Molecular Transformations Using a Sodium Hydride‑Iodide Composite
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Part I: Carbonyl-Olefin Metathesis of Norbornene
Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis……………………………………………………………. -
Title Crystallization of Stereospecific Olefin Copolymers (Special Issue on Physical Chemistry) Author(S) Sakaguchi, Fumio; Kita
Crystallization of Stereospecific Olefin Copolymers (Special Title Issue on Physical Chemistry) Author(s) Sakaguchi, Fumio; Kitamaru, Ryozo; Tsuji, Waichiro Bulletin of the Institute for Chemical Research, Kyoto Citation University (1966), 44(4): 295-315 Issue Date 1966-10-31 URL http://hdl.handle.net/2433/76134 Right Type Departmental Bulletin Paper Textversion publisher Kyoto University Crystallization of Stereospecifie Olefin Copolymers Fumio SAKAGUCHI,Ryozo KITAMARU and Waichiro TSUJI* (Tsuji Laboratory) Received August 13, 1966 The stereoregularity of isotactic poly(4-methyl-1-pentene) was characterized and isomorphism phenomena were examined for the copolymeric systems of 4-methyl-1-pentene with several olefins in order to study the crystallization phenomena in these olefin copoly- mers polymerized with stereospecific catalysts. The structural heterogeneity or the fine crystalline structure of poly(4-methyl-1-pentene) could be correlated with its molecular structure by viewing this stereoregular homopolymer as if it were a copolymer. Cocrystallization or isomorphism phenomenon was recognized for the copolymeric systems of 4-methyl-1-pentene with butene-1, pentene-1, decene-1 and 3-methyl-1-butene, while no evidence of the phenomenon was obtained for the copolymeric systems with styrene and propylene. The degree of the isomorphism of those copolymers was discussed with the informations on the crystalline phases obtained from the X-ray study, on the constitution of the copolymeric chains in the amorphous phases obtained from the viscoelastic studies and on the other thermodynamical properties of these systems. INTRODUCTION Many works have been made with regard to the homopolymerization of olefins with stereospecific catalysts, i. e. complex catalysts composed of the combination of organometallic compound and transitional metallic compound. -
Suplementary Information
Supplementary Material (ESI) for Polymer Chemistry This journal is (c) The Royal Society of Chemistry 2011 SUPLEMENTARY INFORMATION Shedding the hydrophobic mantel of polymersomes René P. Brinkhuis, Taco R. Visser, Floris P. J. T. Rutjes, Jan C.M. van Hest* Radboud University Nijmegen,, Institute for Molecules and Materials, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands; E-mail: [email protected]; [email protected] Contents: Experimental General note Materials Instrumentation α- methoxy ω-methyl ester poly(ethylene glycol) α- methoxy ω-hydrazide poly(ethylene glycol) α- azido ω-methoxy poly(ethylene glycol) Aldehyde terminated polybutadiene Alkyne terminated polybutadiene Polybutadiene-Hz-poly(ethylene glycol) Polybutadiene-b-poly(ethylene glycol) Vesicle preparation Stability studies Notes and References Figures Figure 1: GPC traces of polymer 1 and its constituents. Figure 2: GPC traces of polymer 2 and its constituents. Figure 3: GPC traces of polymer 3 and its constituents. Figure 4: GPC traces of polymer 4 and its constituents. Supplementary Material (ESI) for Polymer Chemistry This journal is (c) The Royal Society of Chemistry 2011 Experimental section General note: All reactions are described for the lower molecular weight analogue, polyethylene glycol 1000, indicated with an A. The procedures for the polyethylene