DOCSLIB.ORG

Isotopic Exchange Reactions Between Thionyl Chloride and Sulfuryl Chloride

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Isotopic Exchange Reactions Between Thionyl Chloride and Sulfuryl Chloride AN ABSTRACT OF THE THESIS OF Ralph Lee Bain for the Doctor of Philosophy in Chemistry (Name) (Degree) (Major) I5 Date thesis is presented ," L: j(,i(y' / Title ISOTOPIC EXCHANGE REACTIONS BETWEEN THIONYL CHLORIDE AND SULFURYL CHLORIDE Abstract approved (Major professor) The rates of chlorine -36 and sulfur -35 exchange between thionyl chloride and su].furyl in the pure solvents have been investi- gated. For the chlorine -36 exchange reaction, the rate law Rate k1(50C12)(502C12) + k2(SOC 12)2(SO2C 12)2 + k3 (SOC 12)3(502C12)2 gives a moderately good fit to the observed rate of exchange. The rate constants are found to be k1 1.51 x lO5litersg-atoday k2 1.80 x l07liters3g-atomday k3 8.41 x lO8liters 4 g-atom -4 day1 The Arrhenius energy of activation in an equimolar mixture of the reactants is found to be 7. 23 kcal/mole for the chlorine -36 exchange reaction. The exchange of sulfur-35 between thionyl chloride and sul- furyl chloride is found to follow the rate law Rate : k1(SOC12)(5O2C12) where k1 is found to be 1. 01 x l0 lite gram-atomday. The Arrhenius energy of activation is found to be 3.8 kcal/mole in excess thionyl chloride and 5. 3 kcal/mole in excess sulfuryl chlor - ide. The exchange reactions are interpreted in terms of a molecular mechanism, rather than as involving any possible ionic dissociation processes. It is conluded that, in contrast to suppositions of other workers, ionic dissociation processes in these media must. be of quite minor significance. Chloride ion (tetramethylammonium chloride) exhibits a strong catalytic effect on the rates of exchange of chlorine-36 and sulfur 35 between thionyl chloride and sulfuryl chloride. The kinetic data for the exchange reactions suggest that complexes between chloride ion and the solvents are formed. For the chlorine -36 exchange reaction in excess sulfuryl chloride, chloride ion exhibits a fourth order kinetic dependency and thionyl chloride exhibits a third order kinetic dependency. In excess thionyl chloride, chloride ion exhibits a first order kinetic dependency and sulfuryl chloride exhibits a second order kinetic dependency. The Arrhenius energy of activation is 16. 7 kcal/mole in excess sulfuryl chloride and 3. 7 kcal/mole in excess thionyl chloride. The sulfur-35 exchange reaction catalyzed by the addition of chloride ion follows the rate law Rate = k (SOC12)(S02C12)(Me4NC1)2 over a wide range of concentrations. The value of k is 0.52 liters3gram-atom3minute in excess sulfuryl chloride and 13. 8 liters3gram-atom3minute in excess thionyl chloride. The Arrhenius energy of activation is 3.3 kcal/ mole in excess sulfuryl chloride and 10. 5 kcal'mole in excess thionyl chloride. The exchange mechanism for this exchange reac - tion has been interpreted in terms of bimolecular interaction be- tween the species S0C13 and S02C13. Antimony pentachloride is found to exchange chlorine-36 rapidly and completely with thionyl chloride but at best only slowly with sulfuryl chloride. The result suggests a greater chloride releasing ability towards a strong Lewis acid on the part of the sulfur (IV) as compared to the sulfur (VI) compound. Antimony pentachloride exhibits a weak catalytic effect on the chlorine-36 exchange reaction between thionyl chloride and sulfuryl chloride. There appears to be no catalysis by antimony pentachloride for the analogous sulfur -35 exchange reaction. Triethylamine catalyzes the exchange of chlorine-36 and sulfur-35 between thionyl chloride and sulfuryl chloride. Sulfur dioxide exhibits no catalytic effect on the exchange of chlorine-36 between thionyl chloride and sulfuryl chloride. In the solvent acetonitrile chloride ion is found