DOCSLIB.ORG

N \F-'P E__ the Writer Wishes to Express His Sincere Gratitude to Dr.R

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

SOME IODINE DERIVATIVES 'OF RYDROXY&DIPHENYL Nl'HER AND RELATED C01fPOUNDS. by Harold S • Choguill ·· A. '.B. College of Emporia, 1927 Submitted to the Department of Chemistry and the Faculty of the Graduate School of the University of Kansas in partial fullfilment of the requirements for the degree of :Master of Arts • Approved by: ~~~ ~~ July 1931 Head of Department. &-n \f-'p e__ The writer wishes to express his sincere gratitude to Dr.R. Q. Brewster and Dr. F. B. Dains for their direction in this work, and for their helpful suggestions and advice~ T.A:BLE OF COMTE1fTS. INTRODUCTION ---------------- --- -- - - - - - 1 LITERAT'W'RE AND HISTORY OF HYDROXY DIPHENYL ETHERS - - - - - - - 2 4-Methoxy Diphenyl Ether ------------------- 3 4-Hyd.roxy Diphenyl Ether ------------------- 4 4-Nitro-4'-Methoxy Diphenyl Ether -------------- 5 2-Methoxy and Hydroxy Diphenyl Ethers - - - - - - - - - 6 Iodination of Diphenyl Ethers -------------- -- - 7 GENERAL METHODS OF INVESTIGATION OF HYDROXY DIPHENYL ETHERS - - -8 Methods of Analysis --------------------- 9 EXPERIMENTAL Preparation of 4-Methoxy Diphenyl Ether - - - - - - - - - - -11 Preparation of 4-Hydroxy Diphenyl Ether - - - - - - - - - - -12 Preparation of Benzoate of 4-E'ydroxy Diphenyl Ether - - - - - 13 Iodination of Benzoate of 4-Hydroxy Diphenyl Ether - - - - - -14 Hydrolysis of Benzoate of 5-Iodo-4-Hydroxy Diphenyl Ether - - 15 Proof of Structure of 4-Hydro:x:y-5-Iodo Diphenyl Ether - - - - 17 Preparation of Benzoyl Derivative of 4-.Amino Diphenyl Ether - 18 Iodination of 4-Benzoyl-Amino Diphenyl Ether - - - - - - - - -18 Hydrolysis of 4-Benzoyl-Amino-5-Iodo-Diphenyl Ether - - - -~: 20- Diazotization of 4-Amino-5-Iodo-Diphenyl Ether and Conversion to 4-Hydroxy-5-Iodo-Diphenyl Ether ----------- 21 Identity of Products of Diazotization and Dir.act Iodination - 22 Preparation of 4-Methoxy-5-Iodo-Diphenyl Ether - - - - - - - 23 Proof of Structure of 4-Methoxy-5-Iodo-Diphenyl Ether - - - - 25 Preparation of 4-Metho:x:y-5-Nitro-Diphenyl Ether - - - - - - - 25 Reduction of 4-Methoxy-5-Nitro-Diphenyl Ether - - - - - - - - 26 Preparation of Benzoyl Derivative of 5-Arnino-4-Nethoxy- Diphenyl Ether -------------------- 28 Acetyl Derivative of 4-Metho:x:y-5-.Amino-Diphenyl Ether - - - - 30 Iodination of Acetyl Derivative of 4-Metho:xy-5-Amino- Diphenyl Ether ----------------- 31 Preparation of 4-Metho:x:y-4'-Nitro-Diphe:nyl Ether - - - - - - 32 Reduction of 4-Methoxy-4'-Nitro-Diphenyl Ether - - - - - - - 34 Preparation of 4-Methoxy-4'-Iodo-Diphenyl Ether - - - -- - - 35 Preparation of 2-Methoxy Diphenyl Ether ----------- 37 Preparation of 2-Hydroxy Diphenyl Ether ----------- 39 Preparation of Acetate of 2-Hydro:x:y Diphenyl Ether - - - - - 41 Iodination of Acetate of 2-Hydroxy Diphenyl Ether - - - - - - 41 Hydrolysis of Acetate of 2-Hydroxy-Iodo-Diphenyl Ether - - - 43 Preparation of 2-Methoxy-Iodo-Diphenyl Ether - - - - - - - - 45 Treatment of 2-Methoxy-Iodo-Diphenyl Ether with Hydriodic Acid - - - - - - - - ~ - - - - - - ~ - - ~ - - - - ~ 46 Preparation of 4'-Nitro-2-Metho.xy Diphenyl'Ether - - - - - - 47 Raductuon of 4'-Nitro-2-1fethoxy Diphenyl Ether - - - - - - - 49 Acetyl Derivative of 2-Methoxy-4'-Amino-Diphenyl Ether - - - 52 SUMMARY Al'ID CONCLUSION ------------ -------- 53 Bibliography ------------ - - - - - ~ - - - - 54 1 SOME IODI1Y.E DERIVATIVES OF HYDROXY DIPHENYL ETHER AND RELATED COMPOUNDS. ImRODUCTION The work embodied in this thesis was carried out in a systematic study of some of the iodine derivatives of eertain substituted diphenyl ethers. In 1927 Harrington and Barger1 • .. i proved by synthesis that thyroxin was a derivative of diphenyl ether. r r ll Nfl~ ~o Ho- -o- e.-e..-C.... 01-\ ~ H 0r OL Since that time, study has been made to determine the active principle of that substance. The work carried on in this institution consisted in researches in ~he iodine derivatives of carbo:xy and amino diphenyl ethers. The study of the iodine derivatives of hydroxy diphenyl ether was another of this series of investi- gations. Two series of hydroxy diphenyl ethers were studied in this investigation~· Series A: Derivatives of 4-bydrolcy' diphenyl ether, or of para-phenoxy-phenol~ 0-o-O-OH 2 Series B: Derivatives of 2-hydroxy diphen;yl ether, or ortho-phenoxy phenol. Series A included study of derivatiyes of two types: those in which the substituting group entered the same benzene nucleus with the hydroxyl group; and those in which the substi- tuting group entered the other benzene nucleus than that hold- ing the hydroxyl group. As an example of the first type oA-x 0- V-GH Asan example of the secmnd type x-0-0-0-oH 3 LITERATURE AND HISTORY OF HYDROXY DIPHENYL ETHERS. 