DOCSLIB.ORG

(12) Patent Application Publication (10) Pub. No.: US 2004/0086650 A1 Behr Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) Patent Application Publication (10) Pub. No.: US 2004/0086650 A1 Behr Et Al US 20040O86650A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2004/0086650 A1 Behr et al. (43) Pub. Date: May 6, 2004 (54) PERFLUOALKYL HALOALKYL ETHERS Related U.S. Application Data AND COMPOSITIONS AND APPLICATIONS THEREOF (62) Division of application No. 09/231,203, filed on Jan. 14, 1999, now Pat. No. 6,653,512, which is a division (75) Inventors: Frederick E. Behr, Woodbury, MN of application No. 08/931,105, filed on Sep. 15, 1997, (US); Richard M. Flynn, Mahtomedi, now Pat. No. 6,552,090. MN (US) Publication Classification Correspondence Address: 3M INNOVATIVE PROPERTIES COMPANY (51) Int. Cl." ....................................................... B05D 3/02 PO BOX 33427 (52) U.S. Cl. .............................................................. 427/384 ST. PAUL, MN 55133-3427 (US) (57) ABSTRACT (73) Assignee: 3M Innovative Properties Company Described are compositions comprising perfluoroalkyl haloalkyl ethers and, optionally, Surfactant; uses for perfluo (21) Appl. No.: 10/689,110 roalkyl haloalkyl ether compounds and compositions thereof, optionally comprising Surfactant; and perfluoroalkyl (22) Filed: Oct. 20, 2003 haloalkyl ethers. US 2004/0O8665.0 A1 May 6, 2004 PERFLUOALKYL HALOALKYL ETHERS AND substitutes will also be low in toxicity, have no measurable COMPOSITIONS AND APPLICATIONS THEREOF flash points (as determined by ASTM D3278-89), have acceptable thermal and chemical Stability for use in a given CROSS-REFERENCE TO RELATED application, and have short atmospheric lifetimes and low APPLICATION global warming potentials. Many compounds have been proposed as Substitutes for Such chlorinated compounds in a 0001) This is a divisional of U.S. Ser. No. 09/231,203, number of different uses and applications. Still, there filed Jan. 14, 1999, now allowed; which is a divisional of remains a need for chemical compounds capable of replac U.S. Ser. No. 08/931,105, filed Sep. 15, 1997, issued as U.S. ing past commonly used chlorinated compounds and that Pat. No. 6,552,090. exhibit one or more of Such useful chemical or physical 0002 The present invention relates to perfluoroalkyl properties. haloalkyl ether compounds, to compositions containing Such compounds, and to the use of Such compounds and compo SUMMARY OF THE INVENTION Sitions. 0007 Perfluoroalkyl haloalkyl ether compounds have been discovered which can be useful by themselves and in BACKGROUND chemical compositions for purposes including but not lim 0003 Chlorinated chemicals (e.g., chlorofluorocarbons, ited to use as Solvents e.g., in cleaning processes Such as dry and hydrochlorofluorocarbons) have been used in the past as cleaning processes, water removal processes, and in coating Solvents within a number of Specialized industrial applica processes. The ethers have a haloalkyl component and a tions. For instance, chlorinated chemicals are known to be perfluorinated alkyl component, and exhibit useful and useful within cleaning applications, including dry cleaning, advantageous properties. These perfluoroalkyl haloalkyl wherein contaminated articles are washed (e.g., immersed in ethers can exhibit, for example, one or more of the following or otherwise contacted) to remove the contaminant. The physical or chemical properties: useful boiling points, high chlorinated chemicals can be used as liquids or vapors, and Solvency, acceptable toxicity properties, chemical and ther at ambient or elevated temperatures (often in cleaning mal Stability, low OZone depletion characteristics, and pref applications accompanied by ultraSonic agitation). Other erably, Substantially no flash point. Additionally, the pres applications wherein chlorinated chemicals are known to be ence of at least one hydrogen on the haloalkyl component useful include using chlorinated chemicals as coating or allows for degradation of the compound, and reduces its deposition solvents, for the removal of