Transformation of 2-Butene Into Propene on WO3/MCM-48: Metathesis and Isomerization of N-Butene
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Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture 2005)**
NOBEL LECTURES DOI: 10.1002/adsc.200600523 Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture 2005)** Robert H. Grubbsa,* a Victor and Elizabeth Atkins Professor of Chemistry Arnold and Mabel Beckman Laboratories of Chemical Synthesis California Institute of Technology, Pasadena, CA 91125, USA Fax : (+1)-626–564–9297 [**] Copyright The Nobel Foundation 2005. We thank the Nobel Foundation, Stockholm, for permission to print this lecture Received: February 21, 2006 This is a story of our exploration of the olefin-meta- ly added to this reaction, 1-butene was again ob- thesis reaction, a reaction that has been the major served. This discovery has since served as the founda- emphasis of my independent research. As with all sto- tion for an amazing array of nickel chemistry and cat- ries of scientific discovery, there are three compo- alysis. In addition, as nickel had been found to possess nents: the discoveries, the resulting applications, and, unexpected reactivity, other metal salts were also in- perhaps the most important of all, the people in- vestigated. In particular, when titanium and zirconium volved. Starting from observations made from seem- halides were used in combination with alkyl alumi- ingly unrelated work, our investigations into the fun- num compounds, a new form of polyethylene was ob- damental chemistry of this transformation have been tained. Natta further demonstrated that similar cata- an exciting journey, with major advances often result- lysts could promote the formation of stereoregular ing from complete surprises, mistakes, and simple in- polymers from propylene. The 1963 Nobel Prize in tuition. Ultimately, these efforts have contributed to Chemistry was awarded to Ziegler and Natta for this olefin metathesis becoming the indispensable synthet- work. -
Part I: Carbonyl-Olefin Metathesis of Norbornene
Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis……………………………………………………………. -
Butenes Separation, Supp. A
PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California 94025 Abstract Process Economics Program Report No. 71A BUTTLENES (October 1982) Demand is fast increasing for lsobutylene, especially that used in manufacturing methyl tertiary-butyl ether, and for high purity butene-1 to use as a copolymer in linear low density polyethylene. Because of their wide availability, mixed butane-butylene streams from oleflns plants and petroleum refineries are being increasingly fed to plants to separate butylenes for use in chemicals. This first supplement to Report No. 71 updates demand projections, production capacities, and separation techniques for high purity butene-1 and lsobutylene. The processes that are now available for separating and purifying both butene-1 and lsobutylene from mixed butyl- ene streams are evaluated and compared. Other procedures for obtaining butylenes, such as dehydrogenatlon, lsomerleatlon, and disproportion&ion, are not updated in this report. PEP’81 JLC Report No. 71A - BUTYLENES SUPPLEMENT A by JOHN L. CHADWICK I I October 1982 f-F0 0 A private report by the m PROCESS ECONOMICS PROGRAM 0 Menlo Park, California 94025 0 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICALECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLDPETROCHEMICALS Program covers major hkdrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORYOF CHEMICALPRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe. ii CONTENTS 1 INTRODUCTION . 1 2 SUMMARY . -
Wacker Oxidation ~Anti-Markovnikov~
