DOCSLIB.ORG

(10) Patent No.: US 9169178 B2

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(10) Patent No.: US 9169178 B2 US009 169178B2 (12) United States Patent (10) Patent No.: US 9,169,178 B2 Oren (45) Date of Patent: Oct. 27, 2015 (54) MANUFACTURING OF STABILIZED (52) U.S. Cl. PROPARGYL BROMIDE CPC ................ C07C 17/16 (2013.01); A0IN 29/02 (2013.01); C07C 17/42 (2013.01) (71) Applicant: BROMINE COMPOUNDS LTD., Beer (58) Field of Classification Search Sheva (IL) CPC ......... C07C 17/16; C07C 17/42: A01N 29/02 See application file for complete search history. (72) Inventor: Jakob Oren, Nesher (IL) (56) References Cited (73) Assignee: Bromine Compounds Ltd., Beer Sheva (IL) U.S. PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this 6,291,731 B1* 9/2001 Stamm .................... C07. patent is extended or adjusted under 35 6,777.375 B2 8/2004 Magin et al. U.S.C. 154(b) by 0 days. 6.825,390 B1 1 1/2004 Herndon 2004/0044259 A1 3/2004 Mero ...................... CO7C 17/16 (21) Appl. No.: 14/429,817 570.261 (22) PCT Filed: Sep. 16, 2013 FOREIGN PATENT DOCUMENTS (86). PCT No.: PCT/L2O13AOSO784 GB 942348 11, 1963 S371 (c)(1), OTHER PUBLICATIONS (2) Date: Mar. 20, 2015 International Search Report from PCT/IL2013/050784: 2 pages; (87) PCT Pub. No.: WO2014/045278 mailed Sep. 1, 2014. PCT Pub. Date: Mar. 27, 2014 * cited by examiner (65) Prior Publication Data Primary Examiner — Shailendra Kumar US 2015/0225318A1 Aug. 13, 2015 (74) Attorney, Agent, Or Firm — Roach Brown McCarthy & Gruber, P.C.; Kevin D. McCarthy Related U.S. Application Data (60) Provisional application No. 61/704,586, filed on Sep. (57) ABSTRACT 24, 2012. This invention provides a process for obtaining propargyl bromide in high yield from propargyl alcohol and phosphorus (51) Int. Cl. bromide, in the form of a stable composition with alkylbro C07C 17/16 (2006.01) mide. AOIN 29/02 (2006.01) C07C 17/42 (2006.01) 18 Claims, No Drawings US 9, 169,178 B2 1. 2 MANUFACTURING OF STABILIZED starts, and a precursor of such alkylhalogenide which can be PROPARGYL BROMIDE brominated by PBr to provide the desired alkylhalogenide. The alkylhalogenide will usually include halogenated paraf This application is a 371 of PCT/IL13/50784, filed Sep. 16, fins having from 1 to 5 carbon atoms in the molecule, the 2013, which claims benefit of 61/704,586, filed Sep. 24, 5 precursor will usually include aliphatic alcohols having from 2012. 3 to 5 carbon atoms in the molecule. The precursor will usually comprise a lower aliphatic alcohol like propanol or FIELD OF THE INVENTION butanol, which will be brominated to the desired bromoal kane having the desired boiling point. In one aspect, the The present invention relates to an industrial process for 10 process according to the invention will comprise steps of i) manufacturing propargyl bromide in a good yield and in a mixing PA, an amine additive, and alkylhalogenide solvent stable form. having a boiling point between 55 and 110° C.; ii) adding PBr; iii) stirring the reaction mixture, and allowing said PBr BACKGROUND OF THE INVENTION to react with said PA, whereby obtaining a mixture containing 15 raw propargyl bromide and AH; and iv) washing and distilling Methyl bromide is an effective fumigant used in control said mixture in any order; thereby obtaining a stable compo ling a large variety of soilborne pests. As methyl bromide is an sition containing propargyl bromide and alkylhalogenide. In oZone depleting agent, and further it is relatively toxic for other aspect of the invention, the process according to the humans, its use has been gradually reduced, and the demands invention will comprise i) mixing PA, an amine additive, and for alternative pesticides have been increasing. A promising an aliphatic alcohol having between 3 and 5 carbon atoms; ii) alternative for methyl bromide is 3-bromopropyne, usually