DOCSLIB.ORG

Supporting Information

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Supporting Information Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2014 Supplementary Material Nickel-Catalyzed Substitution Reactions of Propargyl Halides with Organotitanium Reagents Qing-Han Li,a,b,* Jung-Wei Liao,a Yi-Ling Huang,a Ruei-Tang Chianga and Han-Mou Gaua,* a Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan b College of Chemistry and Environmental Protection Engineering, Southwest University for Nationalities, Chengdu 610041, China e-mail: [email protected] - S1- Table of Contents I. 1H and 13C NMR Spectra of Aryltitanium Reagents S3 1. (2-MeOC6H4)Ti(O-i-Pr)3 (4e) S3 2. (2,6-Me2C6H3)Ti(O-i-Pr)3 (4j) S5 II. 1H and 13C NMR Spectra of Coupling Products S7 1. 1-Phenyl-1,2-propadiene (2aa) S7 2. 1-(4-Methylphenyl)-1,2-propadiene (2ab) S9 3. 1-(2-Methylphenyl)-1,2-propadiene (2ac) S11 4. 1-(4-Methoxyphenyl)-1,2-propadiene (2ad) S13 5. 1-(2-Methoxyphenyl)-1,2-propadiene (2ae) S15 6. 1-(3,5-Dimethylphenyl)-1,2-propadiene (2af) S17 7. 1-(2-Naphthyl)-1,2-propadiene (2ag) S19 8. 1-(4-Trifluoromethylphenyl)-1,2-propadiene (2ah) S21 9. 1-cyclohexyl-1,2-propadiene (2ai) S23 10. 1-(2,6-Dimethylphenyl)-1,2-propadiene (2aj) S25 11. 1-(2,6-Dimethylphenyl)-4-(bromomethyl)-1,2,4-pentatriene (2aj’) S27 12. 3-Phenyl-1,2-pentadiene (2ba) S29 13. 3-(2-Methylphenyl)-1,2-pentadiene (2bc) S31 14. 3-(3,5-Dimethylphenyl)-1,2-pentadiene (2bf) S33 15. 3-(2,6-Dimethylphenyl)-1,2-pentadiene (2bj) S35 16. 3-Phenyl-1,2-butadiene (2ca) S37 17. 3-(2-Methylphenyl)-1,2-butadiene (2cc) S39 18. 1-Phenyl-1,2-butadiene (2da) S41 19. 1-(2-Methylphenyl)-1,2-butadiene (2dc) S43 20. 3-Phenyl-1,2-octadiene (2ea) S45 21. 1-Phenyl-2-octyne (3ea) S47 22. 1-(2-Methylphenyl)-2-octyne (3ec) S49 23. 1-(3,5-Dimethylphenyl)-2-octyne (3ef) S51 24. 3-(2,6-Dimethylphenyl)-1,2-octadiene (2ej) S53 25. 1-(2,6-Dimethyl)-2-octyne (3ej) S55 26. 1,3-Diphenylpropyne (3fa) S57 27. 1-Phenyl-3-(2-methylphenyl)propyne (3fc) S59 28. 1-Phenyl-2-octyne (3ga) S61 - S2- I. 1H and 13C NMR Spectra of Aryltitanium Reagents 1 H NMR Spectrum of (2-MeOC6H4)Ti(O-i-Pr)3 (4e) OMe Ti(O-i-Pr)3 4e - S3- 13 C NMR Spectrum of (2-MeOC6H4)Ti(O-i-Pr)3 (4e) OMe Ti(O-i-Pr)3 4e - S4- 1 H NMR Spectrum of (2,6-Me2C6H3)Ti(O-i-Pr)3 (4j) Ti(O-i-Pr)3 4j - S5- 13 C NMR Spectrum of (2,6-Me2C6H3)Ti(O-i-Pr)3 (4j) Ti(O-i-Pr)3 4j - S6- II. 1H and 13 C NMR Spectra of Coupling Products II.1. 1H NMR Spectrum of 1-Phenyl-1,2-propadiene (2aa) 2aa - S7- 13C NMR Spectrum of 1-Phenyl-1,2-propadiene (2aa) 2aa - S8- II.2. 