Anti-Markovnikov Olefin Functionalization ~Prof. Robert H. Grubbs’ Work~ 4th Literature Seminar July 5, 2014 Soichi Ito (D1) Contents 1. Introduction • Flow of Prof. Grubbs’ Research • Markovnikov’s Rule • Wacker Oxidation 2. Grubbs’ Work • Substrate-Controlled Wacker Oxidation • Catalyst-Controlled Wacker-Type Oxidation 2 Introduction ~Flow of Research~ Olefin Metathesis Anti-Markovnikov Wacker Oxidation of Terminal Olefin Substrate-Controlled Wacker Oxidation of Internal Olefin Z-Selective Metathesis Hydration Ethenolysis + Reduction Hydroamination Z-Selective Ethenolysis Catalyst-Controlled Decarbonylative Dehydration Hydrophosphonation Production of Terminal Olefin Functionalization of Terminal Olefin 3 Introduction ~Markovnikov’s Rule~ Two-Step Two-Step (+1C) 4 Robert H. Grubbs et al. Science, 2011, 333, 1609. Anti-Markovnikov Hydration of Olefins • One-Step William C. Trogler et al. Science 1986, 233, 1069. This work was difficult to reproduce. Inorg. Chem. 1988, 27, 3151. • One-Step with Activated Olefins Robert G. Bergman and F. Dean Toste et al. J. Am. Chem. Soc. 2003, 125, 8696. Ben L. Feringa and Gerard Roelfes et al. Nat. Chem. 2010, 2, 991. • Three-Step 5 Shannon S. Stahl et al. J. Am. Chem. Soc. 2010, 132, 15116. Anti-Markovnikov Wacker Oxidation / Reduction Strategy Oxidation cycle must be compatible with the reduction cycle. aldehyde-selective Wacker Oxidation 6 Robert H. Grubbs et al. Science, 2011, 333, 1609. Introduction ~Wacker-Tsuji Oxidation~ • 1894 F. C. Phillips reported stoichiometric reaction. • 1959 J. Smidt et al. reported the Wacker process. (oxidation of ethylene to acetaldehyde) Investigations for convenient laboratory methods • 1976 J. Tsuji et al. reported PdCl2, CuCl / DMF, H2O method. “Terminal alkenes may be viewed as masked ketones.” 7 Jacques Muzart Tetrahedron 2007, 63, 7505. -
Removal of NO and SO2 by Pulsed Corona Discharge Process
Korean J. Chem. Eng., 18(3), 308-316 (2001) Removal of NO and SO2 by Pulsed Corona Discharge Process Young Sun Mok†, Ho Won Lee, Young Jin Hyun, Sung Won Ham*, Jae Hak Kim** and In-Sik Nam** Department of Chemical Engineering, Cheju National University, Ara, Cheju 690-756, Korea *Department of Chemical Engineering, Kyungil University, Hayang, Kyungbuk 712-701, Korea **Department of Chemical Engineering, Pohang University of Science & Technology, Pohang, Kyungbuk 790-784, Korea (Received 6 September 2000 • accepted 9 March 2001) − Abstract Overall examination was made on the removal of NO and SO2 by pulsed corona discharge process. The mechanism for the removal of NO was found to largely depend on the gas composition. In the absence of oxygen, most of the NO removed was reduced to N2; on the other hand, oxidation of NO to NO2 was dominant in the presence of oxygen even when the content was low. Water vapor was an important ingredient for the oxidation of NO2 to nitric acid rather than that of NO to NO2. The removal of NO only slightly increased with the concentration of ammonia while the effect of ammonia on the removal of SO2 was very significant. The energy density (power delivered/feed gas flow rate) can be a measure for the degree of removal of NO. Regardless of the applied voltage and the flow rate of the feed gas stream, the amount of NO removed was identical at the same energy density. The production of N2O increased with the pulse repetition rate, and the presence of NH3 and SO2 enhanced it. -
INF.20 Economic Commission for Europe Inland Transport Committee Definition Of
INF.20 Economic Commission for Europe Inland Transport Committee Working Party on the Transport of Dangerous Goods 6 March 2012 Joint Meeting of the RID Committee of Experts and the Working Party on the Transport of Dangerous Goods Bern, 19–23 March 2012 Item 5(a) of the provisional agenda Proposals for amendments to RID/ADR/ADN: pending issues Definition of LPG Transmitted by the Government of Switzerland We have observed contradictions in the definition of LPG adopted by the Joint Meeting at its Autumn 2010 session (ECE/TRANS/WP.15/AC.1/120, Annex II) as well as in the German translation we have discussed in Erfurt during the Conference of translation and edition of the German ADR. The actual definitions