adding PBr. whereby obtaining a reaction mixture; iii) stir called propargyl bromide (PB). PB may be prepared by the ring said reaction mixture and allowing said PBr to react with reaction of propargyl alcohol with PBr in the presence of said PA to provide PB, and with said alcohol to provide alkyl pyridine, but the selectivity and yield of the reaction are low. bromide (AB), wherein said AB has a boiling point between U.S. Pat. No. 6,794.551 improved the process by controlling 25 55 and 110°C.; and iv) washing and distilling said mixture in temperature and effecting the reaction under an inert atmo any order, thereby obtaining a stable composition containing sphere without the presence of a base. Another problem about propargyl bromide and alkyl bromide. In a preferred embodi PB is its high flammability, and its vapors may form explosive ment, a method according to the invention comprises i) com mixtures with air. Precariously, propargylbromide is a shock bining propargyl alcohol (PA), a tertiary amine, and an alky and temperature-sensitive material that may detonate. Sev 30 lhalogenide selected from chlorinated and/or brominated eral techniques addressed the problem and stabilized PB by alkanes having a boiling point between 55 and 110°C., at a admixing a solvent forming an azeotropic mixture with the temperature between 0 and 40°C.; ii) adding PBr; iii) stir PB (see WO2004/071192; U.S. Pat. No. 6,777,375; U.S. Pat. ring the mixture obtained in step iii) at a temperature between No. 6,825,390; U.S. Pat. No. 7,015.367). It is an object of the 25 and 50° C. for between 1 and 5 hours, whereby obtaining present invention to provide an industrial process for manu 35 a raw mixture containing PB and AH; iv) washing said raw facturing propargyl bromide in a stable form and in a good mixture of step iii) with water; and v) distilling said raw yield. mixture at lowered pressure at a temperature up to 60° C. It is another object of the present invention to provide a wherein said step of washing and said step of distilling may be composition comprising propargyl bromide in a Sufficiently performed in any order, thereby obtaining a stable composi high concentration for intended applications but without 40 tion containing propargyl bromide and alkyl halogenide. In being impact sensitive. other preferred embodiment, a method according to the It is still another object of the present invention to provide invention comprises i) combining PA, an amine additive, and a composition comprising propargyl bromide which is not an alkylbromide (AB) solvent having a boiling point between explosive on heating. 55 and 110°C.; ii) adding PBr whereby obtaining a reaction Other objects and advantages of present invention will 45 mixture; iii) stirring the reaction mixture of step ii), whereby appear as description proceeds. obtaining a raw mixture containing PB and AB; iv) washing said raw mixture of step iii) with water; and v) distilling said SUMMARY OF THE INVENTION raw mixture at lowered pressure at a temperature up to 60°C., wherein said step washing and said distilling may be per The invention provides a method for preparing a stable 50 formed in any order; thereby obtaining a stable composition propargyl bromide (PB) composition, comprisingi) combin containing propargyl bromide and alkyl bromide. Said amine ing propargyl alcohol (PA), an amine additive, and an alkyl additive is preferably a tertiary amine. Said stable composi halogenide (AH) source selected from halogenated paraffins tion, prepared by the method of the invention, usually com and aliphatic alcohols; ii) adding phosphorus tribromide prises from 30 to 80 wt % propargylbromide, and it usually (PBr) to the mixture of step i) whereby obtaining a reaction 55 comprises from 17 to 67 wt % alkylhalogenide, for example mixture; iii) stirring said reaction mixture and allowing said