The Preparation and Reactions of 3,3-Disubstituted Thietanes and Their Derivatives

Total Page:16

File Type:pdf, Size:1020Kb

The Preparation and Reactions of 3,3-Disubstituted Thietanes and Their Derivatives University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1975 THE PREPARATION AND REACTIONS OF 3,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES MARIS BUZA Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation BUZA, MARIS, "THE PREPARATION AND REACTIONS OF 3,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES" (1975). Doctoral Dissertations. 1089. https://scholars.unh.edu/dissertation/1089 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1. The sign or "target” for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 I 75-23,390 BUZA, Maris, 1937- THE PREPARATION AND REACTIONS OF 3 ,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES. t University of New Hampshire, Ph.D., 1975 Chemistry, organic Xerox University Microfilms f Ann Arbor, Michigan 48106 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. THE PREPARATION AND REACTIONS OF 3,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES by MARIS BUZA B.A. , Rutgers, The State University, 1963 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy Graduate School Department of Chemistry June, 1975 This thesis has been examined and approved. Thesis director, Kenneth K. Andersen Professor of Chemistry / Albert F. Daggett, Professor of Chemistry C7&4a £ QrYUZ^ Paul R. Jones, Professor of Chemistry j/lr..,4-----:- ^ .(//<>----------------- Gloria G. Lyle, Professor of Chemistry Charles E. Wyman, Assistant Professor of Chemical Engineering ir,m5 Date This thesis is dedicated to my parents. ACKNOWLEDGEMENT The author wishes to express his most sincere appreciation to Dr. Kenneth K. Andersen whose guidance, help and encouragement led to the completion of this work. Thanks are also extended to all of the people of this Department and others who have been so helpful during these years, in particular to Dr. Paul R. Jones, Dr. Gloria G. Lyle, Dr. J. John Uebel, Indulis Gleske and Ms. Anne Kohl, among many others too numerous to mention. The author is very grateful for the financial support from the National Science Foundation and the Department, without which this work would have been impossible. TABLE OF CONTENTS LIST OF TABLES.................................................... xi LIST OF FIGURES.................................................xiii ABSTRACT.......................................................... xiv INTRODUCTION........................................................ 1 HISTORICAL...........................................................3 RESULTS AND DISCUSSION................... 15 EXPERIMENTAL.......................................................92 Instrumentation............................................. 92 Materials.....................................................92 I. Preparation of Propane-1, 3-diols.......................... 93 Preparation of 2-Carboalkoxy-3-methyl-3-phenyloxi- ranes (7_4) by the Darzene Condensation. Method 1................................................93 Method 2................................................93 Preparation of Hydratropaldehyde........................ 94 Preparation of 2-Methyl-2-phenylpropane-l,3-diol (75) by the Tollens Condensation...................95 Preparation of Diethyl Methylphenylmalonate...........96 Reduction of Diethyl Methylphenylmalonate..............96 Preparation of 2-Phenylpropane-l, 3-diol (7_6) by the Reduction of Diethyl Phenylmalonate............... 97 Preparation of 2-Carboalkoxy-3-p-bromophenyl-3- methyloxiranes (7_7) by the Darzens Condensation...........................................98 Preparation of p-Bromohydratropaldehyde (7_8)........... 99 Preparation of 2-p-Bromophenyl-2-methylpropane-l,3- diol (2J7) by the Tollens Condensation........... 100 Preparation of Dialkyl Esters of Isopropylphenyl- malonic Acid..........................................101 v Preparation of 2-Phenyl-2-(2-propyl)-propane-1,3- diol (2_6) by the Reduction of the Dialkyl Esters of Isopropylphenylmalonate Acid.......... 103 Preparation of 2-Methyl-2-nitropropane-l,3-diol (79 ) by the Tollens Condensation..................104 Preparation of 3-Cyclohexene-l,1-dimethanol (80) by the Tollens Condensation........................105 Preparation of Cyclohexane-1,1-dimethanol (8_1) by Reduction of 3-Cyclohexene-l,1-dimethanol (80)................................................... 105 Preparation of Isopropyl Chloroacetate................ 106 The Preparation of ,l-Oxa-2-carboisopropoxy-4- methylspiro [2 . 5] octanes (8_2) by the Darzens Condensation..........................................106 Preparation of 2-Methylcyclohexane-l-carboxalde- hydes.................................................. 