Syntheses of Morphine and Codeine (1992 – 2002): Templates for Exploration of Synthetic Tools
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Cyanovinylation of Aldehydes: Organocatalytic Multicomponent Synthesis of Conjugated Cyanomethyl Vinyl Ethers
molecules Article Cyanovinylation of Aldehydes: Organocatalytic Multicomponent Synthesis of Conjugated Cyanomethyl Vinyl Ethers Samuel Delgado-Hernández 1,2 , Fernando García-Tellado 1,* and David Tejedor 1,* 1 Instituto de Productos Naturales y Agrobiología, Consejo Superior de Investigaciones Científicas, Astrofísico Francisco Sánchez 3, 38206 La Laguna, Spain; [email protected] 2 Doctoral and Postgraduate School, Universidad de La Laguna, Apartado Postal 456, 38200 La Laguna, Spain * Correspondence: [email protected] (F.G.-T.); [email protected] (D.T.) Abstract: A novel organocatalytic multicomponent cyanovinylation of aldehydes was designed for the synthesis of conjugated cyanomethyl vinyl ethers. The reaction was implemented for the synthesis of a 3-substituted 3-(cyanomethoxy)acrylates, using aldehydes as substrates, acetone cyanohydrin as the cyanide anion source, and methyl propiolate as the source of the vinyl com- ponent. The multicomponent reaction is catalyzed by N-methyl morpholine (2.5 mol%) to deliver the 3-(cyanomethoxy)acrylates in excellent yields and with preponderance of the E-isomer. The multicomponent reaction manifold is highly tolerant to the structure and composition of the aldehyde (aliphatic, aromatic, heteroaromatics), and it is instrumentally simple (one batch, open atmospheres), economic (2.5 mol% catalyst, stoichiometric reagents), environmentally friendly (no toxic waste), and Citation: Delgado-Hernández, S.; sustainable (easy scalability). García-Tellado, F.; Tejedor, D. Cyanovinylation of -
Brittain-DR-1965-Phd-Thesis.Pdf
POLYMETHYLENE PYRIDINES , A thesis submitted by David Robert Brittain in partial fulfilment of the requirements for the degree of DOCTOR OP PHILOSOPHY in the University of London Organic Chemistry Department, dune, 1965. Imperial College, LONDON, S.W.7. ABSTRACT This thesis describes a series of attempts to syn- thesise 2,5- and 1,4-polymethylene bridged pyridines. Nuclear magnetic resonance theory predicts that protons, which are held directly over an aromatic ring, will be abnormally shielded compared with protons in aliphatic straight-chain hydrocarbons. This prediction has been verified for the central methylene protons of paracyclo- phanes. The degree of shielding, expressed in terms of the distance from the aromatic ring, is a measure of the induced ring current and hence the aromaticity of the benzene ring. Similar measurements upon 2,5- or 1,4— polymethylene bridged pyridines would make it possible to determine the degree of aromaticity of the pyridine ring relative to benzene. A review of the subject of aromaticity is presented in which special reference has been made to its inter- pretation by nuclear magnetic resonance. The synthetic work has not been brougL.t to a truly satisfactory conclusion. However, the synthetic routes to 2,5-dialkylpyridines have been thoroughly investigated and a wide variety of such compounds prepared. The functional groups at the ends of the alkyl chains have been varied in an effort to produce a derivative which would cyclise to give a 2,5-bridged pyridine. The attempted intramolecular oxidative coupling of 2,5-dihex- 51 -ynylpyridine received much attention. In the attempts to obtain a 1,4-bridged pyridine, two tricyclic compounds, each containing two quaternised pyridine rings linked by polymethylene chains, were obtained. -
Tumblr Jessi Brianna Jessi Brianna
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Genl:VE 1970 © World Health Organization 1970
Nathan B. Eddy, Hans Friebel, Klaus-Jiirgen Hahn & Hans Halbach WORLD HEALTH ORGANIZATION ORGANISATION .MONDIALE DE LA SANT~ GENl:VE 1970 © World Health Organization 1970 Publications of the World Health Organization enjoy copyright protection in accordance with the provisions of Protocol 2 of the Universal Copyright Convention. Nevertheless governmental agencies or learned and professional societies may reproduce data or excerpts or illustrations from them without requesting an authorization from the World Health Organization. For rights of reproduction or translation of WHO publications in toto, application should be made to the Division of Editorial and Reference Services, World Health Organization, Geneva, Switzerland. The World Health Organization welcomes such applications. Authors alone are responsible for views expressed in signed articles. The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Director-General of the World Health Organization concerning the legal status of any country or territory or of its authorities, or concerning the delimitation of its frontiers. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. © Organisation mondiale de la Sante 1970 Les publications de l'Organisation mondiale de la Sante beneficient de la protection prevue par les dispositions du Protocole n° 2 de la Convention universelle pour la Protection du Droit d'Auteur. Les institutions gouvernementales et les societes savantes ou professionnelles peuvent, toutefois, reproduire des donnees, des extraits ou des illustrations provenant de ces publications, sans en demander l'autorisation a l'Organisation mondiale de la Sante. Pour toute reproduction ou traduction integrate, une autorisation doit etre demandee a la Division des Services d'Edition et de Documentation, Organisation mondiale de la Sante, Geneve, Suisse. -
First Grade Sight Words "Crash" Activity Words "Crash"
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Investigation of Cyano·Methylation Reaction by Cyano·Hydrine and Its Determination in Tobacco-Smoke. ( Strecker·Reactions )
PERIODICA POLYTECHNICA SER. CHEM. ENG. VOL. 36, NO. 3, PP. 209-2113 {I992} INVESTIGATION OF CYANO·METHYLATION REACTION BY CYANO·HYDRINE AND ITS DETERMINATION IN TOBACCO-SMOKE. ( STRECKER·REACTIONS ) 3 Vikt6ria HORVATH,l Lajos TREZLl, Tibor SZARVAS2, Janos PIPEK , Csaba VIDA 1 and Krisztina BAUER4 1 Department of Organic Chemical Technology, 3Department of Physics Technical University of Budapest, 2 Institute of Isotopes of the Hungarian Academy of Sciences 4 Plant Protection Institute,Hungarian Academy of Sciences. Received: September 9, 1992 Abstract The results of our research work [1-7) of several years aimed at the binding of the unhealthy components of tobacco smoke directed our attention to the analysis and identification of the unknown peak observed during the high sensitivity radiochromatographic analysis of tobacco smoke condensates.It was a fruitless effort to remove the formaldehyde, the ac etaldehyde and hydrogen cyanide present in tobacco smoke, or even to try to eliminate them separately, during the analysis the new, unknown peak appeared again and again on the radiochromatogram. During our research work we stated, that we were facing the Strecker reaction [8-9), known since 1850, that is,with the formation of cyanohydrine of the aldehydes and hydrogen cyanide present in tobacco smoke, corresponding to the new peak. Cyanohydrines to react quickly and energetically with basic aminoacids, during which reaction cyanomethyl derivatives are being formed. This reaction is proceeding also under physiological circumstances with the basic amino groups of proteins, contributing to the development of respiratory and cardiovascular insufficiencies. By means of model reactions and using solutions of tobacco smoke gases the process of the reaction was proved in a primary way, also its circumstances having been cleared. -
Cyanohydrin - Wikipedia, the Free Encyclopedia
Cyanohydrin - Wikipedia, the free encyclopedia http://en.wikipedia.org/wiki/Cyanohydrin Cyanohydrin From Wikipedia, the free encyclopedia A cyanohydrin is a functional group found in organic compounds. Cyanohydrins have the formula R2C(OH)CN, where R is H, alkyl, or aryl. Cyanohydrins are industrially important precursors to carboxylic acids and some amino acids. Cyanohydrins can be formed by the cyanohydrin reaction, which involves treating a ketone or an aldehyde with hydrogen cyanide (HCN) in the presence of excess amounts of sodium cyanide (NaCN) as a catalyst: The structure of a general RR’C=O + HCN → RR’C(OH)CN cyanohydrin. In this reaction, the nucleophilic CN− ion attacks the electrophilic carbonyl carbon in the ketone, followed by protonation by HCN, thereby regenerating the cyanide anion. Cyanohydrins are also prepared by displacement of sulfite by cyanide salts:[1] Cyanohydrins are intermediates in the Strecker amino acid synthesis. Contents 1 Acetone cyanohydrins 2 Other cyanohydrins 3 References 4 External links Acetone cyanohydrins Acetone cyanohydrin, (CH3)2C(OH)CN is the cyanohydrin of acetone. It is generated as an intermediate in the industrial production of methyl methacrylate.