water from Sub long-term presence in the atmosphere. Strates, as a thermal media for heat transfer applications, as 0008 An aspect of the invention relates to a chemical a blowing agent for polymeric foams, as a fire-extinguishing composition containing a perfluoroalkyl haloalkyl ether agent, and as a coolant/lubricant in metal working applica compound and a Surfactant. The perfluoroalkyl haloalkyl tions. compound can be described generally by the formula: 0004. A major concern relating to the use of such chlo R-O-R rinated chemicals is the tendency (especially when used at an elevated temperature) for vapor loss into the atmosphere, 0009 wherein R is perfluoroalkyl and R is haloalkyl. causing pollution. Although care can be exercised to mini Preferred such compounds include those of the formula: mize Such losses (e.g., through good equipment design and vapor recovery Systems), most practical applications result 0010 wherein R is a perfluoroalkyl preferably having at in the loSS of at least Some vapor into the atmosphere. least about 3 carbons, most preferably from about 3 to 15 0005 Popular chlorinated chemicals that have been use carbons, and optionally containing a catenary heteroatom ful in the past (e.g., as cleaning Solvents) include 1,1,2- such as N or O; Xpreferably is from about 1 to 6; y is at least trichloro-1,2,2-trifluoroethane and 1,1,1-trichloroethane. one; W is in the range from 0 to about 2, X is a halogen These are useful alone or in admixture with one or more chosen from bromine, iodine, and chlorine; Z is at least one; co-Solvents Such as aliphatic alcohols or other low molecular and W--y+Z is equal to 2x+1. weight polar compounds. These particular chlorinated com 0011) Another aspect of the invention relates to a process pounds were initially believed to be environmentally benign, for removing contaminants from a Substrate. The process but have now been linked to depletion of the earth's ozone. includes the Step of contacting the Substrate with a compo According to the Montreal Protocol and its attendant amend Sition comprising a perfluoroalkyl haloalkyl ether. The per ments, production of Such Solvents has been discontinued in fluoroalkyl haloalkyl ether can be of the formula: the U.S. (see, e.g., P. S. Zurer, “Looming Ban on Production of CFCs, Halons Spurs Switch to Substitutes,” Chemical & R-O-R; Engineering News, page 12, Nov. 15, 1993). 0012 wherein R is perfluoroalkyl and R is haloalkyl. Preferred such compounds include those of the formula: 0006 Thus, there has developed a need for substitutes or replacements for chlorinated chemicals that have been com monly used in the past. Such substitutes should exhibit one 0013 wherein R is a perfluoroalkyl preferably having at or more useful chemical or physical properties including a least about 3 carbons, most preferably from about 3 to 15 low OZone depletion potential, a boiling range Suitable for carbons, and optionally containing a catenary heteroatom Solvent cleaning applications, and high Solvency, i.e., the such as N or O; x is from about 1 to 6; y is at least one; w ability to readily dissolve or disperse organic and/or inor is in the range from 0 to about 2, X is a halogen chosen from ganic contaminants, Such as water, hydrocarbon-based com bromine, iodine, and chlorine; Z is at least one, and W-y+Z pounds, and fluorocarbon-based compounds. Preferably, is equal to 2x+1. US 2004/0O8665.0 A1 May 6, 2004 0.014. Yet another aspect of the invention relates to per component, compounds also referred to as perfluoroalkyl fluoroalkyl haloalkyl ethers, including n-CF,OCHCl, haloalkyl ethers (also referred to herein as “the ether” or “the n-CFOCHCl, and those of the general formula: ethers'). These perfluoroalkyl haloalkyl ethers can generally R-O-CHFX, be described by the formula: 0.015 wherein R is a perfluoroalkyl having at least 4 carbons and optionally containing a catenary heteroatom such as N or O; x is preferably from 1 to 2; y is at least one; 0022 wherein Rf is perfluoroalkyl and R is haloalkyl. w can be in the range from 0 to about 2, X is a halogen chosen from bromine, iodine, and