107 Preparation of 2-Methylcyclohexane-l,1-dimethanol (83) by the Tollens Condensation..................108 Preparation of l-Oxa-2-carboalkoxy-5-methylspiro- [2. 5] octanes (8_4) by the Darzens Condensation.. 109 Preparation of 3-Methylcyclohexane-l-carboxaldehyde. Method 1 .............................................. 109 Method 2 .............................................. 110 Method 3.............................................. 110 Preparation of 3-Methylcyclohexane-l-dimethanol (85) by the Tollens Condensation.................Ill The Preparation of l-Oxa-2-carboisopropoxy-6- methylspiro [2 . 4] octanes (8_6) by the Darzens Condensation..........................................112 Preparation of 4-Methylcyclohexane-l-carboxalde- hyde................................................... 112 Preparation of 4-Methylcyclohexane-l,1-dimethanol (87 ) by the Tollens Condensation.................113 General Procedure for the Preparation of Dibenzene- sulfonate Esters of Propane-1, 3-diols.............117 Dibenzenesulfonate of 2-Methyl-2-phenylpropane- 1,3-diol 117 Dibenzenesulfonate of 2-Phenylpropane-l,3-diol.......118 Dibenzenesulfonate of 2-(p-Bromopheny1)-2-methyl- propane-1,3-diol.....................................119 vi Dibenzenesulfonate of 2-Phenyl-2-(2-propyl)- propane-1, 3-diol.....................................119 Dibenzenesulfonate of Butane-1, 3-diol................ 120 Dibenzenesulfonate of 2-Methyl-2-nitropropane- 1,3-diol 120 Dibenzenesulfonate of 3-Cyclohexene-l,1- dimethanol............................................121 Dibenzenesulfonate of Cyclohexane-1,1-dimethanol.... 122 Dibenzenesulfonate of 2-Methylcyclohexane-l,1- dimethanol................ ..........................122 Dibenzenesulfonate of 3-Methylcyclohexane-l,1- dimethanol............................................123 Dibenzenesulfonate of 4-Methylcyclohexane-l,1- dimethanol............................................123 Preparation of 3-Methyl-3-phenylthietane (7_) . Preparation..1 ....................................... 130 Preparation..2 ....................................... 132 Preparation of 3-Methy1-3-phenylthietane-l,1- dioxide (3_1) . General Method for Preparation of Sulfones...........................................134 Preparation of 3 - (p-Bromophenyl)-3-methylthietane (9)...........7 ........................................135 Preparation of 3 - (p-Bromophenyl)-3-methylthietane- 1,1-dioxide {32) .....................................136 Preparation of 2-Methylthietane (1JU...................137 Preparation of 3-Phenyl-3-(2-propyl)-thietane (10). Preparation 1
Recommended publications
  • IN-VITRO EVALUATION of the ANTICANCER ACTIVITY of Cu(II)AMINA(CYSTEINE)DITHIOCARBAMATE
    Sys Rev Pharm 2020;11(9):43-51 A multifaceted review journal in the field of pharmacy IN-VITRO EVALUATION OF THE ANTICANCER ACTIVITY OF Cu(II)AMINA(CYSTEINE)DITHIOCARBAMATE Desy Kartina1, Abdul Wahid Wahab 2, Ahyar Ahmad3, Rizal Irfandi 4, Prihantono5, And Indah Raya6* 1Department of Chemistry, Faculty of Mathematics, and Natural Science, Hasanuddin University, Makassar 90245, Indonesia 2Department of Chemistry, Faculty of Mathematics, and Natural Science, Hasanuddin University, Makassar 90245, Indonesia 3Department of Chemistry, Faculty of Mathematics, and Natural Science, Hasanuddin University, Makassar 90245, Indonesia 4Department of Biology Education, Faculty of Teacher Training and Education, Puangrimaggalatung University Sengkang, 90915, Indonesia. 5Departement of Surgery, Faculty of Medicinal, Hasanuddin University, Makassar Indonesia, 90245 6*Department of Chemistry, Faculty of Mathematics, and Natural Science, Hasanuddin University, Makassar 90245, Indonesia ABSTRACT The Complex of Cu(II)cysteinedithiocarbamate has been synthesized, it Keywords: Anticancer, Cu(ll)Amina(cysteine)dithiocarbamate. was prepared by the “in situ method” and characterized by using Correspondance: Ultraviolet-Visible (UV-Vis), Infra-Red (IR) spectroscopy, X-Ray Indah Raya Fluorescence (XRF) instruments. While melting point and conductivity Department of Chemistry, also measured. The presence of UV-Vis maximum spectrums of Faculty of Mathematics, and Natural Science, Cu(II)cysteinedithiocarbamate at 296 nm and 436 nm indicated that Hasanuddin University, electronic transition π → π * dan n → π * of CS2 and N=C=S myotis. The Makassar 90245, Indonesia presence of the wavelength in the region of 399-540 cm-1 of IR spectra Email id : [email protected], [email protected] is indicated that has been coordination occurred between Cu(II) with Sulphur (S), Nitrogen (N), and Oxygen(O) atoms respectively from cysteinedithiocarbamate ligands.