[2] In the laboratory, this liquid serves as a source of HCN, which is inconveniently volatile.[3] Thus, acetone cyanohydrin can be used for the preparation other cyanohydrins, for of HCN to Michael acceptors, and for the formylation of arenes. Treatment of this cyanohydrin with lithium hydride affords anhydrous lithium cyanide: 1 of 3 6/3/10 6:07 PM Cyanohydrin - Wikipedia, the free encyclopedia http://en.wikipedia.org/wiki/Cyanohydrin Other cyanohydrins Mandelonitrile, with the formula C6H5CH(OH)CN, occurs in small amounts in the pits of some fruits.[1] Related cyanogenic glycosides are known, such as amygdalin. -
CO2-Enabled Cyanohydrin Synthesis and Facile Homologation Reactions Martin Juhl†, Allan R
CO2-Enabled Cyanohydrin Synthesis and Facile Homologation Reactions Martin Juhl†, Allan R. Petersen†, Ji-Woong Lee*,† †Department of Chemistry, Nano-Science Center, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, 2100, Denmark KEYWORDS: Carbon Dioxide, Cyanohydrin, Xanthate, Homologation ABSTRACT: Thermodynamic and kinetic control of a chemical process is the key to access desired products and states. Changes are made when desired product is not accessible; one may manipulate the reaction with additional reagents, catalysts and/or protect- ing groups. Here we report the use of carbon dioxide to direct reaction pathways in order to selectively afford desired products in high reaction rates while avoiding the formation of byproducts. The utility of CO2-mediated selective cyanohydrin synthesis was further showcased by broadening Kiliani-Fischer synthesis to offer an easy access to variety of polyols, cyanohydrins, linear al- kylnitriles, by simply starting from alkyl- and arylaldehydes, KCN and atmospheric pressure of CO2. 9 A chemical reaction is governed by kinetics and ther- investigated the role of CO2 in a cyanation reaction, where CO2 modynamics, and a simultaneous control of both parameters is can be used in catalytic amounts to facilitate the stereoselective a common practice in designing and optimizing chemical reac- transformation of activated electrophiles via 1,4-conjugate ad- tions. The manipulation of thermodynamic stability of reactants dition reactions. Cyanohydrin synthesis - 1,2-cyanide addition and products -
Feasibility Study on Opium Licensing in Afghanistan
FEASIBILITY STUDY ON OPIUM LICENSING IN AFGHANISTAN FOR THE PRODUCTION OF MORPHINE AND OTHER ESSENTIAL MEDICINES ﻣﻄﺎﻟﻌﻪ اﻣﮑﺎﻧﺎت در ﻣﻮرد ﺟﻮاز دهﯽ ﺗﺮﻳﺎک در اﻓﻐﺎﻧﺴﺘﺎن ﺑﺮای ﺗﻮﻟﻴﺪ ﻣﻮرﻓﻴﻦ و ادوﻳﻪ ﺟﺎت ﺿﺮوری دﻳﮕﺮ Initial Findings – September 2005 Kabul, Afghanistan The British Institute of International and Comparative Law Hugo Warner • University of Calgary Peter Facchini - Jill Hagel University of Ghent Brice De Ruyver - Laurens van Puyenbroeck University of Kabul Abdul Aziz Ali Ahmad - Osman Babury Cheragh Ali Cheragh - Mohammad Yasin Mohsini University of Lisbon Vitalino Canas - Nuno Aureliano • Shruti Patel • University of Toronto Benedikt Fischer Todd Culbert - Juergen Rehm • Wageningen University Jules Bos - Suzanne Pegge • Ali Wardak • The Senlis Council Gabrielle Archer - Juan Arjona - Luke Bryant Marc Das Gupta - Furkat Elmirzaev - Guillaume Fournier Jane Francis - Thalia Ioannidou - Ernestien Jensema Manna Kamio Badiella - Jorrit Kamminga - Fabrice Pothier Emmanuel Reinert - David Spivack - Daniel Werb FEASIBILITY STUDY ON OPIUM LICENSING IN AFGHANISTAN FOR THE PRODUCTION OF MORPHINE AND OTHER ESSENTIAL MEDICINES Initial Findings – September 2005 Kabul, Afghanistan Study Commissioned by The Senlis Council Study Edited and coordinated by David Spivack Editorial team: Juan Arjona, Jane Francis, Thalia Ioannidou, Ernestien Jensema, Manna Kamio Badiella, Fabrice Pothier. Published 2005 by MF Publishing Ltd 17 Queen Anne’s Gate, London SW1H 9BU, UK ISBN: 0-9550798-2-9 Printed and bound in Afghanistan by Jehoon; Printing Press Other publications -
Bowman Chem 345 Lecture Notes by Topic Cyanohydrin
