DOCSLIB.ORG

Iron-Catalyzed Carbon-Carbon Bond Activation

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Iron-Catalyzed Carbon-Carbon Bond Activation Iron-Catalyzed Carbon-Carbon Bond Activation Von der Fakultät Chemie der Universität Stuttgart zur Erlangung der Würde eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigte Abhandlung vorgelegt von Che-Hung Lin aus Taipei, Taiwan Hauptberichter: Prof. Dr. Bernd Plietker Mitberichterin: Prof. Dr. Sabine Laschat Tag der mündlichen Prüfung: 31.01.2018 Institut für Organische Chemie der Universität Stuttgart 2018 Die vorliegende Arbeit entstand auf Anregung und unter Anleitung von Herrn Prof. Dr. Bernd Plietker am Institut für Organische Chemie der Universität Stuttgart im Zeitraum von Januar 2014 bis Januar 2018. Parts of this thesis have been published: 1. “The evolution of Fe-catalyzed nucleophilic activation of acceptor-substituted vinyl- and arylcyclopropanes” C.-H. Lin, B. Plietker, Isr. J. Chem. 2016, 56, 409-416. 2. “Non-decarbonylative photochemical versus thermal activation of Bu4N[Fe(CO)3(NO)] - the Fe-catalyzed Cloke-Wilson rearrangement of vinyl and arylcyclopropanes” C.-H. Lin, D. Pursley, J. Klein, J. Teske, J. Allen, F. Rami, A. Köhn, B. Plietker, Chem. Sci. 2015, 6, 7034-7043. i Acknowledgements I would like to express my sincere gratitude to my supervisor, Prof. Dr. Bernd Plietker for giving me an opportunity to join his group, interesting research topics, and excellent working conditions. I would also like to thank my dissertation committee members, Prof. Dr. Sabine Laschat and Prof. Dr. Joris van Slageren form the University of Stuttgart for giving me their great help and priceless advice. I would like to thank all the members of Plietker’s group, Cecilia Socolsky, Dihan Zhang, Johannes Klein, Shih-Fan Hsu, Fiene Horeischi, Christine Häcker, Susanne Rommel, Berenice Heid, Samuel Lorenz, Sven Scholz, Isabel Alt, Dominik Pursley, Johannes Teske, Claudia Guttroff, Fabian Rami, Pascal Eisele, Aslihan Baykal, Marie-Idrissa Picher, Lei Guo, Annika Röske, Franziska Ullwer, Frederik Kramm, and Frank Kraus to provide warm working environments and nice discussions during my PhD. I acknowledge Dominik Pursley’s collaboration for in the investigations of Cloke-Wilson rearrangement. I wish to thank my laboratory mate, Johannes Teske, for his company. The appreciation is also expressed to Isabel Alt, Dihan Zhang, and Lei Guo for the daily life assistance. A special thank also goes to Johannes Teske, Fabian Rami, and Lei Guo for revising my thesis. I am also indebted to all the members of the analytical departments, Ms. Twiehaus- Heynhold, Ms. Wohlbold, Mr. Wegner, Mr. Trinker and Mr. Dr. Frey. ii Erklärung über die Eigenständigkeit der Dissertation Hiermit erkläre ich, dass ich die vorliegende Dissertation „Iron-Catalyzed Carbon-Carbon Bond Activation“ selbstständig verfasst und keine anderen als die genannten Quellen und Hilfsmittel verwendet habe. Die aus fremden Quellen entnommenen Passagen und Gedanken sind als solche kenntlich gemacht. Stuttgart, den 31.01.2018 Che-Hung Lin iii “We can only see a short distance ahead, but we can see plenty there that needs to be done.” ― Alan Turing, Computing machinery and intelligence iv Table of Contents Acknowledgements ...................................................................................................................ii Table of Contents ...................................................................................................................... v List of Abbreviations ................................................................................................................ xii I. Theoretical Section ............................................................................................................... 1 1. Introduction ............................................................................................................................ 2 1.1 Transition-Metal-Catalyzed C-C Bond Activations .................................................... 2 1.2 Iron-Catalyzed C-C Bond Activations ......................................................................... 4 1.3 Synthetic Applications of Three- and Four-Membered Rings ................................. 8 1.3.1 Donor-Acceptor Cyclopropanes ........................................................................ 