to inhibit the exchange of chlorine-36 between thionyl chloride and antimony pentachloride, (presumably due to hexachloroantimonate (V). ion formation). ISOTOPIC EXCHANGE REACTIONS BETWEEN THIONYL CHLORIDE AND SULFURYL CHLORIDE by RALPH LEE BAIN A THESIS submitted to OREGON STATE UNIVERSITY in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY June 1964 APPROVED: Professor of Chemistry In Charge of Major Chairman of Department of Chemistry Dean of Graduate School 1 ' Date thesis is presented I Typed by Penny A. Self AC KNOW LEDGMENT I wish to acknowledge my indebtedness to Professor T. H. Norris for his valuable assistance, guidance and patience with all aspects of my research and my studies at Oregon State University. This investigation was sponsored by the United States Atomic Energy Commission under Contract AT (45-1)-244 between the Commission and Oregon State University. TABLE OF CONTENTS Page I. INTRODUCTION .................................... i II. EXPERIMENTAL ................................... 7 A. General ...................................... 7 B. Radioactivity Assay ........................... 9 C. Chemical Analysis ............................. 13 D. Preparation of Materials ....................... 13 1. Chlorine-36 .............................. 13 z. Sulfur-35 ................................ 14 3. Thionyl chloride .......................... 14 4. Chlorine-36 labeled thionyl chloride ........ 15 5. Sulfur-35 labeled thionyl chloride ........... 17 6. Sulfuryl chloride .......................... 18 7. Chlorine-36 labeled sulfuryl chloride ....... 19 8. Sulfur-35 labeled sulfuryl chloride .......... 9. Sulfur dioxide ............................ 23 10. Sulfur-35 labeled sulfur dioxide ............ 23 11. Tetramethylammonium chloride ............ 24 12. Tetraethylammonium chloride ............. 25 13. Chlorine-36 labeled pyridine hydrochloride . 25 14. Antimony pentachioride ................... 26 15. Chlorine-36 labeled antimony pentachloride 28 16. Triethylamine ............................ 30 17. Acetonitrile ............................. 30 III.RUN PROCEDURE AND DATA ....................... 31 A . Radiochiorine Exchange Expe riments between Thionyl Chloride and Sulfuryl Chloride, No Catalyst 31 B. Radiosulfur Exchange Experiments between Thionyl Chloride and Sulfuryl Chloride, No Catalyst ...... 37 C. Radiochiorine Exchange Experiments between Thionyl Chloride and Sulfuryl Chloride in the Presence of Tetramethylammonium Chloride ..... 38 D. Radiosulfur Exchange Experiments between Thionyl Chloride and Sulfuryl Chloride in the Presence of Tetramethylammonium Chloride ................ 39 E . Radiochiorine Exchange Expe riments between Thionyl Chloride and Antimony Pentachioride ..... 40 F. Radiochiorine Exchange Experiments between Sulfuryl Chloride and Antimony Pentachioride . 42 G . Radiochiorine Exchange Expe riments between Thionyl Chloride and Sulfuryl Chloride in the Presence of Antimony Pentachioride ............. 43 H. Radiosulfur Exchange Experiments between Thionyl Chloride and Suif uryl Chloride (Excess) in the Presence of Antimony Pentachioride ............. 44 TABLE OF CONTENTS (Continued) Page I . Radiochiorine Exchange Experiments between Thionyl Chloride and Sulfuryl Chloride (Excess) in the Presence of Triethylamine ................... 44 J. Radiosulfur Exchange Experiment between Thionyl Chloride and Sulfuryl Chloride (Excess) in the Presence of Triethylamine ...................... 45 K. Radiochiorine Exchange Expe riments between Thionyl Chloride and Sulfuryl Chloride in the Presence of Sulfur Dioxide ...................... 45 L. Radiochiorine Exchange Experiments between Thionyl Chloride and Antimony Pentachioride in the Presence of Tetraethylammonium Chloride-- Acetonitrile as the Solvent ....................... 