from 19 to 69 wt % alkylhalogenide. In one embodiment of PBr to react at least with said PA, whereby obtaining a the invention, the stable composition prepared by the method mixture containing raw PB and AH; and iv) washing the of the invention comprises from 50 to 80 wt % propargylbro mixture of step iii) and distilling it at lowered pressure, mide, and it usually comprises from 17 to 47 wt % alkylha wherein the steps of washing and distilling may be performed 60 logenide, for example from 19 to 49 wt % alkylhalogenide. in any order, said Washing comprising separating organic The total amount of propargylbromide and alkylhalogenide phase and discarding water phase; thereby obtaining a stable in said stable composition is preferably at least 90 wt %, for composition containing propargyl bromide and alkylhalo example at least 94 wt %, such as 95 wt % or more. genide. Said AH source will usually include aliphatic mate In one embodiment of the method according to the inven rials having from 1 to 5 carbon atoms in the molecule. The 65 tion, a process is provided comprising steps of i) mixing PA, term alkylhalogenide source aims at including both ready an amine additive, and alkylbromide solvent having a boiling alkylhalogenide added to the mixture before the reaction point between 55 and 110° C., and cooling the mixture to a US 9, 169,178 B2 3 4 temperature below 5° C. and adding dropwise PBr, under having boiling point not too different from the boiling point of stirring, while keeping the temperature between 0 and 40°C.; PB, formed in the reaction mixture during the reaction ii) allowing said PBr to react with said PA, whereby obtain together with the PB. When relating to the boiling point of a ing a mixture containing raw propargyl bromide and AH; and suitable alkylhalogenide, the boiling points of PB and said iii) washing and distilling said mixture in any order; thereby solvent are considered as too different when they differ by obtaining a stable composition containing propargyl bromide more than about 26° C.; a suitable solvent for the present and alkylhalogenide.
Load more

Recommended publications
  • Chemicals, Rare Chemicals, Reagents & Solvents
    Annual Procurement Plan for the Year 2021-22 Consumable List 1 Chemicals, Rare Chemicals, Reagents & Solvents Sl. No. Generic Name Specification Quantity Approx Cost (Rs.) 1. HEPES Molecular biology 1kg 80000/‐ grade 2. MES hydrate Molecular biology 1kg 34000/‐ grade 3. Imidazole Molecular biology 1kg 28000/‐ grade 4. BIS‐TRIS Molecular biology 500g 44000/‐ grade 5. Agarose Type I Molecular biology 1kg 11900/‐ grade 6. CAPS Molecular biology 100g 8000/‐ grade 7. Trizma Base Molecular biology 1kg 31000/‐ grade 8. Glycerol Molecular biology 2.5L*4 8000/‐ grade 9. Ethanol Molecular biology 500ml*10 8000/‐ grade 10. NaCl Molecular biology 1kg 6000/‐ grade 11. Tris Buffer Molecular biology 1 kg 10000/‐ grade 12. Ethyl acetate Molecular biology 500ml*5 6500/‐ grade 13. Acetic acid 25L 11000/‐ 14. Methanol 25L 8000/‐ 15. Urea Molecular biology 1kg 2000/‐ grade 16. Agar Powder, Bacteriological 500g 8000/‐ 17. Trizma Hydrochloride Molecular biology 1kg 15000/‐ grade 18. Acrylamide Molecular biology 500g 4000/‐ grade 19. Phenol Molecular biology 500ml 5000/‐ grade 20. Luria Bertani Broth 2.5kg * 4 90,000 21. Acetone 2.5L 1500/‐ 22. Ni‐NTA beads 100ml 57000/‐ 23. Ammonium persulphate Molecular biology 100g 2000/‐ grade 24. Ampicillin Sodium Molecular biology 100 g 13000/‐ grade 25. Kanaymycin Monosulfate Molecular biology 100g 60000/‐ grade 26. Choramphenicol Molecular biology 100g 40000/‐ grade 27. Isopropyl β‐ d‐1‐thiogalactopyranoside Molecular biology 100g 35000/‐ grade 28. Coomassie Brilliant Blue R‐250 Molecular biology 25g 10,000/‐ grade 29. SDS Molecular biology 100g 2500/‐ grade 30. Isopropanol 25 L 15000/‐ 31. Crystallization screen JCSG‐Plus 1 unit/box 50000/‐ 32.