1H NMR Spectrum of 1-(4-Methylphenyl)-1,2-propadiene (2ab) Me 2ab - S9- 13C NMR Spectrum of 1-(4-Methylphenyl)-1,2-propadiene (2ab) Me 2ab - S10- II.3. 1H NMR Spectrum of 1-(2-Methylphenyl)-1,2-propadiene (2ac) Me 2ac - S11- 13C NMR Spectrum of 1-(2-Methylphenyl)-1,2-propadiene (2ac) Me 2ac - S12- II.4. 1H NMR Spectrum of 1-(4-Methoxyphenyl)-1,2-propadiene (2ad) MeO 2ad - S13- 13C NMR Spectrum of 1-(4-Methoxyphenyl)-1,2-propadiene (2ad) MeO 2ad - S14- II.5. 1H NMR Spectrum of 1-(2-Methoxyphenyl)-1,2-propadiene (2ae) MeO 2ae - S15- 13C NMR Spectrum of 1-(2-Methoxyphenyl)-1,2-propadiene (2ae) MeO 2ae - S16- II. 6. 1H NMR Spectrum of 1-(3,5-Dimethylphenyl)-1,2-propadiene (2af) Me Me 2af - S17- 13C NMR Spectrum of 1-(3,5-Dimethylphenyl)-1,2-propadiene (2af) Me Me 2af - S18- II.7. 1H NMR Spectrum of 1-(2-Naphthyl)-1,2-propadiene (2ag) 2ag - S19- 13C NMR Spectrum of 1-(2-Naphthyl)-1,2-propadiene (2ag) 2ag - S20- II. 8. 1H NMR Spectrum of 1-(4-Trifluoromethylphenyl)-1,2-propadiene (2ah) F3C 2ah - S21- 13C NMR Spectrum of 1-(4-Trifluoromethylphenyl)-1,2-propadiene (2ah) F3C 2ah - S22- II.9. 1H NMR Spectrum of (1,2-Propadienyl)-cyclohexane (2ai) 2ai - S23- 13C NMR Spectrum of 1-cyclohexyl-1,2-propadiene (2ai) 2ai - S24- II.10. 1H NMR Spectrum of 1-(2,6-Dimethylphenyl)-1,2-propadiene (2aj) Me Me 2aj - S25- 13C NMR Spectrum of 1-(2,6-Dimethylphenyl)-1,2-propadiene (2aj) Me Me 2aj - S26- II.11. 1H NMR Spectrum of 1-(2,6-Dimethylphenyl)-4-(bromomethyl)-1,2,4-pentatriene (2aj’) Me Me Br 2aj' - S27- 13C NMR Spectrum of 1-(2,6-Dimethylphenyl)-4-(bromomethyl)-1,2,4-pentatriene (2aj’) Me Me Br 2aj' - S28- II.12. 1H NMR Spectrum of 3-Phenyl-1,2-pentadiene (2ba) Et 2ba - S29- 13C NMR Spectrum of 3-Phenyl-1,2-pentadiene (2ba) Et 2ba - S30- II.13. 1H NMR Spectrum of 3-(2-Methylphenyl)-1,2-pentadiene (2bc) Et Me 2bc - S31- 13C NMR Spectrum of 3-(2-Methylphenyl)-1,2-pentadiene (2bc) Et Me 2bc - S32- II.14. 1H NMR Spectrum of 3-(3,5-Dimethylphenyl)-1,2-pentadiene (2bf) Et Me Me 2bf - S33- 13C NMR Spectrum of 3-(3,5-Dimethylphenyl)-1,2-pentadiene (2bf) Et Me Me 2bf - S34- II.15. 1H NMR Spectrum of 3-(2,6-Dimethylphenyl)-1,2-pentadiene (2bj) Et Me Me 2bj - S35- 13C NMR Spectrum of 3-(2,6-Dimethylphenyl)-1,2-pentadiene (2bj) Et Me Me 2bj - S36- II.16. 1H NMR Spectrum of 3-Phenyl-1,2-butadiene (2ca) Me 2ca - S37- 13C NMR Spectrum of 3-Phenyl-1,2-butadiene (2ca) Me 2ca - S38- II.17. 1H NMR Spectrum of 3-(2-Methylphenyl)-1,2-butadiene (2cc) Me Me 2cc - S39- 13C NMR Spectrum of 3-(2-Methylphenyl)-1,2-butadiene (2cc) Me Me 2cc - S40- II.18. 