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Mechanistic Insights Into the Hydrocyanation Reaction
Mechanistic insights into the hydrocyanation reaction Citation for published version (APA): Bini, L. (2009). Mechanistic insights into the hydrocyanation reaction. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR644067 DOI: 10.6100/IR644067 Document status and date: Published: 01/01/2009 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. -
An Aged Reaction Revisited
TETRAHEDRON Pergamon Tetrahedron 56 (2000) 9705±9711 2-Alkyl-4,6-dialkylamino-1,3,5-triazines via Grignard Alkylation of Cyanuric Chloride: An Aged Reaction Revisited Rita Menicagli,* Simona Samaritani and Valeria Zucchelli Dipartimento di Chimica e Chimica Industriale and Centro di Studi del CNR per le Macromolecole Stereordinate ed Otticamente Attive, Via Risorgimento 35, 56126 Pisa, Italy Received 24 July 2000; revised 8 September 2000; accepted 28 September 2000 AbstractÐSuitable one-pot reaction conditions are suggested to prepare, in good overall yields, some 2-(alk-1 0-ynyl)- and 2-alkyl-4,6- dialkylamino-1,3,5-triazines via reaction of cyanuric chloride with Grignard reagents followed by amination. q 2000 Elsevier Science Ltd. All rights reserved. In our studies1 concerning the protection of paper against The reaction between a benzene (CAUTION) solution of 1 pathogenic fungi, we found that 2-(alk-1 0-ynyl)-4,6- and a THF solution of alk-1 0-ynylmagnesium halides has dimethoxy-1,3,5-triazines showed an appreciable biostatic been reported to afford 2-(alk-1 0-ynyl)-4,6-dichloro-1,3,5- activity.2 Taking into account that alkylamino derivatives of triazines in 50±60% yield.6a Since the puri®cation of these 1,3,5-triazine are generally better biostatic agents than intermediates might have caused an appreciable loss of the alkoxy derivatives,1 preparation of 2-(alk-1 0-ynyl)-4,6- product owing to the well known8 reactivity of the C±Cl dialkylamino-1,3,5-triazines was necessary in order to bonds and the treatment of the crude products with nucleo- compare their antifungal activities with those of 2-(alk-1 0- philes would have lead to complex mixtures of compounds, ynyl)-4,6-dimethoxy-1,3,5-triazines. -
Numerical Simulation of a Two-Phase Flow for the Acrylonitrile Electrolytic Adiponitrile Process in a Vertical/Horizontal Electrolysis Cell
energies Article Numerical Simulation of a Two-Phase Flow for the Acrylonitrile Electrolytic Adiponitrile Process in a Vertical/Horizontal Electrolysis Cell Jiin-Yuh Jang * and Yu-Feng Gan Department of Mechanical Engineering, National Cheng-Kung University, Tainan 70101, Taiwan; [email protected] * Correspondence: [email protected]; Tel.: +886-6-2088573 Received: 7 September 2018; Accepted: 6 October 2018; Published: 12 October 2018 Abstract: This paper investigated the effect of oxygen holdup on the current density distribution over the electrode of a vertical/horizontal electrolysis cell with a two-dimensional Eulerian–Eulerian two-phase flow model in the acrylonitrile (AN) electrolytic adiponitrile (ADN) process. The physical models consisted of a vertical/horizontal electrolysis cell 10 mm wide and 600 mm long. The electrical potential difference between the anode and cathode was fixed at 5 V, which corresponded to a uniform current density j = 0.4 A/cm2 without any bubbles released from the electrodes. The effects of different inlet electrolyte velocities (vin = 0.4, 0.6, 1.0 and 1.5 m/s) on the void fraction and the current density distributions were discussed in detail. It is shown that, for a given applied voltage, as the electrolyte velocity is increased, the gas diffusion layer thickness decreased and this resulted in the decrease of the gas void fraction and increase of the corresponding current density; for a given velocity, the current density for a vertical cell was higher than that for a horizontal cell. Furthermore, assuming the release of uniform mass flux for the oxygen results in overestimation of the total gas accumulation mass flow rate by 2.8% and 5.8% and it will also result in underestimation of the current density by 0.3% and 2.4% for a vertical cell and a horizontal cell, respectively. -
Industry Compliance Programme