8 1.3.1.1 Ring-Opening reactions ............................................................................ 9 1.3.1.2 Cycloaddition reactions .......................................................................... 10 1.3.1.3 Rearrangements ...................................................................................... 12 1.3.2 Cyclobutanes ...................................................................................................... 14 1.4 Photochemistry ............................................................................................................. 17 1.4.1 Introduction ......................................................................................................... 17 1.4.2 Photoredox Catalysis ........................................................................................ 19 2. Photoactive Bu4N[Fe(CO)3NO]-Catalyzed Cloke-Wilson Rearrangement of Vinyl- and Arylcyclopropanes .......................................................................................................... 23 2.1 Purpose of this Research ............................................................................................ 23 2.2 Results and Discussion ............................................................................................... 24 2.2.1 Fe-Catalyzed Cloke-Wilson Rearrangement of Vinylcyclopropanes ......... 24 2.2.1.1 Optimization of the Cloke-Wilson Rearrangement of Vinylcyclopropanes............................................................................................... 24 2.2.1.2 Scope of the Cloke-Wilson Rearrangement of Vinylcyclopropanes 26 2.2.2 Fe-Catalyzed Cloke-Wilson Rearrangement of Arylcyclopropanes .......... 32 2.2.2.1 Optimization of the Cloke-Wilson Rearrangement of Arylcyclopropanes ................................................................................................ 32 2.2.2.2 Scope of the Cloke-Wilson Rearrangement of Arylcyclopropanes.. 33 2.2.3 Investigation of the Reaction Mechanism ...................................................... 38 2.3 Conclusion and Outlook .............................................................................................. 47 3. TBA[Fe]-catalyzed Cyclopropylimine Rearrangement ................................................. 49 3.1 Purpose of this Research ............................................................................................ 49 v 3.2 Results and Discussion ............................................................................................... 50 3.2.1 Cyclopropylimine Synthesis ............................................................................. 50 3.2.2 Optimization of the TBA[Fe]-catalyzed Cyclopropylimine Rearrangement ........................................................................................................................................ 52 3.2.3 Substrate Scope of the TBA[Fe]-Catalyzed Cyclopropylimine Rearrangement ............................................................................................................ 55 3.3 Conclusion and Outlook .............................................................................................. 58 4. TBA[Fe]-Catalyzed Cyclobutane Rearrangement ........................................................ 60 4.1 Purpose of this Research ............................................................................................ 60 4.2 Results and Discussion ............................................................................................... 61 4.2.1 Arylcyclobutane Synthesis ............................................................................... 61 4.2.2 TBA[Fe]-catalyzed Arylcyclobutane Rearrangement ................................... 62 4.2.3 Vinylcyclobutane and Vinylcyclobutanone Synthesis .................................. 64 4.2.4 TBA[Fe]-catalyzed Vinylcyclobutane Rearrangement ................................. 69 4.3 Conclusion and Outlook .............................................................................................. 72 5. Summary and Future Work .............................................................................................. 74 6. Abstract (English) ............................................................................................................... 76 7. Abstract (Deutsch) ............................................................................................................. 