1H NMR Spectrum of 1-Phenyl-1,2-butadiene (2da) Me 2da - S41- 13C NMR Spectrum of 1-Phenyl-1,2-butadiene (2da) Me 2da - S42- II.19. 1H NMR Spectrum of 1-(2-Methylphenyl)-1,2-butadiene (2dc) Me Me 2dc - S43- 13C NMR Spectrum of (1,2-Butadienyl)-2-methyl-benzene (2dc) Me Me 2dc - S44- II.20. 1H NMR Spectrum of 3-Phenyl-1,2-octadiene (2ea) 2ea - S45- 13C NMR Spectrum of 3-Phenyl-1,2-octadiene (2ea) 2ea - S46- II.21. 1H NMR Spectrum of 1-Phenyl-2-octyne (3ea) 3ea - S47- 13C NMR Spectrum of 2-octynylbenzene (3ea) 3ea - S48- II.22. 1H NMR Spectrum of 1-(2-Methylphenyl)-2-octyne (3ec) Me 3ec - S49- 13C NMR Spectrum of 1-(2-Methylphenyl)-2-octyne (3ec) Me 3ec - S50- II.23. 1H NMR Spectrum of 1-(3,5-Dimethylphenyl)-2-octyne (3ef) Me 3ef Me - S51- 13C NMR Spectrum of 1-(3,5-Dimethylphenyl)-2-octyne (3ef) Me 3ef Me - S52- II.24. 1H NMR Spectrum of 3-(2,6-Dimethylphenyl)-1,2-octadiene (2ej) Me Me 2ej - S53- 13C NMR Spectrum of 3-(2,6-Dimethyl)-1,2-octadiene (2ej) Me Me 2ej - S54- II.25. 1H NMR Spectrum of 1-(2,6-Dimethyl)-2-octyne (3ej) Me Me 3ej - S55- 13C NMR Spectrum of 1-(2,6-Dimethyl)-2-octyne (3ej) Me Me 3ej - S56- II.26. 1H NMR Spectrum of 1,3-Diphenylpropyne (3fa) 3fa - S57- 13C NMR Spectrum of 1,3-Diphenylpropyne (3fa) 3fa - S58- II.27. 1H NMR Spectrum of 1-Phenyl-3-(2-methylphenyl)propyne (3fc) Me 3fc - S59- 13C NMR Spectrum of 1-Phenyl-3-(2-methylphenyl)propyne (3fc) Me 3fc - S60- 1H NMR Spectrum of 1-Phenyl-2-octyne (3ga) 3ga - S61- 13C NMR Spectrum of 1-Phenyl-2-octyne (3ag) 3ga - S62-.
Load more

Recommended publications
  • Hydrogenationn of 4-Octyne Catalyzedd by Pd[(M^W'- (CF3)2C6H3)) Bian](Ma) in THF
    UvA-DARE (Digital Academic Repository) Palladium-catalyzed stereoselective hydrogenation of alkynes to (Z)-alkenes in common solvents and supercritical CO2 Kluwer, A.M. Publication date 2004 Link to publication Citation for published version (APA): Kluwer, A. M. (2004). Palladium-catalyzed stereoselective hydrogenation of alkynes to (Z)- alkenes in common solvents and supercritical CO2. General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulations If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl) Download date:04 Oct 2021 5 Kineti5 cc study and Spectroscopic Investigationn of the semi- hydrogenationn of 4-octyne catalyzedd by Pd[(m^w'- (CF3)2C6H3)) bian](ma) in THF 5.11 Introduction Homogeneouss hydrogenation by transition metal complexes has played a key role in the fundamental understandingg of catalytic reactions and has proven to be of great utility in practical applications.