chlorine; Z is at least one; 0023 Preferably, the ethers can exhibit one or more and W-y+Z is equal to 2x+1. Specific Such perfluoroalkyl useful chemical and physical properties including a boiling haloalkyl ether compounds include those of the formulas point in the range from about 25 C. to about 200 C., more c-CFOCHFXx - y w1 azs c-CF, CFOCHFXx, y - w/ azs and preferably from about 25 C. to about 125 C.; essentially no CFOCHF.X. Specific compounds include measurable flash point as determined by ASTM D3278-89; CFOCHCl, CFOCHCl, CFOCHBr, CFOCHI, acceptable toxicological properties, and high Solvency. CFOCHCICH, and CFOCHCHCl. 0024. The perfluorinated component R can be any per 0016 Yet another aspect of the invention relates to per fluorinated group able to provide a perfluoroalkyl haloalkyl fluoroalkyl haloalkyl ethers wherein the perfluoroalkyl com ether with one or more useful chemical or physical proper ponent comprises a catenary nitrogen; i.e., wherein the ties as defined herein. Useful Rf groups are described, for perfluoroalkyl component comprises a perfluorinated amine. example, in Assignee's copending U. S. Pat. No. 5,962,390, Ether-containing perfluorinated amines can be generally and incorporated herein by reference. The RF group can be described by the formula: linear, branched, cyclic, or any combination thereof, and can optionally contain one or more catenary heteroatoms Such as 0017 wherein R is a haloalkyl; R and Rare indepen oxygen or nitrogen. Examples of preferred Rf groups include dently Straight or branched perfluoroalkyl groups preferably linear or branched perfluoroalkyls having from 3 to about 15 having from 1 to 6 carbons, or are independently Straight or carbons, and perfluorocycloalkyl-containing perfluoroalkyls branched perfluoroalkylene groups preferably having from 2 having from 5 to about 15 carbons. Rf groups containing a to about 4 carbons, the perfluoroalkylene groups being perfluorocycloalkyl group can optionally contain one or bonded to each other to form a ring, and R is a linear or more Substituents, e.g., one or more perfluoroalkyl, the branched perfluoroalkylene preferably having from about 1 substituent preferably having from 1 to about 4 carbons.
Load more

Recommended publications
  • Electrophilic Agents James A
    part 1 . PART 1 concordance between cancer in humans and in experimental CHAPTER 1 animals chapter 1. Electrophilic agents James A. Bond and Ronald L. Melnick Introduction or mice and, except for ethylene chloride), the lung (sulfur mustard), oxide, sufficient evidence of carci- the lymphohaematopoietic system In this chapter, electrophilic agents nogenicity from studies of exposed (benzene, 1,3-butadiene, and eth- include direct-acting electrophilic humans. For ethylene oxide, there ylene oxide), nasal tissue (formal- chemicals and chemicals that are was limited evidence of carcinogen- dehyde), and the kidney (TCE). For metabolized to reactive electro- icity in humans, but the classification bis(chloromethyl)ether (BCME), the philes. All of the chemicals discussed of this chemical was raised to carci- lung and the nasal cavity were iden- here are IARC Group 1 agents and nogenic to humans (Group 1) based tified as target organs in humans as such can be characterized as on strong mechanistic evidence and rats, respectively. In addition, carcinogenic to humans. Relevant of mutagenicity and clastogenici- angiosarcomas of the liver, which carcinogens discussed in this chap- ty, including the induction of sister are rare tumours, were identified in ter do not include pharmaceutical chromatid exchange (SCE), chro- humans, rats, and mice exposed to drugs classified in Group 1, which mosomal aberrations (CA), and mi- vinyl chloride. otherwise typically include alkylating cronuclei (MN) in workers exposed In several instances, tumour sites cytotoxic agents. to ethylene oxide. identified in animals were not de- Tumour sites identified in previous Among this group of chemicals, tected in epidemiological studies of IARC evaluations of the carcinogen- there is remarkable concordance in exposed workers.