77 II. Experimental Section ......................................................................................................... 79 8. General Remarks ............................................................................................................... 80 9. IR spectra of TBA[Fe] ........................................................................................................ 81 10. UV spectrum of TBA[Fe] ................................................................................................. 85 11. Fluorescence spectrum of TBA[Fe] .............................................................................. 86 12. TBA[Fe]-Catalyzed Cloke-Wilson Rearrangement of Vinyl- and Arylcyclopropanes ................................................................................................................................................... 87 12.1 Preparation of
Load more

Recommended publications
  • Synthesis and Consecutive Reactions of Α-Azido Ketones: a Review
    Molecules 2015, 20, 14699-14745; doi:10.3390/molecules200814699 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Review Synthesis and Consecutive Reactions of α-Azido Ketones: A Review Sadia Faiz 1,†, Ameer Fawad Zahoor 1,*, Nasir Rasool 1,†, Muhammad Yousaf 1,†, Asim Mansha 1,†, Muhammad Zia-Ul-Haq 2,† and Hawa Z. E. Jaafar 3,* 1 Department of Chemistry, Government College University Faisalabad, Faisalabad-38000, Pakistan, E-Mails: [email protected] (S.F.); [email protected] (N.R.); [email protected] (M.Y.); [email protected] (A.M.) 2 Office of Research, Innovation and Commercialization, Lahore College for Women University, Lahore-54600, Pakistan; E-Mail: [email protected] 3 Department of Crop Science, Faculty of Agriculture, Universiti Putra Malaysia, Serdang-43400, Selangor, Malaysia † These authors contributed equally to this work. * Authors to whom correspondence should be addressed; E-Mails: [email protected] (A.F.Z.); [email protected] (H.Z.E.J.); Tel.: +92-333-6729186 (A.F.Z.); Fax: +92-41-9201032 (A.F.Z.). Academic Editors: Richard A. Bunce, Philippe Belmont and Wim Dehaen Received: 20 April 2015 / Accepted: 3 June 2015 / Published: 13 August 2015 Abstract: This review paper covers the major synthetic approaches attempted towards the synthesis of α-azido ketones, as well as the synthetic applications/consecutive reactions of α-azido ketones. Keywords: α-azido ketones; synthetic applications; heterocycles; click reactions; drugs; azides 1. Introduction α-Azido ketones are very versatile and valuable synthetic intermediates, known for their wide variety of applications, such as in amine, imine, oxazole, pyrazole, triazole, pyrimidine, pyrazine, and amide alkaloid formation, etc.
    [Show full text]
  • Tracking of Bacterial Metabolism with Azidated Precursors and Click- Chemistry”
    Tracking of bacterial metabolism with azidated precursors and click-chemistry Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften vorgelegt beim Fachbereich für Biowissenschaften (15) der Johann Wolfang Goethe Universität in Frankfurt am Main von Alexander J. Pérez aus Nürnberg Frankfurt am Main 2015 Dekanin: Prof. Dr. Meike Piepenbring Gutachter: Prof. Dr. Helge B. Bode Zweitgutachter: Prof. Dr. Joachim W. Engels Datum der Disputation: 2 Danksagung Ich danke meinen Eltern für die stete und vielseitige Unterstützung, deren Umfang ich sehr zu schätzen weiß. Herrn Professor Dr. Helge B. Bode gilt mein besonderer Dank für die Übernahme als Doktorand und für die Gelegenheit meinen Horizont in diesen mich stets faszinierenden Themenbereich in dieser Tiefe erweitern zu lassen. Seine persönliche und fachliche Unterstützung bei der Projektwahl und der entsprechenden Umsetzung ist in dieser Form eine Seltenheit und ich bin mir dieser Tatsache voll bewusst. Gerade die zusätzlich erworbenen Kenntnisse im Bereich der Biologie, sowie der Wert interdisziplinärer Zusammenarbeit ist mir durch zahlreiche freundliche und wertvolle Mitglieder der Arbeitsgruppe bewusst geworden und viele zündenden Ideen wären ohne sie womöglich nie aufgekommen. Einen besonderen Dank möchte ich in diesem Kontext Wolfram Lorenzen und Sebastian Fuchs, die gerade in der Anfangszeit eine große Hilfe waren, ausdrücken. Dies gilt ebenso für die „N100-Crew“ und sämtliche Freunde, die in dieser Zeit zu mir standen und diesen Lebensabschnitt unvergesslich gemacht haben.
