Acid Catalysed Dimerisation of 2,3-Dimethylbutadiene By
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Synthesis of Polycyclic Natural Products Jianmin Shi Iowa State University
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1990 Synthesis of polycyclic natural products Jianmin Shi Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Shi, Jianmin, "Synthesis of polycyclic natural products " (1990). Retrospective Theses and Dissertations. 9891. https://lib.dr.iastate.edu/rtd/9891 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. JLÎMI MICROFILMED 1991 INFORMATION TO USERS The most advanced technology has been used to photograph and reproduce this manuscript from the microfihn master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. -
Pinacol Rearrangement
Pinacol rearrangement The pinacol–pinacolone rearrangement is a method for converting a 1,2-diol to a carbonyl compound in organic chemistry. The 1,2-rearrangement takes place under acidic conditions. The name of the rearrangement reaction comes from the rearrangement of pinacol to pinacolone.[1] This reaction was first described by Wilhelm Rudolph Fittig in 1860 of the famed Fittig reaction involving coupling of 2 aryl halides in presence of sodium metal in dry ethereal solution.[2] Contents Mechanism Example of asymmetrical pinacol rearrangement Stereochemistry of the rearrangement History See also References Mechanism In the course of this organic reaction, protonation of one of the –OH groups occurs and a carbocation is formed. If the – OH groups are not alike (i.e. the pinacol is asymmetrical), then the one which creates a more stable carbocation participates in the reaction. Subsequently, an alkyl group from the adjacent carbon migrates to the carbocation center. The driving force for this rearrangement step is believed to be the relative stability of the resultant oxonium ion. Although the initial carbocation is already tertiary, the oxygen can stabilize the positive charge much more favorably due to the complete octet configuration at all centers. It can also be seen as the -OH's lone pairs pushing an alkyl group off as seen in the asymmetrical pinacol example. The migration of alkyl groups in this reaction occurs in accordance with their usual migratory aptitude, i.e.hydride > phenyl carbanion > tertiary carbanion (if formed by migration) > secondary carbanion (if formed by migration) > methyl carbanion. {Why carbanion? Because every migratory group leaves by taking electron pair with it.} The conclusion is that the group which stabilizes the carbocation more effectively is migrated. -
Perfluoroalkyl-Iodo Norbornane Compounds and Their Use As
Europâisches Patentamt (g) ÛJ)) European Patent Office (0) Publication number: O 002 74 1 Office européen des brevets Bl © EUROPEAN PATENT SPECIFICATION @ Date of publication of patent spécification: 18.11.81 @© Int.lnt.CI.3: Cl.3: C 07 C 61/12, C07C 103/19, number: 78101696.9 @ Application CC07C 07 C 103/737,103/737 @ Date offiling: 15.12.78 C 07 D 209/76, C07B 29/04, C07C 69/74, C 07 D 307/77, B 01 F 17/00 (54) Perfluoroaikyl-iodo norbornane compounds and their use as surfactants. (§) Priority: 27.12.77 US 865060 @ Proprietor: CIBA-GEIGY AG Patentabteilung Postfach CH-4002 Basel (CH) (43) Date of publication of application: 11.07.79 Bulletin 79/14 (72) Inventor: Brace, Neal O. 1 022 East North Path (45) Publication of the grant of the European patent: Wheaton Illinois 60187 (US) 18.11.81 Bulletin 81/46 (84) Designated Contracting States: CH DE FR GB (56) References cited: NL - A - 68 08078 Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1 ) European patent convention). Courier Press, Leamington Spa, England. The compounds of this invention are perfluoroalkyliodo norbornane derivatives of the formula wherein Y is independently oxygen or the group >NR, R is independently hydrogen or alkyl of 1 to 24 carbon atoms or each group - YR is independently halogen with the proviso that if two halogen atoms are present these are identical and Rf is a straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by a perfluoroalkoxy group of 2 to 6 carbon atoms. -
Revised Group Additivity Values for Enthalpies of Formation (At 298 K) of Carbon– Hydrogen and Carbon–Hydrogen–Oxygen Compounds
Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon– Hydrogen and Carbon–Hydrogen–Oxygen Compounds Cite as: Journal of Physical and Chemical Reference Data 25, 1411 (1996); https://doi.org/10.1063/1.555988 Submitted: 17 January 1996 . Published Online: 15 October 2009 N. Cohen ARTICLES YOU MAY BE INTERESTED IN Additivity Rules for the Estimation of Molecular Properties. Thermodynamic Properties The Journal of Chemical Physics 29, 546 (1958); https://doi.org/10.1063/1.1744539 Critical Evaluation of Thermochemical Properties of C1–C4 Species: Updated Group- Contributions to Estimate Thermochemical Properties Journal of Physical and Chemical Reference Data 44, 013101 (2015); https:// doi.org/10.1063/1.4902535 Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15 K Journal of Physical and Chemical Reference Data 17, 1637 (1988); https:// doi.org/10.1063/1.555814 Journal of Physical and Chemical Reference Data 25, 1411 (1996); https://doi.org/10.1063/1.555988 25, 1411 © 1996 American Institute of Physics for the National Institute of Standards and Technology. Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon-Hydrogen and Carbon-Hydrogen-Oxygen Compounds N. Cohen Thermochemical Kinetics Research, 6507 SE 31st Avenue, Portland, Oregon 97202-8627 Received January 17, 1996; revised manuscript received September 4, 1996 A program has been undertaken for the evaluation and revision of group additivity values (GAVs) necessary for predicting, by means of Benson's group additivity method, thermochemical properties of organic molecules. This review reports on the portion of that program dealing with GAVs for enthalpies of formation at 298.15 K (hereinafter abbreviated as 298 K) for carbon-hydrogen and carbon-hydrogen-oxygen compounds. -
NXP Semiconductors NXP List of Hazardous Substances in Products
NXP Semiconductors NX3-00119 NXP List of Hazardous Substances Sustainability 01-October-2012 in Products and Packaging Sustainability Page 1 of 7 Supersedes: NX3-00119 01-October-2010 Table of contents 1 Objectives ............................................................................................................................. 2 2 Scope ................................................................................................................................... 2 3 Responsibilities, Records & Risks......................................................................................... 2 3.1 Roles and Responsibilities .................................................................................................... 2 3.2 Records ................................................................................................................................ 2 3.3 Risks .................................................................................................................................... 3 4 References ........................................................................................................................... 3 5 Definitions/Abbreviations ...................................................................................................... 3 5.1 Definitions ............................................................................................................................. 3 5.2 Abbreviations ....................................................................................................................... -
The Photochemistry of Some Substituted 2-Cyclohexenones and the Excited States Involved
PHOTOCHEMISTRY OF SUBSTITUTi':D 2... CYCLOHE:XE;NONES THE PHOTOCHEMISTRY OF S0~1E SUBSTITUTED 2~CYCLOHEXENONES AND THE EXCITED STATES INVOLVED By FLOlTI FP~ERICK SNYDER, B.Sce .A Thesis Submitted to the Faculty of Graduate Studies in Partial Fulfilment of the Requirements for the Degree Master of Science McMaster University October 1969 To MOM and DAD on Your 25th Anniversary MASTER OF SCIENCE (1969) McMASTER UNIVERSITY (Ghemi stry) Hamilton, Ontario. TITLE: The Photochemistry of some Substituted 2-Cyclohexenones and the Excited States Involved AUTHOR: Floyd Frederick Snyder, B.Sc. '(University of Alberta) SUPERVISOR: Dr. J. J. McCullough NUMBER OF PAGES: viii, 87 SCOPE AND CONTENTS: The photoadditions of 3~phenyl-2-cyclohexenone to bicyclo [2.2.1] hepta-2,5-diene, bicyclo [2.2.1] hept-2mene and cyclopentene have been studied. In all cases £.!1! fused cyclobutane products were obtained. Quenching and sensitization experiments indicated a singlet excited state to be active in photocycloaddition. Phosphorescence and fluorescence emission were observed from 3-phenyl-2-cyclohexenoneo Energy transfer to the lo~.rest triplet of 3-phenyl-2-cyclohexenone was evident from the quenching of Michler's ketone phosphorescence. Two norbornene dimers were detected in the photolysis of 3-phenyl-2-cyclo hexenone and norbornene giving evidence for a higher triplet excited state of the enone. The photoaddition of 3-methyl-2-cyclohexenone to cyclopentene l.ras studied for comparison and both .£!..! and !.r..!.U! fused adducts l-Tere obtained. In photolyses with bicyclo [2e2el] hepta-2,5 diene or cyclopentene, 2-phenyl... 2-cyclohexenone lvas unreactive. iii ACKNOWLEDGEMENTS It is a pleasure to express my gratitude to Dr. -
Boronic Acids