    [Show full text]
  • Chemical Compatibility Guide
    45678 Chemical Compatibility Guide Guide Chemical Compatibility Elastomeric Compounds Chemical Compatibility Guide HIGH-PERFORMANCE MATERIALS APPLYING THE COMPATIBILITY GUIDE Greene, Tweed offers customized-engineered components that optimize The ratings contained in this guide (see chart on the next pages) the total system. We have 100 years of experience developing high- are based on existing published data, laboratory soak tests and performance materials for a range of industries, from medical, informed decisions on the part of Greene, Tweed personnel. Most aerospace and defense, to fluid handling, oilfield and semiconductor. ratings are based on ambient temperature, low pressure and 100 We currently manufacture more than 300 unique elastomeric percent concentrations. Exposure conditions differing from stated compounds and over 300 plastic production compounds from eight conditions could affect these ratings. distinct plastic families. It is important to recognize real world differences when applying Greene, Tweed formulates a variety of compounds to meet specific laboratory and empirical information to actual field situations. Soak characteristics such as durometer, modulus, compression set, tests usually employ full immersion of the test sample, in a pure temperature, fluid compatibility, etc. Because we believe in fluid, at room temperature, without pressure or other stresses. In collaborating with customers to match the specific needs of their actual service, however, the seal is likely to experience a mixture of applications, we can customize one of our many compounds to fluids, be exposed only on one edge, be compressed in a sealing extend the performance of any process. Our engineers work side by gland and/or be subjected to process pressure, elevated tempera- side with customers to design the best solution for each individual tures and possibly abrasive particles.
    [Show full text]
  • UNITED STATES PATENT of FICE
    Patented Dec. 27, 1949 2,492,266 UNITED STATES PATENT of FICE 2,492,266 TETRAHYDRODICYCLOPENTADENE ETHER COMPOUNDS AND INSECTC DES THERE OF George Allen Buntin, Wilmington, Del, assignor to Hercules Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application October 15, 1947, Serial No. 780,102 11. Claims. (C. 16-30) 2 This invention relates to new polychloro ethers g-chloroethoxytetrahydrodicyclopentadienes were and, more particularly, to chlorinated ethers of tested for their insecticidal activity against house hydroxydihydrodicyclopentadiene and to insecti flies. In this and the following examples, the test cidal compositions containing these new products for insecticidal activity against houseflies was as the toxic ingredient. made in the following manner and is referred to It is known that ethers of hydroxydihydrodicy in this Specification as the bell jar method. clopentadiene may be obtained by the addition of Approximately 100 five-day old flies (Musca an alcohol to one of the double bonds of dicyclo domestica) were placed in a bell jar and a prede pentadiene in the presence of an acidic catalyst. termined quantity of the insecticide to be tested The remaining double bond of the dicyclopenta 10 was atomized into the bell jar. The quantity of diene ring will undergo further addition reactions, insecticide used was equal to the amount of the as with halogen, etc. These dihalo ethers, such Official Test Insecticide which was necessary to as the dichloro ether, have many valuable prop give a 30%-55% kill and must be within the lim erties but lack any insecticidal activity. its of 0.4–0.6 ml.
    [Show full text]
  • Notice of Proposed Rulemaking
    DEPARTMENT OF ENERGY AND ENVIRONMENT NOTICE OF PROPOSED RULEMAKING Water Quality Standards - 2016 Triennial Review The Director of the Department of Energy and Environment (DOEE or Department), in accordance with the authority set forth in the District Department of the Environment Establishment Act of 2005, effective February 15, 2006 (D.C. Law 16-51; D.C. Official Code § 8-151.01 et seq. (2013 Repl. and 2016 Supp.)); sections 5 and 21 of the Water Pollution Control Act of 1984, effective March 16, 1985 (D.C. Law 5-188; D.C. Official Code §§ 8-103.04 and 8-103.20 (2013 Repl. & 2016 Supp.)); and Mayor’s Order 98-50, dated April 15, 1998, as amended by Mayor’s Order 2006-61, dated June 14, 2006, hereby gives notice of the proposed rulemaking action to amend Chapter 11 (Water Quality Standards) of Title 21 (Water and Sanitation) of the District of Columbia Municipal Regulations (DCMR). The Department’s Water Quality Division is conducting a triennial review of the District of Columbia’s Water Quality Standards regulations as required by section 5(a) of the Water Pollution Control Act (D.C. Official Code § 8-103.04(a)) and section 303(c) of the federal Clean Water Act (33 U.S.C. § 1313(c)). Proposed changes to the water quality standards include updates to the aquatic life criteria for ammonia and cadmium, and human health criteria for ninety-four (94) constituents. Proposed updates to the ammonia criteria are based on EPA’s latest scientific studies and new toxicity data on freshwater mussels and gill-breathing snails in the 2013 Aquatic Life Ambient Water Quality Criteria for Ammonia – Freshwater, published by EPA (EPA 822-R-13-001).