    [Show full text]
  • Interstellar Ices and Radiation-Induced Oxidations of Alcohols
    The Astrophysical Journal, 857:89 (8pp), 2018 April 20 https://doi.org/10.3847/1538-4357/aab708 © 2018. The American Astronomical Society. All rights reserved. Interstellar Ices and Radiation-induced Oxidations of Alcohols R. L. Hudson and M. H. Moore Astrochemistry Laboratory, NASA Goddard Space Flight Center, Greenbelt, Maryland, 20771, USA; [email protected] Received 2017 May 2; revised 2018 March 8; accepted 2018 March 9; published 2018 April 18 Abstract Infrared spectra of ices containing alcohols that are known or potential interstellar molecules are examined before and after irradiation with 1 MeV protons at ∼20 K. The low-temperature oxidation (hydrogen loss) of six alcohols is followed, and conclusions are drawn based on the results. The formation of reaction products is discussed in terms of the literature on the radiation chemistry of alcohols and a systematic variation in their structures. The results from these new laboratory measurements are then applied to a recent study of propargyl alcohol. Connections are drawn between known interstellar molecules, and several new reaction products in interstellar ices are predicted. Key words: astrochemistry – infrared: ISM – ISM: molecules – molecular data – molecular processes 1. Introduction 668 cm−1 was produced in solid propargyl alcohol’sIR spectrum after the compound was irradiated with 2 keV Interstellar ices are now recognized as an important comp- electrons (Sivaraman et al. 2015, hereafter SMSB from the onent of the interstellar medium (ISM). The results of multiple coauthors final initials). That IR peak was assigned to benzene infrared (IR) surveys have led to over a dozen assignments of (C H ), which was said “to be the major product from spectral features to molecular ices, with the more abundant 6 6 propargyl alcohol irradiation.” However, a full mid-IR interstellar ices being H O, CO, and CO (Boogert et al.
    [Show full text]
  • Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling
    University of Mary Washington Eagle Scholar Student Research Submissions Spring 5-7-2018 Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling Poornima Sunder Follow this and additional works at: https://scholar.umw.edu/student_research Part of the Biochemistry Commons Recommended Citation Sunder, Poornima, "Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling" (2018). Student Research Submissions. 226. https://scholar.umw.edu/student_research/226 This Honors Project is brought to you for free and open access by Eagle Scholar. It has been accepted for inclusion in Student Research Submissions by an authorized administrator of Eagle Scholar. For more information, please contact [email protected]. Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling Poornima Rachel Sunder Thesis submitted to the faculty of University of Mary Washington in partial fulfillment of the requirements for graduation with Honors in Chemistry (2018) ABSTRACT Click reactions are a highly versatile class of reactions that produce a diverse range of products. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reactions require an azide and a terminal alkyne and produce a coupled product that is “clicked” through a triazole ring that can have a variety of substituents. In this work, bromo-terminated phosphonate films on copper oxide surfaces were explored as the platform for click coupling, as the terminal azide needed for the reaction can be generated through an in situ SN2 reaction with a terminal bromo group. The reactions were characterized using model reactions in solution before being conducted on modified copper oxide surfaces.
    [Show full text]
  • Transport of Dangerous Goods
    ST/SG/AC.10/1/Rev.16 (Vol.I) Recommendations on the TRANSPORT OF DANGEROUS GOODS Model Regulations Volume I Sixteenth revised edition UNITED NATIONS New York and Geneva, 2009 NOTE The designations employed and the presentation of the 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. ST/SG/AC.10/1/Rev.16 (Vol.I) Copyright © United Nations, 2009 All rights reserved. No part of this publication may, for sales purposes, be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, electrostatic, magnetic tape, mechanical, photocopying or otherwise, without prior permission in writing from the United Nations. UNITED NATIONS Sales No. E.09.VIII.2 ISBN 978-92-1-139136-7 (complete set of two volumes) ISSN 1014-5753 Volumes I and II not to be sold separately FOREWORD The Recommendations on the Transport of Dangerous Goods are addressed to governments and to the international organizations concerned with safety in the transport of dangerous goods. The first version, prepared by the United Nations Economic and Social Council's Committee of Experts on the Transport of Dangerous Goods, was published in 1956 (ST/ECA/43-E/CN.2/170). In response to developments in technology and the changing needs of users, they have been regularly amended and updated at succeeding sessions of the Committee of Experts pursuant to Resolution 645 G (XXIII) of 26 April 1957 of the Economic and Social Council and subsequent resolutions.