Global Chemical Industry Compliance Programme GC-ICP Chemical Weapons Convention December 2006 Version 1.0 GLOBAL CHEMICAL INDUSTRY COMPLIANCE PROGRAMME FOR IMPLEMENTING THE CHEMICAL WEAPONS CONVENTION The purpose of the handbook is to provide guidance to chemical facilities, traders and trading companies in developing a Global Chemical Industry Compliance Programme (GC-ICP) to comply with the Chemical Weapons Convention (CWC). The GC-ICP focuses first on determining if there is a reporting requirement to your National Authority and second on collecting the relevant support data used to complete the required reports. The GC-ICP is designed to provide a methodology to comply with the CWC and establish systems that facilitate and demonstrate such compliance. Each facility/company should also ensure that it follows its country’s CWC specific laws, regulations and reporting requirements. • Sections 2, 3, and 4 guide you through the process of determining if chemicals at your facility/ company should be reported to your National Authority for compliance with the CWC. • Section 5 provides recommended guidance on information that you may use to determine your reporting requirements under the CWC and administrative tools that your facility/company may use to ensure compliance with the CWC. • Section 6 provides a glossary of terms and associated acronyms. • Section 7 provides a listing of all National Authorities by country. CWC Global Chemical Industry Compliance Programme 1 TABLE OF CONTENTS Section 1 Overview What is the Chemical Weapons Convention? -
Transport of Dangerous Goods
ST/SG/AC.10/1/Rev.16 (Vol.I) Recommendations on the TRANSPORT OF DANGEROUS GOODS Model Regulations Volume I Sixteenth revised edition UNITED NATIONS New York and Geneva, 2009 NOTE The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. ST/SG/AC.10/1/Rev.16 (Vol.I) Copyright © United Nations, 2009 All rights reserved. No part of this publication may, for sales purposes, be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, electrostatic, magnetic tape, mechanical, photocopying or otherwise, without prior permission in writing from the United Nations. UNITED NATIONS Sales No. E.09.VIII.2 ISBN 978-92-1-139136-7 (complete set of two volumes) ISSN 1014-5753 Volumes I and II not to be sold separately FOREWORD The Recommendations on the Transport of Dangerous Goods are addressed to governments and to the international organizations concerned with safety in the transport of dangerous goods. The first version, prepared by the United Nations Economic and Social Council's Committee of Experts on the Transport of Dangerous Goods, was published in 1956 (ST/ECA/43-E/CN.2/170). In response to developments in technology and the changing needs of users, they have been regularly amended and updated at succeeding sessions of the Committee of Experts pursuant to Resolution 645 G (XXIII) of 26 April 1957 of the Economic and Social Council and subsequent resolutions. -
Nomenclature Worksheet Part 2-Binary Molecular Compounds
Nomenclature Worksheet Part 2-Binary Molecular Compounds. When two different elements combine, they form a binary compound. We have seen some ionic binary compounds such as sodium chloride, NaCl, or copper(II) oxide, CuO. But, non-metals can also form binary compounds, the most famous of which is water, H2O. We have learned how to name binary ionic compounds. In this worksheet, we will practice naming binary molecular compounds. Binary molecular compounds are held together by covalent bonds. As in ionic compounds, the more metallic element is listed first, and the less metallic is listed second. This coincides with the concept of electronegativity (and the converse, electropositivity) that we discussed in class. So, another way of stating this is the more electropositive element is written first followed by the more electronegative element. An example of this is SF6, Notice that sulfur is more electropositive than fluoride and is written first. If both elements are in the same group, the element with the higher period number goes first. We see this in the formulas of SO2 and IBr. Binary molecular compounds differ from ionic compounds in a key way: we can’t use charge to name the compound. So how will we distinguish CO2 from CO, NO2 from N2O? We will use need a different system from ionic nomenclature. In ionic nomenclature, we use charges and the position on the periodic table to indicate the number and types of ions in the compounds. The charges are whole numbers. Binary molecules can have fractional charges and multiple compounds for the combination of elements. -
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. -
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 -
CHEM 1000 Practice Final a (Answers)
