DOCSLIB.ORG

UC Berkeley UC Berkeley Electronic Theses and Dissertations

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
UC Berkeley UC Berkeley Electronic Theses and Dissertations UC Berkeley UC Berkeley Electronic Theses and Dissertations Title Nitroacetylenes Harnessed by Cobalt Permalink https://escholarship.org/uc/item/1kt888tn Author Windler, Gary Kenneth Publication Date 2011 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California Nitroacetylenes Harnessed by Cobalt By Gary Kenneth Windler, Jr. A dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate Division of the University of California, Berkeley Committee in charge: Professor K. Peter C. Vollhardt, chair Dr. Philip F. Pagoria (LLNL) Professor Robert G. Bergman Professor Clayton J. Radke Fall 2011 Nitroacetylenes Harnessed by Cobalt © 2011 by Gary Kenneth Windler, Jr. 1 Abstract Nitroacetylenes Harnessed by Cobalt by Gary Kenneth Windler, Jr. Doctor of Philosophy in Chemistry University of California, Berkeley Professor K. Peter C. Vollhardt, Chair The syntheses and characterization of nitroacetylenes have been studied with respect to their large-scale production, purification, and NMR spectra, respectively. The 13 C NMR spectrum of 1-nitro-2-(trimethylsilyl)ethyne ( 18 ) evidenced 13 C–14 N coupling between the alkynyl carbon and the attached nitrogen, in agreement with the previously reported spectrum of 1-nitroethyne ( 16 ). The multi-gram preparation of high purity 18 is described. A history of previous work with nitroacetylenes is reviewed. The stabilization of nitroacetylenes as hexacarbonyl dicobalt alkyne complexes was investigated. In conjunction with appropriate oxidizers, such complexes were shown to be long-term storage media for free nitroalkynes. The syntheses and complete characterization of the first two nitroalkyne transition metal complexes, [µ-1-nitro-2- (trimethylsilyl)ethyne-1,2-diyl]bis(tricarbonylcobalt)( Co –Co ) ( 25 ) and [µ-1-nitroethyne- 1,2-diyl]bis(tricarbonylcobalt)( Co –Co ) ( 26 ), are described. Phosphine derivatives of 25 were prepared and studied. The synthesis of [µ-1,2-dinitroethyne-1,2- diyl]bis(tricarbonylcobalt)( Co –Co ) ( 24 ) by direct ligation, transformation of functional groups on existing complexes, and nitration of such complexes was unsuccessful. Complexes 25 and 26 were applied to the synthesis of organic molecules. While they did not yield cyclopentenones via the Pauson-Khand cyclization, they rendered benzene derivatives by the [2 + 2 + 2] cobalt-mediated cyclotrimerization. In addition to two nitroindanes and a nitrotetralin, several new trinitrobenzene isomers were made, all potential precursors to energetic materials. The X-ray crystal structure of one of these, 1,3,5-trinitro-2,4,6-tris(trimethylsilyl)benzene ( 325 ), showed a planar, but distorted aromatic ring. i For my mother, Rev. Dr. Diane Earle Windler, who taught me to never, never, never give up. ii Table of Contents Abbreviations and Acronyms ......................................................................................... iv Acknowledgements .......................................................................................................... vi Chapter 1. Introduction: History of Explosives and Goals of this Thesis 1.1 Examples of Explosives .............................................................................. 1 1.1.1 Nitric Esters..................................................................................... 1 1.1.2 Nitroarenes ...................................................................................... 2 1.1.3 Nitroalkanes .................................................................................... 3 1.1.4 Nitramines ....................................................................................... 5 1.1.5 Nitroalkenes .................................................................................... 5 1.2 Nitroacetylenes ........................................................................................... 5 1.3 Goals ........................................................................................................... 7 1.3.1 Production of Nitroacetylenes .........................................................7 1.3.2 Stabilization of Nitroacetylenes as Metal Complexes .................... 7 1.3.3 Preparation of Hexacarbonyldicobalt Dinitroacetylene .................. 8 1.3.4 Nitroacetylene Complexes as Synthons .......................................... 8 Chapter 2. Preparation and Properties of Nitroacetylenes 2.1 Introduction ............................................................................................... 10 2.2 General Properties of Nitroacetylenes ...................................................... 