46 M . Radiochiorine Exchange Experiments between Thionyl Chloride and Antimony Pentachloride in the Presence of Triethylamine ....................... 46 N. Radiochiorine Exc hange Experiments between Thionyl Chloride and Sulfuryl Chloridè (Excess) in the Presence of Triethylamine and Antimony Penta- chloride ....................................... 47 O. Radiochlorine Exchange Experiment between Sulfuryl Chloride and Antimony Pentachioride in the Presence of Triethylamine ....................... 48 IV. CALCULATIONS ..................................... 75 A. The Concentrations ............................. 75 B. Exchange Rate .................................. 76 C. Sample Calculation .............................. 86 V. RESULTS AND DISCUSSION ........................... 95 A . Non -c atalyzed Exchange Exper iments Between Thionyl Chloride and Sulfuryl Chloride ............ 95 1. Cl-36 Exchange Reactions ................. 95 2. S-35 Exchange Reactions ................... 113 3. Discussion ............................... 125 B. Exchange Reactions Between Thionyl Chloride and Sulfuryl Chloride in the Presence of Chloride Ion Catalyst ....................................... 128 1. Cl-36 Exchange Reactions .................. 128 2. S-35 Exchange Reactions ................... 144 3. Discussion ................................ 158 C. Exchange Experiments with Antimony Penta- chloride...................................... 160 1. Cl-36 Exchange Experiments between Thionyl Chloride and Antimony Pentachloride ........ 160 TABLE OF CONTENTS (Continued) Page 2. Cl-36 Exchange Experiments between Sulfuryl Chloride and Antimony Pentachioride ........ 162 3. Cl-36 Exchange Experiments between Thionyl Chloride and Sulfuryl Chloride in the Presence of Antimony Pentachioride ................. 163 4. S-35 Exchange Experiments between Thionyl Chloride and Sulfuryl Chloride in the Presence of Antimony Pentachloride .................. 166 D. Exchange Experiments Between Thionyl Chloride and Sulfuryl Chloride in the Presence of Non-ionic Catalysts .....................................
Load more

Recommended publications
  • [19] [11] Patent Number: 4518808
    Ulllted States Patent [19] [11] Patent Number: 4,518,808 Wang et a1. [45] Date of Patent: May 21, 1985 [54] PREPARATION OF [56] References Cited 2,5-DICHLOROHYDROQUINONE Us. PATENT DOCUMENTS _ 2,151,137 3/1939 Moness .............................. .. 568/765 [75] Inventors: Richard H. S. Wang; Garry L. Myers, 2,777,002 1/1957 Sullivan . 1 . .. 568/779 both of Kingsport, Tenn. 2,902,518 9/1959 Hurdis et a1. .... .. .. 568/726 X FOREIGN PATENT DOCUMENTS [73] Asslgnee: Eastman Kodak Company’ 839972 6/1960 United Kingdom .............. .. 568/779 Rochester, NY. Primary Examiner—Bernard Hel?n Attorney, Agent, or Firm—Clyde L. Tootle; J. Frederick [21] Appl. No; 537,227 Thomsen [57] ABSTRACT . _ 7 [22] Flled' Sep' "9’ 1983 Disclosed is a process for the preparation of certain dichloro-hydroxy and alkoxy aromatic compounds by [51] Int. Cl.3 ............................................ .. C07C 37/62 reacting the corresponding unchlorinated compound [52] US. Cl. .................................. .. 568/765; 568/633; with sulfuryl chloride in the presence of acetic acid, 568/634; 568/656; 568/726; 568/737; 568/779 propionic acid or lower alkyl esters thereof. [58] Field of Search ............. .. 568/779, 656, 726, 737, 568/765, 649 1 Claim, N0 Drawings 4,518,808 - 1 2 methyl and methoxy being the most common. The aryl PREPARATION OF substituent may be phenyl or alkyl-substituted phenyl. 2,5-DICHLOROHYDROQUINONE The chlorination temperatures used may be varied widely, e.g. from about 15° to 110° C., depending on the DESCRIPTION particular compound being chlorinated. The chlorina This invention relates to a novel process for the prep~ tion promoting temperature preferably is in the range of aration of dichloro-hydroxy and alkoxy aromatic com about 30° to 80° C.