    [Show full text]
  • Recent Advances in Microwave-Assisted Copper-Catalyzed Cross-Coupling Reactions
    catalysts Review Recent Advances in Microwave-Assisted Copper-Catalyzed Cross-Coupling Reactions Younis Baqi Department of Chemistry, College of Science, Sultan Qaboos University, P.O. Box 36, Muscat 123, Oman; [email protected]; Tel.: +968-2414-1473 Abstract: Cross-coupling reactions furnishing carbon–carbon (C–C) and carbon–heteroatom (C–X) bond is one of the most challenging tasks in organic syntheses. The early developed reaction protocols by Ullmann, Ullman–Goldberg, Cadiot–Chodkiewicz, Castro–Stephens, and Corey–House, utilizing elemental copper or its salts as catalyst have, for decades, attracted and inspired scientists. However, these reactions were suffering from the range of functional groups tolerated as well as severely restricted by the harsh reaction conditions often required high temperatures (150–200 ◦C) for extended reaction time. Enormous efforts have been paid to develop and achieve more sustainable reaction conditions by applying the microwave irradiation. The use of controlled microwave heating dramatically reduces the time required and therefore resulting in increase in the yield as well as the efficiency of the reaction. This review is mainly focuses on the recent advances and applications of copper catalyzed cross-coupling generation of carbon–carbon and carbon–heteroatom bond under microwave technology. Keywords: cross-coupling reaction; Cu catalyst; microwave irradiation; methodology; synthesis 1. Introduction Carbon–carbon (C–C) and carbon–heteroatom (C–X) bond formations through cross- Citation: Baqi, Y. Recent Advances in coupling reactions represents as one of the most useful strategy in the synthetic organic Microwave-Assisted chemistry, hence many procedures and methodologies have been developed and published Copper-Catalyzed Cross-Coupling in the literature.
    [Show full text]
  • Copper ( II ) Chloride
    Copyright © Tarek Kakhia. All rights reserved. http://tarek.kakhia.org Copper Contents 1 Introduction 2 History o 2.1 Copper Age o 2.2 Bronze Age o 2.3 Antiquity and Middle Ages o 2.4 Modern period 3 Characteristics o 3.1 Color o 3.2 Group 11 of the periodic table o 3.3 Occurrence o 3.4 Mechanical properties o 3.5 Electrical properties o 3.6 Corrosion . 3.6.1 Pure water and air/oxygen . 3.6.2 In contact with other metals . 3.6.3 Sulfide media . 3.6.4 Ammonia media . 3.6.5 Chloride media o 3.7 Germicidal effect o 3.8 Isotopes 4 Production 5 Applications o 5.1 Piping o 5.2 Electrical applications o 5.3 Architecture / Industry o 5.4 Household products o 5.5 Coinage o 5.6 Biomedical applications o 5.7 Chemical applications o 5.8 Other 6 Alloys 7 Compounds 8 Biological role 9 Recycling 1 Copyright © Tarek Kakhia. All rights reserved. http://tarek.kakhia.org 1 Introduction : Copper is a chemical element with the symbol Cu ( Latin : cuprum ) and atomic number 29 . It is a ductile metal with very high thermal and electrical conductivity. Pure copper is rather soft and malleable and a freshly - exposed surface has a pinkish or peachy color. It is used as a thermal conductor, an electrical conductor, a building material, and a constituent of various metal alloys. Copper metal and alloys have been used for thousands of years. In the Roman era, copper was principally mined on Cyprus, hence the origin of the name of the metal as Cyprium, "metal of Cyprus", later shortened to Cuprum.