    [Show full text]
  • Synthesis and Antiplasmodial Activity Testing of (1)-N-(4-Methoxybenzyl)-1,10-Phenanthrolinium Bromide
    Indo. J. Chem., 2007, 7 (2), 197-201 197 SYNTHESIS AND ANTIPLASMODIAL ACTIVITY TESTING OF (1)-N-(4-METHOXYBENZYL)-1,10-PHENANTHROLINIUM BROMIDE 1,* 2 2 3 3 Ruslin Hadanu , Sabirin Mastjeh , Jumina , Mustofa , Mahardika Agus Widjayanti and Eti Nurwening Sholikhah3 1Department of Chemistry, Pattimura University, Ambon, Indonesia. 2Laboratorium of Organic Chemistry, Department of Chemistry, Universitas Gadjah Mada, Yogyakarta, Indonesia 55281. 3Medical Faculty, Universitas Gadjah Mada, Yogyakarta, Indonesia 55281. Received 7 April 2007; Accepted 25 May 2007 ABSTRACT Synthesis of (1)-N-(4-methoxybenzyl)-1,10-phenanthroline bromide from 1,10-phenanthroline monohydrate and 4-methoxybenzaldehyde as starting material and evaluation of its antiplasmodial activities have been carried out. The 4-methoxybenzyl alcohol was prepared from 4-methoxy-benzaldehyde using sodium borohydride (NaBH4) reagent and ethanol absolute solution. The mixture was refluxed for 3 h. To yield colorless dilution compound with 90.41 % in efficiency. Furthermore, bromination of 4-methoxybenzyl alcohol with phosphorus bromide (PBr3) was conducted by refluxing for 3 h. The product of this reaction was yellow liquid of 4-methoxybenzyl bromide, 79.03% yield and 95.34 % purity. The final step of reaction was benzylation of 1,10-phenanthroline monohydrate with 4- methoxybenzyl bromide reagent. It was conducted by refluxing in aceton for 8 h at 55 oC. The yield of the reaction was (1)-N-(4-methoxybenzyl)-1,10-phenanthroline bromide (77.63%). It is pink solid form, and its melting point is 192-193 oC. Identification of the product was carried out by means of GC-MS, IR and 1H-NMR spectrometers. The in vitro antiplasmodial activity on chloroquine-resistant Plasmodium falciparum FCR-3 strain and chloroquine sensitive P.
    [Show full text]
  • Adducts of Propargyl Alcohol and Their Use As Corrosion Inhibitors in Acidizing Systems
    Europaisches Patentamt 19) s European Patent Office © Publication number: 0 239 770 Office europeen des brevets A1 © EUROPEAN PATENT APPLICATION © Application number: 87102356.0 © Int. CI.3: C 23 F 11/12 E 21 B 41/02, E 21 B 37/06 © Date of filing: 19.02.87 © Priority: 28.02.86 US 834526 © Applicant: BASF Corporation 9 Campus Drive Parsippany, NJ 07054(US) © Date of publication of application: 07.10.87 Bulletin 87/41 © Inventor: Perry, Christine 22335 Nixon © Designated Contracting States: Riverview Michigan 481 92(US) DE FR GB NL © Inventor: Crema,Stefano Carlo 1874 20th Street Wyandotte Michigan 48192(US) © Inventor: Davis, Pauls 30027 White Gibraltar Michigan 48173(US) @ Representative: Holler, Klaus, Dr. et al, BASF Aktiengesellschaft Carl-Bosch-Strasse 38 D-6700 Ludwigshafen(DE) © Adducts of propargyl alcohol and their use as corrosion inhibitors in acidizing systems. © The invention relates to an acidizing system comprising: (a) an acidizing solution; and (b) an effective corrosion inhibiting amount of a prop- argyl alcohol adduct having the following structural formula I: _ _ HC a C-CH2-0- -(CH2)5C-^ -H (I) wherein n = 1 or 3 and R = H if n = 3 and R = CH3 if n = 1 ; and x = 1 to 5. Corrosion of ferrous metals is inhibited by treating the surface thereof with the acidizing system. o IN M CM 0. Ul Croydon Printing Company Ltd. BASF Corporation ADDUCTS OF PROPARGYL ALCOHOL AND THEIR USE AS CORROSION INHIBITORS IN ACIDIZING SYSTEMS This invention relates to acidizing systems for oil and gas recovery containing propylene oxide and/or butylene oxide adducts of propargyl alcohol as corrosion inhibitors.
