percent on the use for which the solvent is required, e.g. the of the three stabilising components when added to degreasing procedure to be utilised, for example gether is necessarily 100 percent. whether a cold cleaning or a vapour cleaning technique 4,356,038 3 4. is to be used. Even with a small fraction of one mole per thane due to the presence of metals which comprising liter total concentration of the three stabilising compo incorporating in said solvent a stabilising mixture of nents, the improved results of the present invention are tertiary butanol nitromethane and nitropropane or ni obtained. Obviously a large excess of stabilisers over troethane as hereinbefore described. The invention also what is required to confer the desired degree of stability includes a method of degreasing metal and other articles to the solvent is unnecessary and wasteful. Generally which comprise bringing them into contact with 1,1,1- however, it is usual to employ a total of from 0.3 to 1.5 trichloroethane or the vapour thereof containing a moles per liter of the stabilising components; preferably Stabilising mixture of tertiary butanol, nitromethane and there is employed a total of from 0.6 to 1.2 moles per nitropropane or nitroethane as hereinbefore described. liter of the components. 10 The following Examples illustrate the invention. The stabilisation of 1,1,1-trichloroethane against cor rosive attack by light metals, especially aluminium, is EXAMPLE 1. highly desirable but is not the only requirement for Solvent compositions were made up consisting of adequate stabilisation of 1,1,1-trichloroethane. Thus for 1,1,1-trichloroethane containing specific molar frac example in typical vapour degreasing processes using 15 tions percent of tertiary butanol, nitromethane and 1 stabilised 1,1,1-trichloro ethane, the liquid composition nitropropane.
Load more

Recommended publications
  • Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances 2017
    INTERNATIONAL NARCOTICS CONTROL BOARD Precursors and chemicals frequently used in the illicit manufacture of narcotic drugs and psychotropic substances 2017 EMBARGO Observe release date: Not to be published or broadcast before Thursday, 1 March 2018, at 1100 hours (CET) UNITED NATIONS CAUTION Reports published by the International Narcotics Control Board in 2017 The Report of the International Narcotics Control Board for 2017 (E/INCB/2017/1) is supplemented by the following reports: Narcotic Drugs: Estimated World Requirements for 2018—Statistics for 2016 (E/INCB/2017/2) Psychotropic Substances: Statistics for 2016—Assessments of Annual Medical and Scientific Requirements for Substances in Schedules II, III and IV of the Convention on Psychotropic Substances of 1971 (E/INCB/2017/3) Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances: Report of the International Narcotics Control Board for 2017 on the Implementation of Article 12 of the United Nations Convention against Illicit Traffic in Narcotic Drugs and Psychotropic Substances of 1988 (E/INCB/2017/4) The updated lists of substances under international control, comprising narcotic drugs, psychotropic substances and substances frequently used in the illicit manufacture of narcotic drugs and psychotropic substances, are contained in the latest editions of the annexes to the statistical forms (“Yellow List”, “Green List” and “Red List”), which are also issued by the Board. Contacting the International Narcotics Control Board The secretariat of the Board may be reached at the following address: Vienna International Centre Room E-1339 P.O. Box 500 1400 Vienna Austria In addition, the following may be used to contact the secretariat: Telephone: (+43-1) 26060 Fax: (+43-1) 26060-5867 or 26060-5868 Email: [email protected] The text of the present report is also available on the website of the Board (www.incb.org).
    [Show full text]
  • Safe Handling and Disposal of Chemicals Used in the Illicit Manufacture of Drugs
    Vienna International Centre, PO Box 500, 1400 Vienna, Austria Tel.: (+43-1) 26060-0, Fax: (+43-1) 26060-5866, www.unodc.org Guidelines for the Safe handling and disposal of chemicals used in the illicit manufacture of drugs United Nations publication USD 26 Printed in Austria ISBN 978-92-1-148266-9 Sales No. E.11.XI.14 ST/NAR/36/Rev.1 V.11-83777—September*1183777* 2011—300 Guidelines for the Safe handling and disposal of chemicals used in the illlicit manufacture of drugs UNITED NATIONS New York, 2011 Symbols of United Nations documents are composed of letters combined with figures. Mention of such symbols indicates a reference to a United Nations document. ST/NAR/36/Rev.1 UNITED NATIONS PUBLICATION Sales No. E.11.XI.14 ISBN 978-92-1-148266-9 eISBN 978-92-1-055160-1 © United Nations, September 2011. All rights reserved. The designations employed and the presentation of material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. Requests for permission to reproduce this work are welcomed and should be sent to the Secretary of the Publications Board, United Nations Headquarters, New York, N.Y. 10017, U.S.A. or also see the website of the Board: https://unp.un.org/Rights.aspx. Governments and their institutions may reproduce this work without prior authoriza- tion but are requested to mention the source and inform the United Nations of such reproduction.