in each language are the following: ""Gaz de pétrole liquéfié (GPL)", un gaz liquéfié à faible pression contenant un ou plusieurs hydrocarbures légers qui sont affectés aux numéros ONU 1011, 1075, 1965, 1969 ou 1978 seulement et qui est principalement constitué de propane, de propène, de butane, des isomères du butane, de butène avec des traces d’autres gaz d’hydrocarbures. “‘Liquefied Petroleum Gas (LPG)’ means a low pressure liquefied gas composed of one or more light hydrocarbons which are assigned to UN Nos. 1011, 1075, 1965, 1969 or 1978 only and which consists mainly of propane, propene, butane, butane isomers, butene with traces of other hydrocarbon gases. „Flüssiggas (LPG)*: Unter geringem Druck verflüssigtes Gas, das aus einem oder mehreren leichten Kohlenwasserstoffen besteht, die nur der UN-Nummer 1011, 1075, 1965, 1969 oder 1978 zugeordnet sind und das hauptsächlich aus Propan, Propen, Butan, Butan-Isomeren und Buten mit Spuren anderer Kohlenwasserstoffgase besteht.“ One important point is different between French from one side and English and German from the other side, that is that in French the repetition of the “de” in the enumeration of possible gases brings to the conclusion that the main constituent of the LPG is one of the listed gases. -
Supplement of Compilation and Evaluation of Gas Phase Diffusion Coefficients of Reactive Trace Gases in the Atmosphere
Supplement of Atmos. Chem. Phys., 15, 5585–5598, 2015 http://www.atmos-chem-phys.net/15/5585/2015/ doi:10.5194/acp-15-5585-2015-supplement © Author(s) 2015. CC Attribution 3.0 License. Supplement of Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: Volume 2. Diffusivities of organic compounds, pressure-normalised mean free paths, and average Knudsen numbers for gas uptake calculations M. J. Tang et al. Correspondence to: M. J. Tang ([email protected]) and M. Kalberer ([email protected]) The copyright of individual parts of the supplement might differ from the CC-BY 3.0 licence. Table of Contents 1 Alkanes and cycloalkanes ............................................................................................ 1 1.1 CH 4 (methane), C 2H6 (ethane), and C 3H8 (propane) ............................................. 1 1.2 C 4H10 (butane, methyl propane) ............................................................................ 3 1.3 C 5H12 (n-pentane, methyl butane, dimethyl butane) ............................................. 5 1.4 C 6H14 (n-hexane, 2,3-dimethyl butane) ................................................................ 7 1.5 C 7H16 (n-heptane, 2,4-dimethyl pentane).............................................................. 9 1.6 C 8H18 (n-octane, 2,2,4-trimethyl pentane) .......................................................... 11 1.7 C 9H20 (n-nonane), C 10 H22 (n-decane, 2,3,3-trimethyl heptane) and C 12 H26 (n- dodecane) ................................................................................................................. -
Self-Metathesis of 1-Octene Using Alumina-Supported Re2o7 in Supercritical CO2
Top Catal DOI 10.1007/s11244-008-9154-4 ORIGINAL PAPER Self-Metathesis of 1-Octene Using Alumina-Supported Re2O7 in Supercritical CO2 Massimo Fabris Æ Cindy Aquino Æ Antony J. Ward Æ Alvise Perosa Æ Thomas Maschmeyer Æ Maurizio Selva Ó Springer Science+Business Media, LLC 2009 Abstract In this contribution we describe the use of basic science has been applied for the benefit of man, heterogeneous catalysts for the liquid-phase self-metathesis society and the environment’’.1 Their contribution was of 1-octene in supercritical CO2. Our work aims at recognized for understanding the mechanism, and for addressing the mass-transfer problems associated with such developing very efficient and selective discrete metal- reaction systems. By coupling a heterogeneous supported based catalysts. Re2O7 catalyst with the use of scCO2, the self-metathesis Nonetheless, one should not forget that the metathesis