11 2.3 The Synthesis of Nitroacetylenes ............................................................. 14 2.3.1 Unsuccessful Strategies ................................................................ 14 2.3.2 Successful Strategies ..................................................................... 21 2.4 Historical Approaches to Dinitroacetylene (DNA) .................................. 31 2.5 Reactions of Nitroacetylenes .................................................................... 36 2.6 Theoretical Studies of Nitroacetylenes ..................................................... 49 2.7 Results and Discussion ............................................................................. 52 2.7.1 Iodonitroacetylene, (Tributylstannyl)nitroacetylene, and (Trimethylstannyl)nitroacetylene .................................................. 53 2.7.2 Nitroacetylene ............................................................................... 55 2.7.3 (Trimethylsilyl)nitroacetylene ...................................................... 56 2.8 Conclusion ................................................................................................ 63 Chapter 3. Hexacarbonyldicobalt Nitroalkyne Complexes 3.1 Introduction ............................................................................................... 64 3.2 General Properties of Hexacarbonyldicobalt Alkyne Complexes ............ 66 3.3 Results and Discussion ............................................................................. 73 3.3.1 Trapping Strategy ......................................................................... 73 3.3.2 Functional Group Transformation Strategy .................................. 75 3.3.3 Strategy of Nitration of Alkyne[Co2(CO)6] Complexes ............... 82 3.3.4 A Milestone: Hexacarbonyldicobalt (Trimethylsilyl)nitroacetylene ...................................................... 93 3.3.5 Another Milestone: Hexacarbonyldicobalt Nitroacetylene ........ 115 3.4 Conclusion .............................................................................................. 128 Chapter 4. Nitroalkyne Complexes as Precursors to Organic Compounds 4.1 Introduction ............................................................................................. 129 4.2 Attempted Pauson-Khand Reactions ...................................................... 129 4.3 [2 + 2 + 2] Cobalt-mediated Cyclotrimerizations ................................... 135 iii 4.3.1 Reaction of 25 and 26 with α,ω Diynes ..................................... 141 4.3.1.1 Cyclization to Indanes .................................................... 141 4.3.1.2 Cyclization to Tetralins ................................................... 144 4.3.2 All-Intermolecular Cyclization of 25 with Symmetrical and Unsymmetrical Alkynes ............................................................. 147 4.3.2.1 Reaction of 25 with Symmetrical Alkynes 182 and 197 ............................................................................ 147 4.3.2.2 Reaction of 25 with 18 (Trimethylsilylnitroacetylene) .. 149 4.4 Conclusion .............................................................................................. 157 Chapter 5. Experimental ............................................................................................. 158 References ...................................................................................................................... 184 Appendix A: Definitions and Formulae A1 Explosive Terminology .......................................................................... 201 A2 Explosive Detonation Velocities ............................................................ 202 A3 Oxygen Balance ...................................................................................... 203 A4 Explosive Heats of Formation ................................................................ 203 Appendix B: Crystallographic Data B1 [μ-1-Nitro-2-(trimethylsilyl)ethyne-1,2-diyl]bis (tricarbonylcobalt)(Co–Co) (25) ............................................................. 204 B2 [μ-1-Nitroethyne-1,2-diyl]bis(tricarbonylcobalt)(Co–Co) (26) .............. 206 B3 1,3,5-Trinitro-2,4,6-tris(trimethylsilyl)benzene (325) ............................ 208 Appendix C: Numbered List of Compounds .............................................................. 215 iv Abbreviations and Acronyms Ac - Acyl HMDS - Hexamethyldisilizane BDE - Bond Dissociation Energy HMX - High Melting explosive, Boc - N-t-Butoxycarbonyl octahydro-1,3,5,7-tetranitro-1,3,5,7- Bu - Butyl tetrazocine sec-Bu - sec-Butyl HNB - Hexanitrobenzene t-Bu - tert-Butyl IR - Infrared Bz - Benzoyl LAH - Lithium Aluminum Hydride CAN - Ceric Ammonium Nitrate LLNL - Lawrence Livermore National CL-20 - China Lake formulation 20, Laboratory 2,4,6,8,10,12-hexanitro- Me - Methyl 2,4,6,8,10,12-hexaazaisowurtzitane