    [Show full text]
  • Title 35 Public Health and Safety
    TITLE 35 - PUBLIC HEALTH AND SAFETY CHAPTER 1 - ADMINISTRATION ARTICLE 1 - IN GENERAL 35-1-101. Local contributions; disposition. All monies paid to the state treasurer representing contributions by city councils, county commissioners, trustees of school districts, or other public agencies, for public health purposes, shall be set up and designated on the books of the state treasurer in a separate account, and shall be expended and disbursed upon warrants drawn by the state auditor against said account when the vouchers therefor have been approved by the department of health. 35-1-102. Sanitation of public institutions. It shall be the duty of the officers, managers, superintendents, proprietors and lessees of all hospitals, asylums, infirmaries, prisons, jails, schools, theaters, public places and public institutions to remedy any and all defects relating to the unsanitary condition of such institution, or institutions, as may be under their control, when such defects shall have been called to their attention in writing by the department of health. 35-1-103. Neglect or failure of officials to perform duty. Any member of the department of health, any county health officer, or any officer, superintendent, or principal of any city, town, county or institution named in this act, who shall fail or neglect to perform any of the duties herein required of them, shall be guilty of a misdemeanor and upon conviction thereof shall be fined in the sum of not less than one hundred dollars ($100.00) nor more than one thousand dollars ($1,000.00), or shall be confined in the county jail for a period of not less than six (6) months, nor more than a year, or both.
    [Show full text]
  • Multi-Step Processing in a Microstructured Flow Reactor: Direct Nitration of Propane–A Proof of Principle
    DOI 10.1515/gps-2012-0054 Green Process Synth 2012; 1: 439–448 Holger Löwe* , Gong Wei , Ma Jiang, Christian Hofmann , Hans-Joachim Kost and Christian Schütt Multi-step processing in a microstructured flow reactor: direct nitration of propane–a proof of principle Abstract: The vapor phase nitration of propane was suc- nitric acid decomposes at temperatures above 350 ° C to ‧ ‧ ‧ cessfully investigated in a multi-step microstructured give mainly OH and NO2 or ONO radicals. If propane is reactor. The concept integrates heating, evaporation of used as starting material the expected compounds 1-nitro- reactants, the reaction channel, and the quenching and propane or 2-nitropropane can be obtained by perform- cooling of the product mixture; all done in a reactor with ing the reaction at high temperatures, for example, above one plate. The nitration of propane with evaporated nitric 400 ° C. In addition, a cleavage of propane can be expected acid was carried out at 380 ° C–450 ° C. This radical chain and therefore nitromethane and nitroethane were also reaction was subsequently quenched, in a fast manner due found in the reaction mixture [ 1 , 2 ]. Not much informa- to the high surface-to-volume ratio of the reaction channel. tion about this process could be found in the literature, Therefore, the conversion of propane was deliberately kept nevertheless, the vapor-phase process is used in industry low (approx. 2%) but at favor of selectivity for 2-nitropro- [ 3 , 4 ]. Some information is given about equipment and pane which increases remarkably. The harsh reaction con- use of catalysts or additives, such as oxygen or halides [ 3 , ditions require a sophisticated microreactor concept, the 5 , 6 ], to enhance the nitration process.
    [Show full text]
  • 2-Nitropropane)
    Screening Assessment for the Challenge Propane, 2-nitro- (2-Nitropropane) Chemical Abstracts Service Registry Number 79-46-9 Environment Canada Health Canada July 2010 Screening Assessment CAS RN 79-46-9 Synopsis Pursuant to section 74 of the Canadian Environmental Protection Act, 1999 (CEPA 1999), the Ministers of the Environment and of Health have conducted a screening assessment of propane, 2-nitro-, also known as 2-nitropropane, Chemical Abstracts Service Registry Number 79-46-9. This substance was identified in the categorization of the Domestic Substances List as a high priority for action under the Challenge. 2- Nitropropane was identified as a high priority as it was determined to present an intermediate potential for exposure of individuals in Canada and had been classified by other agencies on the basis of carcinogenicity. Although 2-nitropropane met the ecological categorization criteria for persistence, it did not meet the criteria for bioaccumulation potential or inherent toxicity to aquatic organisms. Therefore, the focus of this assessment relates primarily to human health risks. According to information reported in response to a notice under section 71 of the Canadian Environmental Protection Act, 1999 (CEPA 1999), no companies in Canada reported manufacturing 2-nitropropane in a quantity greater than or equal to the reporting threshold of 100 kg for the 2006 calendar year. According to information submitted by Canadian companies, the total quantity imported into Canada in 2006 was between 100 and 1000 kg. Potential sources of exposure identified in the publicly available literature include residual concentrations in vegetable oils for human consumption and pharmaceutical products, as well as formulated products including inks, paints, adhesives, varnishes, polymers, and synthetic materials that may contain 2-nitropropane.