4-HYDROXY Al'ID 4-1VfETHOXY DIPHENYL ETHER In literature, three methods are given for the prep- aration of 4-llydroxy ether, two of which depend in their production from the corresponding methoxy ether. I. Diazotization of 4-amino-diphenyl ether and con- version of the amino group to hydroxyl by treatment with hot 50% sulfuric acid. II. Fusion of the alkali salt of the monomethyl ether of hydroquinone with bromobenzene at a temperature of 240° for 2ra hours, and comversion of the methoxy group to hydroxyl by refluxing the ether with anliydrous aluminum chloride in benzene solution for 2 hours. III. Fusion of the potassium salt of phenol with p-bromoani~ol~ at a temperature of 200-210° for 4 hours, and conversion to the hydroxy ether by refluxing with aluminum chloride in benzene solution for two hours. Of these methods, diazotization of 4-amino-diphenyl ether results in poor yields and a large amount of tarry mat- erial. Consequently, preparation from the corresponding methoxy derivatives is both more convenient and economical. :METHOXY-DIPHEUYL ETHER In preparation of 4-metho=cy-diphenyl ether, Robinson2 used the potassium salt of the mono-methyl ether of bydroquinone in fusion with bromobenzene, using a slight excess of the phenol ether. He describes the substance as a 4 thick yellow oil which .distills with steam. The boiling point recorded was 186° at 32rmn. One hundred per cent yields were obtained by this method. Oesterlin3 employed the potassium salt of phenol ( f2 mols) with :p-bromo-anisole. The boiling point is the same as that given for Robinson. However. Oesterlin does not give yields in his article. In this thesis, Oesterlin's method was used with a few modifications for the preparation of methoxy-diphenyl ether. The p-bromoanisole vms obtained in almost quantitative yields by the direct bromination of anisole in glacial acetic acid. 4-HYDROXY DIPHENYL ETHER. In order to obtain the corresponding hydroxy ether from 4-methoxy-diphenyl ether, Osterlin dissolved the oil in benzene, refluxing this solution with anhydrous aluminum chlor- ide for two hours. The phenol was set free from its aluminum salt with concentrated acid and the benzene layer extracted with alkali. The product was precipitated from its alkaline so- lution with hydrochloric acid. In investigation, two other methods were found to give the hydro:xy eompomid. The most successful vra.s the general method of breaking alkyl ethers by treatment with hydriodic acid. Raiford and Colbert4 found that concentrated hydro- bromic acid removed the alkyl group from alkyl-phenyl ethers, but that diphenyl ethers were unchanged by this treatment. For this reason,. bydriodic acid was employed giving almost 100% yields of hydroxy diphenyl ether, without the ·phenyl ether 5 bonding being ruptured. The other method was direct fusion of methoxy diphenyl ether with anhydrous aluminum chlorfde. This resulted in the rupture of both ether bondings contaminating the product with phenol, thus making it unsuitable. Details of the method used will be given later. Some study of had been made of 4-methoxy and 4- bydroxy-diphenyl ether in England and ·in Germany. Robinson5 nitrated 4-methoxy-diphenyl ether in glacial acetic acid solution, obtaining 3-nitro-4-methoxy-diphenyl ether. The substance erystallized from alcohol in yellowish white crystals melting at 73°. He also produced 4-hydroxy-3-nitro ether by refluxing the nitrated methoxy compound for 60 hours in a copper flask. This product was a yellow solid of melting point 51~520. It was found in later work, that the same pro~ duct could be obtained by careful fusion of 3-nitro-methoxy- diphenyl ether with aluminum chloride for 1 hour at 130°. The product obtained crystallized from petroleum ether in yellow needles, was soluble in alkali, and gave the same melting point, 520, as the compound described by Robinson~ Qsterlin6 recently carried on a stua.Y of hydroxy diphenyl ether as a source of making more complex ethers. Some of those prepared were and CH3o-Q-o-<=)ao-Q 6 4-NITR0-4LMETHOXY DIPHENYL ETHER. Oesterlin7 also studied 4-nitro-4~methox.y-diphenyl ether which he prepared by fusion of p-chloronitrobenzene with the potassium salt of the monomethyl ether of hydroquinome, according to the reaction He reduced this compound to the corresponding amine by the action of glacial acetic acid with iron powder. However, he makes no mention of the preparation of 4-bydroxy-4'-nitro- diphenyl ether; 2-METHOXY Alill HYDROXY DIPHElITL ETHER. In regard to 2-hydroxy-diphenyl ether, little work is recorded. Ullmann and Stein8 prepared 2-methoxy ether and 2-2'-dimethoxy diphenyl ether. The monomethyl ether was pre- pared by fusion of the potassium salt of gu.aiacol with bromo- benzene. A second method employed the fusion of the potassium salt of phenol with o-l>romoanisole ~ The first method gave better yields than the second. 2-Bydroxy-diphenyl ether was prepared from 2-methoxy by refluxing with anhydrous aluminum chloride in benzene solu- tion for two hours. 2-2'-Dimethoxy ether was likewise converted · to the hydroxy ether and made to diphenylene oxide. 7 IODINATION OF DIPHENYL ETHERS. A number of iodination products of diphenyl ether have • been prepared of derivatives other than the :hydroxy ether. Those prepared by Scarb~rough9 include 4-iodo-4'-nitro, 4-iodo- 4'-acetamido, 4-iodo-4'-amido, 4-4'-diiodo diphenyl ether.
Recommended publications
  • Bromobenzene D5