Boronic Acids Boronic Acids www.alfa.com INCLUDING: • Boronic Esters • Oxazaborolidine Reagents • Coupling and Hydroboration Catalysts • Phosphine Ligands • Borylation Reagents www.alfa.com Where Science Meets Service Quality Boronic Acids from Alfa Aesar Alfa Aesar is known worldwide for a variety of chemical compounds used in research and development. Recognized for purity and quality, our products and brands are backed by technical and sales teams dedicated to providing you the best service possible. In this catalog, you will find details on our line of boronic acids, esters and related compounds, which are manufactured to the same exacting standards as our full offering of over 33,000 products. Also included in this catalog is a 28-page introduction to boronic acids, their properties and applications. This catalog contains only a selection of our wide range of chemicals and materials. Also included is a selection of novel coupling catalysts and ligands. Many more products, including high purity metals, analytical products, and labware are available in our main catalog or online at www.alfa.com. Table of Contents About Us _____________________________________________________________________________ II How to Order/General Information ____________________________________________________ III Introduction __________________________________________________________________________ 1 Alkenylboronic acids and esters _____________________________________________________ 29 Alkylboronic acids and esters ________________________________________________________ -
Ring Size Effects on the Pinacol Rearrangement by Ramanujan Srinivasa a Thesis Submitted in Partial Fulfillment of the Requireme
Ring size effects on the pinacol rearrangement by Ramanujan Srinivasa A thesis submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Chemistry Montana State University © Copyright by Ramanujan Srinivasa (1979) Abstract: The pinacol rearrangement of 1.1'-bicycloalkyl diols, symmetrical and unsymmetrical, under acidic conditions is discussed. The present study has attempted to probe some very controversial aspects such as whether carbonium ion stability or product stability is the driving force for the ring size effects on the course of the rearrangement. The results of the present study point out the importance of the reaction conditions. When evaluating the ring size effects on the course of the pinacol rearrangement it is essential that the reaction conditions be well defined for otherwise interpretation of results may lead to erroneous conclusions. For instance, the rear-arangement of cyclopentyl cyclohexane-1,1'-diol with concentrated sulfuric acid at 0° yields mainly Spiro [4,6] undecan-6-one as the primary rearrangement product reflecting carbonium ion stability as the chief factor in the course of the rearrangement. On the other hand, the rearrangement with dilute sulfuric acid at reflux produces mainly Spiro [5,5] undecan-7-one, the thermodynamically more stable product. This is consistent with the secondary skeletal rearrangement of the initially formed product. Further, it was attempted to study the possibilities of the rearrangement occurring under non-acidic conditions. It was found that -
The Synthesis and Chemistry of Strained Bicyclic Systems
AN ABSTRACT OF THE THESIS OF LOUIS SCERBO for the Ph. D. (Name) (Degree) in CHEMISTRY presented on S.41_0C 6 1 (Date) (Major) Title: THE SYNTHESIS AND CHEMISTRY OF STRAINED BICYCLIC SYSTEMS Abstract approved Dr. F. Thomas Bond A facile route to bicyclo(2. 1. 1)hexanes was developed involving the intramolecular photocyclization of 1, 5- hexadien -3 -one to bicyclo(2. 1. 1)hexan- 2 -one. A study of the chemistry of bicyclo- (2. 1. 1)hexan -2 -one was undertaken. Deuterium exchange and boro- hydride reduction demonstrated the strain present in the ketone. Further evidence was obtained from the failure to introduce substi- tuents alpha to the carbonyl group, a usually facile reaction and a necessary step in desired ring contraction studies. After numerous unsuccessful attempts to introduce a double bond into the bicyclo(2. 1. 1) hexane system, a successful route to the parent bicyclo(2. 1. 1) hexene was achieved. The key step involved dehydrohalogenation of 2- bromobicyclo(2. 1. 1)hexane. Some prelimi- nary studies of the olefin have been carried out and its thermolysis studied. The Synthesis and Chemistry of Strained Bicyclic Systems by Louis Scerbo A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 1968 APPROVED: Assistant Professor of Chemistry in charge of major Chairman of the Department of Chemistry Dean of Graduate School Date thesis is presented VA, (\rah .ClI le g Typed by Marion F. Palmateer for Louis Scerbo ACKNOWLEDGEMENT The author wishes to express appreciation to Dr. -
Organic Reactions VOLUME IV