    [Show full text]
  • Oh Epa Letter Re
    foOOOOOOs' OttoEFft Slate oi Ohio Environmental Protection Agency PO Box 1049 1800 WaterMark Dr • • vsj; " Columbus. Ohio 43266-0149 Program November 5, 1987 Cupper? Scdlcn Richard F Celeste Uove" Re: Coshocton Landfill ARARs Anthony Rutter, Project Manager Waste Management Division EPA Region 5 Records Ctr. U.S. EPA Region V 230 South Dearborn Street Chicago, Illinois 60604 242458 Dear Mr. Rutter: .»<<- This letter 1s meant to serve as amplification of my August 18, \Wa7, letter which Identified applicable or relevant and appropriate state requirements (ARAR's) for any remedial action to be taken at the Coshocton Landfill, Superfund site 1n Coshocton County, Ohio. Based on a review of the July, 1987 draft Feasibility Study, special emphasis should be given to the following applicable or relevant and appropriate state requirement for hazardous waste: 3745-50-10(A)(26) "Facility" or "hazardous waste facility" mean all contiguous land, and any structures, other appurtenances, and Improvements on the land, used for treating, storing, or disposing of hazardous waste. 3745-66-ll(A) A hazardous waste facility shall be closed 1n a manner that minimizes the need for further maintenance. 3745-66-11(8) A hazardous waste facility shall be closed 1n a manner that controls, minimizes, or eliminates, to the extent necessary to protect human health and the environment, post-closure escape of hazardous waste, hazardous waste constituents, leachate, contaminated rainfall, or waste decomposition products to the groundwater or surface water, or to the atmosphere. m5-50-10(A)(45) •Landfill" means a disposal facility or part of a facility where hazardous waste 1s placed 1n or on land and which 1s not a land treatment facility, a surface Impoundment, or an Injection well.
    [Show full text]
  • A Copper-Catalyzed Double Coupling Enables a 3-Step Synthesis of The
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue A copper-catalyzed double coupling enables a 3- step synthesis of the quassinoid core architecture† Cite this: Chem. Sci.,2019,10,768 All publication charges for this article Matthew L. Condakes, Rachel Z. Rosen, Stephen J. Harwood have been paid for by the Royal Society and Thomas J. Maimone * of Chemistry The quassinoids are a fascinating class of degraded triterpene natural products which possess, among other attributes, potent anti-cancer activity. Their complex polycyclic ring systems also serve as inspiration for the development of new chemical methods and strategies – especially those pertaining to C–C bond Received 28th August 2018 formation. Herein we disclose a novel tandem cross coupling/S 20 reaction of vicinal epoxy vinyl triflates Accepted 28th October 2018 N with simple Grignard reagents catalyzed by Cu(I). Using this transformation, the polycyclic core DOI: 10.1039/c8sc03835j architecture of the quassinoids can be generated in only three linear steps from carvone epoxide, rsc.li/chemical-science forming five carbon–carbon bonds in the process. 2 Creative Commons Attribution 3.0 Unported Licence. Introduction principle, this reaction could formally introduce two sp frag- ments in a single step and with high diastereocontrol. From the Rapid generation of molecular complexity is a major driving outset, however, we were aware of the paucity of Kumada-type force for 21st century organic synthesis, and natural products couplings of vinyl triates and Grignard reagents catalyzed by continue to provide an ideal testing ground for such explora- tion.1 In particular, the highly complex family of quassinoid natural products appears to be an area wherein novel method- ologies could lead to great synthetic simplication.