    Bromobenzene D5

    Safety data sheet according to Regulation (EC) No. 1907/2006 (REACH), amended by 2015/830/EU Bromobenzene D5 99,5 Atom%D article number: HN93 date of compilation: 2020-09-02 Version: 1.0 en SECTION 1: Identification of the substance/mixture and of the company/ undertaking 1.1 Product identifier Identification of the substance Bromobenzene D5 99,5 Atom%D Article number HN93 Registration number (REACH) It is not required to list the identified uses be- cause the substance is not subject to registration according to REACH (< 1 t/a) EC number 224-013-8 CAS number 4165-57-5 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified uses: laboratory chemical laboratory and analytical use 1.3 Details of the supplier of the safety data sheet Carl Roth GmbH + Co KG Schoemperlenstr. 3-5 D-76185 Karlsruhe Germany Telephone: +49 (0) 721 - 56 06 0 Telefax: +49 (0) 721 - 56 06 149 e-mail: [email protected] Website: www.carlroth.de Competent person responsible for the safety data : Department Health, Safety and Environment sheet: e-mail (competent person): [email protected] 1.4 Emergency telephone number Name Street Postal code/ Telephone Website city National Poisons Inform- Dudley Rd B187QH Birm- 844 892 0111 ation Service ingham City Hospital Emergency information service +49/(0)89 19240 SECTION 2: Hazards identification 2.1 Classification of the substance or mixture Classification according to Regulation (EC) No 1272/2008 (CLP) Classification acc. to GHS Section Hazard class Hazard class and cat- Hazard egory state- ment 2.6 flammable liquid (Flam.
  • OFR Staff Plan