    [Show full text]
  • Transformation of Phenanthrene by Mycobacterium Sp. ELW1 and the Formation of Toxic Metabolites
    AN ABSTRACT OF THE THESIS OF Jill E. Schrlau for the degree of Master of Science in Environmental Engineering presented on September 20, 2016. Title: Transformation of Phenanthrene by Mycobacterium sp. ELW1 and the Formation of Toxic Metabolites. Abstract approved: _____________________________________________________________________ Lewis Semprini Staci Simonich The ability of Mycobacterium sp. ELW1, a novel microbe capable of alkene oxidation, to co-metabolize phenanthrene (PHE) was studied. ELW1 was able to completely co-metabolize PHE, at different concentrations below its water solubility limit, in an aqueous environment. The alkene monooxygenases in ELW1, used to initiate oxidation of PHE, were effectively inhibited by 1-octyne despite some PHE transformation observed. PHE metabolites consisted of only hydroxyphenanthrenes (OHPHEs) with trans-9,10-dihydroxy-9,10-dihydrophenanthrene (trans-9,10-PHE), the primary product, comprising more than 90% of the total metabolites formed in both PHE-exposed cells and 1-octyne controls. Mass balance was estimated by summing the zero-order formation rates of OHPHE metabolites and comparing these to the zero-order transformation rates PHE in PHE-exposed cells. The transformation rates of PHE and were in good agreement with the formation rates of the metabolites. PHE transformation followed first-order rates that, when normalized by biomass, were in the range of those estimated by the ratio of the Michaelis-Menten kinetic variables of maximum transformation rate (kmax) to the half-saturation constant (KS). Estimated values for kmax to KS obtained through both non-linear and linearization methods resulted in kmax/KS estimates that were a factor of ~3 lower compared to experimental values.
    [Show full text]
  • Organic Seminar Abstracts
    Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/organicsemin1971752univ / a ORGANIC SEMINAR ABSTRACTS 1971-1972 Semester II School of Chemical Sciences Department of Chemistry- University of Illinois Urbana, Illinois 3 SEMINAR TOPICS II Semester 1971-72 Reactions of Alkyl Ethers Involving n- Complexes on a Reaction Pathway 125 Jerome T. Adams New Syntheses of Helicenes 127 Alan Morrice Recent Advances in Drug Detection and Analysis I36 Ronald J. Convers The Structure of Carbonium Ions with Multiple Neighboring Groups 138 William J. Work Recent Reactions of the DMSO-DCC Reagent ll+O James A. Franz Nucleophilic Acylation 1^2 Janet Ollinger The Chemistry of Camptothecin lU^ Dale Pigott Stereoselective Syntheses and Absolute Configuration of Cecropia Juvenile Horomone 1U6 John C. Greenfield Uleine and Related Aspidosperma Alkaloids 155 Glen Tolman Strategies in Oligonucleotide Synthesis 162 Graham Walker Stable Carbocations: C-13 Nuclear Magnetic Resonance Studies 16U Moses W. McMillan Organic Chlorosulfinates 166 Steven W. Moje Recent Advances in the Chemistry of Penicillins and Cephalosporins 168 Ronald Stroshane Cerium (iv) Oxidations 175 William C. Christopfel A New Total Synthesis of Vitamin D 18 William Graham Ketone Transpositions 190 Ann L. Crumrine - 125 - REACTIONS OF ALKYL ETHERS INVOLVING n-COMPLEXES ON A REACTION PATHWAY Reported by Jerome T. Adams February 2k 1972 The n-complex (l) has been described as an intermediate on the reaction pathway for electrophilic aromatic substitution and acid catalyzed rearrange- ment of alkyl aryl ethers along with sigma (2) and pi (3) type intermediates. 1 ' 2 +xR Physical evidence for the existence of n-complexes of alkyl aryl ethers was found in the observation of methyl phenyl ononium ions by nmr 3 and ir observation of n-complexes of anisole with phenol.