    [Show full text]
  • Thiirane-Terminated Polysulfide Polymers Thiiran-Terminierte Polysulfidpolymere Polymères Polysulfures À Terminaison Thiirane
    (19) & (11) EP 2 121 807 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08G 75/00 (2006.01) 26.05.2010 Bulletin 2010/21 (86) International application number: (21) Application number: 08707985.1 PCT/EP2008/050540 (22) Date of filing: 18.01.2008 (87) International publication number: WO 2008/090086 (31.07.2008 Gazette 2008/31) (54) THIIRANE-TERMINATED POLYSULFIDE POLYMERS THIIRAN-TERMINIERTE POLYSULFIDPOLYMERE POLYMÈRES POLYSULFURES À TERMINAISON THIIRANE (84) Designated Contracting States: • KOTTNER, Nils AT BE BG CH CY CZ DE DK EE ES FI FR GB GR D-78628 Rottweil (DE) HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT • ZEITLER, Michael RO SE SI SK TR D-53347 Alfter (DE) (30) Priority: 23.01.2007 EP 07101024 (74) Representative: Schalkwijk, Pieter Cornelis et al 02.02.2007 US 899273 P Akzo Nobel N.V. Intellectual Property Department (43) Date of publication of application: P.O. Box 9300 25.11.2009 Bulletin 2009/48 6800 SB Arnhem (NL) (73) Proprietor: Akzo Nobel N.V. (56) References cited: 6824 BM Arnhem (NL) WO-A-03/076487 WO-A1-2004/099283 JP-A- 2004 062 057 US-A- 5 173 549 (72) Inventors: • WITZEL, Silke D-42103 Wuppertal (DE) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations.
    [Show full text]
  • Copper Monosulfide (Cus) Powder SAFTY DATA SHEET
    Copper Monosulfide (CuS) Powder US Research Nanomaterials, Inc. www.us-nano.com SAFTY DATA SHEET Revised Date 2/21/2016 1. PRODUCT AND COMPANY IDENTIFICATION 1.1 Product identifiers Product name: Copper Monosulfide (CuS) Powder Product Number : US1126M Copper Monosulfide (CuS) CAS#: 1317-40-4 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified uses : Research 1.3 Details of the supplier of the safety data sheet Company: US Research Nanomaterials, Inc. 3302 Twig Leaf Lane Houston, TX 77084 USA Telephone: +1 832-460-3661 Fax: +1 281-492-8628 1.4 Emergency telephone number Emergency Phone # : (832) 359-7887 2. HAZARDS IDENTIFICATION 2.1 Classification of the substance or mixture This substance or mixture is not hazardous and is not classified under GHS. May cause irritation of skin, eyes, and respiratory tract. For the full text of the H-Statements mentioned in this Section, see Section 16. 2.2 GHS Label elements, including precautionary statements Pictogram Signal word None Hazard statement(s) H319 Causes serious eye irritation. H335 May cause respiratory irritation. Precautionary statement(s) P261 Avoid breathing dust/ fume/ gas/ mist/ vapors/ spray. P264 Wash skin thoroughly after handling. P271 Use only outdoors or in a well-ventilated area. P280 Wear protective gloves/ eye protection/ face protection. P304 + P340 IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P312 Call a POISON CENTER or doctor/ physician if you feel unwell.
