DOCSLIB.ORG

OF 9-Azid0feu0aen2

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
OF 9-Azid0feu0aen2 THE M20HANISM OF- TIG K3TQNIG SCmilDT REACTION AND KIHLTICS OF THE ACID-CATALYSED REARRÂI^GEMENT OF 9-AZID0FEU0aEN2 being a thesis submitted to the University of London for the degree of Doctor of Philosophy in the Faculty of Science by John Vineent Evans, B.Sc. (Lend.) Battersea College of Technology January, 1958. C) ; ProQuest Number: 10804731 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 com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uesL ProQuest 10804731 Published by ProQuest LLO (2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLO. ProQuest LLO. 789 East Eisenhower Parkway P.Q. Box 1346 Ann Arbor, Ml 48106- 1346 ABSTRACT OF THE THESIS Fluor enone, dis solved in 96 and 100 % sulphuric acid, has been allowed to react with sodium aside and the resultant mixtures diluted with both water and anhydrous methanol • 9-Methoxyphenanthridine,the product to be expected from nucleophilic attack by the methanol,was not formed and phenanthridine was obtained in good yield from all experiments. The formation of this compound both under anhydrous conditions and in the presence of water shows Smith's mechanism for the kotonic Schmidt reaction, which involves dehydration to a Beckmann-type intermediate and subsequent rehydration, to be unlikely. l\n alternative mechanism involving a hydrogen- bonded cyclic intermediate is suggested. The rate of decomposition of 9-azidofluorene in anhydrous sulphuric-acetic acid has been followed by the measurement of the evolution of nitrogen under constant-pressure conditions. Determination of initial rates and times for half and seven-tenths reaction showed the decomposition to be substantially of the first order both in azide-concentration, with values of 1.09, 1.04, and 1.02, and in acid-strength of the solution, as given by ( negative antilogarithm of Mammetts 4cidity Function ), with values 1.03, 1.07, and 1.09 . The activation energy of the reaction, measured between 25° and 45° was found to be approximately 23.4 kcal./mole. A mechanism for the acid-catalysed rearrangement of 9-azidofluorene to phenanthridine is put forward in which reaction proceeds via the decomposition and rearrangement of the mono-protonated azide (v/hich probably exists largely as the ion-pair with bisulphate ion) present in equilibrium with the more stable non-protonatod azide. The evidence for simultaneity of rearrangement and nitrogen-release is discussed both for the above azide and for the diarylazido-methanes and -ethanes which have been investigated by McEwen and his co-workers. The work described in this Thesis was carried out in the laboratories of the Chemistry Department, Battersea Polytechnic, under the supervision of Dr. C. L. Arcus* The writer wishes to express his sincere appreciation of the help and encouragement received from Dr. C. L. Arcus. PREFACE. The subject matter of this Thesis has, for the sake of convenience, been divided into three topics, each dealt with in a separate part with its own introduction, discussion, and experimental. In addition to the intro­ ductions to each topic a general historical introduction to the work as a whole is also included. CONTENTS Historical Introduction The Schmidt and Certain Related Reactions..................... 1 The Mechanism of the Schmidt and Certain Related Reactions...2 Part I Hydration of the Ketonic Schmidt Reaction Introduction................ 24 Object of the Work ................ .25 Description of the Work............. 26 Discussion................. 28 Experimental Fluorenone, Preparation of ....... ....37 , Recovery of from Sulphuric Acid Solutions....37 , Schmidt Reaction With........ ............ ..39 , Schmidt Reaction With, Using Methanol Quenching...,.39 Sulphuric Acid 100^.................. 38 9-Methoxyphenanthridine, Preparation of Phenanthridine ............ .41 9-Chlorophenanthrid ine ...... ...42 9-Methoxyphenanthridine. ..................43 , Recovery of from a Methanol- . Sulphuric AcidMixture .......... 43 Part II A Study of the Aold-Catalysed Decomposition of 9-Azidofluorene Introduction. ........................ 45 Object of the Work ..... ..52 Description of the Investigation Preparation of Reagents and Preliminary Decomposition....53 Quantitative Rate Measurements......................... .,58 Treatment of Result s ..... .63 Sulphuric-Acetic Acid Solutions Properties of Sulphuric-Acetic Acid Solutions............ 67 Acidity Functions ................. 74 Application of Ho to Sulphuric-Acetic Acid Solutions.....78 Acidity Function and Reaction Rate........................83 Discussion Mechanism of the Decomposition of 9-Azidofluorene in Sulphuric-Acetic Acid Solution.90 Mechanics of the 9-Azidofluorene Rearrangement........... 94 Inference as to the Mechanism of thé Acid-Catalysed Reaction between Fluoren-9-ol and HN^.;.......97 Related Work............................ .102 Experimental Preparation of Reagents [l] Fluoren-9-ol ....... 112 Reduction of Fluorenone with Sodium Amalgam Reduction of Fluorenone with Aluminium Iso- Propoxide. [ II] 9-Chlorofluorene ........... 115 [ill] 9-Azidofluorene................... 115 Reaction of Sodium Azide and 9-Chlorofluorene Attempted Reaction of Hydrazoic Acid with Fluoren .-9-ol in the Presence of Trichloroacetic Acid Phenanthridine............. 117 Anhydrous Sulphuric Acid ......... .118 Anhydrous Acetic Acid........ ..121 Preliminary Acid-Catalysed Decomposition Experiments on 9-Azidofluorene.......123 Preliminary Quantitative Rate Measurements................. 127 Quantitative Rate Measurements Apparatus - - - - Gas Measuring Apparatus. ...... .127 Nitrometer Standardisât ion...... .130 Reaction Vessel ......... .132 Standardisation of Thermometers ..... .134 Standardisation of Stop-Watches..........................135 Experimental Procedure for Quantitative Runs............... 136 Treatment of Results Products of the Decomposition........... .....139 Effect of Phenanthridine on the Reaction Rate........... 143 Initial Temperature Rise................ ... *...... ......143 Init ial Gas-Evolut ion ..... *........... 146 Corrections to the Gas Volume............... .149 Calculation of Kinetic Results.......................... 150 Results of the Quantitative Rate Measurements Preliminary Rate Measurements........................... 157 Variation of Initial Azide Concentration............... 159 Variation of Sulphuric Acid Concentration..............161 Variation of Reaction Temperature,...................... 163 Individual Runs...... .165 Part III The Thermal Decomposition of 9-Azidofluorone Introduct ion...... 185 Object of the Present Work..................... ,186 Description of the Work. ...... ........187 Discussion. ................... ,188 Experimental Thermal Decomposition of 9-Azidofluorùne..............,.190 Thermal Decomposition of 9-Azidofluorene in Styrene Solution..190 Thermal Decomposition of a Styrene Solution of 9-Azid.o- flporonc in the Presence of t-Butylhydroperoxide......191 Attempted Condensation of 9-Azidofluorene with Styrene.192 Addendum to the Experimental Sections Melting-points 193 Mixed Melt ing-point s, ................ .193 Bibliography....... 