    OFR Staff Plan

    Staff Briefing Package Project Plan: Organohalogen Flame Retardant Chemicals Assessment July 1, 2020 CPSC Consumer Hotline and General Information: 1-800-638-CPSC (2772) CPSC's Web Site: http://www.cpsc.gov THIS DOCUMENT HAS NOT BEEN REVIEWED CLEARED FOR PUBLIC RELEASE OR ACCEPTED BY THE COMMISSION UNDER CPSA 6(b)(1) Acknowledgments The preparation, writing, and review of this report was supported by a team of staff. We acknowledge and thank team members for their significant contributions. Michael Babich, Ph.D., Directorate for Health Sciences Charles Bevington, M.P.H., Directorate for Health Sciences Xinrong Chen, Ph.D., D.A.B.T., Directorate for Health Sciences Eric Hooker, M.S., D.A.B.T., Directorate for Health Sciences Cynthia Gillham, M.S., Directorate for Economic Analysis John Gordon, Ph.D., Directorate for Health Sciences Kristina Hatlelid, Ph.D., M.P.H., Directorate for Health Sciences Barbara Little, Attorney, Office of the General Counsel Joanna Matheson, Ph.D., Directorate for Health Sciences ii THIS DOCUMENT HAS NOT BEEN REVIEWED CLEARED FOR PUBLIC RELEASE OR ACCEPTED BY THE COMMISSION UNDER CPSA 6(b)(1) Table of Contents Briefing Memo ............................................................................................................................... iv 1. Executive summary .............................................................................................................. 5 2. Introduction .........................................................................................................................
  • Chem 353: Grignard

    Chem 353: Grignard

    GRIG.1 ORGANIC SYNTHESIS: BENZOIC ACID VIA A GRIGNARD REACTION TECHNIQUES REQUIRED : Reflux with addition apparatus, rotary evaporation OTHER DOCUMENTS Experimental procedure, product spectra INTRODUCTION In this experiment you will synthesise benzoic acid using bromobenzene to prepare a Grignard reagent, which is then reacted with carbon dioxide, worked-up and purified to give the acid. This sequence serves to illustrate some important concepts of practical synthetic organic chemistry : preparing and working with air and moisture sensitive reagents, the "work-up", extractions, apparatus set-up, etc. The synthesis utilises one of the most important type of reagents discussed in introductory organic chemistry, organometallic reagents. In this reaction, the Grignard reagent (an organomagnesium compound), phenylmagnesium bromide is prepared by reaction of bromobenzene with magnesium metal in diethyl ether (the solvent). The Grignard reagent will then be converted to benzoic acid via the reaction of the Grignard reagent with excess dry ice (solid CO2) followed by a "work-up" using dilute aqueous acid : The aryl (or alkyl) group of the Grignard reagent behaves as if it has the characteristics of a carbanion so it is a source of nucleophilic carbon. It is reasonable to represent the structure of the - + Grignard reagent as a partly ionic compound, R ....MgX. This partially-bonded carbanion is a very strong base and will react with acids (HA) to give an alkane: RH + MgAX RMgX + HA Any compound with suitably acidic hydrogens will readily donate a proton to destroy the reagent. Water, alcohols, terminal acetylenes, phenols and carboxylic acids are just some of the functional groups that are sufficiently acidic to bring about this reaction which is usually an unwanted side reaction that destroys the Grignard reagent.
  • TOXICOLOGICAL REVIEW of BROMOBENZENE (CAS No