    [Show full text]
  • Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides
    Proceedings of the Iowa Academy of Science Volume 61 Annual Issue Article 26 1954 Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides B. R. Bluestein Coe College Albert Hybl Coe College Yoshimi Al Nishioka Coe College Let us know how access to this document benefits ouy Copyright ©1954 Iowa Academy of Science, Inc. Follow this and additional works at: https://scholarworks.uni.edu/pias Recommended Citation Bluestein, B. R.; Hybl, Albert; and Nishioka, Yoshimi Al (1954) "Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides," Proceedings of the Iowa Academy of Science, 61(1), 225-232. Available at: https://scholarworks.uni.edu/pias/vol61/iss1/26 This Research is brought to you for free and open access by the Iowa Academy of Science at UNI ScholarWorks. It has been accepted for inclusion in Proceedings of the Iowa Academy of Science by an authorized editor of UNI ScholarWorks. For more information, please contact [email protected]. Bluestein et al.: Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlor Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides By B. R. BLUESTEIN, ALBERT HYBL* AND YosHIMI AL NISHIOKA INTRODUCTION The reaction kinetics of the alcoholysis of substituted benzoyl chlorides was studied. The mechanism of the alcoholysis reaction, which is most generally accepted ( 1), shows that the overall re­ action should be second-order and that the reaction should be first-order with respect to the acid chloride and first-order with respect to the alcohol. This rate study was carried out using a large excess of alcohol as the solvent, thus obtaining pseudo-first order rate constants, first-order with respect to the acid chloride only.
    [Show full text]
  • Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts
    Organic Process Research & Development 2010, 14, 1501–1505 Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts Heiner Eckert* and Johann Auerweck Department of Chemistry, Technische UniVersitaet Muenchen, Lichtenbergstr. 4, Garching 85747, Germany Abstract: Scheme 1. Decomposition of triphosgene (1a) into carbon tetrachloride, carbon dioxide, and 1 equiv of phosgene (3) Phosgene is quantitatively formed from solid triphosgene in a solvent-free and safe process without any reaction heat, catalyzed by planar N-heterocycles with deactivated imino functions. The rate of phosgene generation is adjustable to the rate of phosgene consumption in the subsequent phosgenation reaction by thermal control, catalyst concentration, and in some cases, specific proper- ties of selected metal phthalocyanines. A thermal runaway reaction of this process is impossible. phosgene in most reactions, yet several phosgenation reactions are advantageously carried out with phosgene, that is, when excessive triphosgene is difficult to remove during the reaction Introduction workup because of its high boiling point of over 200 °C. Its Phosgene (3) is a highly useful and versatile chemical in excess can be destroyed by hydrolysis, when phosgenation performing syntheses.1a Although consisting of only four atoms, products are not sensitive to moisture as are carbonates, four important transformations can be carried out with it in carbamates, ureas, diarylketones, alkylhalides, cyanides, and organic
    [Show full text]
  • Material Safety Data Sheet Scction I -IDENTIFICATION
    CREAf IN6 TO ORROW Material Safety Data Sheet Scction I -IDENTIFICATION Product Name: LITHIUM SULFURYL CHLORIDE CELLS AND BATTERIES (all hermetically sealed Electrochem CSC/PMX cells) Manufacturer: Electrochem Solutions (Subsidiary of Greatbatch, lnc) 670 Paramount Drive Raynham, MA 02767 USA Telephone: 781-830-5800 Fax: 781-575-1545 Transportation Emergency Number -CHEMTREC 1-800424-9300 Revision Date -2-1 5-201 3 Section 2 - COMPOSITION/INFORMATION ON INGREDIENTS Hazardous Components: 1 ) Lithium- CAS#7439-93-2: TLV/PEL: None est. 2) Sulfuryl Chloride -CAS#7791 -25-5 TLV/PEL: None established 3) Chlorine (Cl2) -CAS# 7782-50-5 ACGIH: 0.5m9/m3 TWA/1ppm STEL 4) Carbon CAS# 1333-86-4 ACGIH: 3.5 mg/m3 TWA For cell lithium content, refer to technical datasheet information. Scction 3-HAZARDS IDENTIFICATION DANGER - lnternal contents are extremely hazardous. Leaking fluid is corrosive and dangerous upon inhalation. Battery may be explosive at higher temperatures. Do not expose to temperatures above the maximum rated temperature as specified by the manufacturer due to potential leak hazard. lf batterv leaks or vents: Primary Routes of Entry: Inhalation or skin contact Carcinogenicity: Not listed by NTP, IARC, or regulated by OSHA Health Hazards: Acute -Vapors are very irritating to skin, eyes, and mucous membranes. lnhalation of sulfuryl chloride or thionyl chloride vapors can result in pulmonary edema. Chronic - Overexposure can cause symptoms of non-fibrotic lung injury. Signs and symtoms of exposure : Eye and mucous membrane irritation. Medical conditions generally aggravated by exposure: Asthma, or other respiratory conditions, skin allergies, and eczema. MSDS-OOO3 Rev. B ECO# I 1598 Page 1 (/atltlrvc toinoRpow Scction 4 -FIRST AID MEASURES Eye Contact: Flush with running water for at least 15 minutes while holding eyelids apart.