    [Show full text]
  • Synthesis and Structural Characterization of Semiconductors Based on Kesterites
    Synthesis and Structural Characterization of Semiconductors based on Kesterites vorgelegt von Anna Ritscher, Bakk.rer.nat M.Sc. aus Villach, Österreich von der Fakultät II - Mathematik und Naturwissenschaften der Technischen Universität Berlin zur Erlangung des akademischen Grades Doktorin der Naturwissenschaften - Dr.rer.nat. - genehmigte Dissertation Promotionsausschuss: Vorsitzende: Prof. Dr. Regine von Klitzing Gutachter: Prof. Dr. Martin Lerch Gutachter: Prof. Dr. Manfred Mühlberg Tag der wissenschaftlichen Aussprache: 28.10.2016 Berlin, 2016 “There is a theory which states that if ever anyone discovers exactly what the Universe is for and why it is here, it will instantly disappear and be replaced by something even more bizarre and inexplicable. There is another theory mentioned, which states that this has already happened.” Douglas Adams, The Hitchhiker’s Guide to the Galaxy Abstract The here-presented thesis provides detailed investigations on the structural characteris- tics of the chalcogenide Cu2ZnSnS4 (CZTS). This semiconductor material is a promising candidate for absorber layers in solar cells due to its desirable properties for thin film photovoltaic applications. Yet, compared to current used chalcopyrite-based devices, effi- ciencies are significantly lower. This could be attributed to structural effects. Fundamental understanding of the structural characteristics of potential thin film absorber compounds is crucial for proper materials design in the field of solar technology. Therefore, intensive research is necessary to obtain knowledge on so far unexplored structural features or to certify and extend current literature data. The main objective of the here-presented work was to deepen the understanding of the quaternary sulfide 2Cu ZnSnS4. Primary, this implied the full characterization of structural properties of the compound using various diffraction techniques.
    [Show full text]
  • Functionalisation of Colloidal Transition Metal Sulphides Nanocrystals: a Fascinating and Challenging Playground for the Chemist
    crystals Review Functionalisation of Colloidal Transition Metal Sulphides Nanocrystals: A Fascinating and Challenging Playground for the Chemist Silvia Gross 1,2,*, Andrea Vittadini 1,2 and Nicola Dengo 1,2 1 Istituto di Chimica della Materia Condensata e di Tecnologie per l’Energia, ICMATE-CNR, via Marzolo 1, I-35131 Padova, Italy; [email protected] (A.V.); [email protected] (N.D.) 2 Dipartimento di Scienze Chimiche, Università degli Studi di Padova and INSTM, UdR Padova, via Marzolo 1, I-35131 Padova, Italy * Correspondence: [email protected]; Tel.: +39-049-827-5736 Academic Editor: Roberto Comparelli Received: 27 December 2016; Accepted: 24 March 2017; Published: 14 April 2017 Abstract: Metal sulphides, and in particular transition metal sulphide colloids, are a broad, versatile and exciting class of inorganic compounds which deserve growing interest and attention ascribable to the functional properties that many of them display. With respect to their oxide homologues, however, they are characterised by noticeably different chemical, structural and hence functional features. Their potential applications span several fields, and in many of the foreseen applications (e.g., in bioimaging and related fields), the achievement of stable colloidal suspensions of metal sulphides is highly desirable or either an unavoidable requirement to be met. To this aim, robust functionalisation strategies should be devised, which however are, with respect to metal or metal oxides colloids, much more challenging. This has to be ascribed, inter alia, also to the still limited knowledge of the sulphides surface chemistry, particularly when comparing it to the better established, though multifaceted, oxide surface chemistry.
    [Show full text]
  • Synthesis and Spectral Studies of Ni (II) Dithiocarbamate Complexes
    Hindawi Publishing Corporation Journal of Chemistry Volume 2016, Article ID 1293790, 9 pages http://dx.doi.org/10.1155/2016/1293790 Research Article Synthesis and Spectral Studies of Ni(II) Dithiocarbamate Complexes and Their Use as Precursors for Nickel Sulphides Nanocrystals Azile Nqombolo and Peter A. Ajibade Department of Chemistry, University of Fort Hare, Private Bag Box X1314, Alice 5700, South Africa Correspondence should be addressed to Peter A. Ajibade; [email protected] Received 15 July 2016; Revised 13 September 2016; Accepted 20 September 2016 Academic Editor: Henryk Kozlowski Copyright © 2016 A. Nqombolo and P. A. Ajibade. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Ni(II) dithiocarbamate complexes have been synthesized and characterized by UV-Vis, FTIR, and NMR spectroscopic techniques. Electronic spectra measurements indicate that the complexes are four-coordinate square planar geometry while the FTIR confirmed that the dithiocarbamates act as bidentate chelating ligands. The compounds were used as single source precursors and thermolysed ∘ at 220 C to prepare HDA-capped NiS nanocrystals which were characterized by absorption and photoluminescence (PL) spectra measurements, powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). Absorption spectra studies showed that the synthesized NiS nanoparticles are blue- shifted relative to the bulk material and PL studies showed emission maxima that are red-shifted compared to the absorption band edges. The XRD patterns of the as-prepared NiS nanoparticles revealed cubic crystalline phases.