    TOXICOLOGICAL REVIEW of BROMOBENZENE (CAS No

    EPA/635/R-07/002F www.epa.gov/iris TOXICOLOGICAL REVIEW OF BROMOBENZENE (CAS No. 108-86-1) In Support of Summary Information on the Integrated Risk Information System (IRIS) September 2009 U.S. Environmental Protection Agency Washington, DC DISCLAIMER This document has been reviewed in accordance with U.S. Environmental Protection Agency policy and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. ii CONTENTS−TOXICOLOGICAL REVIEW OF BROMOBENZENE (CAS No. 108-86-1) LIST OF TABLES......................................................................................................................... vi LIST OF FIGURES ....................................................................................................................... ix LIST OF ABBREVIATIONS AND ACRONYMS ....................................................................... x FOREWORD ................................................................................................................................. xi AUTHORS, CONTRIBUTORS, AND REVIEWERS ................................................................ xii 1. INTRODUCTION ..................................................................................................................... 1 2. CHEMICAL AND PHYSICAL INFORMATION RELEVANT TO ASSESSMENTS .......... 3 3. TOXICOKINETICS .................................................................................................................. 6 3.1. ABSORPTION ................................................................................................................
  • The Ozonolysis of Phenyl Grignard Reagent

    The Ozonolysis of Phenyl Grignard Reagent

    University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 1971 The ozonolysis of phenyl Grignard reagent Gale Manning Sherrodd The University of Montana Follow this and additional works at: https://scholarworks.umt.edu/etd Let us know how access to this document benefits ou.y Recommended Citation Sherrodd, Gale Manning, "The ozonolysis of phenyl Grignard reagent" (1971). Graduate Student Theses, Dissertations, & Professional Papers. 8297. https://scholarworks.umt.edu/etd/8297 This Thesis is brought to you for free and open access by the Graduate School at ScholarWorks at University of Montana. It has been accepted for inclusion in Graduate Student Theses, Dissertations, & Professional Papers by an authorized administrator of ScholarWorks at University of Montana. For more information, please contact [email protected]. THE OZONOLYSIS OF PHENYL GRIGNARD REAGENT By Gale M. Sherrodd B.S., Rocky Mountain College, I969 Presented in partial fulfillment of the requirements for the degree of Master of Arts for Teachers UNIVERSITY OF MONTANA 1971 Approved by: Chairman, Board of Examiners De^ , Graduate *School / n ? / Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: EP39098 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMT DiMMtstion PuWiahing UMI EP39098 Published by ProQuest LLC (2013). Copyright in the Dissertation held by the Author.
  • Polybrominated Diphenyl Ethers (Pbdes)

    Polybrominated Diphenyl Ethers (Pbdes)

    America’s Children and the Environment, Third Edition DRAFT Indicators Biomonitoring: Polybrominated diphenyl ethers (PBDEs) EPA is preparing the third edition of America’s Children and the Environment (ACE3), following the previous editions published in December 2000 and February 2003. ACE is EPA’s compilation of children’s environmental health indicators and related information, drawing on the best national data sources available for characterizing important aspects of the relationship between environmental contaminants and children’s health. ACE includes four sections: Environments and Contaminants, Biomonitoring, Health, and Special Features. EPA has prepared draft indicator documents for ACE3 representing 23 children's environmental health topics and presenting a total of 42 proposed children's environmental health indicators. This document presents the draft text, indicator, and documentation for the PBDEs topic in the Biomonitoring section. THIS INFORMATION IS DISTRIBUTED SOLELY FOR THE PURPOSE OF PRE- DISSEMINATION PEER REVIEW UNDER APPLICABLE INFORMATION QUALITY GUIDELINES. IT HAS NOT BEEN FORMALLY DISSEMINATED BY EPA. IT DOES NOT REPRESENT AND SHOULD NOT BE CONSTRUED TO REPRESENT ANY AGENCY DETERMINATION OR POLICY. For more information on America’s Children and the Environment, please visit www.epa.gov/ace. For instructions on how to submit comments on the draft ACE3 indicators, please visit www.epa.gov/ace/ace3drafts/. March 2011 DRAFT: DO NOT QUOTE OR CITE Biomonitoring: Polybrominated Diphenyl Ethers (PBDEs) 1 Polybrominated Diphenyl Ethers (PBDEs) 2 3 Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardant chemicals 4 that have been incorporated into a variety of manufactured products, including foam cushioning 5 used in furniture and plastics used in televisions and computers.
  • TOXICOLOGICAL REVIEW of BROMOBENZENE (CAS No