Load more

Recommended publications
  • Journal of Applicable Chemistry, 2012, 1 (2):250-256 (International Peer Reviewed Journal)
    Available online at www.joac.info ISSN: 2278-1862 Journal of Applicable Chemistry, 2012, 1 (2):250-256 (International Peer Reviewed Journal) Synthesis & Characterization of Novel Aniline—Formaldehyde-- α - Napthol Terpolymers M. N. Narule*K. Chawhan1 K. M. Wasnik2 P. K. Rahangdale *Dept. of Chemistry, Vidya vikas Art, Commerce & Science College, Samudrapur, Wardha-, India. 1Sai Polytechnic, Chandrapur. 2R. S. Bidkar College, Higanghat E-mail: [email protected], kavi_2605 @rediffmail.com ____________________________________________________________________________ ABSTRACT The present manuscript reported the synthesis of organic terpolymers of aniline, formaldehyde & α-naphthol. The reaction is catalyzed by strong acids, weak acids, organic acids and also by Lewis acids. The composition of terpolymers has been determined by elemental analysis and spectral studies such as UV, IR and NMR have been carried out to elucidate the structure of the terpolymers. The polymer exhibit high temperature resistance better thermal properties as evident from the TGA data. The polymer undergo degradation under inert atmosphere at increasing temperature provides good for nature. Spectroscopic data revels that long chain polymer hold together not only by C-C bond, but also the electrons are delocalized in conjugation showing coloured aniline- formaldehyde-α-naphthol terpolymers. Keywords: Terpolymerization, aniline, formaldehyde, α-naphthol. ______________________________________________________________________________ INTRODUCTION Polymer science[1-9]has
    [Show full text]
  • Robert Wilhelm Bunsen Und Sein Heidelberger Laboratorium Heidelberg, 12
    Historische Stätten der Chemie Robert Wilhelm Bunsen und sein Heidelberger Laboratorium Heidelberg, 12. Oktober 2011 Gesellschaft Deutscher Chemiker 1 Mit dem Programm „Historische Stätten der Chemie“ würdigt Robert Wilhelm Bunsen – die Gesellschaft Deutscher Chemiker (GDCh) Leistungen von geschichtlichem Rang in der Chemie. Als Orte der Erinnerung eine biographische Skizze werden Wirkungsstätten beteiligter Wissenschaftlerinnen und Wissenschaftler in einem feierlichen Akt ausgezeichnet. Eine Broschüre bringt einer breiten Öffentlichkeit deren wissenschaft- Bunsen war einer der Wegbereiter der Physikalischen Chemie liches Werk näher und stellt die Tragweite ihrer Arbeiten im und ein bedeutender Vertreter der anorganisch-analytischen aktuellen Kontext dar. Ziel dieses Programms ist es, die Erinne- Richtung. Seine wissenschaftliche Bedeutung liegt in der Ent- rung an das kulturelle Erbe der Chemie wach zu halten und die wicklung und Perfektionierung von Methoden und Instrumen- Chemie mit ihren historischen Wurzeln stärker in das Blickfeld ten. Diese Arbeitsschwerpunkte hat Bunsen von Beginn seiner der Öffentlichkeit zu rücken. Karriere an verfolgt und systematisch ausgebaut. Am 12. Oktober 2011 gedenken die GDCh, die Deutsche 1811 als jüngster von vier Söhnen einer bürgerlichen protestan- Bunsen-Gesellschaft für Physikalische Chemie (DBG), die Che- tischen Familie in Göttingen geboren, begann Bunsen dort 1828 mische Gesellschaft zu Heidelberg (ChGzH) und die Ruprecht- das Studium der Naturwissenschaften. Seine wichtigsten Lehrer Karls-Universität
    [Show full text]
  • WO 2008/084303 Al
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date PCT (10) International Publication Number 17 July 2008 (17.07.2008) WO 2008/084303 Al (51) International Patent Classification: (US). SCHAUM, Robert, Philip [CA/US]; Pfizer Global C07D 471/04 (2006.01) A61P 3/10 (2006.01) Research and Development, 50 Pequot Avenue, New A61K 31/437 (2006.01) London, CT 06320 (US). (21) International Application Number: (74) Agent: FULLER, Grover, E ; c/o GEORGE, Nancy Mc- PCT/IB2007/003844 Graw, Pfizer Inc. MS8260-1615, Eastern point Road, Gro ton, CT 06340 (US). (22) International Filing Date: 3 December 2007 (03.12.2007) (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, (25) Filing Language: English AT,AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, (26) Publication Language: English ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, (30) Priority Data: LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, 60/876,334 2 1 December 2006 (21.12.2006) US MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, 60/970,653 7 September 2007 (07.09.2007) US PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, (71) Applicant (for all designated States except US): PFIZER ZM, ZW PRODUCTS INC.