    [Show full text]
  • Alphabetical Index of Substances and Articles
    ALPHABETICAL INDEX OF SUBSTANCES AND ARTICLES - 355 - NOTES TO THE INDEX 1. This index is an alphabetical list of the substances and articles which are listed in numerical order in the Dangerous Goods List in Chapter 3.2. 2. For the purpose of determining the alphabetical order the following information has been ignored even when it forms part of the proper shipping name: numbers; Greek letters; the abbreviations “sec” and “tert”; and the letters “N” (nitrogen), “n” (normal), “o” (ortho) “m” (meta), “p” (para) and “N.O.S.” (not otherwise specified). 3. The name of a substance or article in block capital letters indicates a proper shipping name. 4. The name of a substance or article in block capital letters followed by the word “see” indicates an alternative proper shipping name or part of a proper shipping name (except for PCBs). 5. An entry in lower case letters followed by the word “see” indicates that the entry is not a proper shipping name; it is a synonym. 6. Where an entry is partly in block capital letters and partly in lower case letters, the latter part is considered not to be part of the proper shipping name. 7. A proper shipping name may be used in the singular or plural, as appropriate, for the purposes of documentation and package marking. - 356 - INDEX Name and description Class UN No. Name and description Class UN No. Accumulators, electric, see 4.3 3292 Acid mixture, nitrating acid, see 8 1796 8 2794 8 2795 Acid mixture, spent, nitrating acid, see 8 1826 8 2800 8 3028 Acraldehyde, inhibited, see 6.1 1092 ACETAL 3 1088
    [Show full text]
  • Chemical Name Federal P Code CAS Registry Number Acutely
    Acutely / Extremely Hazardous Waste List Federal P CAS Registry Acutely / Extremely Chemical Name Code Number Hazardous 4,7-Methano-1H-indene, 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro- P059 76-44-8 Acutely Hazardous 6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10- hexachloro-1,5,5a,6,9,9a-hexahydro-, 3-oxide P050 115-29-7 Acutely Hazardous Methanimidamide, N,N-dimethyl-N'-[2-methyl-4-[[(methylamino)carbonyl]oxy]phenyl]- P197 17702-57-7 Acutely Hazardous 1-(o-Chlorophenyl)thiourea P026 5344-82-1 Acutely Hazardous 1-(o-Chlorophenyl)thiourea 5344-82-1 Extremely Hazardous 1,1,1-Trichloro-2, -bis(p-methoxyphenyl)ethane Extremely Hazardous 1,1a,2,2,3,3a,4,5,5,5a,5b,6-Dodecachlorooctahydro-1,3,4-metheno-1H-cyclobuta (cd) pentalene, Dechlorane Extremely Hazardous 1,1a,3,3a,4,5,5,5a,5b,6-Decachloro--octahydro-1,2,4-metheno-2H-cyclobuta (cd) pentalen-2- one, chlorecone Extremely Hazardous 1,1-Dimethylhydrazine 57-14-7 Extremely Hazardous 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4,4a,5,6,7,8,8a-octahydro-1,4-endo-endo-5,8- dimethanonaph-thalene Extremely Hazardous 1,2,3-Propanetriol, trinitrate P081 55-63-0 Acutely Hazardous 1,2,3-Propanetriol, trinitrate 55-63-0 Extremely Hazardous 1,2,4,5,6,7,8,8-Octachloro-4,7-methano-3a,4,7,7a-tetra- hydro- indane Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]- 51-43-4 Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, P042 51-43-4 Acutely Hazardous 1,2-Dibromo-3-chloropropane 96-12-8 Extremely Hazardous 1,2-Propylenimine P067 75-55-8 Acutely Hazardous 1,2-Propylenimine 75-55-8 Extremely Hazardous 1,3,4,5,6,7,8,8-Octachloro-1,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime 26419-73-8 Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime.