    TOXICOLOGICAL REVIEW of BROMOBENZENE (CAS No

    DRAFT - DO NOT CITE OR QUOTE EPA/635/R-07/002 www.epa.gov/iris TOXICOLOGICAL REVIEW OF BROMOBENZENE (CAS No. 108-86-1) In Support of Summary Information on the Integrated Risk Information System (IRIS) June 2007 NOTICE This document is an interagency review draft. It has not been formally released by the U.S. Environmental Protection Agency and should not at this stage be construed to represent Agency position on this chemical. It is being circulated for review of its technical accuracy and science policy implications. U.S. Environmental Protection Agency Washington, DC DISCLAIMER This document is a preliminary draft for review purposes only and does not constitute U.S. Environmental Protection Agency policy. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. 6/7/07 ii DRAFT – DO NOT CITE OR QUOTE CONTENTSCTOXICOLOGICAL REVIEW OF BROMOBENZENE (CAS No. 108-86-1) LIST OF FIGURES ....................................................................................................................... vi LIST OF TABLES........................................................................................................................ vii LIST OF ABBREVIATIONS AND ACRONYMS ........................................................................x FOREWORD ................................................................................................................................. xi AUTHORS, CONTRIBUTORS, AND REVIEWERS ................................................................ xii
  • Exposure and Use Assessment for Five PBT Chemicals

    Exposure and Use Assessment for Five PBT Chemicals

    EPA Document # EPA-740-R1-8002 June 2018 United States Office of Chemical Safety and Environmental Protection Agency Pollution Prevention Exposure and Use Assessment of Five Persistent, Bioaccumulative and Toxic Chemicals Peer Review Draft June 2018 Contents TABLES ................................................................................................................................................................... 7 FIGURES ................................................................................................................................................................. 7 1. EXECUTIVE SUMMARY ................................................................................................................................ 15 2. BACKGROUND ............................................................................................................................................. 15 3. APPROACH .................................................................................................................................................. 17 4. DECABROMODIPHENYL ETHER (DECABDE) .................................................................................................. 21 4.1. Chemistry and Physical-Chemical Properties ................................................................................ 21 4.2. Uses ................................................................................................................................................ 21 4.3. Characterization of Expected Environmental Partitioning
  • Certificate of Analysis

    Certificate of Analysis

    National Institute of Standards and Technology Certificate of Analysis Standard Reference Material 2257 PBDE Congeners in 2,2,4-Trimethylpentane This Standard Reference Material (SRM) is a solution of 38 polybrominated diphenyl ether (PBDE) congeners in 2,2,4-trimethylpentane. This SRM is intended primarily for use in the calibration of chromatographic instrumentation used for the determination of PBDE congeners. A unit of SRM 2257 consists of five 2 mL ampoules, each containing approximately 1.2 mL of solution. Certified Concentrations of Constituents: The certified concentration values and estimated uncertainties for the select constituents, expressed as mass fractions, are given in Table 1 along with the Chemical Abstract Service (CAS) Registry Numbers. The certified concentration values are based on results obtained from the gravimetric preparation of this solution and from the analytical results determined by using gas chromatography. A NIST certified value is a value for which NIST has the highest confidence in its accuracy in that all known or suspected sources of bias have been investigated or accounted for by NIST [1]. The measurands are the total concentrations of analytes shown on Table 1. Values are metrologically traceable to the International System of Units (SI) derived unit for mass fraction expressed as micrograms per gram. Expiration of Certification: The certification of SRM 2257 is valid, within the measurement uncertainty specified, until 31 July 2028, provided the SRM is handled and stored in accordance with the instructions given in this certificate (see “Instructions for Handling, Storage, and Use”). The certification is nullified if the SRM is damaged, contaminated, or modified.
  • And Dechlorane Plus (DP) Flame Retardants in Marine Mussels (Mytilus Galloprovincialis) Enrique Barón, Awantha Dissanayake, Judit Vila, Charlotte Crowther, James W

    And Dechlorane Plus (DP) Flame Retardants in Marine Mussels (Mytilus Galloprovincialis) Enrique Barón, Awantha Dissanayake, Judit Vila, Charlotte Crowther, James W