glycol 2000 analogues, indicated with B, are the same, starting with equimolar amounts. Materials: Sec-butyllithium (ALDRICH 1.4M in hexane), 1,3 butadiene (SIGMA ALDRICH, 99+%), 3- bromo-1-(trimethylsilyl-1-propyne) (ALDRICH, 98%), tetrabutylammonium fluoride (TBAF) (ALDRICH, 1.0M in THF), polyethylene glycol 1000 monomethyl ether (FLUKA), polyethylene glycol 2000 monomethyl ether (FLUKA), methanesulfonyl chloride (MsCl) (JANSSEN CHIMICA, 99%), sodium azide (ACROS ORGANICS, 99% extra pure), sodium hydride (ALDRICH, 60% dispersion in mineral oil), copper bromide (CuBr) (FLUKA, >98%), N,N,N’,N’,N”-penta dimethyldiethylenetriamine (PMDETA) (Aldrich,99%), hydrazine (ALDRICH, 1M in THF) were used as received. -
194 Recent Advances in the Synthesis of New Pyrazole Derivatives
194 RECENT ADVANCES IN THE SYNTHESIS OF NEW PYRAZOLE DERIVATIVES DOI: http://dx.medra.org/ 10.17374/targets.2019.22.194 Juan - Carlos Castillo a,b , Jaime Portilla a * a Bioorganic Compounds Research Group, Department of Chemistry, Universi dad de los Andes, Carrera 1 No. 18A - 10, Bogotá, Colombia b Grupo de Cat álisis, E scuela de Ciencias Químicas, Universidad Pedagógica y Tecnológica de Colombia UPTC, Av enida Central del Norte, Tunja, Colombia (e - mail : [email protected] ) Abstract. Pyrazoles have attracted great attention in organic and medicinal chemistry, due to their proven utility as synthetic intermediates for the preparation of diverse bioactive compounds, of coordination complexes, as well as in the design of functional materials. Consequently , the synthesis of functionalized pyrazoles is an important focus of research for synthetic organic chemists. Likewise, fuse d pyrazoles such as pyrazolo[1,5 - a]pyrimidines and pyrazolo[3,4 - b]pyridines have been widely studied due to their varied biological and physicochemical applications based on the important electronic properties of th ese N - heterocycles. Therefore, the preparation of these fused heterocycles and of their functionalized derivatives is of notable interest to both uncover novel derivatives and explore new applications. Several methods have been described in the literature for the synthesis of pyrazoles and of their fused systems in recent years , which mainly involve classi cal cyclocondensation reactions , some of these are presented in th is contribution. Contents 1. Introduction 2. Functionalized pyrazoles 2.1. Aminopyrazoles 2.2. Formylpyrazoles 3. Fused pyrazoles 3.1. Pyrazolo[1,5 - a ]pyrimidines 3.2. Pyrazolo[3,4 - b ]pyridines 3.3. -
Syntheses and Eliminations of Cyclopentyl Derivatives David John Rausch Iowa State University
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1966 Syntheses and eliminations of cyclopentyl derivatives David John Rausch Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Rausch, David John, "Syntheses and eliminations of cyclopentyl derivatives " (1966). Retrospective Theses and Dissertations. 2875. https://lib.dr.iastate.edu/rtd/2875 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received 66—6996 RAUSCH, David John, 1940- SYNTHESES AND ELIMINATIONS OF CYCLOPENTYL DERIVATIVES. Iowa State University of Science and Technology Ph.D., 1966 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan SYNTHESES AND ELIMINATIONS OF CYCLOPENTYL DERIVATIVES by David John Rausch A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Organic Chemistry Approved : Signature was redacted for privacy. Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Iowa State University Of Science and Technology Ames, Iowa 1966 ii TABLE OF CONTENTS VITA INTRODUCTION HISTORICAL Conformation of Cyclopentanes Elimination Reactions RESULTS AND DISCUSSION Synthetic Elimination Reactions EXPERIMENTAL Preparation and Purification of Materials Procedures and Data for Beta Elimination Reactions SUMMARY LITERATURE CITED ACKNOWLEDGEMENTS iii VITA The author was born in Aurora, Illinois, on October 24, 1940, to Mr. -