    [Show full text]
  • Toxic Screening Level Justification for 75-52-5
    MICHIGAN DEPARTMENT OF ENVIRONMENTAL QUALITY INTEROFFICE COMMUNICATION TO: File for Nitromethane (CAS# 75-52-5) FROM: Robert Sills, AQD Toxics Unit Supervisor SUBJECT: Nitromethane ITSL change in the averaging time from 24 hrs to annual DATE: September 9, 2015 3 The current ITSL for nitro methane (70 ug/m ) has a justification (attached) dated May 29, 2008. The averaging time (AT) assigned at that time was 24 hours, as per the default methodology (Rule 232(2)(b)). The current file review concludes that the AT may appropriately be set at annual, based on the nature and duration of the key study and the ITSL value derivation, as allowed under Rule 229(2)(b). Therefore, the AT is being changed from 24 hours to annual at this time. MICHIGAN DEPARTMENT OF ENVIRONMENTAL QUALITY INTEROFFICE COMMUNICATION TO: Memo to File for Nitromethane [CAS# 75-52-5] FROM: Margaret M. Sadoff, Toxics Unit DATE: May 29, 2008 · SUBJECT: Update of Interim ITSL and IRSL/SRSL Development A search of the literature and the following databases was performed for information regarding nitromethane: American Conference of Governmental Industrial Hygienists (ACGIH) Threshold Limit Values, National Institute for Occupational Safety and Health (NIOSH) Pocket Guide to Hazardous Chemicals, EPA Integrated Risk Information System (IRIS), EPA High Production Volume Information System, Registry of Toxic Effects of Chemical Substances (RTECS), Environmental Protection Bureau Library, International Agency for Research on Cancer (IARC) Monographs, CAS Registry Online, Hazardous Substance Data Bank (HSDB), National Library of Medicine/Toxline, National Library of Medicine ToxSeek, Health Effects Assessment Summary Tables (HEAST), National Toxicology Program (NTP) Study Database, Entrez PubMed, Scirus, IPCS lntox Databank and CaiEPA's Toxicity Values Database General Information 1 (Source: Chemlnfo, ToxlineHSDB, Report on Carcinogens, 11 h ed.) Nitromethane is a colorless, oily liquid with a moderately strong disagreeable odor which falls into the class of chemicals known as nitroparaffins.
    [Show full text]
  • New Addition Reactions Op Nitro Compounds with Olefinic Systems
    NEW ADDITION REACTIONS OP NITRO COMPOUNDS WITH OLEFINIC SYSTEMS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By JUNIOR FRANKLIN CONRAD, B.A., M.S. A 9 9 The Ohio State University 1952 Approved byj j f J l f Adviser -i- ACKNOWLEDGMENTS j The author takes this opportunity to express his gratitude to Dr. Harold Shechter for his generous counsel and assistance in this problem. Thanks are also due to Dr. Ralph B. Kaplan, Dr. Harry L. Cates, and Dr. Larry Zeldin for their many helpful suggestions. The author also wishes to express his appreciation to the Office of Naval Research, who generously supplied the funds that made this research possible. S 0 0 4 4 3 -ii- TABLE OP CONTENTS Page ACKNOWLEDGMENTS; i SECTION I: ADDITION OP DINITROGEN TETROXIDE AND NITRYL CHLORIDE TO OLEPINIC SYSTEMS 1 PART I: Addition of Dinitrogen Tetroxide to Methyl Acrylate. 2 A. Background and Purpose 2 B. Results of Present Research 10 C. Discussion of Results 13 D. Conclusions 20 E. Experimental 21 (1) Reaction of Dinitrogen Tetroxide and Methyl Acrylate. 21 (2) Reaction of Methyl 2-Hydroxy-3-nitro- propionate with Acetyl Chloride; Methyl 3-Nitroacrylate. 24 (3) Hydrolysis of Methyl 2-Hydroxy-3- nitropropionate. 24 a. 2-Hydroxy-3-nitropropionic Acid 24 b. Oxalic Acid. 25 (4) Condensation of Glyoxylic Acid and Nitromethane; 2-Hydroxy-3-nitro- propionic Acid. 25 PART II: Addition of Nitryl Chloride to Methyl Acrylate, Acrylic Acid, and Acrylonitrile. 27 A. Background and Purpose 27 B.