    [Show full text]
  • Gfsorganics & Fragrances
    Chemicals for Flavors GFSOrganics & Fragrances GFS offers a broad range of specialty organic chemicals Specialized chemistries we as building blocks and intermediates for the manufacture of offer include: flavors and fragrances. • Alkynes Over 5,500 materials, including 1,400 chemicals from natural sources, are used for flavor • Alkynols enhancements and aroma profiles. These aroma chemicals are integral components of • Olefins the continued growth within consumer products and packaged foods. The diversity of products can be attributed to the broad spectrum of organic compounds derived from • Unsaturated Acids esters, aldehydes, lactones, alcohols and several other functional groups. • Unsaturated Esters • DIPPN and other Products GFS Chemicals manufactures a wide range of organic intermediates that have been utilized in a multitude of personal care applications. For example, we support Why GFS? several market leading companies in the manufacture and supply of alkyne based aroma chemicals. • Specialized Chemistries • Tailored Specifications As such, we understand the demanding nature of this fast changing market and are fully • From Grams to Metric Tons equipped to overcome process challenges and manufacture the novel chemical products • Responsive Technical Staff that you need, when you need them. We offer flexible custom manufacturing services to produce high purity products with the assurance of quality and full confidentiality. • Uncompromised Product Quality Our state-of-the-art manufacturing facility, located in Columbus, OH is ISO 9001:2008 certified. As a U.S. based manufacturer we have a proven record of helping you take products from development to commercialization. Our technical sales experts are readily accessible to discuss your project needs and unique product specifications.
    [Show full text]
  • Nuclear Spin-Induced Optical Rotation of Functional Groups in Hydrocarbons Petr Štěpánek1 Supplementary Information
    Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is © the Owner Societies 2020 Nuclear spin-induced optical rotation of functional groups in hydrocarbons Petr Štěpánek1 Supplementary Information Contents 1 List of molecules 2 2 Basis set benchmark 5 1 3 Effect of cis/trans isomerism on H NSOR of T1 atom type in alkenes 5 4 Effect of conformation on NSOR 6 5 Extended Figure for NSOR of dienes 7 6 Effect of cis/trans isomerism in dienes 8 7 Supporting data for solvent and geometry effects 8 1NMR Research Unit, Faculty of Science, University of Oulu, P.O. Box 3000, FI-90014 Oulu, Finland; petr.stepanek@oulu.fi 1 1 List of molecules Tables below list the molecules included in the study. The test cases of the contribution model are not included. Table S 1: Alkane molecules methane 2-methyl-propane 2,3-dimethyl-butane ethane 2-methyl-butane 2,2-dimethyl-propane propane 2-methyl-pentane 2,2-dimethyl-pentane butane 3-methyl-pentane 2,3-dimethyl-pentane pentane 2,2-dimethyl-butane 3,3-dimethyl-pentane hexane Table S 2: Alkene molecules ethene 2,3,3-trimethyl-butene 5-methyl-heptene propene 2,4-dimethyl-pentene 6-methyl-heptene trans-but-2-ene 2-methyl-hexene cis-5,5-dimethyl-hex-2-ene cis-pent-2-ene 3,3-dimethyl-pentene cis-6-methyl-hept-2-ene trans-hex-2-ene 3,4-dimethyl-pentene trans-5,5-dimethyl-hex-2-ene trans-pent-2-ene 3-methyl-hexene trans-6-methyl-hept-2-ene trans-hex-3-ene 4-methyl-hexene 5,6-dimethyl-heptene 2-methyl-propene cis-4,4-dimethyl-pent-2-ene cis-6,6-dimethyl-hepte-2-ene 2-methyl-butene
    [Show full text]
  • Cycloadditions for Rapid, Scalable Access to Alkynylated Polycyclic Aromatic Cite This: Chem