194 HISTORICAL INTRODUCTION — 1 — HISTORICAL INTRODUGTION The Sclimidt and Certain Related Reactions. Whilst carrying out studies on the reactions of the imine radical in 1923, Karl Friedrich Schmidt (1, 2, 3), introduced benzophenone into a reaction mixture containing hydrazoic and sulphuric acid. A vigorous reaction ensued, yielding nitrogen and a quantitative amount of benzanilide, this being the first example of the Schmidt reaction. The latter class of reactions is now taken to cover the action o i equimolar quantities of hydrazoic acid on carbonyl compounds in the presence of strong acid*: aldehydes yield nitriles and formyl derivatives of aminesj ketones form amides. R.CO.R + HHg --- ^ R.CO.NHR + Ng R.CHO + HNg H.CO.NHR + R.CN + Ng + HgO The modified carbonyl group of a carboxylic acid is also available for reaction with hydrazoic acid in a Schmidt reaction# R.COOH + ENg —— R.NHg + COg + Ng It was in this form that the Schmidt reaction attracted most attention as it offers an alternative to the Hofmann or Curtius -2- reactlon In the degradation of a carboxylic acid to an amine with one less carbon atom. As a one stage process it was a superior method. Analogous to the Schmidt reaction is the formation of ketimines by the interaction of hydrazoic acid with certain alcohols and olefins in the presence of a strong acid. R.CHOH.R + HNg --- ^ R.CH = N,R + HgO + Ng Rg .0 = CHg + HNg R r- C - CHg + 11 N - R The large number of compounds which react with hydrazoic acid in the presence of a strong acid with the introduction of an HH group into the molecule, with or without loss of carbondioxide, has given the reaction many uses both for preparative synthesis, and as a degradation agent for the elucidation of complex structures. The Mechanism of the Sphmidt and Certain Related React]ons. The first tentative mechanism for the Schmidt reaction was put forward by K. P. Schmidt after his studies on the imine radical NH , formed by the acid decomposition of hydrazoic acid. On decomposing hydrazoic acid in the presence of concentrated sulphuric acid and
Load more

Recommended publications
  • The Air Oxidation of 4,6-Di (2-Phenyl-2-Propyl) Pyrogallol. Spectroscopic and Kinetic Studies of the Intermediates
    Carlsberg Res. Commun. Vol. 42, p. 11-25 THE AIR OXIDATION OF 4,6-DI (2-PHENYL-2-PROPYL) PYROGALLOL. SPECTROSCOPIC AND KINETIC STUDIES OF THE INTERMEDIATES. by HENRY I. ABRASH Department of Chemistry, Carlsberg Laboratory Gamle Carlsbergvej 10 - DK-2500 Copenhagen, Valby~ 1) Current address: Department of Chemistry, California State University at Northridge, Northridge, California 91324, USA Key words: 4,6-di (2-phenyl-2-propyl) pyrogallol, consecutive reactions, oxidation, oxygen, pH, quinone, semiquinone, spectra Two colored extinction bands, one with ~'max near 520 nm and the other near 770 nm, form and decay during air oxidations of 4,6-di(2-phenyl-2-propyl)pyrogallol in alkaline methanol. The 770 nm band appears to be due to the semiquinone monoanion while the extinction near 500 nm is thought to be due to both the semiquinone and 3-hydroxy-o-quinone. Although the rates of formation and decay of the two bands are indistinguishable in the presence of excess dissolved oxygen, the 770 nm band disappears slightly before the 500 nm extinction when the pyrogallol reactant is initially in excess of the dissolved oxygen. Except at high methoxide concentrations, the kinetics indicate a system of two consecutive reactions with pseudo first-order rate constants k~ and k 2. The pH' dependence of k~ indicates that the neutral pyrogallol, its monoanion and dianion all react, the rate increasing with the negative charge of the species. The k2/k~ ratio is constant at 5 from pH' 11 to 16. Extinction coefficients at both wavelengths increase with pH'. The 770 nm extinction disappears immediately after acidification while the 500 nm extinction decays at a rate consistent with oxidation.