    [Show full text]
  • United States Patent Office Patented Jan
    3,119,666 United States Patent Office Patented Jan. 28, 1964 1. 2 solvent is immaterial, since in practical operation, I re 3,119,666 use the solvent for the reaction after the suspended phos METHOS FOR THE PREPARATION OF phorus pentabromide is removed therefrom by filtration PHOSPHORUS PENTABROMIDE or by centrifuging after the reaction is completed. There Richard C. Nametz, St. Louis, Mich., assignor to fore, upon the first use of the solvent it becomes satu Michigan Chemical Corporation, St. Louis, Mich., a rated with the small amount of phosphorus pentabromide corporation of Michigan which it will dissolve, and will dissolve no more of the No Drawing. Fied Nov. 12, 1957, Ser. No. 695,548 product upon reuse. 12 Claims. (C. 23-205) In this method, I utilize substantially equimolar quan This invention relates to an improved method for the O tities of bromide and of phosphorus tribromide, together production of phosphorus pentabromide. with an amount of the co-solvent for bromine and phos Phosphorus pentabromide (phosphoric bromide) is a phorus tribromide relative to the quantities of the re known compound having a melting point above 100 C., actants used which is within the range which will suspend at which temperature it decomposes to form phosphorus the phosphorus pentabromide as a slurry which can be tribromide with the evolution of bromine. Due to its 5 readily stirred and which at the end of the reaction can heat sensitivity, phosphorus pentabromide cannot be puri be readily filtered, but which does not provide an un wieldly bulk of material to handle.
    [Show full text]
  • Synthesis of Propargyl Alcohol Author(S)
    Studies on ethinylation reactions, II : synthesis of propargyl Title alcohol Author(s) Suzuki, Keizo The Review of Physical Chemistry of Japan (1954), 23(2): 66- Citation 72 Issue Date 1954-02-15 URL http://hdl.handle.net/2433/46699 Right Type Departmental Bulletin Paper Textversion publisher Kyoto University The Review of Physical Chemistry of Japan Vol. 23 No. 2 (1953) STUDIES ON ETHINYLATION REACTIONS, II Synthesis of Propargyl Alcohol By Ka¢c~ Sczcxi Introduction Propargyl alcohol is usually produced as the intermediate when butynediol-1, 4 is synthesized from acetylene and fornaldehyde, but it is to be possible to obtain propargyl alcohol as the main product if the conversion to butynediol can be checked by control- ling suitably the reaction conditions. W. Reppeil has obtained the satisfactory results in the synthesis of propargyl alcohol in a continuous process, while the unsuccessful result has been reported so far as a continuous process is adoptedzl. Therefore, it is expected that the synthesis of propargyl alcohol as the main product is difficult in com- parison with the case of butynediol. From the previous studies on the kinetics of the reaction of acetylene with aqueous formaldehyde solutiona~^>and the synthesis of butynediol in a continuous process sl, the results of the investigations on the propargyl alcohol synthesis are summarized as follows. The rate, the apparent equilibrium concentration of propargyl alcohol and the ratio in moles of the quantity of the propargyl alcohol formed to that of formaldehyde consumed, PfF increase when acetylene pressure is raised. In the cases where pH is low and the methanol content contained in an aqueous formaldehyde solution is high, the concentration of propargyl alcohol formed and P/F come to exceed the cases where pH is high and the methanol content is low, though the reaction rate is slow at the earlier stage.