    Chemical Science EDGE ARTICLE View Article Online View Journal | View Issue Site-selective [2 + 2 + n] cycloadditions for rapid, scalable access to alkynylated polycyclic aromatic Cite this: Chem. Sci., 2020, 11,3028 hydrocarbons† All publication charges for this article have been paid for by the Royal Society of Chemistry Gavin R. Kiel, Harrison M. Bergman and T. Don Tilley * Polycyclic aromatic hydrocarbons (PAHs) are attractive synthetic building blocks for more complex conjugated nanocarbons, but their use for this purpose requires appreciable quantities of a PAH with reactive functional groups. Despite tremendous recent advances, most synthetic methods cannot satisfy these demands. Here we present a general and scalable [2 + 2 + n](n ¼ 1 or 2) cycloaddition strategy to access PAHs that are decorated with synthetically versatile alkynyl groups and its application to seven structurally diverse PAH ring systems (thirteen new alkynylated PAHs in total). The critical discovery is the site-selectivity of an Ir-catalyzed [2 + 2 + 2] cycloaddition, which preferentially cyclizes tethered diyne units with preservation of other (peripheral) alkynyl groups. The potential for generalization of the site- Creative Commons Attribution-NonCommercial 3.0 Unported Licence. selectivity to other [2 + 2 + n] reactions is demonstrated by identification of a Cp2Zr-mediated [2 + 2 + 1]/metallacycle transfer sequence for synthesis of an alkynylated, selenophene-annulated PAH. The new PAHs are excellent synthons for macrocyclic conjugated nanocarbons. As a proof of concept, four were subjected to alkyne metathesis catalysis to afford large, PAH-containing arylene ethylene macrocycles, which possess a range of cavity sizes reaching well into the nanometer regime. Notably, these high- Received 2nd December 2019 yielding macrocyclizations establish that synthetically convenient pentynyl groups can be effective for Accepted 15th February 2020 metathesis since the 4-octyne byproduct is sequestered by 5 A˚ MS.
    [Show full text]
  • Polycyclic Organic Compounds, Polarizing
    (19) TZZ ZZ¥_T (11) EP 2 260 035 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07D 471/04 (2006.01) C07D 487/04 (2006.01) 20.08.2014 Bulletin 2014/34 C07D 487/22 (2006.01) C07D 495/16 (2006.01) C07C 15/38 (2006.01) (21) Application number: 09717753.9 (86) International application number: (22) Date of filing: 04.03.2009 PCT/GB2009/050218 (87) International publication number: WO 2009/109781 (11.09.2009 Gazette 2009/37) (54) POLYCYCLIC ORGANIC COMPOUNDS, POLARIZING ELEMENTS AND METHOD OF PRODUCTION THEREOF POLYCYCLISCHE ORGANISCHE VERBINDUNGEN, POLARISIERUNGSELEMENTE UND VERFAHREN ZU DEREN HERSTELLUNG COMPOSÉS ORGANIQUES POLYCYCLIQUES, ÉLÉMENTS POLARISANTS ET LEUR PROCÉDÉ DE FABRICATION (84) Designated Contracting States: • DATABASE CAPLUS [Online] CHEMICAL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR ABSTRACTS SERVICE, COLUMBUS, OHIO, US; HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL 7 October 2007 (2007-10-07), XP002543542 PT RO SE SI SK TR retrieved from STN Database accession no. 2007: 1167020 & VAKULIN, I. V. ET AL.: "Quantum- (30) Priority: 04.03.2008 GB 0804082 chemical study of formation of complexes of aromatic Schiff bases with transition metals (43) Date of publication of application: using the UB3LYP/3-21G(d) approximation" 15.12.2010 Bulletin 2010/50 BASHKIRSKII KHIMICHESKII ZHURNAL, vol. 14, no. 1, 2007, pages 124-128, Bashkir State (73) Proprietor: CRYSOPTIX K.K. University, Ufa; RU ISSN: 0869-8406 Tokyo (JP) • LIANG, B. ET AL.: "HIGH-EFFICIENCY RED PHOSPHORESCENT IRIDIUM DENDRIMERS (72) Inventors: WITH CHARGE-TRANSPORTING DENDRONS: • NOKEL, Alexey SYNTHESIS AND ELECTROLUMINESCENT Moscow 119619 (RU) PROPERTIES" ADVANCED FUNCTIONAL • LAZAREV, Pavel I.