    [Show full text]
  • Free-Radical Clocks in the Aliphatic S[Subscript RN]1 Process and Reactions of Nucleophiles with 1,1-Dinitro-2,2-Diphenylethylen
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1983 Free-radical clocks in the aliphatic S[subscript RN]1 process and reactions of nucleophiles with 1,1-dinitro-2,2-diphenylethylene Douglas Frederick Dedolph Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Dedolph, Douglas Frederick, "Free-radical clocks in the aliphatic S[subscript RN]1 process and reactions of nucleophiles with 1,1-dinitro-2,2-diphenylethylene " (1983). Retrospective Theses and Dissertations. 7706. https://lib.dr.iastate.edu/rtd/7706 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity.
    [Show full text]
  • New Reactions of Nitro Compounds
    This dissertation has been 62-2176 microfilmed exactly as received KAPLAN, Ralph Benjamin, 1920- NEW REACTIONS OF NITRO COMPOUNDS. The Ohio State University, Ph.D., 1950 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan NEW REACTIONS OF NITRO COMPOUNDS DISSERTATION Presented In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University By RALPH B. KAPLAN, B.A., The Ohio State University 1950 Approved by: Adviser TABLE OF CONTENTS Page INTRODUCTION Acknowledgments Statement of the Problem SECTION I REACTION OF SODIUM NITROALKANES WITH VARIOUS NITRATING AGENTS 1 I. Discussion 1 A. Introduction 1 B. Agents Investigated 2 1. Nltryl Chloride 2 a. Preparation 2 b. Review of thé Reactions of Nltryl Chloride With Organic Reagents U c. Reaction of Sodium 2-Nltropropane With Nltryl Chloride 6 d. Reaction of Sodium 2-Nltropropane with Nltryl Chloride and Aluminum Chloride 11 2. Mixed Nitric and Sulfuric Acid 12 a. Reaction of Sodium 2-Nltropropane With Mixed Nitric and Sulfuric Acid 12 3. Methyl Nitrate Ih a. Reaction of Sodium 2-Nltropropane and of Potassium Nltroethane l4 I. Alkyl Nitrates as Nitrating Agents 14 II. Discussion of Results 15 Page II. Experimental 21 A. Agents Investigated 21 1. Nltryl Chloride 21 a. Preparation 21 1. Intermediates; Chlorosulfonlc Acid and Nitric Acid, Anhydrous 11. Procedure for Making Nltryl-Chloride h. Reaction of Nltryl Chloride with a Secondary Nltroalkane 2k 1. 2-Nltropropane 11. Sodium 2-Nltropropane c. Reaction of Sodium 2-Nltropropane, Nltryl Chloride and Aluminum Chloride. 27 2. Reaction of Sodium 2-Nltropropane With Mixed Nitric and Sulfuric Acids 28 3.
    [Show full text]
  • Chemical Compatibility Guide Chemical Compatibility Guide Chemical Compatibility
    DICHTOMATIK O-RING HANDBOOK SECTION FIVE CHEMICAL COMPATIBILITY GUIDE CHEMICAL COMPATIBILITY GUIDE CHEMICAL COMPATIBILITY 5 DICHTOMATIK O-RING HANDBOOK CHEMICAL COMPATIBILITY GUIDE CHEMICAL COMPATIBILITY TABLES These tables are intended to assist the user in determining the suitability of various elastomers in many different chemical environments. The ratings are based on a combination of published literature, laboratory tests, actual field experience, and informed judgments. As laboratory tests do not necessarily predict end-use performance, users of DICHTOMATIK products should conduct their own evaluations to determine application suitability. NOTE: Ratings are based on volume swell which is only one indicator of elastomer fluid compatibility and may be based on the solubility parameter alone. Fluid attack on the backbone of the polymer may show up as a change in physical properties such as tensile strength, elongation at break, and hardness. Elevated temperatures and extended exposure times may create more aggressive conditions than cited in this guide. This information is believed to be reliable, but no representation, guarantees or warranties of any kind are made to its accuracy or suitability for any purpose. The information presented is based on laboratory testing and does not necessarily indicate end product performance. It is recommended that users of DICHTOMATIK products conduct their own evaluations to determine suitability for the intended application. COMPATIBILITY RATING SYSTEM RATING DESCRIPTION VOLUME CHANGE COMMENTS 1 Little or no effect <10% Elastomer may exhibit slight swelling and/or loss of physical properties under severe conditions. 2 Possible loss of 10–20% Elastomer may exhibit swelling in addition to a physical properties change in physical properties.