    [Show full text]
  • MO STUDIES of SOME NONBENZENOID AROMATIC SYSTEMS Electrons
    MO STUDIESOFSOME NONBENZENOID AROMATIC SYSTEMS MIcL J. S. DEWAR Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, USA ABSTRACT A new version of(MINDO/3) of the MINDO semiempirical SCF MO method has been developed which seems to avoid the serious defects of earlier treat- ments. Very extensive tests show that it gives results at least comparable with those of the best ab initio SCF procedures at one-hundred-thousandth of the cost. Calculations are reported for the benzynes, for various cyclic polymethines, including (CH), (CH)3, (CH), (CH)4, (CH), (CH)5, (CH), (CI{), and (CH)18, for azulene and pentalene, for the cycloheptatriene—norcaradiene equilibrium, for spironoatetraene, for silabenzene, for a variety of poly- azines and polyazoles, and for various aromatic and potentially aromatic sulphur-containing compounds. INTRODUCTION While theoretical organic chemistry has long been based on the results of quantum mechanical treatments, in particular simplified versions of the molecular orbital (MO) method, these until recently have been too inaccurate to give results of more than qualitative significance. Many problems have therefore remained outside the scope of current theory since their solution depended on quantitative estimates of the relative energies of atoms and molecules. Recently it has become possible to carry out such quantitative calculations and the results are already proving of major chemical interest in a number of areas. The purpose of this lecture is to report some preliminary studies of this kind of various aromatic systems and problems connected with them. There is of course no question of obtaining accurate solutions of the Schrodinger equation for molecules large enough to be of chemical interest.
    [Show full text]
  • Unesco – Eolss Sample Chapters
    ORGANIC AND BIOMOLECULAR CHEMISTRY – Vol. I - Stereochemistry - Franco Cozzi STEREOCHEMISTRY Franco Cozzi Dipartimento di Chimica Organica e Industriale, Universita' degli Studi di Milano, Italy Keywords: Symmetry, chirality, chirotopicity, stereogenicity, stereoisomerism, conformation, configuration, stereochemical descriptors, enantiomeric composition, optical activity, stereoselectivity, stereoselective synthesis. Contents 1. Introduction 2. Symmetry 3. Chirality 4. Stereogenicity 5. Conformation and configuration 6. Configuration descriptors 7. Dependence of the properties of chiral molecules on the enantiomeric composition 8. How to obtain stereoisomerically pure compounds Glossary Bibliography Biographical Sketch Summary The aim of this chapter is to provide the reader with the basic concepts necessary to deal with the stereochemical aspects of organic chemistry. As in any other interpretation of stereochemistry that aspires to be rational, also in this one a detailed knowledge of the symmetry properties of a molecule and of the relationship between symmetry properties and molecular behavior at all levels is considered of fundamental importance. Another central point is the strict distinction between chirality and stereogenicity that underlines all the discussion both as an inspiring principle and guidance to the use of a correct stereochemical language. In addition to classic topics such as isomer classification, stereochemicalUNESCO descriptors, and conseque nces– ofEOLSS enantiomeric composition, a short presentation of the principal methods for obtaining enantiomerically pure compounds is included. 1. IntroductionSAMPLE CHAPTERS According to the Merriam-Webster Online Dictionary, stereochemistry is: "a branch of chemistry that deals with the spatial arrangement of atoms and groups in molecules". The Oxford Dictionary of English defines stereochemistry: "the branch of chemistry dealing with composition of matter as affected by relations of atoms in space".