of 1-octene takes place by and large much more rapidly reaction using heterogeneous catalysis has been an estab- than in traditional solvent media, and furthermore, by using lished industrial process since 1966, based on the use of scCO2 the overall efficiency and sustainability of the supported (usually on silica and alumina) metal oxides transformation can be improved. such as tungsten, nickel, cobalt, rhenium, and molybde- num. Three significant examples come to mind and are Keywords Metathesis Á 1-Octene Á Supercritical CO2 Á here recalled briefly. [1]. Re/Al O 2 3 1. The historic Phillips triolefin process for the produc- tion of ethene and 2-butene from propene using a WO /SiO catalyst, [2] that was shut down in 1972 1 Introduction 3 2 after 6 years of operation due to increased demand for propene, and later reutilized in the reverse direction to The metathesis of olefins is a very elegant and widely produce propene. -
Reactions of Alkenes and Alkynes
05 Reactions of Alkenes and Alkynes Polyethylene is the most widely used plastic, making up items such as packing foam, plastic bottles, and plastic utensils (top: © Jon Larson/iStockphoto; middle: GNL Media/Digital Vision/Getty Images, Inc.; bottom: © Lakhesis/iStockphoto). Inset: A model of ethylene. KEY QUESTIONS 5.1 What Are the Characteristic Reactions of Alkenes? 5.8 How Can Alkynes Be Reduced to Alkenes and 5.2 What Is a Reaction Mechanism? Alkanes? 5.3 What Are the Mechanisms of Electrophilic Additions HOW TO to Alkenes? 5.1 How to Draw Mechanisms 5.4 What Are Carbocation Rearrangements? 5.5 What Is Hydroboration–Oxidation of an Alkene? CHEMICAL CONNECTIONS 5.6 How Can an Alkene Be Reduced to an Alkane? 5A Catalytic Cracking and the Importance of Alkenes 5.7 How Can an Acetylide Anion Be Used to Create a New Carbon–Carbon Bond? IN THIS CHAPTER, we begin our systematic study of organic reactions and their mecha- nisms. Reaction mechanisms are step-by-step descriptions of how reactions proceed and are one of the most important unifying concepts in organic chemistry. We use the reactions of alkenes as the vehicle to introduce this concept. 129 130 CHAPTER 5 Reactions of Alkenes and Alkynes 5.1 What Are the Characteristic Reactions of Alkenes? The most characteristic reaction of alkenes is addition to the carbon–carbon double bond in such a way that the pi bond is broken and, in its place, sigma bonds are formed to two new atoms or groups of atoms. Several examples of reactions at the carbon–carbon double bond are shown in Table 5.1, along with the descriptive name(s) associated with each. -
Plasma-Pd/Γ-Al203 Catalytic System for Methane, Toluene and Propene Oxidation: Effect of Temperature and Plasma Input Power
22nd International Symposium on Plasma Chemistry July 5-10, 2015; Antwerp, Belgium Plasma-Pd/γ-Al203 catalytic system for methane, toluene and propene oxidation: effect of temperature and plasma input power T. Pham Huu1, 2, P. Da Costa3, S. Loganathan1 and A. Khacef1 1 GREMI-UMR 6744, CNRS-Université d'Orléans, 14 rue d’Issoudun, P.O. Box 6744, FR-45067 Orléans Cedex 02, France 2 Institute of Applied Material Science, Vietnam Academy of Science and Technology, 1 Mac Dinh Chi, HCMC, Vietnam 3 Sorbonne Universités, UPMC Paris 6, Institut Jean Le Rond d’Alembert, CNRS UMR 7190, 2 place de la gare de ceinture, FR-78210 Saint Cyr l’école, France Abstract: A pulsed non-thermal plasma and 1 wt% Pd/γ-Al2O3 catalyst was used to investigate the CH4, C3H6, and C7H8 oxidation in air. Effects of temperature and specific input energy on the VOCs conversion were studied. The plasma-catalyst interaction revealed the benefit effect on the VOCs oxidation even at low temperature leading to high CO2 selectivity. The synergistic effect of combining plasma with catalyst in one-stage configuration is observed only for toluene. Keywords: non-thermal plasma, Pd/γ-Al203, synergistic effect, methane, propene, toluene, oxidation 1. Introduction 2. Experimental Volatile organic compounds (VOCs) emitted from The plasma reactor is a cylindrical DBD gives the various industrial and domestic processes are important possibility to combine the catalyst with plasma reactor in sources of air pollution and therefore, become a serious single stage (IPC) or two-stage (PPC) configuration as problem for damaging the human health and the shown in Fig. -