1 Name: ________________________ Student Number: _____________________ Chemistry 1000 Practice Final Exam A Based on Fall 2009 Test (Content Updated to Fall 2012 Curriculum) INSTRUCTIONS 1) Read the exam carefully before beginning. There are 19 questions on pages 2 to 12 followed by 2 pages of “Data Sheet” (including periodic table) and a blank page for any rough work. Please ensure that you have a complete exam. If not, let an invigilator know immediately. All pages must be submitted at the end of the exam. 2) If your work is not legible, it will be given a mark of zero. 3) Marks will be deducted for incorrect information added to an otherwise correct answer. 4) You may use a calculator. 5) Show your work for all calculations. Answers without supporting calculations will not be given full credit. 6) Marks will be deducted for improper use of significant figures and for numerical answers with incorrect/missing units. 7) Do not open the exam until you are told to begin. Beginning prematurely will result in removal of your exam paper and a mark of 0. 8) You have 3 hours to complete this exam. Nobody may leave the exam room during the first hour or the last 15 minutes of the exam. Q Mark Q Mark 1 / 23 11 / 7 2 / 3 12 / 9 3 / 5 13 / 8 4 / 3 14 / 3 5 / 3 15 / 4 6 / 2 16 / 10 7 / 4 17 / 6 8 / 3 18 / 2 9 / 12 19 / 1 10 / 2 Total / 110 2 Name: ________________________ Student Number: _____________________ 1. -
Anaerobic Degradation of Methanethiol in a Process for Liquefied Petroleum Gas (LPG) Biodesulfurization
Anaerobic degradation of methanethiol in a process for Liquefied Petroleum Gas (LPG) biodesulfurization Promotoren Prof. dr. ir. A.J.H. Janssen Hoogleraar in de Biologische Gas- en waterreiniging Prof. dr. ir. A.J.M. Stams Persoonlijk hoogleraar bij het laboratorium voor Microbiologie Copromotor Prof. dr. ir. P.N.L. Lens Hoogleraar in de Milieubiotechnologie UNESCO-IHE, Delft Samenstelling promotiecommissie Prof. dr. ir. R.H. Wijffels Wageningen Universiteit, Nederland Dr. ir. G. Muyzer TU Delft, Nederland Dr. H.J.M. op den Camp Radboud Universiteit, Nijmegen, Nederland Prof. dr. ir. H. van Langenhove Universiteit Gent, België Dit onderzoek is uitgevoerd binnen de onderzoeksschool SENSE (Socio-Economic and Natural Sciences of the Environment) Anaerobic degradation of methanethiol in a process for Liquefied Petroleum Gas (LPG) biodesulfurization R.C. van Leerdam Proefschrift ter verkrijging van de graad van doctor op gezag van de rector magnificus van Wageningen Universiteit Prof. dr. M.J. Kropff in het openbaar te verdedigen op maandag 19 november 2007 des namiddags te vier uur in de Aula Van Leerdam, R.C., 2007. Anaerobic degradation of methanethiol in a process for Liquefied Petroleum Gas (LPG) biodesulfurization. PhD-thesis Wageningen University, Wageningen, The Netherlands – with references – with summaries in English and Dutch ISBN: 978-90-8504-787-2 Abstract Due to increasingly stringent environmental legislation car fuels have to be desulfurized to levels below 10 ppm in order to minimize negative effects on the environment as sulfur-containing emissions contribute to acid deposition (‘acid rain’) and to reduce the amount of particulates formed during the burning of the fuel. Moreover, low sulfur specifications are also needed to lengthen the lifetime of car exhaust catalysts. -
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. -
Purification and Characterization of a Novel Nitrilase of Rhodococcus
JOURNAL OF BACTERIOLOGY, Sept. 1990, p. 4807-4815 Vol. 172, No. 9 0021-9193/90/094807-09$02.00/0 Copyright X3 1990, American Society for Microbiology Purification and Characterization of a Novel Nitrilase of Rhodococcus rhodochrous K22 That Acts on Aliphatic Nitriles MICHIHIKO KOBAYASHI,* NORIYUKI YANAKA, TORU NAGASAWA, AND HIDEAKI YAMADA Department ofAgricultural Chemistry, Faculty ofAgriculture, Kyoto University, Sakyo-ku, Kyoto 606, Japan Received 18 April 1990/Accepted 8 June 1990 A novel nitrilase that preferentially catalyzes the hydrolysis of aliphatic nitriles to the corresponding carboxylic acids and ammonia was found in the cells of a facultative crotononitrile-utilizing actinomycete isolated from soil. The strain was taxonomically studied and identified as Rhodococcus rhodochrous. The nitrilase was purified, with 9.08% overall recovery, through five steps from a cell extract of the stain. After the last step, the purified enzyme appeared to be homogeneous, as judged by polyacrylamide gel electrophoresis, analytical centrifugation, and double immunodiffusion in agarose. The relative molecular weight values for the native enzyme, estimated from the ultracentrifugal equilibrium and by high-performance liquid chromatog- raphy, were approximately 604,000 + 30,000 and 650,000, respectively, and the enzyme consisted of 15 to 16 subunits identical in molecular weight (41,000). The enzyme acted on aliphatic olefinic nitriles such as crotononitrile and acrylonitrile as the most suitable substrates. The apparent Km values for crotononitrile and acrylonitrile were 18.9 and 1.14 mM, respectively. The nitrilase also catalyzed the direct hydrolysis of saturated aliphatic nitriles, such as valeronitrile, 4-chlorobutyronitrile, and glutaronitrile, to the correspond- ing acids without the formation of amide intermediates.