    [Show full text]
  • Ionic Liquid Precursors for Multicomponent Inorganic Nanomaterials
    Institut für Chemie – Supramolekulare Chemie Ionic liquid precursors for multicomponent inorganic nanomaterials Kumulative Dissertation Zur Erlangung des akademischen Grades “doctor rerum naturalium” (Dr. rer. nat.) in der Wissenschaftsdisziplin Materialchemie eingereicht an der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Potsdam von Ahed Abouserie geboren am 29.03.1987 in Giza, Egypt Potsdam, den 28. März 2018 Published online at the Institutional Repository of the University of Potsdam: URN urn:nbn:de:kobv:517-opus4-418950 http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-418950 Supervision 1. Prof. Dr. Andreas Taubert, University of Potsdam 2. Prof. Dr. Stefanie Dehnen, University of Marburg 3. Prof. Dr. Peer Schmidt, Brandenburg University of Technology *Prof. Peter Strauch, of blessed memory, acted as my second supervisor. iii Dedication Dedicated to My parents My brother, Mohanad My brother, Kaream Derya Yildirim v Abstract Abstract A series of relatively low-cost ionic liquids (ILs), based on the N-alkylpyridinium cations, and 2- tetrachloridometallate [MCl4] (M = Cu, Co, Zn, or Cu/Co) and hexachloridodicuprate(II) 2- [Cu2Cl6] anions were synthesized for non-enzymatic amperometric detection and organic photovoltaic cells. The packing diagram of these ILs and the interaction between the cations and the anions have been investigated by single-crystal X-ray diffraction. The single crystal analysis shows that all crystal structures are stabilized by several non- classical hydrogen bonding, and all ILs based on the same chain pyridinium cation are isostructural. The ILs based on short chain cation are monoclinic and crystallize in the space group P21/n, while the crystals of the ILs based on long chain cation are triclinic and form in the space group P1̅.
    [Show full text]
  • A Facile Chemical Route to Copper Sulfide Cus Nanocrystallites – Ph Effect of the Morphology and the Shape of Them
    JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS Vol. 8, No. 2, April 2006, p. 597 - 600 A facile chemical route to copper sulfide CuS nanocrystallites – pH effect of the morphology and the shape of them C. M. SIMONESCU* , L. PATRONa, V. S. TEODORESCUb, M. BREZEANU, C. CAPATINAc Department of Inorganic Technology and Environmental Protection, Faculty of Applied Chemistry and Materials Science, University “Politehnica” of Bucharest, Polizu Street, no. 1-7, RO-011061,Bucharest, Romania aRomanian Academy, Physical and Chemical Institute I. G. Murgulescu, Splaiul Independentei Street, No.202, Bucharest, Romania bNational Institute R&D for Materials Physics, P.O.Box. Mg-7, Bucharest-Magurele, Ro-77125, Romania cDepartment of Environmental Engineering, University “Constantin Brancusi”, Genova Street, no. 3, RO-210152, Targu-Jiu, Gorj, Romania A facile chemical route for the synthesis of copper sulfide (CuS) nanocrystallites consists of the reaction between . Cu(CH3COO)2 H2O and Na2S2O3 5H2O. In this reaction the influence of the following factors was pursued: pH value, reaction time, molar ratios, temperature and others. In this article we tried to establish the evolution of the morphology and the shape of the CuS nanocrystallites with the pH value. The CuS nanocrystallites obtained were studied by X ray diffraction, IR spectrometry, TEM – transmission electron microscopy and SAED selected area electron diffraction. The CuS crystallites are formed in spherical or “discoidal” particles which are bonded in bigger aggregates. The reaction pH value was varied from a slightly acid value to an alkali value. In case of alkali medium the crystallites dimensions were smaller than their value in slightly acid medium.