Aniline and Aniline Hydrochloride
SOME AROMATIC AMINES AND RELATED COMPOUNDS VOLUME 127 This publication represents the views and expert opinions of an IARC Working Group on the Identification of Carcinogenic Hazards to Humans, which met remotely, 25 May–12 June 2020 LYON, FRANCE - 2021 IARC MONOGRAPHS ON THE IDENTIFICATION OF CARCINOGENIC HAZARDS TO HUMANS ANILINE AND ANILINE HYDROCHLORIDE 1. Exposure Characterization 1.1.2 Structural and molecular formulae, and relative molecular mass 1.1 Identification of the agent (a) Aniline 1.1.1 Nomenclature NH2 (a) Aniline Chem. Abstr. Serv. Reg. No.: 62-53-3 EC No.: 200-539-3 Molecular formula: C H N IUPAC systematic name: aniline 6 7 Relative molecular mass: 93.13 (NCBI, 2020a). Synonyms and abbreviations: benzenamine; phenylamine; aminobenzene; aminophen; (b) Aniline hydrochloride aniline oil. NH2 (b) Aniline hydrochloride Chem. Abstr. Serv. Reg. No.: 142-04-1 EC No.: 205-519-8 HCl IUPAC systematic name: aniline hydro - Molecular formula: C6H8ClN chloride Relative molecular mass: 129.59 (NCBI, Synonyms: aniline chloride; anilinium chlo- 2020b). ride; benzenamine hydrochloride; aniline. HCl; phenylamine hydrochloride; phenylam- monium chloride. 1.1.3 Chemical and physical properties of the pure substance Aniline is a basic compound and will undergo acid–base reactions. Aniline and its hydrochlo- ride salt will achieve a pH-dependent acid–base equilibrium in the body. 109 IARC MONOGRAPHS – 127 (a) Aniline Octanol/water partition coefficient (P): log Kow, 0.936, predicted median (US EPA, 2020b) Description: aniline appears as a yellowish Conversion factor: 1 ppm = 5.3 mg/m3 [calcu- to brownish oily liquid with a musty fishy lated from: mg/m3 = (relative molecular odour (NCBI, 2020a), detectable at 1 ppm 3 mass/24.45) × ppm, assuming temperature [3.81 mg/m ] (European Commission, 2016; (25 °C) and pressure (101 kPa)]. -
Synthetic Turf Scientific Advisory Panel Meeting Materials
California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update ..... -
Synthesis of Pyrazoles Containing Benzofuran and Trifluoromethyl Moieties As Possible Anti-Inflammatory and Analgesic Agents
Z. Naturforsch. 2015; 70(7)b: 519–526 Awatef A. Farag, Mohamed F. El Shehry, Samir Y. Abbas*, Safaa N. Abd-Alrahman, Abeer A. Atrees, Hiaat Z. Al-basheer and Yousry A. Ammar Synthesis of pyrazoles containing benzofuran and trifluoromethyl moieties as possible anti-inflammatory and analgesic agents DOI 10.1515/znb-2015-0009 and anti-inflammatory drugs present a wide range of prob- Received January 9, 2015; accepted February 4, 2015 lems such as efficacy and undesired effects including gas- trointestinal tract (GIT) disorders and other unwanted effects. This situation highlights the need for novel, safe and Abstract: Searching for new anti-inflammatory and anal- effective analgesic and anti-inflammatory compounds [1–3]. gesic agents, we have prepared a series of novel pyrazoles Since the first pyrazolin-5-one was prepared by Knorr containing benzofuran and trifluoromethyl moieties. The [4] in 1883, many papers have reported on the anti-inflam- pyrazole derivatives have been synthesized via two routes matory, analgesic and antipyretic evaluation of several starting from 5-(3-(trifluoromethyl)phenyl azo) salicylal- pyrazoles, pyrazolin-3-ones and pyrazolidine-3,5-diones