    [Show full text]
  • Bis(Chloromethyl) Ether and Chloromethyl Methyl Ether Canada
    Canadian Environmental Protection Act Priority Substances List Assessment Report Bis(Chloromethyl) Ether and Chloromethyl Methyl Ether Government Gouvernement of Canada du Canada Environment Environnement Canada Canada Health Santé Canada Canada Canada CANADA'S GREEN PLAN Canadian Environmental Protection Act PRIORITY SUBSTANCES LIST ASSESSMENT REPORT Bis(CHLOROMETHYL) ETHER AND CHLOROMETHYL METHYL ETHER Government of Canada Environment Canada Health and Welfare Canada Also available in French under the title: Loi canadienne sur la protection de l’environnement Liste des substances d’intérêt prioritaire Rapport d’évaluation Oxybis(chlorométhane) et oxyde de chlorométhyle et de méthyle CANADIAN CATALOGUING IN PUBLICATION DATA Main entry under title: Bis(chloromethyl) ether and chloromethyl methyl ether (Priority substances list assessment report) Issued also in French under title: Oxybis (chlorométhane) et oxyde chlorométhyle et de méthy1e. At head of title: Canadian Environmental Protection Act. Includes bibliographical references. ISBN 0-662-20377-1 DSS cat. no. En40-215/8E 1. Chloromethyl group -- Toxicity testing. 2. Methyl ether -- Toxicity testing. 3. Environmental monitoring – Canada. I. Canada. Environment Canada. II. Canada. Health and Welfare Canada. III. Series. TD196.C5B5 1993 363.73’84 C93-099468-X ©Minister of Supply and Services Canada 1993 Catalogue No. En 40-215/8E ISBN 0-662-20377-1 BEAUREGARD PRINTERS LIMITED Bis(Chloromethyl) Ether and Chloromethyl Methyl Ether TABLE OF CONTENTS Synopsis.............................................................................................................................
    [Show full text]
  • Propargyl Claisen Rearrangement: Allene Synthesis and Beyond David Tejedor,*A Gabriela Méndez-Abt,A Leandro Cotosa and Fernando García-Tellado*A
    Journal Name Dynamic Article Links ► Cite this: DOI: 10.1039/c0xx00000x www.rsc.org/xxxxxx ARTICLE TYPE Propargyl Claisen Rearrangement: Allene Synthesis and Beyond David Tejedor,*a Gabriela Méndez-Abt,a Leandro Cotosa and Fernando García-Tellado*a Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X DOI: 10.1039/b000000x 5 The propargyl Claisen rearrangement is a known protocol to gain access to functionalized allenes through the [3,3]-sigmatropic transformation of propargyl vinyl ethers. The correct use of appropriate propargyl vinyl ethers as starting materials coupled with suitable reaction conditions can aid in the development of new domino methodologies in which the allenes are valuable intermediates in route to a wide range of important classes of organic compounds. propargyl vinyl ethers 3 (Scheme 1). Although allenes are Introduction themselves a sought after class of organic compounds,8 they are th in many cases excellent intermediates in route to other arrays of 10 On the 100 anniversary of the discovery of the Claisen functional groups. As recent scientific literature reveals, this may rearrangement,1 most organic chemists would undoubtedly regard 45 be particularly the case for those allenes synthesized via the it as one of the fundamental reactions of the field. Classically, the aliphatic acetylenic Claisen rearrangement of appropriate starting Claisen rearrangement can be described as the [3,3]-sigmatropic materials. Indeed, a wide range of important classes of organic transformation of an allyl vinyl ether 1 into a ,-unsaturated compounds have been synthesized in this way. More importantly, 15 carbonyl compound 2 (Scheme 1). Many variations of this they are often synthesized without the need to isolate the allene reaction are known regarding the substitution pattern of the vinyl 50 intermediates, via domino reactions that always begin with the group or the introduction of an aryl group, heteroatoms (most Claisen rearrangement.