    [Show full text]
  • Heterocyclic Chemistry at a Glance Other Titles Available in the Chemistry at a Glance Series
    Heterocyclic Chemistry at a Glance Other Titles Available in the Chemistry at a Glance series: Steroid Chemistry at a Glance Daniel Lednicer ISBN: 978-0-470-66084-3 Chemical Thermodynamics at a Glance H. Donald Brooke Jenkins ISBN: 978-1-4051-3997-7 Environmental Chemistry at a Glance Ian Pulford, Hugh Flowers ISBN: 978-1-4051-3532-0 Natural Product Chemistry at a Glance Stephen P. Stanforth ISBN: 978-1-4051-4562-6 The Periodic Table at a Glance Mike Beckett, Andy Platt ISBN: 978-1-4051-3299-2 Chemical Calculations at a Glance Paul Yates ISBN: 978-1-4051-1871-2 Organic Chemistry at a Glance Laurence M. Harwood, John E. McKendrick, Roger Whitehead ISBN: 978-0-86542-782-2 Stereochemistry at a Glance Jason Eames, Josephine M Peach ISBN: 978-0-632-05375-9 Reaction Mechanisms at a Glance: A Stepwise Approach to Problem-Solving in Organic Chemistry Mark G. Moloney ISBN: 978-0-632-05002-4 Heterocyclic Chemistry at a Glance Second Edition JOHN A. JOULE The School of Chemistry, The University of Manchester, UK KEITH MILLS Independent Consultant, UK This edition fi rst published 2013 © 2013 John Wiley & Sons, Ltd Registered offi ce John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offi ces, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. The right of the author to be identifi ed as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988.
    [Show full text]
  • Template for Electronic Submission to ACS Journals
    This item is the archived peer-reviewed author-version of: Ligand-driven anion-π interaction-induced silver(I) coordination chemistry Reference: Safin Damir A., Robeyns Koen, Babashkina Maria G., Vande Velde Christophe, Filinchuk Yaroslav.- Ligand-driven anion-π interaction-induced silver(I) coordination chemistry Crystal growth & design - ISSN 1528-7483 - 16:7(2016), p. 3763-3770 Full text (Publishers DOI): http://dx.doi.org/doi:10.1021/ACS.CGD.6B00277 To cite this reference: http://hdl.handle.net/10067/1337140151162165141 Institutional repository IRUA Ligand-driven Anion–π Interaction-induced Silver(I) Coordination Chemistry Damir A. Safin,*† Koen Robeyns,† Maria G. Babashkina,† Christophe M. L. Vande Velde,‡ and Yaroslav Filinchuk† Dedicated to Professor Wolfgang Kaim on the Occasion of his 65th Birthday. †Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium ‡Faculty of Applied Engineering, Advanced Reactor Technology, University of Antwerp, Salesianenlaan 90, BE-2660 Hoboken, Belgium ABSTRACT Three novel coordination compounds were successfully isolated using rare and poorly studied 5-phenyl-2,2'-bipyridine (LI) and completely unexplored 6-phenyl-3-(pyridin-2- II I yl)-1,2,4-triazine (L ) ligands with AgNO3, namely [Ag(L )2]NO3∙0.5H2O (1), I II [Ag(L )PPh3NO3]∙0.5CH2Cl2 (2) and [Ag2(L )2(H2O)2](NO3)2 (3). 1 can be converted into 2 upon reacting with PPh3, while no conversion was observed for 3. The formation of 3 was – templated through anion-π-system interactions between the NO3 anions and the electron deficient 1,2,4-triazine ring of LII, which play a crucial role in the supramolecular assembly.