    [Show full text]
  • Triphenylphosphine Phenylimide 의 전기화학적인 환원 Electrochemical
    DAEHAN HWAHAK HWOEJEE (Journal of the Korean Chemical Society) Vol. 18, No. 5, 1974 Printed in Republic of Korea Triphenylphosphine Phenylimide 의 전기화학적인 환원 朴鍾民* , Wilson M. Gulick, Jr. 미국 후로리다주립대학교 화학과 (1974. 7. 13 접수 ) Electrochemical Reduction of Triphenylphosphine Phenylimide Chong Min *Pak and Wilson M. Gulick, Jr. Department of Chemistry^ Floridia State University^ Tallahassee, Florida 32306, U, S. A. 요 약 . Triphenylphosphine phenylimid合의 비수용액에서의 전기화학적인 환원반응을 polaro- graphy, cyclic voltammetry, controlled-potential coulometry 및 electron spin resonance 법 을 써 서 고 찰하였다 . 이 유기 인화합물은 cme-electon transfer 에 따라서 anion radical 형성되 나 순간일 뿐이 고 protonation 과 재차 one-electon reduction 결과 인과 질소사이의 이중결합이 끊어진다 . 그 결과 아 닐린이 주요 반응생성물로서 발견되었다 . 또 한편 동반하는 화학반응결과 생긴 주산물의 하나인 triphenylposphine oxide 의 환원결과 인과 페닐사이의 단일결합이 끊어지는 것도 관찰할 수 있었다 . Abstract. The electrochemical reduction of triphenylphosphine penylimide in nonaqueous media has been examined by polarography, cyclic voltammetry, controlled-potential coulometry and electron spin resonance spectroscopy. The reduction of tiiphe교 ylphosphine phenylimide proceeds by a one- electron transfer to form anion radical which undergoes both protonation and a second one-electron reduction followed by cleavage of the phosphorus-nitrogen double bond. Aniline is a major product. The cleavage of a phosphours-phenyl bond was also observed after reduction of triphenylphosphine oxide which is one of the major products of the chemical reaction which follow the primary process. synthesis and ligands in coordination chemistry. 1. Introduction The range of application of phosphorus com­ Phosphorus compounds have become increas­ pounds in modern technology is extremely broad ingly important as intermediates in organic and varied.
    [Show full text]
  • Mediated Azide-Alkyne Cycloaddition Reactions Using Chelating Azides Wendy S
    Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2012 Development of Copper(II)-Mediated Azide-Alkyne Cycloaddition Reactions Using Chelating Azides Wendy S. Brotherton Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES DEVELOPMENT OF COPPER(II)-MEDIATED AZIDE-ALKYNE CYCLOADDITION REACTIONS USING CHELATING AZIDES By WENDY S. BROTHERTON A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy Degree Awarded: Spring Semester, 2012 Wendy S. Brotherton defended this dissertation on December 8, 2011. The members of the supervisory committee were: Lei Zhu Professor Directing Dissertation P. Bryant Chase University Representative Gregory B. Dudley Committee Member Igor V. Alabugin Committee Member Michael G. Roper Committee Member The Graduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii This manuscript is dedicated to my mother for all of her encouragement and sacrifices over the many years of my education. I would also like to dedicate this to my fiancé, Travis Ambrose, who has been so supportive and encouraging throughout this entire process. iii ACKNOWLEDGEMENTS I would like to thank Professor Lei Zhu for his guidance, support and assistance over the course of my graduate studies. I would like to express my gratitude to the past and present members of the Zhu group for their support and friendship over the years: Dr.
    [Show full text]
  • Synthetic Approaches to Heterocyclic Bicyclo[2.1.0]Pentanes
    SYNTHETIC APPROACHES TO HETEROCYCLIC BICYCLO[2.1.0]PENTANES Rabah N. Alsulami A THESIS Submitted to the Graduate College of Bowling Green State University in partial fulfillment of The requirements for the degree of MASTER OF SCIENCE August 2011 Committee: Thomas H. Kinstle (Advisor) Marshall Wilson Alexander N. Tarnovsky ABSTRACT Thomas H. Kinstle, Advisor Bicyclic systems such as bicyclo[2.1.0]pentanes and 5-oxabicyclo[2.1.0]pentanes are known to display a variety of unique chemical properties associated with their high strain energy. To the best of our knowledge, there were no reports regarding synthesis and investigation of 5- azabicyclo[2.1.0]pentanes. Therefore, the initial goal of this research was synthesis of 5-azabicyclo[2.1.0]pentane and investigation of its chemical properties. The cycloaddition reaction of azides (58, 59, 61) to olefins (54, 55) with further elimination of nitrogen was chosen as a synthetic method in order to obtain the compounds of interest. Starting olefins (3,3-dimethyl-1-cyclobutene-1-carboxylic acid (54) and methyl 3,3-dimethyl-1-cyclobutene-1-carboxylate (55) and azides phenyl azide (58), p- toluenesulfonyl azide (59), and picryl azide (61) were successfully synthesized and characterized by NMR spectroscopy and GCMS spectrometry. The addition reaction between azides and olefins was performed under various conditions, such as different solvents and temperature; however, according to NMR spectroscopy and GCMS spectrometry, olefins (54, 55) do not undergo cycloaddition reaction with azides (58, 59, 61). In order to investigate that behavior, cycloaddition reactions of more reactive olefins (66, 68) with azides (58, 59, 61) were performed under a variety of conditions.