    [Show full text]
  • Solvent Deuterium Isotope Effect on Hydrolysis of Nd3+ Ion , and As Was
    Notizen 1493 Solvent Deuterium Isotope Effect on Hydrolysis Experimental of Nd3+ Ion Reagents and apparatus A neodymium perchlorate sample solution and Mastjnobu Ma e d a *, T oshihiko A m ay a , and other reagents used were prepared and analyzed H id e t a k e K ak iha na according to the same procedures as those in the *Department of Applid Chemistry, previous papers5-6. Nagoya Institute of Technology, All the apparatus employed were the same as Gokiso, Showa-ku, Nagoya 466, Japan those in Ref. 7. Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, Preparation of a test solution O-okayama, Meguro-ku, Tokyo 152, Japan A test solution was prepared as follows. A (Z. Naturforsch. 32 b, 1493-1495 [1977]; received August 30, 1977) slightly acidic neodymium perchlorate solution, which had been freed from CO 2 by passing purified Deuterium Isotope Effect, Formation Constant, Heavy Water, Hydrolysis, Neodymium Ion N2 gas, was electrolyzed to reduce L+ ions by using a d. c. power supply until precipitates appeared. In order to saturate the solution with Nd(OL )3 precipi­ The hydrolysis equilibria of Nd3+ ion in tates the mixture was stirred with a magnetic rod light- and heavy-water solutions containing for two days. The precipitates of Nd(OL )3 were 3 mol dm -3 (Li)C104 as an ionic medium were removed by filtration with G 4 glass filters. All the studied at 25 °C by measuring the lyonium- procedures were carried out under an atmosphere ion concentration with a glass electrode. of N 2 gas in a room kept at 25 ± 1 °C.
    [Show full text]
  • Chapter 1 Chemistry of Non-Aqueous Solutions
    EFOP-3.4.3-16-2016-00014 projekt Lecture notes in English for the Chemistry of non-aqueous solutions, melts and extremely concentrated aqueous solutions (code of the course KMN131E-1) Pál Sipos University of Szeged, Faculty of Science and Informatics Institute of Chemistry Department of Inorganic and Analytical Chemistry Szeged, 2020. Cím: 6720 Szeged, Dugonics tér 13. www.u-szeged.hu www.szechenyi2020.hu EFOP-3.4.3-16-2016-00014 projekt Content Course description – aims, outcomes and prior knowledge 5 1. Chemistry of non-aqueous solutions 6 1.1 Physical properties of the molecular liquids 10 1.2 Chemical properties of the molecular liquids – acceptor and donor numbers 18 1.2.1 DN scales 18 1.2.1 AN scales 19 1.3 Classification of the solvents according to Kolthoff 24 1.4 The effect of solvent properties on chemical reactions 27 1.5 Solvation and complexation of ions and electrolytes in non-aqueous solvents 29 1.5.1 The heat of dissolution 29 1.5.2 Solvation of ions, ion-solvent interactions 31 1.5.3 The structure of the solvated ions 35 1.5.4 The effect of solvents on the complex formation 37 1.5.5 Solvation of ions in solvent mixtures 39 1.5.6 The permittivity of solvents and the association of ions 42 1.5.7 The structure of the ion-pairs 46 1.6 Acid-base reactions in non-aqueous solvents 48 1.6.1 Acid-base reactions in amphiprotic solvents of high permittivity 50 1.6.2 Acid-base reactions in aprotic solvents of high permittivity 56 1.6.3 Acid-base reactions in amphiprotic solvents of low permittivity 61 1.6.4 Acid-base reactions in amphiprotic solvents of low permittivity 61 1.7 The pH scale in non-aqueous solvents 62 1.8 Acid-base titrations in non-aqueous solvents 66 1.9 Redox reactions in non-aqueous solutions 70 2 EFOP-3.4.3-16-2016-00014 projekt 1.7.1 Potential windows of non-aqueous solvents 74 1.10 Questions and problems 77 2.