    [Show full text]
  • Industrial Hydrocarbon Processes
    Handbook of INDUSTRIAL HYDROCARBON PROCESSES JAMES G. SPEIGHT PhD, DSc AMSTERDAM • BOSTON • HEIDELBERG • LONDON NEW YORK • OXFORD • PARIS • SAN DIEGO SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Gulf Professional Publishing is an imprint of Elsevier Gulf Professional Publishing is an imprint of Elsevier The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK 30 Corporate Drive, Suite 400, Burlington, MA 01803, USA First edition 2011 Copyright Ó 2011 Elsevier Inc. All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: [email protected]. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/ permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made British Library Cataloguing in Publication Data
    [Show full text]
  • Es PATENT OFFICE
    Patented Oct. 27, 1953 2,657,241 Es2,657,241 PATENT OFFICE HEMIACETALs Georgederson, W. Yonkers, Mast, South N. Salem,Y., assignors and Floyd to NeperaE. An Chemical Co., Inc., Nepera Park, Yorikers, N.Y., a corporation of New York NoDrawing. Application May 21, 1952, Serial No. 289,216 5 Claims. (Cl. 260-611) This invention relates to certain novel hemiace 3-methyl-1-pentyne-3-ol tal compounds and relates more particularly to 2-methyl-3-butyne-2-ol hemiacetals of chloral, i.e. trichloroacetaldehyde. Propargylalcohol An object of this invention is the production 3-butyne-2-ol . of hemiacetals of chloral wherein the alcohol 5 3-methyl-1-pentyne-3-ol residue in said hemiacetal structure contains an 3-butyne-1-ol unsaturated, acetylenic carbon to carbon link 3-ethyl-1-pentyne-3-ol age. 2-heptyne-i-ol Another object of this invention is the produc 3-heptyne-1-Ol tion of hemiacetals of chloral which exhibit de 10 2-octyne-1-ol sirable hypnotic and sedative activity. 3-octyne-1-ol Other objectS of this invention Will appear from 2-nonyne-1-ol the following detailed description. 3-nonyne-1-ol The novel compounds of our invention may be 15 3,4-dimethyl-1-pentyne-3-ol represented by the following general structural 3-isopropyl-4-methyl-1-pentyne-3-ol3,4-dimethyl-1-hexyne-3-ol - formula: 3-isopropyl-1-hexyne-3-ol OEI R. 1-nonyne-3-ol 3-methyl-1-nonyne-3-ol clic-en-o--(c H2)-CSC-Ra 20 1-methyl-2-Octyne-1sol; and R2 1-methyl-1-ethyl-2-octyne-1-ol wherein n is to 0 to 3, and R1, R2, and R3 are As is well known, acetal formation takes place members of the group consisting of hydrogen and at the carbonyl group of the aldehyde, the reac Saturated alkyl radicals having from 1 to 6 carbon tion resulting not only in the formation of a hy atoms.
    [Show full text]
  • The Liquid-Phase Hydrogenation of 1-Heptyne Over Pd–Au/Tio2 Catalysts Prepared by the Combination of Incipient Wetness Impregn
    The liquid-phase hydrogenation of 1-heptyne over Pd‒Au/TiO2 catalysts prepared by the combination of incipient Title wetness impregnation and deposition‒precipitation Kittisakmontree, Prathan; Pongthawornsakun, Boontida; Yoshida, Hiroshi; Fujita, Shin-ichiro; Arai, Masahiko; Author(s) Panpranot, Joongjai Journal of Catalysis, 297, 155-164 Citation https://doi.org/10.1016/j.jcat.2012.10.007 Issue Date 2013-01 Doc URL http://hdl.handle.net/2115/52085 Type article (author version) File Information joc297_155-164.pdf Instructions for use Hokkaido University Collection of Scholarly and Academic Papers : HUSCAP The liquid-phase hydrogenation of 1-heptyne over Pd-Au/TiO2 catalysts prepared by the combination of incipient wetness impregnation and deposition-precipitation Prathan Kittisakmontreea, Boontida Pongthawornsakuna, Hiroshi Yoshidab, Shin-ichiro Fujitab, Masahiko Araib, and Joongjai Panpranota,* aCenter of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand bDivision of Chemical Process Engineering, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan Date: October 4, 2012 Submitted to: Journal of Catalysis *To whom all correspondence should be addressed. Tel.: 66-2218-6869 Fax: 66-2218-6877 E-mail: [email protected] 1 Abstract TiO2 supported Pd-Au catalysts were prepared with Pd (0.5 wt-%) by impregnation and then Au (1.0 wt-%) by deposition – precipitation (Au/Pd/TiO2) and vice versa (Pd/Au/TiO2). For the former sample, the state of dispersion of Pd on TiO2 changed during the loading of Au, resulting in the formation of small Au – Pd alloy particles and thus changing the electronic properties of Pd species.