Introduction
1 Chapter 1 INTRODUCTION Significant research efforts in the field of transition metal catalysis have led to the development of powerful methods for the formation of C–C and C–heteroatom bonds. Appropriate design of the catalyst and reaction conditions, along with careful choice of the substrate, can enable new and challenging transformations to proceed in high yield and selectivity. In this thesis, three categories of such transformations are presented: cross- coupling reactions to form carbon–silicon bonds, aldehyde-selective Wacker oxidations of fluorinated olefins, and olefin metathesis catalyzed by aminophosphine-ligated ruthenium complexes. Nickel-catalyzed cross-coupling has proven to be a very effective strategy for the addition of organometallic reagents to unactivated alkyl electrophiles. In particular, secondary alkyl halides are useful coupling partners, despite previously being considered to exhibit poor reactivity in comparison to aryl and alkenyl electrophiles, due to challenging oxidative addition and competitive b-hydride elimination. While this class of reactions has predominantly been applied to the formation of C–C bonds, the extension of this strategy to the formation of C–B bonds presented by Fu and coworkers inspired the work presented in the second chapter of this thesis, which details the development of a nickel-catalyzed cross- coupling reaction of unactivated alkyl bromides and silylzinc nucleophiles, resulting in C–Si bond formation. A brief overview of established strategies to form C–Si bonds, as well as some of the current challenges, is discussed. The palladium-catalyzed Wacker oxidation is a powerful tool for the oxidation of terminal olefins. However, controlling the regioselectivity of this process (i.e. -
Me2si(Benz[E]Indenyl)
Propene Polymerization Using Homogeneous MAO-Activated Metallocene Catalysts: Me2Si(Benz[e]lndenyI)2ZrClu'MAO vs. Me2Si(2-Me-Benz[e]lndenyI)2ZrClu'MAO STEPHAN JUNGLlNG,t ROLF MULHAUPT,b UDO STEHLlNG/ HANS-HERBERT BRINTZINGER/ DAVID FISCHER/ and FRANZ LANGHAUSER3 'Institut fOr Makromolekulare Chemie and Freiburger Materialforschungszentrum der Albert-Ludwigs-Universitat Freiburg, 0-79104 Freiburg, Germany; 2Fakultat fOr Chemie, Universitat Konstanz, 0-78434 Konstanz, Germany; and 3BASF AG Abteilung ZKP, 0-67056 Ludwigshafen, Germany SYNOPSIS Propene was polymerized at 40°C and 2-bar propene in toluene using methylalumoxane (MAO) activated rac-Me2Si(Benz[elIndenyl)2ZrCI2 (BI) and rac-Me2Si(2-Me Benz[elIndenyl)2ZrCl2 (MBI). Catalyst BI/MAO polymerizes propene with high activity to afford low molecular weight polypropylene, whereas MBI/MAO is less active and produces high molecular weight polypropylene. Variation of reaction conditions such as propene concentration, temperature, concentration of catalyst components, and addition of hydrogen reveals that the lower molecular weight polypropylene produced with BI/MAO results from chain transfer to propene monomer following a 2,1-insertion. A large fraction of both me tallocene catalyst systems is deactivated upon 2,1-insertion. Such dormant sites can be reactivated by H2-addition, which affords active metallocene hydrides. This effect of H2- addition is reflected by a decreasing content of head-to-head enchainment and the formation of polypropylene with n-butyl end groups. Both catalysts show a strong dependence of activity on propene concentration that indicates a formal reaction order of 1. 7 with respect to propene. MBI/MAO shows a much higher dependence of the activity on temperature than BI/MAO.