    [Show full text]
  • Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides
    Molecules 2015, 20, 10487-10495; doi:10.3390/molecules200610487 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Communication Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides Emily R. Vogel, William Jackson and Douglas S. Masterson * Department of Chemistry and Biochemistry, the University of Southern Mississippi, 118 College Drive #5043, Hattiesburg, MS 39406, USA; E-Mails: [email protected] (E.R.V.); [email protected] (W.J.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-601-266-4714. Academic Editor: Derek J. McPhee Received: 17 May 2015 / Accepted: 4 June 2015 / Published: 8 June 2015 Abstract: Oxidized L-glutathione was esterified to the tetra methyl ester using thionyl chloride in methanol solvent. Other alcohols were tested and the reaction progress was monitored via ESI-MS. This procedure proved to be compatible with other small peptides not containing serine and cysteine residues. In contrast to previously reported methods this procedure provided convenient access to esterified peptides requiring no purification, extended reaction times, or complicated reaction setups. Keywords: esterification; peptide esterification; amino acids; carboxylic acids; esters 1. Introduction The design and synthesis of novel glutathione analogues are studied extensively for their pharmacological properties in the treatment of a wide range of diseases [1–3]. Reduced glutathione (GSH), -L-glutamyl-L-cysteinyl-glycine, is prone to reactivity at the sulfhydryl, terminal amino group, and both carbonyls. Thus, the synthesis of GSH analogues are a synthetic challenge to chemists, and the clever manipulation of protecting groups are needed to prevent unwanted reactions.
    [Show full text]
  • Aldrich Organometallic, Inorganic, Silanes, Boranes, and Deuterated Compounds
    Aldrich Organometallic, Inorganic, Silanes, Boranes, and Deuterated Compounds Library Listing – 1,523 spectra Subset of Aldrich FT-IR Library related to organometallic, inorganic, boron and deueterium compounds. The Aldrich Material-Specific FT-IR Library collection represents a wide variety of the Aldrich Handbook of Fine Chemicals' most common chemicals divided by similar functional groups. These spectra were assembled from the Aldrich Collections of FT-IR Spectra Editions I or II, and the data has been carefully examined and processed by Thermo Fisher Scientific. Aldrich Organometallic, Inorganic, Silanes, Boranes, and Deuterated Compounds Index Compound Name Index Compound Name 1066 ((R)-(+)-2,2'- 1193 (1,2- BIS(DIPHENYLPHOSPHINO)-1,1'- BIS(DIPHENYLPHOSPHINO)ETHAN BINAPH)(1,5-CYCLOOCTADIENE) E)TUNGSTEN TETRACARBONYL, 1068 ((R)-(+)-2,2'- 97% BIS(DIPHENYLPHOSPHINO)-1,1'- 1062 (1,3- BINAPHTHYL)PALLADIUM(II) CH BIS(DIPHENYLPHOSPHINO)PROPA 1067 ((S)-(-)-2,2'- NE)DICHLORONICKEL(II) BIS(DIPHENYLPHOSPHINO)-1,1'- 598 (1,3-DIOXAN-2- BINAPH)(1,5-CYCLOOCTADIENE) YLETHYNYL)TRIMETHYLSILANE, 1140 (+)-(S)-1-((R)-2- 96% (DIPHENYLPHOSPHINO)FERROCE 1063 (1,4- NYL)ETHYL METHYL ETHER, 98 BIS(DIPHENYLPHOSPHINO)BUTAN 1146 (+)-(S)-N,N-DIMETHYL-1-((R)-1',2- E)(1,5- BIS(DI- CYCLOOCTADIENE)RHODIUM(I) PHENYLPHOSPHINO)FERROCENY TET L)E 951 (1,5-CYCLOOCTADIENE)(2,4- 1142 (+)-(S)-N,N-DIMETHYL-1-((R)-2- PENTANEDIONATO)RHODIUM(I), (DIPHENYLPHOSPHINO)FERROCE 99% NYL)ETHYLAMIN 1033 (1,5- 407 (+)-3',5'-O-(1,1,3,3- CYCLOOCTADIENE)BIS(METHYLD TETRAISOPROPYL-1,3- IPHENYLPHOSPHINE)IRIDIUM(I)
    [Show full text]
  • 9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019