    [Show full text]
  • Total of 10 Pages Only May Be Xeroxed
    THE ACID CATALYZ D HYDROLYSIS OF M THYL ISOCYANIDE CENTRE FOR NEWFOUNDLAND STUDIES TOTAL OF 10 PAGES ONLY MAY BE XEROXED (Without Author's Permission) Y J Y lal V ( IM) 334618 THE ACID CATALYZED HYDROLYSIS OF METHYL ISOCYANIDE by © Yu-YUan Liew (Lim) A Thesis S'ubmi t ted to Memorial University of Newfoundland in partial fulfillment of the requirements for the degree of Master of Science Department of Chemistry May, 1972 ·.: '· ·. •, - i - ··.\., ACKNOWLEDGEMENT I wish to express my sju.::ere gratitude to Dr. A. R. Stein for his help, guidance and encouragement in making this investi- gation possible. I l-TOuld also like to thank Mr. D.H. Seymour for ::- the glass work, Drs. G. Ling and I. Mazurkiewicz (Department of Pharmacology, ~niversity of Ottawa) for their encouragement and help and my friends who helped make this thesis possible. I am also grateful to the National Research Council of Canada and Memorial University of Newfoundland for financial assistance. ii ·TAaLE .Of CONTENTS ACKNOWLEDGEMENT. • • • • • . • • • • • . • . • . • • . • . • . • • . • . • . • • • . • . • • • . i TABLE OF CONTENTS. • • • • • . • • . • . • • • . • . • • . • . • • . • • • . • . • • • . • • . • • . • • • . • • • • • . • i i LIST OF TABLES. • . i v LIST OF FIG'URES. • • • . • . • • • . • . • • . • . • . • . • • . • • . • . • . • . • vi ABSTRACT . .... .. ...................................... .. r • ~ ............... viii INTRODU~ .ION . ......•.•.•............ , • . • . • . 1 EXPERimNTAL. • . • . • . • . 13 1. General Considerations. • • • • • • • • • •
    [Show full text]
  • SI Analytics Ph Handbook
    pH handbook HELPFUL GUIDE FOR PRACTICAL APPLICATION AND USE Welcome to SI Analytics! We express our core competence, namely the production of analytical instruments, with our company name SI Analytics. SI also stands for the main products of our company: sensors and instruments. As part of the history of SCHOTT® AG, SI Analytics has more than 75 years experience in glass technology and in the development of analytical equipment. As always, our products are manufactured in Mainz with a high level of innovation and quality. Our electrodes, titrators and capillary viscometers will continue to be the right tools in any location where expertise in analytical measurement technology is required. In 2011 SI Analytics became part of the listed company Xylem Inc., headquartered in Rye Brook / N.Y., USA. Xylem is a leading international provider of water solutions. We look forward to presenting the pH handbook to you! The previous publication "Interesting facts about pH measurement" has been restructured, made clearer and more engaging, and extra information has been added. The focus has been consciously put on linking general information with our lab findings and making this accessible to you in a practical format. Complemented by the reference to our range of products and with practical recommendations for use with specific applications, the pH primer is an indispensable accompaniment for everyday lab work. We at SI Analytics would be happy to work successfully together with you in the future. SI Analytics GmbH Dr. Robert Reining CEO CONTENTS SECTION 1 Basic concepts of potentiometry and pH measurement 1.1 Definition of acid and base .........................................................
    [Show full text]
  • Redox-Driven Conformational Dynamics in a Photosystem-II-Inspired
    Redox-driven Conformational Dynamics in a Photosystem-II-inspired β-hairpin Maquette Determined through Spectroscopy and Simulation Hyea Hwang†,1, Tyler G. McCaslin†,2,3 Anthony Hazel4, Cynthia V. Pagba2,3 Christina M. ∗ Nevin2,3, Anna Pavlova4, Bridgette A. Barry2,3 and James C. Gumbart2,3,4, 1School of Materials Science and Engineering, 2School of Chemistry and Biochemistry, 3Petit Institute for Bioengineering and Biosciences, and 4School of Physics, Georgia Institute of Technology, Atlanta, GA 30332 † These authors contributed equally to this work. ∗ To whom correspondence should be addressed; Email: [email protected]; Phone: 404-385-0797 1 Abstract Tyrosine-based radical transfer plays an important role in photosynthesis, respiration, and DNA synthesis. Radical transfer can occur either by electron transfer (ET) or proton coupled electron transfer (PCET), depending on the pH. Reversible conformational changes in the surrounding protein matrix may control reactivity of radical intermediates. De novo designed Peptide A is a synthetic 18 amino-acid β-hairpin, which contains a single tyrosine (Y5) and carries out a kinetically significant PCET reaction between Y5 and a cross-strand histidine (H14). In Peptide A, amide II’ (CN) changes are observed in the UV resonance Raman (UVRR) spectrum, associated with tyrosine ET and PCET; these bands were attributed previously to a reversible change in secondary structure. Here, we use molecular dynamics simulations to define this conformational change in Peptide A and its H14-to-cyclohexylalanine variant, Peptide C. Three different Y5 charge states, tyrosine (YH), tyrosinate (Y–), and neutral tyrosyl radical (Y•), are considered. The simulations show that Peptide A-YH and A-Y– retain secondary structure and noncovalent interactions, whereas A-Y• is unstable.