    [Show full text]
  • Some Features of Excited States Density Matrix Calculation And
    Some Features of Excited States Density Matrix Calculation and Their Pairing Relations in Conjugated Systems Myriam Segre de Giambiagi and Mario Giambiagi Centro Brasileiro de Pesquisas Fisieas, CBPF/CNPq, Rio de Janeiro, RJ-Brasil Z. Naturforsch. 38 a, 595-600 (1983); received February 8, 1983 Direct PPP-type calculations of self-consistent (SC) density matrices for excited states are described and the corresponding "thawn" molecular orbitals (MO) are discussed. Special atten- tion is addressed to particular solutions arising in conjugated systems of a certain symmetry, and to their chemical implications. The U(2) and (7(3) algebras are applied, respectively, to the 4- electron and 6-electron cases; a natural separation of excited states in different cases follows. A simple approach to the convergence problem for excited states is given. The complementarity relations, an alternative formulation of the pairing theorem valid for heteromolecules and non- alternant systems, allow some fruitful experimental applications. Together with the extended pairing relations shown here, they may help to rationalize general trends. 1. Introduction soon as the "frozen" scheme is loosened [13, 14], for they are functions of the specific state. On the other SCF methods confront substantial difFiculties hand, Mehrotra and Hoffmann [15] have set forth when dealing rigorously with excited states [1 — 3], an attractive way of recovering the primitive signifi- and much interesting work was done with the cance of the Mulliken-Walsh diagrams. They pro- simpler methods ([4], p. 106). Methods involving pose an "average state" (resembling Hall's reference different degrees of sophistication have been pro- state) as a compromise between all the electronic posed in order to overcome the problem that the states of a molecule taken "in a democratic fashion", excited state functions are usually not orthogonal to their tempered orbital energies being quite appeal- the ground state functions [5 — 7], ing.
    [Show full text]
  • Nobel Lecture, December 12, 1945
    L EOPOLD Multimembered rings, higher terpene compounds and male sex hormones Nobel Lecture, December 12, 1945 This lecture should have been delivered in December 1939*, but owing to a postponement of 6 years forced by the intervention of war, I have been able to use some results obtained in the meantime to round off the overall picture. Consequently I can now report on the results of 25 years of laboratory work in two fields of the chemistry of alicyclic compounds: multimembered rings and higher terpene compounds (polyterpenes), to which the third group named in the title, the male sex hormones, is closely related. Alicyclic compounds scarcely differ in their chemical properties from their aliphatic analogues. Many investigations, especially during the past twenty- five years, have shown, however, that in spite of this close chemical similarity aliphatic compounds and their alicyclic analogues can exhibit entirely different physiological properties. We see that certain well-defined physiological prop- erties may appear or disappear in the transition from an aliphatic to an alicyclic compound or vice versa. As a result of the accumulation of such observations, alicyclic compounds to which only scant biochemical importance was at- tached as little as 20-25 years ago, have now advanced to the forefront of interest. Multimembered rings After Kekulé, in 1865, first introduced the carbon ring into structural chem- istry in his formula for benzene, the 6-membered ring maintained its unique position in the taxonomy of organic chemistry for several decades. Indeed, a heterocyclic 5-membered ring containing nitrogen became known in 1870 as a result of Adolf von Baeyer’s work on indigo; but this did not imme- * Data available at that time formed the subject of a number of lectures which I de- livered between December 1939 and April 1940 in Zurich, Zagreb, Utrecht, Amster- dam, Delft, Liége, Brussels and Paris.