Organic Reactions VOLUME IV EDITORIAL BOARD ROGER ADAMS, Editor-in-Chief WERNER E. BACHMANN LOUIS F. FIESER A. H. BLATT JOHN R. JOHNSON HAROLD R. SNYDER ASSOCIATE EDITORS JAMES CASON MILTON C. KLOETZEL WILLIAM S. EMERSON S. M. MCELVAIN H. L. HOLMES ERICH MOSETTIG WALTER S. IDE DAVID TODD NEW YORK JOHN WILEY & SONS, INC. LONDON: CHAPMAN & HALL, LIMITED COPYRIGHT, 1948 BY ROGER ADAMS All Rights Reserved This book or any part thereof must not be reproduced in any form without the written permission of the ptihlisher. PRINTED IN THE UNITED STATES OF AMERICA PREFACE TO THE SERIES In the course of nearly every program of research in organic chemistry the investigator finds it necessary to use several of the better-known synthetic reactions. To discover the optimum conditions for the appli cation of even the most familiar one to a compound not previously subjected to the reaction often requires an extensive search of the liter ature; even then a series of experiments may be necessary. When the results of the investigation are published, the synthesis, which may have required months of work, is usually described without comment. The background of knowledge and experience gained in the literature search and experimentation is thus lost to those who subsequently have occasion to apply the general method. The student of preparative organic chemistry faces similar difficulties. The textbooks and labora tory manuals furnish numerous examples of the application of various syntheses, but only rarely do they convey an accurate conception of the scope and usefulness of the processes. For many years American organic chemists have discussed these problems. -
"Hydrocarbons," In: Ullmann's Encyclopedia of Industrial Chemistry
Article No : a13_227 Hydrocarbons KARL GRIESBAUM, Universit€at Karlsruhe (TH), Karlsruhe, Federal Republic of Germany ARNO BEHR, Henkel KGaA, Dusseldorf,€ Federal Republic of Germany DIETER BIEDENKAPP, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany HEINZ-WERNER VOGES, Huls€ Aktiengesellschaft, Marl, Federal Republic of Germany DOROTHEA GARBE, Haarmann & Reimer GmbH, Holzminden, Federal Republic of Germany CHRISTIAN PAETZ, Bayer AG, Leverkusen, Federal Republic of Germany GERD COLLIN, Ruttgerswerke€ AG, Duisburg, Federal Republic of Germany DIETER MAYER, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of Germany HARTMUT Ho€KE, Ruttgerswerke€ AG, Castrop-Rauxel, Federal Republic of Germany 1. Saturated Hydrocarbons ............ 134 3.7. Cumene ......................... 163 1.1. Physical Properties ................ 134 3.8. Diisopropylbenzenes ............... 164 1.2. Chemical Properties ............... 134 3.9. Cymenes; C4- and C5-Alkylaromatic 1.3. Production ....................... 134 Compounds ...................... 165 1.3.1. From Natural Gas and Petroleum . .... 135 3.10. Monoalkylbenzenes with Alkyl Groups 1.3.2. From Coal and Coal-Derived Products . 138 >C10 ........................... 166 1.3.3. By Synthesis and by Conversion of other 3.11. Diphenylmethane .................. 167 Hydrocarbons . .................. 139 4. Biphenyls and Polyphenyls .......... 168 1.4. Uses ............................ 140 4.1. Biphenyl......................... 168 1.5. Individual Saturated Hydrocarbons ... 142 4.2. Terphenyls...................... -
Standards on the Management of Certain Chemical Substances (Version 10)
Standards on the Management of Certain Chemical Substances (Version 10) Established date: December 22, 2003 Issue date: April 23, 2015 Implementation date: May 7, 2015 KYOCERA Document Solutions Inc. Table of contents ・・・ P. 1 Introduction ・・・ P. 2 Chapter 1. Policy on management of Substances Included in Products 1-1. Purpose ・・・ P. 3 1-2. Scope of Application ・・・ P. 3 1-3. Terms and Definitions ・・・ P. 3 - 4 1-4. Revision of Chemical Substances Management Standards ・・・ P. 4 Chapter 2. Chemical Substances Management Standards 2-1. Banned Substances in Products 2-1-1. List of banned substances in products ・・・ P. 4 - 6 2-1-2. Scope of banned substances in products, thresholds, exemptions, applicab ・・・ P. 6 - 11 laws and regulations 2-2. Restricted Substances in Products 2-2-1. List of restricted substances in products ・・・ P. 11 - 12 2-2-2. Scopes, thresholds, scheduled prohibition date and applicable laws for ・・・ P. 12 - 13 restricted substances in products 2-3. Monitored Substances in Products 2-3-1. List of monitored substances in products ・・・ P. 13 - 14 2-3-2. Scope of monitored substances in products, monitoring thresholds, related ・・・ P. 14 - 16 laws and regulations 2-4. Surveyed Substances in Products 2-4-1. JAMP declarable substance list (Ver.4.030) ・・・ P. 16 2-5. Banned Substances in Production 2-5-1. List of Banned Substances in Production ・・・ P. 16 2-5-2. Applicable processes and laws for Banned Substances in Production ・・・ P. 17 Chapter 3. Request to customers 3-1. Compliance with the Chemical Substances Management Standards ・・・ P. 17 3-2. System for management of Substances Included in Products ・・・ P.