    [Show full text]
  • B* Hydrochloric Acid And. Perchloric Acid 77
    University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Fall 1964 KINETICS AND MECHANISM OF THE PROTONOLYSIS OF CERTAIN ALLYLTINS JOSEPH ANTHONY VERDONE Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation VERDONE, JOSEPH ANTHONY, "KINETICS AND MECHANISM OF THE PROTONOLYSIS OF CERTAIN ALLYLTINS" (1964). Doctoral Dissertations. 795. https://scholars.unh.edu/dissertation/795 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. KINETICS AND MECHANISM OF THE PROTONOLYSIS OP CERTAIN ALLYLTINS BY JOSEPH ANTHONY VERDONE B.S., Lebanon Valley College, 1958 A THESIS Submitted to tbe University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy Graduate School Department of Chemistry November 1965 This thesis has been examined and approved. / 'u f * t 7 1 - ' y ■'‘'I'-- .r / v. ' A 'r J x r H ' ^ - 1 Xs\ + \uAj*- ( 3 z c c £ £ ? . ^ I T L A A (Date) ACKNOWLEDGEMENTS The author wishes to thank Dr. Henry G. Kuivila for his guidance and patience throughout the course of this work. Financial support from the Air Force Office of Scientific Research for part of this work is gratefully acknowledged. iii TABLE OP CONTENTS Page LIST OP TABLES............................. vi LIST OP F I GURES .................... .... viii I. INTRODUCTION ............................ 1 II. RESULTS AND DISCUSSION. • 6 1.
    [Show full text]
  • Natural Sulfide Minerals As Electrode Materials for Electrochemical Analysis in Dipolar Aprotic Solvents
    Int. J. Electrochem. Sci., 13 (2018) 11113 – 11135, doi: 10.20964/2018.11.74 International Journal of ELECTROCHEMICAL SCIENCE www.electrochemsci.org Review Natural Sulfide Minerals as Electrode Materials for Electrochemical Analysis in Dipolar Aprotic Solvents Zorka Stanić University of Kragujevac, Faculty of Science, Department of Chemistry, R. Domanović 12, P.O. Box 60, 34000 Kragujevac, Serbia E-mail: [email protected], [email protected] Received: 20 August 2018 / Accepted: 19 September 2018 / Published: 1 October 2018 Dipolar aprotic solvents are compounds with the relative permittivity higher than 15 and a dipole moment greater than 2 D. Solvents of this type are applied in the field of kinetic, catalytic and electrochemical studies. Many organic molecules with high molecular weight are readily dissolved in dipolar aprotic solvents. These solvents have relatively high pKS and wide-area working potential which allows the determination of a large number of compounds in them. This review was written to provide the insight of electrochemistry in non-aqueous solutions, primarily based on the characterization and application of some solid-state sensors in a non-aqueous environment. Firstly, it highlights the results obtained over many years of investigation in our laboratory with the aim to contribute to the development of pure and applied chemistry in non-aqueous solutions. The review is divided into two main parts. The first part contains a discussion of solvent properties which further basically determine their application in electrochemistry. Second part mainly deals with the characteristics and use of the natural sulfide minerals (pyrite, chalcopyrite, and arsenopyrite) as electrochemical sensors in non-aqueous solutions for different purposes.