    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Plymouth Marine Science Electronic Archive (PlyMSEA) Subscriber access provided by UNIV OF PLYMOUTH Article Evaluation of the genotoxic and physiological effects of decabromodiphenyl ether (BDE-209) and dechlorane plus (DP) flame retardants in marine mussels (Mytilus galloprovincialis) Enrique Barón, Awantha Dissanayake, Judit Vila, Charlotte Crowther, James W. Readman, Awadhesh Jha, Ethel Eljarrat, and Damia Barcelo Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.5b05814 • Publication Date (Web): 01 Feb 2016 Downloaded from http://pubs.acs.org on February 4, 2016 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain.
  • Synthesis of Organobromines As a Tool for Their Characterisation and Environmental Occurrence Assessment

    Synthesis of Organobromines As a Tool for Their Characterisation and Environmental Occurrence Assessment

    Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment Andreas Rydén Department of Materials and Environmental Chemistry Stockholm University Stockholm 2013 i Doctoral Thesis 2013 Department of Materials and Environmental Chemistry Stockholm University SE-106 91 Stockholm Sweden Abstract Polybrominated diphenyl ethers (PBDEs) have been intensively used as flame retardants (FRs) and have become ubiquitous environmental pollutants. PBDEs form hydroxylated PBDEs (OH-PBDEs) as metabolites. Further, some OH-PBDEs and methoxy-PBDEs (MeO-PBDEs) are natural products. These are all compounds of environmental and health concern and it is therefore important to confirm their identity and to assess their environmental levels and toxicities. Hence, it is vital to obtain authentic reference standards of individual PBDEs and OH/MeO-PBDEs. The thesis main aim was to develop synthesis methods of congener specific PBDEs, OH- and MeO-PBDEs. The second aim was to identify and quantify PBDEs, OH- and MeO-PBDEs in environmental samples. The third was to propose an abbreviation system for FRs. O-Arylation of brominated phenols, using either symmetrical or unsymmetrical brominated diphenyliodonium salts, was selected for synthesis of PBDEs and OH- /MeO-PBDEs. A total of 16 MeO-PBDEs, 11 OH-PBDEs, 1 diMeO-PBDE and 1 EtO-MeO-PBDE were synthesised. Three novel unsymmetrical diaryliodonium triflates were synthesised and used in synthesis. Optimisations were made to construct a reliable general method for congener specific PBDE synthesis, which was used in the synthesis of 8 representative PBDE congeners. The products were generally characterised by electron ionisation mass spectrometry (EIMS) and nuclear magnetic resonance (NMR) spectroscopy.
  • Diphenyl and Phenyl Ether Method Number: PV2022 Target Concentration

    Diphenyl and Phenyl Ether Method Number: PV2022 Target Concentration

    Diphenyl and Phenyl ether Method number: PV2022 Target concentration: Diphenyl 0.2 ppm (1 mg/m3) OSHA TWA PEL Phenyl ether 1 ppm (7 mg/m3) OSHA TWA PEL Phenyl ether-Biphenyl mixture 1 ppm (7 mg/m3) OSHA TWA PEL Procedure: Samples are collected by drawing a known volume of air through an XAD-7 tube. Samples are desorbed with carbon disulfide and analyzed by gas chromatography with a flame ionization detector (GC-FID). Air volume and sampling rate studied: 100 minutes at 0.2 Lpm (20 L) Status of method: Partially Validated method. This method has been only partially evaluated and is presented for information and trial use. May 1988 Mary E. Eide SOLVENTS BRANCH OSHA Salt Lake Technical Center Salt Lake City UT 84115-1802 1 of 11 1 General Discussion 1.1 Background 1.1.1 History of procedure The OSHA Laboratory recently received air samples collected on XAD-7 sample tubes requesting analysis for diphenyl and phenyl ether. Desorption with carbon disulfide was tried and found to give desorption efficiencies of 99.7% for diphenyl and 98.6% for phenyl ether. Storage and retention efficiencies were similar. 1.1.2 Potential workplace exposure (Ref 5.1, 5.2, and 5.3) Diphenyl-phenyl ether mixture is used as a heat transfer agent. Diphenyl is also used as a fungistat for citrus fruit on wrappers and cardboard boxes and in organic synthesis. Phenyl ether is used in perfumes, soaps, and organic synthesis. 1.1.3 Toxic Effects (This section is for information purposes and should not be taken as the basis for OSHA policy.) (Ref 5.1 and 5.3) The mixture of diphenyl and phenyl ether is mildly irritating to skin, eyes, and mucous membranes, and can cause nausea.