dehyde. The first route involved the synthesis of 2-acetylb- [5–9]. Many of these derivatives such as phenylbutazone, enzofuran and then treatment with aldehydes to afford febrazone, feclobuzone, mefobutazone, suxibuzone and the corresponding chalcones. The cyclization of the latter ramifenazone have found their clinical application as chalcones with hydrazine hydrate led to the formation of nonsteroidal anti-inflammatory drugs (NSAIDs) [10]. new pyrazoline derivatives. The second route involved the The benzofuran derivatives have attracted due to their synthesis of benzofuran-2-carbohydrazide and then treat- biological activities and potential application as pharma- ment with formylpyrazoles, chalcones and ketene dith- cological agents [11]. -
Properties and Synthesis. Elimination Reactions of Alkyl Halides
P1: PBU/OVY P2: PBU/OVY QC: PBU/OVY T1: PBU Printer: Bind Rite JWCL234-07 JWCL234-Solomons-v1 December 8, 2009 21:37 7 ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS. ELIMINATION REACTIONS OF ALKYL HALIDES SOLUTIONS TO PROBLEMS 7.1 (a) ( E )-1-Bromo-1-chloro-1-pentene or ( E )-1-Bromo-1-chloropent-1-ene (b) ( E )-2-Bromo-1-chloro-1-iodo-1-butene or ( E )-2-Bromo-1-chloro-1-iodobut-1-ene (c) ( Z )-3,5-Dimethyl-2-hexene or ( Z )-3,5-Dimethylhex-2-ene (d) ( Z )-1-Chloro-1-iodo-2-methyl-1-butene or ( Z )-1-Chloro-1-iodo-2-methylbut-1-ene (e) ( Z,4 S )-3,4-Dimethyl-2-hexene or ( Z,4 S )-3,4-Dimethylhex-2-ene (f) ( Z,3 S )-1-Bromo-2-chloro-3-methyl-1-hexene or (Z,3 S )-1-Bromo-2-chloro-3-methylhex-1-ene 7.2 < < Order of increasing stability 7.3 (a), (b) H − 2 ∆ H° = − 119 kJ mol 1 Pt 2-Methyl-1-butene pressure (disubstituted) H2 − ∆ H° = − 127 kJ mol 1 Pt 3-Methyl-1-butene pressure (monosubstituted) H2 − ∆ H° = − 113 kJ mol 1 Pt 2-Methyl-2-butene pressure (trisubstituted) (c) Yes, because hydrogenation converts each alkene into the same product. 106 CONFIRMING PAGES P1: PBU/OVY P2: PBU/OVY QC: PBU/OVY T1: PBU Printer: Bind Rite JWCL234-07 JWCL234-Solomons-v1 December 8, 2009 21:37 ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS 107 H H (d) > > H H H (trisubstituted) (disubstituted) (monosubstituted) Notice that this predicted order of stability is confirmed by the heats of hydro- genation. -
The Reaction of Sodium Borohydride
THE REACTION OF SODIUM BOROHYDRIDE WITH N-·ACYLANILINES By ROBERT FRA.."\\JK LINDEl"J.ANN Ir Bachelor of Arts Wittenberg College Springfield, Ohio 1952 Submitted to the Faculty of the Graduate School of the Oklahoma Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of MA.STER OF SCIENCE August, 19.54 i THE REACTION OF SODIUM BOROHYDRIDE WITH N-ACYLANILINES Thesis Approved: ~ - Dean of the Graduate School ii l!l Al C! 0~ 11J/~~. 2t"'I'Ii .ACKN01rJLEDGEMENT The author-wishes to express his gratitude to Dr. H. Po Johnston for the invaluable assistance and guidance given. This project was made possible by the Chemistry Department in the form of a Graduate Fellowship and by an unnamed sponsor through the Research Foundation. iii TABLE OF CONTENTS Page · I. .Introduction ...................................... ., o ••••••·· .... 1 II o Historical ... o o • .,, • (I .. ., •.••• G ••••.•••••••• .is •••••••• "' •. o o •••••• o '°. 2 Preparation of Sodium Borohydride ........................... 2 Physical Properties ofSodium Borohydrj.de ................... 3 Chemical Properties of · Sodium Borohydride .............. " •••• 3 III. Experimental. 0 ·• •• ·•. 0 •••• 0 ·• •••• 0. (I •••• 0 0 • 0 Q • .., ••• Q e. 0. 0. 0 D. 0 e 8 Purification of Sodium Borohydride ........................... 8 Reaction of Sodium Borohydride w:i. th Acetanilide ..........._ •• 9 Reaction of Sodium Borohydride w:i. th For.manilide oo •• oe.,. .... 27 Discussion ••• o o. o. o o o o. o ·O fl o • .e. o o ........ o. o. o o • ., o ~. o" o (Io o o o .29 IV. S11ITil11ary •• 0. Cl Ct. 0 0 0. 0. 0 -0 DO O O O C. c,.. 0. 0 4 11) 0 0 0 -0 0 0 0 -0 a O O .0 0 0 .0. -