    [Show full text]
  • 14.5 Conversion of Alkynes Into Aldehydes and Ketones 655
    14_BRCLoudon_pgs4-2.qxd 11/26/08 9:04 AM Page 654 654 CHAPTER 14 • THE CHEMISTRY OF ALKYNES PROBLEMS 14.7 Give the product that results from the addition of one equivalent of Br2 to 3-hexyne. What are the possible stereoisomers that could be formed? 14.8 The addition of HCl to 3-hexyne occurs as an anti-addition. Give the structure, stereochem- istry, and name of the product. CONVERSION OF ALKYNES INTO 14.5 ALDEHYDES AND KETONES A. Hydration of Alkynes Water can be added to the triple bond. Although the reaction can be catalyzed by a strong acid, it is faster, and yields are higher, when a combination of dilute acid and mercuric ion (Hg2ϩ) catalysts is used. O 2 S Hg |, H2SO4 (dilute) C' CH H2O C CH3 (14.4) 0L + 0L L cyclohexylacetylene cyclohexyl methyl ketone (91% yield) The addition of water to a triple bond, like the corresponding addition to a double bond, is called hydration. The hydration of alkynes gives ketones (except in the case of acetylene itself, which gives an aldehyde; see Study Problem 14.1, p. 656). Let’s contrast the hydration reactions of alkenes (Sec. 4.9B) and alkynes. The hydration of an alkene gives an alcohol. H2SO4 R CH CH2 + H2O R CH CH3 (14.5a) an alkene OH an alcohol Because addition reactions of alkenes and alkynes are closely analogous, it might seem that an alcohol should also be obtained from the hydration of an alkyne: OH 2 H2SO4, Hg | RCC' H H2O R "C A CH2 (14.5b) LLan alkyne + Lan enol An alcohol containing an OH group on a carbon of a double bond is called an enol (pronounced en´-ôl).¯ In fact, enols are formed in the hydration of alkynes.
    [Show full text]
  • Applications of Click Chemistry in Drug Discovery
    APPLICATIONS OF CLICK CHEMISTRY IN DRUG DISCOVERY, BIOCONJUGATION AND MATERIAL SCIENCE by XINGHAI NING (Under the Direction of Geert-Jan Boons) ABSTRACT Click chemistry is a chemical philosophy introduced by Sharpless in 2001 and describes chemistry tailored to generate substances quickly and reliably by joining small units together. This dissertation has focused on the applications of click chemistry in three most relevant categories including drug discovery, bioconjugation, and materials science. The first application is developing new anti-influenza drugs by using click chemistry. We designed the novel anti-influenza reagents based on the Altermune method, which would stimulate the immune system to attack influenza viruses using a Linker Molecule(LM), which can recognize the viruses and also be recognized by immune system. The LM then redirects the immune response to the influenza viruses. The second application is developing a new bioconjugation strategy basing on the “click philosophy”. We developed a new click reagent, 4- dibenzocyclooctynol, which reacts exceptionally fast with azido compounds to give stable triazoles in the absence of any catalyst. A biotin-modified derivative is ideally suited for visualizing and tracking glycoconjugates of living cells that are metabolically labeled with azido- containing monosaccharides. In addition, we also developed a novel quantitative isotopic and chemoenzymatic tagging (QUIC-Tag) containing 4-dibenzocyclooctynol for monitoring the dynamics sialylation in vivo using quantitative mass spectrometry-based proteomics. Because sialic acid is a terminal glycan residue with a notably increased expression in cancers, this method will help to delineate the molecular basis for aberrant glycosylation in cancer and could ultimately be applied for diagnostic and therapeutic.
    [Show full text]