Bowman Chem 345 Lecture Notes by Topic Cyanohydrin: Important approximate pKa’s to know for this section: pKa ~ 10 pKa ~ -5 pKa ~ 0 pKa ~ 5 pKa ~ 15 + H H O HCl H3O O 2 H SO 2 4 N R ROH R H OH R R=H or sp3 C O H C N Cyanide is a moderate base (pKa of HCN ~ 10). It is also a good nucleophile. Like Grignards and organolithiums, it can add to carbonyls. Standard conditions for cyanohydrin formation is a cyanide salt and a weak acid like acetic acid.1 KCN CN O cyanohydrin AcOH racemic OH O AcOH=acetic acid= OH Mechanism: The first step is cyanide attacking the carbonyl. Though this is not a favorable reaction pKa wise, it is still possible as an alcohol and HCN have very close pKa’s (the difference is ≤ 6). The second step is favorable as acetate is a weaker base than an alkoxide (negative O). This step you can write as reversible or not (though it is on the boundary reversible/irreversible boundary (>6 but ≤ 10). [Technically, cyanohydrins are slightly more acidic (pKa~13) than normal alcohols due to the inductive effect of the nitrile. One of the most common mistakes in this mechanism is to protonate the carbonyl. Though technically, acetic acid can barely protonate the carbonyl, the cyanide being a stronger base than acetate would rather irreversibly deprotonate a protonated carbonyl than add to the carbonyl carbon. 1 Brunner, A.; Hintermann, L. Chem. Euro. J. 2016, 22, 2787-2792 Bowman Chem 345 Lecture Notes by Topic Unlike Grignard and organolithium reactions, the cyanohydrin formation can be reversed. -
Provisional Peer-Reviewed Toxicity Values for Acetone Cyanohydrin (Casrn 75-86-5)
EPA/690/R-12/001F l Final 10-01-2012 Provisional Peer-Reviewed Toxicity Values for Acetone Cyanohydrin (CASRN 75-86-5) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 AUTHORS, CONTRIBUTORS, AND REVIEWERS CHEMICAL MANAGER Scott C. Wesselkamper, PhD National Center for Environmental Assessment, Cincinnati, OH DRAFT DOCUMENT PREPARED BY ICF International 9300 Lee Highway Fairfax, VA 22031 PRIMARY INTERNAL REVIEWERS Zheng (Jenny) Li, PhD, DABT National Center for Environmental Assessment, Washington, DC Anuradha Mudipalli, MSc, PhD National Center for Environmental Assessment, Research Triangle Park, NC This document was externally peer reviewed under contract to Eastern Research Group, Inc. 110 Hartwell Avenue Lexington, MA 02421-3136 Questions regarding the contents of this document may be directed to the U.S. EPA Office of Research and Development’s National Center for Environmental Assessment, Superfund Health Risk Technical Support Center (513-569-7300). ii Acetone cyanohydrin TABLE OF CONTENTS COMMONLY USED ABBREVIATIONS ................................................................................... iv BACKGROUND .............................................................................................................................1 DISCLAIMERS ...............................................................................................................................1 QUESTIONS REGARDING -
JUN 1 51998 Science
Efforts Toward the Syntheses of Natural Products: Part A: Paeoniflorin Part B: (+)-Taxusin A thesis presented by Rebecca J. Carazza B.S. Chemistry University of Massachusetts, Amherst, 1993 Submitted to the Department of Chemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry at the Massachusetts Institute of Technology June 1998 © 1998 Massachusetts Institute of Technology. All rights reserved. SinatureofAuthor: SignatureT- -~- -- .. -uof -Author: -- I- ----- D4pdrtment o('ihemistry May 26, 1998 Certified by: ,Scott C. Virgil Thesis Advisor Acceuted bv: Dietmar Seyferth Chairman, Departmental Committee on Graduate Students O-V .Z\ . JUN 1 51998 Science UR PAES This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: Professor Rick L. Danheiser - Chairman Professor Scott C. Virgil / Th/sis Supervisor Professor Peter H. Seeberger Efforts Toward the Syntheses of Natural Products: Part A: Paeoniflorin Part B: (+)-Taxusin by Rebecca J. Carazza Submitted to the Department of Chemistry on May 26, 1998 in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry Massachusetts Institute of Technology ABSTRACT Part A Efforts toward the synthesis of the monoterpene glycoside paeoniflorin (1) are discussed. Optimization of the previous synthetic route was successful. Synthesis of the key cc-diazo intermediate 30 was achieved and the construction of the carbocyclic frame was completed. Key reactions of the strategy involve a ring contraction via a Wolff rearrangement, and formation of the lactone 78 which undergoes diisobutylaluminum hydride reduction followed by acid catalyzed cyclization to the paeoniflorin ring system 80. A new synthetic strategy was initiated to prepare the key [3.2.1]bicyclooctanone 81 using a palladium mediated olefin cyclization of the acyloin substrate 82.