    Facility DEC ID: 9290900045 PERMIT Under the Environmental Conservation Law (ECL) IDENTIFICATION INFORMATION Permit Type: Air State Facility Permit ID: 9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019 Permit Issued To:TWIN LAKE CHEMICAL INC 520 MILL ST PO BOX 411 LOCKPORT, NY 14094-0411 Contact: JAMES D HODAN TWIN LAKE CHEMICAL INC PO BOX 411 LOCKPORT, NY 14095 (716) 433-3824 Facility: TWIN LAKE CHEMICAL INC 520 MILL ST LOCKPORT, NY 14094 Contact: WILLIAM CASWELL TWIN LAKE CHEMICAL INC 520 MILL ST LOCKPORT, NY 14094-1712 (716) 433-3824 Description: This Air State Facility permit incorporates monitoring conditions for Twin Lake Chemical located in Lockport New York. The facility is a manufacturer of various organic acid chlorides used as intermediaries in the production of other compounds and encompasses two main production buildings and 8 reactors. The primary products produced are trimellitic trichloride, trimellitic Anhydride Monoacid chloride,isophthaloyl chloride, orthophthaloyl chloride, terephthaloyl chloride, and phosphorous pentachloride (2-200 gallon nickel reactors). Phosgene and thionyl chloride are used as chlorinating agents. The phosgene is purchased in 1 ton containers from Vandemark Chemical located next to the facility. Raw materials are added to the batch reactors along with a chlorinating agent and a catalyst. Prior to opening the reactor for chemical addition, the reactor is put under vacuum to remove gases. During the reaction process, the reactor is under slight pressure. Reactor temperatures are monitored. After the reaction is completed, the material is transferred to a distillation unit to refine and separate the product. Air strippers remove chlorinated hydrocarbons from wastewater prior to discharge to Lockport WWTP.
    [Show full text]
  • Material Safety Data Sheet
    Material Safety Data Sheet Sulfuryl chloride fluoride, distilled, 99% ACC# 88306 Section 1 - Chemical Product and Company Identification MSDS Name: Sulfuryl chloride fluoride, distilled, 99% Catalog Numbers: AC176260000, AC176260100, AC176260250 Synonyms: Chloro fluoro sulfone; Chlorosulfonyl fluoride; Fluorosulfonyl chloride; Sulfonyl chloride fluoride; Sulfuryl chlorofluoride; Sulfuryl fluorochloride Company Identification: Acros Organics N.V. One Reagent Lane Fair Lawn, NJ 07410 For information in North America, call: 800-ACROS-01 For emergencies in the US, call CHEMTREC: 800-424-9300 Section 2 - Composition, Information on Ingredients CAS# Chemical Name Percent EINECS/ELINCS 13637-84-8 Sulfuryl chloride fluoride, distilled 99 237-126-2 Section 3 - Hazards Identification EMERGENCY OVERVIEW Appearance: clear, colorless clear liquid. Danger! Corrosive. Causes eye and skin burns. May cause severe respiratory tract irritation with possible burns. May cause severe digestive tract irritation with possible burns. Moisture sensitive. Target Organs: No data found. Potential Health Effects Eye: Causes eye burns. May cause chemical conjunctivitis and corneal damage. Skin: Causes skin burns. May cause skin rash (in milder cases), and cold and clammy skin with cyanosis or pale color. Ingestion: May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns. May cause perforation of the digestive tract. May cause systemic effects. Inhalation: Causes chemical burns to the respiratory tract. Inhalation may be fatal as a result of spasm, inflammation, edema of the larynx and bronchi, chemical pneumonitis and pulmonary edema. May cause systemic effects. May cause burning sensation, coughing, wheezing, laryngitis, shortness of breath, headache, nausea, and vomiting. Chronic: Effects may be delayed. Section 4 - First Aid Measures Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids.