    [Show full text]
  • Base-Catalyzed Synthesis of Aryl Amides from Aryl Azides and Aldehydes
    Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2015 SUPPORTING INFORMATION Base-Catalyzed Synthesis of Aryl Amides from Aryl Azides and Aldehydes Sheng Xie,aYang Zhang,a Olof Ramström,*,a and Mingdi Yan*,a,b aDepartment of Chemistry, KTH - Royal Institute of Technology, Teknikringen 36, S-10044 Stockholm, Sweden bDepartment of Chemistry, University of Massachusetts Lowell, 1 University Ave., Lowell, MA 01854, USA *E-mail: [email protected], [email protected] Table of Contents General procedures ................................................................................................................................... S1 Figure S1. 1H NMR spectra of model reaction ......................................................................................... S2 Figure S2. Azide decomposition temperatures ......................................................................................... S2 Table S1. Optimization of conditions for reaction of α-unsubstituted aldehyde with phenyl azide. ....... S3 Synthesis of azides .................................................................................................................................... S3 Synthesis of products ................................................................................................................................ S7 References .............................................................................................................................................. S16 Characterization
    [Show full text]
  • Hale Ronnie L 196812 Phd 326
    In presenting the dissertation as a partial fulfillment of the requirements for an advanced degree from the Georgia Institute of Technology, I agree that the Library of the Institute shall make it available for inspection and circulation in accordance with its regulations governing materials of this type. I agree that permission to copy from, or to publish from, this dissertation may be granted by the professor under whose direction it was written, or, in his absence, by the Dean of the Graduate Division when such copying or publication is solely for scholarly purposes and does not involve potential financial gain. It is under- stood that any copying from, or publication of, this dis- sertation which involves potential financial gain will not be allowed without written permission. 7/25/68 ,^; I lid PART I THE AZIDE-OLEFIN REACTION PART II STUDIES IN THE SYNTHESES OF EREMOPHILANE SESQUITERPENES A THESIS Presented to The Faculty of the Graduate Division by Ronnie Lee Hale In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology October, 1968 PART I THE AZIDE-OLEFIN REACTION PART II STUDIES IN THE SYNTHESES OF EREMOPHILANE SESQUITERPENES Approved: . A 4:Chlrmari (j im CJ Date approved by Chairman /11*-49 , 'TU11111[11.. ii ACKNOWLEDGEMENTS The author expresses gratitude to Dr. Leon H. Zalkow for his invaluable guidance and counsel during the course of this study and in preparation of this dissertation. The author also wishes to thank Drs. John R. Dyer and Drury S. Caine, III for serving as members of the read- ing committee.
    [Show full text]
  • (19) United States (12) Patent Application Publication (10) Pub
    US 20090069569Al (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/0069569 A1 Nolan et al. (43) Pub. Date: Mar. 12, 2009 (54) CYCLOADDITION OF AZIDES AND Related US. Application Data ALKYNES (60) Provisional application No. 60/971,779, ?led on Sep. 12, 2007. (75) Inventors: Steven P. Nolan, Tarragona (ES); Silvia Diez-Gonzalez, Publication Classi?cation Barakaldo-Vizcaya (ES) (51) Int. C1. 0070 249/04 (2006.01) Correspondence Address: (52) us. c1. ...................................................... .. 548/255 McGLINCHEY STAFFORD, PLLC (57) ABSTRACT Attn: IP Group 301 Main Street, 14th Floor This invention provides a process Which comprises contact BATON ROUGE, LA 70802 (US) ing, in a reaction Zone, at least one organic aZide, at least one alkyne, and at least one N-heterocyclic carbene copper com pound in Which the ligands are either (i) a halide and an (73) Assignees: Institut Catala d’Investigacio N-heterocyclic carbene or (ii) tWo N-heterocyclic carbenes Quimica, Tarragona (ES); and a BF; or PF; anion, to form a l,2,3-triaZole in Which at Institucio Catalana de Recerca i least the l and 4 positions each has a substituent. The N-het Estudis Avancats, Barcelona (ES) erocyclic carbene either an imidaZol-2-ylidene in Which the l and the 3 positions each has a substituent Which has at least (21) Appl. No.: 12/209,323 one carbon atom, or a 4,5-dihydro-imidaZol-2-ylidene in Which the l and the 3 positions each has a substituent Which (22) Filed: Sep. 12, 2008 has at least one carbon atom. US 2009/0069569 A1 Mar.