    [Show full text]
  • Solvolytic Displacement Reactions Burns Lab
    Bálint Gál Solvolytic displacement reactions Burns Lab Outline Key players 1. Brief history and current picture of displacement reactions 2. Neighboring group participation (halogens) 3. Salt effects and ion pairs 4. Role of the solvent Key references • “Ion pairing in nucleophilic substitution reactions.” Eugene Kwan, April 2014 • “Medium effects on the rates and mechanisms of solvolytic reactions." Bentley, T.W.; Schleyer, P.v.R. Advances in Physical Organic Chemistry 1977, 14, 1-67 • “Ions and ion pairs in solvolysis reactions”. Raber, D.J.; S. Winstein A. Streitweiser P. v. R. Schleyer Harris, J.M.; Schleyer, P.v.R. Advances in Physical Organic UCLA Berkeley (Princeton, Erlangen, Chemistry. 1972, 2, 248-274. Georgia) • “Solvolytic displacement reactions.” Streitweiser A. Chem. Rev. 1956, 56, 571 Definition of solvolysis First introduced by Steigman and Hammett for first-order Winstein S. JACS series nucleophilic displacements by solvent present in large excess. “The role of neighboring groups in displacement reactions.” They also noted the “strange” tendency of rates: tertiary > “Correlation of solvolysis rates.” secondary > primary. “Salt effects and ion pairs in solvolysis and related reactions.” Steigman, J. and Hammett, L. P. JACS 1937, 59, 2536 This is a large field, this presentation will focus on mechanistic IUPAC definition. “Generally, reaction with a solvent, or with studies most relevant to dihalide solvolysis. a lyonium ion or lyate ion involving the rupture of one or more bonds in the reacting solute. More specifically the term is used for substitution elimination and fragmentation reactions in which a solvent species is the nucleophile ('alcoholysis' if the solvent is an alcohol, etc.).” Bálint Gál Solvolytic displacement reactions Burns Lab Hughes-Ingold Scheme Winstein’s modification to the SN1 mechanism involves contact The classical mechanism details two limiting mechanisms (SN1 ion pairs and solvent-separated ion pairs.
    [Show full text]
  • Electrochemistry in Nonaqueous Solutions Related Titles
    Kosuke Izutsu Electrochemistry in Nonaqueous Solutions Related Titles Endres, F., MacFarlane, D., Abbott, A. (eds.) Electrodeposition from Ionic Liquids 2008 ISBN: 978-3-527-31565-9 Eftekhari, A. (ed.) Nanostructured Materials in Electrochemistry 2008 ISBN: 978-3-527-31876-6 Hamann, C. H., Hamnett, A., Vielstich, W. Electrochemistry Second, Completely Revised and Updated Edition 2007 ISBN: 978-3-527-31069-2 Kosuke Izutsu Electrochemistry in Nonaqueous Solutions Second, Revised and Enlarged Edition The Author All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Prof. Dr. Kosuke Izutsu publisher do not warrant the information contained 4-31-6-208 Kichijoji-honcho in these books, including this book, to be free of Musashino 180-0004 errors. Readers are advised to keep in mind that Japan statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de. # 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
    [Show full text]
  • Glossary of Terms Used in Physical Organic Chemistry