    [Show full text]
  • Reactions of Enantiopure Cyclic Diols with Sulfuryl Chloride
    Organic & Biomolecular Chemistry Reactions of enantiopure cyclic diols with sulfuryl chloride Journal: Organic & Biomolecular Chemistry Manuscript ID: OB-ART-01-2014-000042.R1 Article Type: Paper Date Submitted by the Author: 06-Feb-2014 Complete List of Authors: Stevenson, P J; Queens University, School of Chemistry and Chemical Engineering Boyd, D; Queens University, Department of Chemistry Sharma, Narain; Queens University, Department of Chemistry Kaik, Magdalena; Queens University, Department of Chemistry McIntyre, Peter; Queens University, Department of Chemistry Malone, John; The Queens University of Belfast, School of Chemistry & Chemical Engineering Note: The following files were submitted by the author for peer review, but cannot be converted to PDF. You must view these files (e.g. movies) online. graphicalextract.cdx Page 1 of 9 Journal Name Organic & Biomolecular Chemistry Dynamic Article Links ► Cite this: DOI: 10.1039/c0xx00000x www.rsc.org/xxxxxx ARTICLE TYPE Reactions of enantiopure cyclic diols with sulfuryl chloride Derek R. Boyd, Narain D. Sharma, Magdalena Kaik, Peter B. A. M cIntyre, John F. Malone and Paul J. Stevenson* 5 Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x Monocyclic allylic cis -1,2-diols reacted with sulfuryl chloride at 0 oC in a regio- and stereo-selective manner to give 2-chloro-1-sulfochloridates, which were hydrolysed to yield the corresponding trans -1,2- o 10 chlorohydrins. At -78 C, with very slow addition of sulfuryl chloride, cyclic sulfates were formed in good yields, proved to be very reactive with nucleophiles and rapidly decomposed on attempted storage. Reaction of a cyclic sulfate with sodium azide yielded a trans -azidohydrin without evidence of allylic rearrangement occurring.
    [Show full text]
  • Halogenation Reagents
    Halogenation Reagents Halogenation is a basic and fundamental transformation in organic chemistry, and halogenated compounds are of extreme importance as building blocks in organic synthesis. The development of modern coupling reactions, such as the [P2140] Suzuki-Miyaura and Mizoroki-Heck reactions, have greatly increased the demand for halogenated compounds as starting materials. P2140 (2.3 eq.) On the other hand, introduction of fluorine into a certain position of bioactive compound such as a pharmaceutical and an agricultural chemical may remarkably reduce the toxicity of the compound, or improve the efficiency of medicine. This is due to the structurally mimic and blocking effect characterized by fluorine. P2140 (3 eq.) In response to this situation, a number of novel halogenation reagents have been developed. 4-tert-Butyl-2,6-dimethylphenylsulfur trifluoride (FLUOLEAD™) [B3664] is introduced as below: B3664 is a novel nucleophilic 1-Fluoro-3,3-dimethyl-1,2-benziodoxole [F0957] is a hypervalent fluorinating agent which was first reported by Umemoto et al.1) iodine derivative developed by Stuart et al.3) F0957 is stable to air Differing from other existing fluorinating agents, such as DAST, and moisture and used as an electrophilic fluorinating reagent for B3664 is a crystalline solid with high thermal stability and less a α-monofluorination of β-ketoesters in the presence of fuming character, which makes it easier to handle. B3664 triethylamine trihydrofluoride. fluorinates a hydroxyl or carbonyl group to afford the corresponding fluorinated compounds in good yields.1) F I O [F0957] O O Ph OEt F0957(2eq.) F O O Et3N-3HF(2.7eq.) [B3664] Ph OEt CH2Cl2 O O 40oC,24h Ph OEt F F Dibromoisocyanuric acid (DBI) [D3753] which was first reported by Gottardi, is a mild and highly effective brominating agent,4a,b,c) and has superior brominating ability when compared with N-bromosuccinimide (NBS), which is frequently used in organic IF5-Pyridine-HF (Hara Reagent) [P2140] is also a novel synthesis.