    [Show full text]
  • Copper-Catalyzed Azide Alkyne Cycloaddition Polymer Networks
    COPPER-CATALYZED AZIDE ALKYNE CYCLOADDITION POLYMER NETWORKS by Abeer Ahmed Alzahrani M.S., Chemistry, King Abdul-Aziz University, 2005 B.S. Chemistry, University of Umm Al-Qura University, 2000 A thesis submitted to the Faculty of the Graduate School of the University of Colorado in partial fulfillment of the requirement for the degree of Doctor of Philosophy, Department of Department of Chemistry and Biochemistry, 2014 This thesis entitled: Copper-Catalyzed Azide Alkyne Cycloaddition Polymer Networks written by Abeer Ahmed Alzahrani has been approved for the Department of Chemistry and Biochemistry ___________________________ Christopher N. Bowman, PhD. Date____________ ___________________________ Jeffrey W. Stansbury, PhD. Date____________ Committee members: Christopher N. Bowman, Jeffrey W. Stansbury Devatha P Nair, Daniel L. Feldheim, and Wei Zhang The final copy of this thesis has been examined by The signatories, and we find that both the content and the form meet acceptable presentation standards of scholarly work in the above mentioned discipline. COPPER-CATALYZED AZIDE ALKYNE CYCLOADDITION POLYMER NETWORKS Alzahrani, Abeer Ahmed, Ph.D., Dept. of Department of Chemistry and Biochemistry Thesis directed by Patten Professor, Christopher N. Bowman Abstract The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide- alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction.
    [Show full text]
  • Phosphonamidate Peptide Synthesis by Staudinger Reactions of Silylated Phosphinic Acids Supporting Information
    Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2010 Phosphonamidate peptide synthesis by Staudinger reactions of silylated phosphinic acids and esters Ina Wilkening, Guiseppe del Signore and Christian P. R. Hackenberger Institute of Chemistry and Biochemistry Freie Universität Berlin Takustr. 3, 14195 Berlin Fax: +49-(0)30-838-52551 E-mail: [email protected] Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2010 Phosphonamidate peptide synthesis by Staudinger reactions of silylated phosphinic acids Supporting Information 1 GENERAL INFORMATION 3 2 SYNTHESIS OF ORGANIC COMPOUNDS 4 2.1 SYNTHESIS OF AZIDO COMPOUNDS 4 2.1.1 SYNTHESIS OF BENZYL AZIDE (9B) 4 2.1.2 SYNTHESIS OF PHENYLIC AZIDES 9A AND 9C-E 4 2.1.2.1 Phenyl azide (9a) 4 2.1.2.2 1-Azido-4-fluorobenzene (9c) 5 2.1.2.3 1-Azido-4-nitrobenzene (9d) 5 2.1.2.4 1-Azido-4-methoxybenzene (9e) 5 2.1.2.5 2-Azido-9H-fluorene (9g) 6 2.1.3 4-AZIDO BENZOIC ACID (9F) 6 2.2 SYNTHESIS OF PHOSPHINIC ESTERS 7 AND ACIDS 11 6 2.2.1 METHOD A: HEWITT REACTION 6 2.2.1.1 Methyl phenylphosphinate (7a) 7 2.2.1.2 Benzyl phenylphosphinate (7c) 7 2.2.1.3 Methyl octylphosphinate (7d) 8 2.2.2 SYNTHESIS OF 2-NITROBENZYL PHENYLPHOSPHINATE (7E) 8 2.2.3 SYNTHESIS OF OCTYL PHOSHINIC ACID (11B) 9 2.2.4 SYNTHESIS OF LEUCINE AND ALANIN PHOSPHINIC ACID DERIVATIVES 9 2.2.4.1 1-(Benzhydrylamino)-3-methylbutylphosphinic acid 9 2.2.4.2 1-amino-3-methylbutylphosphinic acid 10 2.2.4.3 1-(benzyloxycarbonylamino)-3-methylbutylphosphinic
    [Show full text]
  • The Synthesis and Characterisation of Halogen and Nitro Phenyl Azide