    [Show full text]
  • Synthesis and Inclusion Studies of Stable
    The copyright of this thesis vests in the author. No quotation from it or information derived from it is to be published without full acknowledgementTown of the source. The thesis is to be used for private study or non- commercial research purposes only. Cape Published by the University ofof Cape Town (UCT) in terms of the non-exclusive license granted to UCT by the author. University SYNTHESIS AND INCLUSION STUDIES OF STABLE ALLICIN MIMICS AS NOVEL ANTIMICROBIAL AGENTS BY Nashia StellenboomTown Cape Thesis Presentedof for the Degree of DOCTOR OF PHILOSOPHY In the Department of Chemistry UniversityUNIVERSITY OF CAPE TOWN April 2008 Supervisors Professor Roger Hunter and Professor Mino R. Caira Table of Contents ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ Chapter 1 : Introduction 1 1.1 Overview of Garlic 1 1.2 Allicin 2 1.3 Thiosulfinates 12 1.4 The Disulfide Bond 14 1.5 Review of Unsymmetrical Disulfide Synthesis 22 1.6 Cyclodextrins 55 1.7 Aims and Objectives 63 Chapter 2 : Unsymmetrical Disulfides 64 2.1 Unsymmetrical Disulfide Synthesis 64 Chapter 3 : S-Alkyl Arylthiosulfinates 109 Town 3.1 Overview 109 3.2 The Chemistry of Oxidation of Unsymmetrical Disulfides 113 3.3 Electron-Rich systems 118 3.4 Electron-Deficient systems Cape 120 3.5 π-Deficient Heteroaromatic System 121 3.6 Stability Tests of S-alkyl arylthiosulfinatesof 128 3.7 S-p-Methoxyphenyl Alkylthiosulfinates 130 Chapter 4 : Cyclodextrin Inclusion 142 4.1 Overview 142 4.2 Experimental, Methods and Materials 142 4.3 Results andUniversity Discussion 146 4.4 Conclusion 161 Chapter 5 : Summary and Conclusion 162 Chapter 6 : Experimental 163 6.1 General Procedure 163 6.2 Synthesis and Purification of Disulfides 164 6.3 Compounds 166 References 193 Abstract ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ABSTRACT Allicin, a known constituent of garlic, is a potent but unstable antimicrobial agent.
    [Show full text]
  • The Chemistry of Heterocycles Structure, Reactions, Syntheses
    The Chemistry of Heterocycles Structure, Reactions, Syntheses, and Applications Mohammad Jafarzadeh Faculty of Chemistry, Razi University The Chemistry of Heterocycles, (Second Edition). By Theophil Eicher and Siegfried Hauptmann, Wiley-VCH Veriag GmbH, 2003 1 24 3 Three-Membered Heterocycles 3.2 Thiirane 24 3 Three-Membered Heterocycles 3.2 Thiirane Thiiranes are also known as episulfides. As a result of the greater atomic radius of the S-atom, the three atoms form an acute-angled triangle (see Fig. 3.2). [A] Thiiranes are also known as episulfides. As a result of the greater atomic radius of the S-atom, the 3.2 Thiirane three atoms form an acute-angled triangle. Fig. 3.2 Structure of thiirane (bond lengths in pm, bond angles in degrees) The thermochemically determined strainThenthalpye thermochemicallof thiiraney determineof 83 kJd molstrai-1n isenthalplessythan of thiiranthateof ofoxirane 83 kJ mo. H is less than that of oxirane. The ionization potential amounts to 9.05TheV,e ionizatiothe dipolen potentiamomentl amountto 1.66s toD 9.0. Both5 eVvalues, the dipolaree belowmomenthoset to 1.66 D. Both values are below Thiiranes are also known aofsoxirane episulfides. The chemical. Ashiftss a resulin the NMRt thosofspectrae thof oxiranee greateare. �ThH e= chemica2r. 27atomi, �l Cshift= 18sc i .n1radiu .the NMRs spectrof ath are S ^S-atom = 2.27, Sc ,=18.1. the three atoms form an acute-angled triangle (see Fig. 3.2)Th.e properties of the thiiranes are primarily due to ring strain. In spite of the smaller strain en- [B] The properties of the thiiranes are primarilythalpydue, tothiiranringestrain is thermall.
    [Show full text]