    PUre & AppL. Chem,, Vol. 51, pp. 1725-1801. 0033-4545/79/0801-1725 $02.00/0 Pergamon Press Ltd. 1979. Printed in Great Britain. ©IUPAC PROVISIONAL INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY ORGANIC CHEMISTRY DIVISION COMMISSION ON PHYSICAL ORGANIC CHEMISTRY* GLOSSARY OF TERMS USED IN PHYSICAL ORGANIC CHEMISTRY Compiled and Edited by VICTOR GOLD Comments on these proposals should be sent within 8 months of Publication to the S=etary of the Commission: Dr. J. R. PENTON Technisch-Chenmches Laboratorium der EidgenOssischen Technischen Hochschule Zürich Universitlltstrasse 6 CH-8092 Zürich, Switzerland Comments from the viewpoint of languages other than English are encouraged. These may have special significance regarding the eventual publication in various countries of translations of the nomenclature finally approved by IUPAC. *The mernbership of the Commission during the period in which this Glossary was prepared was as follows: J. F. DUNNETT (Titular Mernber, 1973-79; Chairman, 1978-; USA) A. R. H. COLE (Associate Member, 1974-79; Australia) V. GOLD (Titular Mernber, 1973·79; UK) R. D. GUTHRJE (Associate Mernber, 1977-81; USA) G.ILLUMINATI (Titular Mernber, 1977-81; ltaly) R. A. Y. JONES(AssociateMernber,l977-81; UK) J. MARCH(AssociateMernber,1977-81; USA) J. R. PENTON (Titular Mernber and Secretary, 1973·79; Switzerland) M. J. PERKINS (Titular Mernber, 1977-81; UK) J. REEDIJK (AssociateMernber,1977-81; Netherlands) C. RÜCHARDT (Titular Mernber, 1973-77; Federal Republic ofGermany) K. SCHWETLICK (Titular Mernber, 1977-81; German Dernocratic Republic) A. STREITWIESER(Titular Member, 1973-77; Associate Mernber, 1977-81; USA) J. TOUL!,l!C (TitularMernber,l973-79; France) H. ZOLLINGER (Titular Mernber, 1973-79; Chairman, 1973-78; Switzerland) CONTRIBUTORS TO THE GLOSSARY w.
    [Show full text]
  • Autoprotolysis Constants Aqueous Organic
    Pure & App!. Chem., Vol. 59, No. 12, pp. 1693—1702, 1987. Printed in Great Britain. © 1987 IUPAC INTERNATIONALUNION OF PURE AND APPLIED CHEMISTRY ANALYTICAL CHEMISTRY DIVISION COMMISSION ON ELECTROANALYTICAL CHEMISTRY* AUTOPROTOLYSIS CONSTANTS IN NONAQUEOUS SOLVENTS AND AQUEOUS ORGANIC SOLVENT MIXTURES Prepared for publication by S. RONDININI, P. LONGHI, P. R. MUSSINI AND T. MUSSINI Department of Physical Chemistry and Electrochemistry, University of Milan, 1-20133 Milano, Italy * Membershipof the Commission during the preparation of the report (1985—1987) was as follows: Chairman: K. Izutsu (Japan); Vice-Chairman: E. Pungor (Hungary); Secretary: M. Senda (Japan); Titular Members: J. Buffle (Switzerland); J. Juillard (France); K. M. Kadish (USA); R. Kalvoda (Czechoslovakia); Associate Members: A. K. Covington (UK); W. Davison (UK); R. A. Durst (USA); M. Gross (France); H. Kao (China); R. C. Kapoor (India); H. P. van Leeuven (Netherlands); Y. Marcus (Israel); T. Mussini (Italy); J. G. Osteryoung (USA); N. Tanaka (Japan); K. Tóth (Hungary); National Representatives: G. E. Batley (Australia); B. Gilbert (Belgium); W. C. Purdy (Canada); A. A.Vlek (Czechoslovakia); H. B. Nielsen (Denmark); H. Monien (FRG); M. L'Her (France); Gy. Farsang (Hungary); G. Prabhakara Rao (India); W. F. Smyth (Ireland); E. Grushka (Israel); S. R. Cavallari (Italy); W. Frankvoort (Netherlands); Z. Galus (Poland); G. Johans- son (Sweden); M. L. Berkem (Turkey); H. Thompson (UK); J. Jordan (USA); I. Piljac (Yugoslavia). Republication of this report is permitted without the need for formal JUPAC permission on condition that an acknowledgement, with full reference together with IUPAC copyright symbol (© 1987 IUPAC), is printed. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant JUPAC National Adhering Organization.
    [Show full text]