    [Show full text]
  • The Nitro-Mannich Reaction
    The Nitro-Mannich Reaction Adam Noble† and James C. Anderson,*,† †Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, U.K. CONTENTS 1. Introduction 3 2. Early Developments 5 2.1. The First Reports 6 2.2. Heterocycle Synthesis 16 2.3. Nitroalkene Synthesis 21 2.4. Synthesis of Dinitroamines 23 2.5. Reactions with Pre-Formed Imines 25 2.6. Conjugate Addition Nitro-Mannich Reactions 27 2.7. Reactions of Nitroesters 30 3. Non-Catalytic Examples 33 3.1. Base-Mediated Reactions 33 3.2. Reactions of α-Amido Sulfones 36 3.3. Auxiliary Controlled Stereoselective Reactions 40 3.4. Reformatsky-Type Reactions 43 3.5. Electrochemically Induced Reactions 45 1 4. Indirect Metal-Catalyzed Reactions 46 4.1. Racemic Reactions 46 4.2. Asymmetric Reactions 47 5. Direct Metal-Catalyzed Reactions 49 5.1. Racemic Reactions 50 5.2. Asymmetric Reactions 54 6. Organocatalytic Reactions 66 6.1. Racemic Reactions 66 6.2. Asymmetric Reactions 68 6.2.1. Urea/Thiourea Catalysts 68 6.2.2. Brønsted Acid Catalysts 79 6.2.3. Phase Transfer Catalysts 83 6.2.4. Brønsted Base Catalysts 88 7. Reactions of Ketimines 90 7.1. Racemic Reactions 90 7.2. Auxiliary Controlled Reactions 92 7.3. Catalytic Asymmetric Reactions 94 8. Reactions of α-Nitroesters 96 9. Reactions of α-Nitrophosphonates 103 10. Conjugate Addition Nitro-Mannich Reactions 106 10.1. Organocatalytic Reactions with Carbon Nucleophiles 106 10.2. Reactions with Organometallic Nucleophiles 111 10.3. Aza-Morita-Baylis-Hillman Reactions 114 10.4. Synthesis of 3-Nitrochromene Derivatives 117 2 10.5.
    [Show full text]
  • A Study of the Kinetics Op Neutralization Op Cyclic
    A STUDY OF THE KINETICS OP NEUTRALIZATION OP CYCLIC, BICYCLIC, AND ARYLALKYL NITRO COMPOUNDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University By PAT WAYNE KEITH FLANAGAN, B.S, The Ohio State University 19<7 Approved by: Advlser Department of Chemistry ACKNOWLEDGEMENTS I would like to express my appreciation to Dr. Harold Shechter for suggesting this problem and for his guidance during the course of this investigation. I am grateful to the National Science Foundation and to the Allied Chemical and Dye Company for fellowship funds. ii TABLE OP CONTENTS Page I. INTRODUCTION. ............ ........ 1 II. THEORY AND HISTORY. ....... .......... 4 Structure and Reactivity.. of Acidic........ Nltro Compounds.......................... 4 Deuterium Effects on,Kinetics of...... .. .. Reaction........ '........................21 Factors Affecting Reactivities., of ....... Cyclic and Blcycllc Systems ............ 25 III. DISCUSSION OP RESULTS OP THE PRESENT. INVESTIGATION ............................. 56 Kinetics of Neutralization............... .36 Nltrocycloalkanes, ............. 36 The Deuterium Isotope Effect In Neutralization of Nltro­ cycloalkanes with Hydroxide Ion......... 51 Blcycllc Nltro Compounds ............ 53 Meta and Para-Sùbstitutod 1-Phenylnltroethanes ............. 59 The Ultraviolet Absorption Spectra of Cyclic and Blcycllc Nltro Compounds. 64 IV. EXPERIMENTAL...................................71 Preparation and Purification of Nltro Compounds......................... 71 Endo-4-nltroblcvclo 2 2 1 heptene-2. 71 Exo-5-nltrobicvclo 2 2 1 heptene-2 . 72 Endo-2-nltroblcvclo 2 2 1 heptane. ?4 Exo-2-nltroblcvclo 2 2 1 heptane . 75 Endo-5-nltroblcyolo 2 2 2 octene-2 . 76 2-Nltroblcyclo 2 2 2 octane........... 77 Exo-4-nltroblcvclo 2 2 2 octene-2. 78 1-Phenylnltreethane. .......... 79 l_(g_Nltrophenyl)nltroethane ....
    [Show full text]