    [Show full text]
  • The Journal of Organic Chemistry 1957 Volume.22 No.3
    THE JOURNAL OF Organic Chemistry Volume 22, Number 3 by the society Ap«i 29, 1957 ____ Maxell [C ontribution p r o m t h e C h e m i c a l L aboratories o p t h e U n i v e r s i t y o p N o t r e D a m e ] Racemization of Phenylalkanes in Presence of Lewis Acids ERNEST L. ELIEL, PHILIP H. WILKEN,1 a n d FABIAN T. FANG Received September J, 1956 Optically active 2-phenylbutane racemizes rapidly and completely in the presence of aluminum chloride at 0°C. at which temperature there is little disproportionation to m- and p-di-s«c-butylbenzene. Racemization appears to be due to formation of the 2-phenyl-2-butylcarbonium ion followed by transfer of a hydride ion from a 2-phenylbutane molecule in a chain reaction, since in the presence of a,f}-dideuterocumene, substantial amounts of deuterium are transferred to the 2-phenyl­ butane. Optically active a-deuteroethylbenzene is not completely racemized under much more drastic conditions. Burwell and Shields2 3 have recently reported on d-C6H5CH(CH3)C2Hs + AlCl., + HC1 — >- the racemization of 2-phenylpentane in the pres­ C0H6 + dZ-CH3C+HC2H5 + AlCLr-— > ence of aluminum chloride. In the course of an in­ dZ-C6H6CH(CH3)C2H,, + AlCl, + HC1 (a) vestigation which was nearly complete when we d-C6H6CH(CH3)C2H6 + A id, + HC1 — > learned of the prior work of Burwell and Shields df-C6H5C+(CH3)C2H5 + AlCl«" + H2 we have confirmed and extended certain observa­ dbC6H5C+(CH3)C2H5 + d-C6H5CH(CH3)C2H6 — > tions of these authors using 2-phenylbutane and a- dZ-C6H6CH(CH3)C6H6 + dZ-C6H5C+(CH3)C2H6 (b) deuteroethylbenzene as substrates.
    [Show full text]
  • Molecular Tools for G-Protein Coupled Receptors: Synthesis
    Molecular Tools for G-Protein Coupled Receptors: Synthesis, Pharmacological Characterization and [3H]-Labeling of Subtype-selective Ligands for Histamine H4 and NPY Y2 Receptors Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften (Dr. rer. nat.) an der Fakultät für Chemie und Pharmazie der Universität Regensburg vorgelegt von Paul Baumeister aus Zinzenzell 2014 Die vorliegende Arbeit entstand in der Zeit von April 2010 bis April 2014 unter der Anleitung von Herrn Prof. Dr. Armin Buschauer am Institut für Pharmazie der Naturwissenschaftlichen Fakultät IV – Chemie und Pharmazie – der Universität Regensburg. Das Promotionsgesuch wurde eingereicht im Juni 2014. Tag der mündlichen Prüfung: 18.07.2014 Prüfungsausschuss: Prof. Dr. J. Heilmann (Vorsitzender) Prof. Dr. A. Buschauer (Erstgutachter) Prof. Dr. S. Elz (Zweitgutachter) Prof. Dr. J. Wegener (Drittprüfer) „If you don’t turn your life into a story, you just become a part of someone else’s story.“ Terry Pratchett I Danksagung An dieser Stelle möchte mich ganz herzlich bei allen bedanken, die zum Gelingen dieser Arbeit beigetragen haben und mich während der Promotionszeit begleitet haben. Besonders möchte ich danken: Meinem Doktorvater Herrn Prof. Dr. Armin Buschauer für das Vertrauen und die Möglichkeit dieses interessante und herausfordernde Projekt zu verwirklichen, seine wissenschaftlichen Anregungen, für die mir gewährte forscherische Freiheit, seine konstruktive Kritik bei der Durchsicht der Arbeit, sein stets offenes Ohr, sowie die Mentorenschaft in der Emil-Fischer-Graduiertenschule; Herrn Prof. Dr. Günther Bernhardt für seine stete Hilfsbereitschaft und sein Interesse am Fortschritt der Arbeit, sein Fachwissen, die Durchsicht der Arbeit, die Co-Mentorenschaft in der Emil-Fischer- Graduiertenschule, sowie für hervorragenden Sommerfeste; Herrn Prof. Dr.