    [Show full text]
  • 1006134632-Mckeown-1960.Pdf
    PROOF OF STRUCTURE OF SOME CONTROVERSIAL SULFONYL CHLORIDES by GEORGE BAKER McKEOWN H A THESIS Submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemistry in the School of Chemistry in the Graduate School of the University of Alabama UNIVERSITY, ALABAMA 1960 I ACKNOWLEDGMENT I wish to express my great indebtedness to Dr. R. B. Scott, Jr. for his supervision and numerous suggestions during the course of this work. G. B. M. CONTENTS Page INTRODUCTION • • • • • • • • • • • • • • • • • • • 1 THE PHOTOCHEMICAL CHLOROSULFANYLATION OF ALKANES ••••••••••••• . 3 TERTIARY SULFONYL CHLORIDES •• . 9 DECOMPOSITION OF SULFONYL CHLORIDES • • 13 CONCERNING A CLAIM AND A COUNTER-CLAIM TO PREP.A~ING TERTIARY SULFONYL CHLORIDES PHOTOCHEMICALLY • • • • • • • • • 15 EXPERIMENTAL • • • • • • • • • • • • • • • • • • 17 Preparation of 4-Chloro-2-methyl-l-butanesulfonyl Chloride from 4-Chloro-2-Methylbutane. • • • • . 17 Preparation of 4-Hydroxy-2-methyl-l-butanesulfonic Acid Sultone. • • • . • • • • • • • • • • . • . • • • 18 Conversion of 4-Chloro-2-methyl-l-butanesulfonyl Chloride to 2-Methyl -1-butanethiol • . .. • • . • • • 19 Preparation of 2-Methyl-1-butanethiol from 2-Methyl- 1-butanol. • • • • • • • • • • . • • • • . • • • . • 21 Preparation of 4-Chloro-2-methyl-1-pentanesulfonyl Chloride • • . • • • • • . • • • • • • • • • • • • • • 23 Preparation of 4-Hydroxy-2-methyl-l-pentanesulfonic Acid Sultone . • • • • • • • • • • • • • • • • • • • 25 Conversion of 4-Chloro-2-methyl-1-pentanesulfonyl Chloride to 2-Methyl-1-pentanethiol
    [Show full text]
  • How to Use This Guide Dielectric Constant Table
    Dielectric Constant Table.xls Dielectric Constant Table Dielectric Constant (k) is a number relating the ability of a material to carry alternating current to the ability of vacuum to carry alternating current. The capacitance created by the presence of the material is directly related to the Dielectric Constant of the material. Alphabetic Table A B C D Knowing the Dielectric Constant (k) of a material is needed to properly E F G H design and apply instruments such as level controls using radar, RF I J K L admittance, or capacitance technologies. There are also analytical M N O P reasons to know the (k) of a material. Q R S T U V W X How to use this guide Y Z # CLIPPER CONTROLS has compiled an extensive list of products with Dielectric Constants. Many of these Dielectric Constants are given at specific temperatures. If your product's temperature is significantly different from those listed there is a good chance that the Dielectric Constant may be different from the values listed. The products in this reference are listed in alphabetical order and are grouped in sections by the first letter of their name. Proper chemical names were used, and any trade names are the trademark of their respective owners. If you know the correct spelling of the name of the product you wish to review then use the "Search" feature on the web browser to locate the name in the list. You may also click on the letter from the alphabetical table to go directly to the beginning of that alphabetic section.
    [Show full text]