    [Show full text]
  • Isatin Derivatives As a New Class of Aldose Reductase Inhibitors with Antioxidant Activity
    Isatin Derivatives as a New Class of Aldose Reductase Inhibitors With Antioxidant Activity Wenchao Liu Beijing Institute of Technology Huan Chen Beijing Institute of Technology Xiaonan Zhang Beijing Institute of Technology Xin Zhang Beijing Institute of Technology Long Xu Beijing Institute of Technology Yanqi Lei Beijing Institute of Technology Changjin Zhu Beijing Institute of Technology Bing Ma ( [email protected] ) Beijing Institute of Technology Research Article Keywords: Aldose reductase inhibitors, Isatin derivatives, Antioxidant activity, Diabetic complications Posted Date: May 10th, 2021 DOI: https://doi.org/10.21203/rs.3.rs-489101/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Isatin derivatives as a new class of aldose reductase inhibitors with antioxidant activity Wenchao Liu, Huan Chen, Xiaonan Zhang, Xin Zhang, Long Xu, Yanqi Lei, Changjin Zhu and Bing Ma* ✉ Bing Ma [email protected] School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Zhongguancun South Street, Beijing, China Abstract: In this work, isatin was employed as the scaffold to design aldose reductase inhibitors with antioxidant activity. Most of the isatin derivatives were proved to be excellent in the inhibition of aldose reductase (ALR2) with IC50 values at submicromolar level, and (E)-2-(5-(4-methoxystyryl)-2,3-dioxoindolin-1-yl) acetic acid (9g) was identified as the most effective with an IC50 value of 0.015 μM. Moreover, compounds 9a-h with styryl side chains at the C5 position of isatin showed potent antioxidant activity. Particularly, the phenolic compound 9h demonstrated similar antioxidant activity with the well-known antioxidant Trolox.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 8,168.212 B2 12 N
    USOO81 68212B2 (12) United States Patent (10) Patent No.: US 8,168.212 B2 Ptchelintsev et al. (45) Date of Patent: May 1, 2012 (54) TOPICAL COMPOSITIONS COMPRISING (52) U.S. Cl. ........................................ 424/401: 514/439 NON-PROTEOGENICAMINOACDS AND (58) Field of Classification Search .................. 424/401; METHODS OF TREATING SKIN 5147439 See application file for complete search history. (75) Inventors: Dmitri S. Pitchelintsev, Jersey City, NJ (US); Laurence Dryer, Long Beach, CA (56) References Cited (US); Xiaochun Luo, New City, NY (US) U.S. PATENT DOCUMENTS 5, 122,514 A 6/1992 Boger et al. (73) Assignee: Avon Products, Inc., New York, NY 5,508,295 A 4/1996 Hanson et al. (US) 5,851,994 A 12/1998 Schreiber et al. 6,267,978 B1* 7/2001 Sang et al. .................... 424/401 *) NotOt1Ce: Subjubject to anyy d1Sclaimer,disclai theh term off thisthi 2005, 0188427 A1 8, 2005 Li et al. patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS U.S.C. 154(b) by 0 days. WO 2007/056464 A1 5/2007 (21) Appl. No.: 12/747,272 OTHER PUBLICATIONS Jones et al (J. Am. Chem. Soc., 1950, 72 (10), pp. 4526-4529).* (22) PCT Filed: Nov. 14, 2008 Noblesse et al., “Lysyl Oxidase-Like and Lysyl Oxidase are present in the Dermis and Epidermis...”. J. Invest Dermatol. Mar. 2004; 122 (86). PCT No.: PCT/US2O08/083490 (3):621-30. Kiety et al., Elastic fibres; J. Cell Sci., Jul. 15, 2002; 115 (Pt 14):2817 S371 (c)(1), 28. (2), (4) Date: Jun. 10, 2010 (Continued) (87) PCT Pub.
    [Show full text]
  • Design and Synthesis of Modular Reagents for Chemical Biology
    DESIGN AND SYNTHESIS OF MODULAR REAGENTS FOR CHEMICAL BIOLOGY by BereketAb T. Mehari ____________________________ Copyright © Bereketab T. Mehari 2018 A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY WITH A MAJOR IN CHEMISTRY In the Graduate College THE UNIVERSITY OF ARIZONA 2018 1 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of the requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that an accurate acknowledgement of the source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: BereketAb T. Mehari 3 ACKNOWLEDGEMENTS I would like to first extend my gratitude to my research advisor, Dr. John Jewett, for his guidance throughout my graduate career. It has been a great experience working under his mentorship. I would also like to thank my committee members for their advice in preparing for this work. I would like to thank my lab mates for both their chemistry input and moral support. I have made many friends in the department who have assisted me in becoming a better scientist.
    [Show full text]