    [Show full text]
  • Management of Hazardous Chemical Wastes at Ut Memphis
    PART I: MANAGEMENT OF HAZARDOUS CHEMICAL WASTES AT UT MEMPHIS The management of hazardous chemical waste at UT Memphis consists of the coordination and direction of the waste generated in hundreds of laboratories and other campus facilities. To manage this large program effectively, it is necessary to use the services and technical expertise of the University Committee on Safety, Security and Occupational Health, faculty, and staff members. This section describes the functions and responsibilities for hazardous chemical waste management. A. SAFETY OFFICER The Safety Officer is responsible for the administration of policy pertaining to institutional safety and health related matters. The Safety Officer oversees the administration of safety policies reporting through the Vice Chancellor for Administration. B. COMMITTEE ON SAFETY, SECURITY AND OCCUPATIONAL HEALTH The Committee on Safety, Security and Occupational Health advises the Safety Officer and Deans on matters pertaining to chemical safety within the University. The Committee periodically reviews safety guidelines and the chemical safety educational activities of the University. The Committee also advises the Safety Officer on issues relating to the criteria for development and implementation of new chemical and biological safety programs. C. SAFETY OFFICE Safety Office is responsible for surveillance of all laboratory activities involving the use of toxic agents and all additional chemical and biological problem areas within the confines of UT Memphis. Specific duties of the department include: 1. Implementation of policies set by UT Memphis. 2. Design and improvement of disposal procedures for chemical waste materials. 3. Preparation, submission and maintenance of records, reports, and manifests as required by government regulations. 4.
    [Show full text]
  • Chemical Kinetics
    CHEMICAL KINETICS EDITED BY C. H. BAMFORD M.A., Ph.D., Sc.D. (Cantab.), F.R.I.C., F.R.S. Campbell-Brown Professor of Industrial Chemistry, University of Liverpool AND C. F. H. TIPPER Ph.D. (Bristol), D.Sc. (Edinburgh) Senior Lecturer in Physical Chemistry, University of Liverpool VOLUME 5 DECOMPOSITION AND ISOMERISATION OF ORGANIC COMPOUNDS ELSEVIER PUBLISHING COMPANY AMSTERDAM - LONDON - NEW YORK 1972 Contents Preface VII Chapter 1 (K. J. LAIDLER AND L. F. LOUCKS) The decomposition and isomerization of hydrocarbons ' 1. INTRODUCTION 1 2. REACTIONS OF CYCLIC HYDROCARBONS 2 2.1 Cyclopropane 3 2.2 Substituted cyclopropanes 12 2.3 Cyclobutane 17 2.4 Substituted cyclobutanes 19 2.5 Higher cyclic paraffins 22 2.6 Cyclobutenes 22 2.7 Reactions of excited cyclic hydrocarbons 24 3. CIS-TRANS ISOMERIZATIONS ABOUT DOUBLE BONDS 28 3.1 Thermal cis-trans isomerizations 29 3.2 Catalyzed isomerizations 34 3.2.1 Photochemical isomerizations 35 3.2.2 Photosensitized isomerizations 35 3.2.3 Radiolytic isomerizations 36 4. PYROLYSIS 36 4.1 Molecular processes 41 4.2 Methane 43 4.3 Ethane 47 4.4 Propane 52 4.5 n-Butane 55 4.6 Higher paraffins 58 4.7 Ethylene 59 4.8 Propene 62 4.9 Other hydrocarbon pyrolyses 64 5. PHOTOLYSIS 64 5.1 Methane 65 5.2 Ethane 69 5.3 Propane 74 5.4 H-Butane 78 5.5 Isobutane 80 5.6 Isopentane 83 5.7 Neopentane 85 5.8 Ethylene 86 5.9 Propene 90 5.10 Cis- and fran.s-butene-2 92 5.11 Butene-1 and isobutene 94 X CONTENTS 5.12 Acetylene 95 5.13 Propyne 97 5.14 Benzene 98 5.15 Substituted benzenes 101 5.16 Cyclopropane 102 5.17 Cyclobutane 103 5.18 Cyclopentane 104 5.19 Cyclohexane 106 5.20 Methylenecycloalkanes 107 6.
    [Show full text]