    Dissertation zur Erlangung des Dokorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilans-Universität München The synthesis and characterisation of halogen and nitro phenyl azide derivatives as highly energetic materials. von David Adam aus Glasgow , Schottland 2001 Index Acknowledgements 1 Abstract 3 1. Introduction 4 1.1 Azides 4 1.2 Nitro compounds 13 1.3 Nitrocarbons 16 1.4 Explosives 18 1.5 Theoretical Calculations 20 1.6 Pentazoles 23 2 Halogen substitued phenyl azides 27 2.1 2,4,6-tribromophenyl azide 27 2.2 2,4,6-trichlorophenyl azide 35 2.3 2,5,6-trichlorophenyl azide 42 2.4 2,4-dibromophenyl azide 43 2.5 2,4-dichlorophenyl azide 44 2.6 2,4,6-trifluorophenyl azide 44 2.7 2,3,4,5,6-pentafluorophenyl azide 47 2.8 2,6-diiodo-4-nitrophenyl azide 50 2.9 2,3,4,5,6-pentachlorophenyl azide 59 3. Nitro compounds 65 3.1 o-nitrophenyl azide 65 3.2 m-nitrophenyl azide 68 3.3 2,4-dinitrophenyl azide 70 3.4 2,4,6-trintrophenyl azide 72 3.5 1,3,5-triazido-2,4-dinitrobenzene 94 3.6 1,3,5-triazido-2,4,6-trinitrobenzene 100 3.7 hexakis (azidomethyl) benzene. 106 3.8 hexakis (methylnitrate) benzene 108 4. Decomposition and explosion experiments 111 4.1 Thermal decomposition of TNMA , DNTA and TNTA 111 4.2 Computational Aspects 118 4.3 Thermal decomposition of halogen substituted phenyl azides 121 4.4 Thermal decomposition of hexakis (azidomethyl) benzene 122 4.5 Drophammer Tests of TNMA, DNTA and TNTA 125 4.6 Calculation of the detonation velocity from molecular formula and structure for TNMA , DNTA and TNTA 133 4.7 Calculation of the detonation velocity from molecular formula and structure for a series of azido and nitro substituted benzenes 135 5 Calculation of compounds of the type C6 (NO2)6-n (N3)n 138 5.1 Structural discussion 144 5.2 Molecular structures 145 6.
    [Show full text]
  • Advancements in the Mechanistic Understanding of the Copper-Catalyzed Azide–Alkyne Cycloaddition
    Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition Regina Berg* and Bernd F. Straub* Review Open Access Address: Beilstein J. Org. Chem. 2013, 9, 2715–2750. Organisch-Chemisches Institut, Ruprecht-Karls-Universität doi:10.3762/bjoc.9.308 Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany Received: 09 August 2013 Email: Accepted: 30 October 2013 Regina Berg* - [email protected]; Bernd F. Straub* - Published: 02 December 2013 [email protected] Associate Editor: M. Rueping * Corresponding author © 2013 Berg and Straub; licensee Beilstein-Institut. Keywords: License and terms: see end of document. alkyne; azide; Click; copper; CuAAC; DFT study; Huisgen–Meldal–Sharpless cycloaddition; kinetics; reaction mechanism Abstract The copper-catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most broadly applicable and easy-to-handle reactions in the arsenal of organic chemistry. However, the mechanistic understanding of this reaction has lagged behind the plethora of its applications for a long time. As reagent mixtures of copper salts and additives are commonly used in CuAAC reactions, the struc- ture of the catalytically active species itself has remained subject to speculation, which can be attributed to the multifaceted aggre- gation chemistry of copper(I) alkyne and acetylide complexes. Following an introductory section on common catalyst systems in CuAAC reactions, this review will highlight experimental and computational studies from early proposals to very recent and more sophisticated investigations, which deliver more detailed insights into the CuAAC’s catalytic cycle and the species involved. As diverging mechanistic views are presented in articles, books and online resources, we intend to present the research efforts in this field during the past decade and finally give an up-to-date picture of the currently accepted dinuclear mechanism of CuAAC.
    [Show full text]