Reactions of Alkenes and Alkynes
05 Reactions of Alkenes and Alkynes Polyethylene is the most widely used plastic, making up items such as packing foam, plastic bottles, and plastic utensils (top: © Jon Larson/iStockphoto; middle: GNL Media/Digital Vision/Getty Images, Inc.; bottom: © Lakhesis/iStockphoto). Inset: A model of ethylene. KEY QUESTIONS 5.1 What Are the Characteristic Reactions of Alkenes? 5.8 How Can Alkynes Be Reduced to Alkenes and 5.2 What Is a Reaction Mechanism? Alkanes? 5.3 What Are the Mechanisms of Electrophilic Additions HOW TO to Alkenes? 5.1 How to Draw Mechanisms 5.4 What Are Carbocation Rearrangements? 5.5 What Is Hydroboration–Oxidation of an Alkene? CHEMICAL CONNECTIONS 5.6 How Can an Alkene Be Reduced to an Alkane? 5A Catalytic Cracking and the Importance of Alkenes 5.7 How Can an Acetylide Anion Be Used to Create a New Carbon–Carbon Bond? IN THIS CHAPTER, we begin our systematic study of organic reactions and their mecha- nisms. Reaction mechanisms are step-by-step descriptions of how reactions proceed and are one of the most important unifying concepts in organic chemistry. We use the reactions of alkenes as the vehicle to introduce this concept. 129 130 CHAPTER 5 Reactions of Alkenes and Alkynes 5.1 What Are the Characteristic Reactions of Alkenes? The most characteristic reaction of alkenes is addition to the carbon–carbon double bond in such a way that the pi bond is broken and, in its place, sigma bonds are formed to two new atoms or groups of atoms. Several examples of reactions at the carbon–carbon double bond are shown in Table 5.1, along with the descriptive name(s) associated with each. -
Introduced B.,Byhansen, 16
LB301 LB301 2021 2021 LEGISLATURE OF NEBRASKA ONE HUNDRED SEVENTH LEGISLATURE FIRST SESSION LEGISLATIVE BILL 301 Introduced by Hansen, B., 16. Read first time January 12, 2021 Committee: Judiciary 1 A BILL FOR AN ACT relating to the Uniform Controlled Substances Act; to 2 amend sections 28-401, 28-405, and 28-416, Revised Statutes 3 Cumulative Supplement, 2020; to redefine terms; to change drug 4 schedules and adopt federal drug provisions; to change a penalty 5 provision; and to repeal the original sections. 6 Be it enacted by the people of the State of Nebraska, -1- LB301 LB301 2021 2021 1 Section 1. Section 28-401, Revised Statutes Cumulative Supplement, 2 2020, is amended to read: 3 28-401 As used in the Uniform Controlled Substances Act, unless the 4 context otherwise requires: 5 (1) Administer means to directly apply a controlled substance by 6 injection, inhalation, ingestion, or any other means to the body of a 7 patient or research subject; 8 (2) Agent means an authorized person who acts on behalf of or at the 9 direction of another person but does not include a common or contract 10 carrier, public warehouse keeper, or employee of a carrier or warehouse 11 keeper; 12 (3) Administration means the Drug Enforcement Administration of the 13 United States Department of Justice; 14 (4) Controlled substance means a drug, biological, substance, or 15 immediate precursor in Schedules I through V of section 28-405. 16 Controlled substance does not include distilled spirits, wine, malt 17 beverages, tobacco, hemp, or any nonnarcotic substance if such substance 18 may, under the Federal Food, Drug, and Cosmetic Act, 21 U.S.C.