    [Show full text]
  • Acutely / Extremely Hazardous Waste List
    Acutely / Extremely Hazardous Waste List Federal P CAS Registry Acutely / Extremely Chemical Name Code Number Hazardous 4,7-Methano-1H-indene, 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro- P059 76-44-8 Acutely Hazardous 6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10- hexachloro-1,5,5a,6,9,9a-hexahydro-, 3-oxide P050 115-29-7 Acutely Hazardous Methanimidamide, N,N-dimethyl-N'-[2-methyl-4-[[(methylamino)carbonyl]oxy]phenyl]- P197 17702-57-7 Acutely Hazardous 1-(o-Chlorophenyl)thiourea P026 5344-82-1 Acutely Hazardous 1-(o-Chlorophenyl)thiourea 5344-82-1 Extemely Hazardous 1,1,1-Trichloro-2, -bis(p-methoxyphenyl)ethane Extemely Hazardous 1,1a,2,2,3,3a,4,5,5,5a,5b,6-Dodecachlorooctahydro-1,3,4-metheno-1H-cyclobuta (cd) pentalene, Dechlorane Extemely Hazardous 1,1a,3,3a,4,5,5,5a,5b,6-Decachloro--octahydro-1,2,4-metheno-2H-cyclobuta (cd) pentalen-2- one, chlorecone Extemely Hazardous 1,1-Dimethylhydrazine 57-14-7 Extemely Hazardous 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4,4a,5,6,7,8,8a-octahydro-1,4-endo-endo-5,8- dimethanonaph-thalene Extemely Hazardous 1,2,3-Propanetriol, trinitrate P081 55-63-0 Acutely Hazardous 1,2,3-Propanetriol, trinitrate 55-63-0 Extemely Hazardous 1,2,4,5,6,7,8,8-Octachloro-4,7-methano-3a,4,7,7a-tetra- hydro- indane Extemely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]- 51-43-4 Extemely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, P042 51-43-4 Acutely Hazardous 1,2-Dibromo-3-chloropropane 96-12-8 Extemely Hazardous 1,2-Propylenimine P067 75-55-8 Acutely Hazardous 1,2-Propylenimine 75-55-8 Extemely Hazardous 1,3,4,5,6,7,8,8-Octachloro-1,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran Extemely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime 26419-73-8 Extemely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime.
    [Show full text]
  • Predicting OH Stretching Fundamental Wavenumbers of Alcohols for Conformational Cite This: Phys
    PCCP View Article Online PAPER View Journal | View Issue Predicting OH stretching fundamental wavenumbers of alcohols for conformational Cite this: Phys. Chem. Chem. Phys., 2021, 23, 5629 assignment: different correction patterns for density functional and wave-function-based methods† Robert Medel * and Martin A. Suhm A model is presented for the prediction of OH stretching fundamental wavenumbers of alcohol conformers in the gas phase by application of a small set of empirical anharmonicity corrections to calculations in the harmonic approximation. In contrast to the popular application of a uniform scaling factor, the local chemical structure of the alcohol is taken into account to greatly improve accuracy. Interestingly, different correction patterns emerge for results of hybrid density functional (B3LYP-D3 and PBE0-D3) and wave-function-based Creative Commons Attribution 3.0 Unported Licence. methods (SCS-LMP2, LCCSD(T*)-F12a and CCSD(T)-F12a 1D). This raises questions about electronic structure deficiencies in these methods and differences in anharmonicity between alcohols. After its initial construction on the basis of literature assignments the model is tested with Raman jet spectroscopy of propargyl alcohol, Received 24th January 2021, cyclohexanol, borneol, isopinocampheol and 2-methylbutan-2-ol. For propargyl alcohol a spectral splitting Accepted 24th February 2021 attributed to tunneling is resolved. PBE0-D3 is identified as a well performing and broadly affordable À1 DOI: 10.1039/d1cp00342a electronic structure method for this model. A mean absolute error of 1.3 cm and a maximum absolute error of 3 cmÀ1 result for 46 conformers of 24 alcohols in a 60 cmÀ1 range, when a single parameter is rsc.li/pccp adjusted separately for each alcohol substitution class(methanol,primary,secondary,tertiary).
    [Show full text]