DOCSLIB.ORG

Preparation of Aromatic Carbonyl Compounds

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Preparation of Aromatic Carbonyl Compounds ~" ' MM II II II Ml I III II II I Ml II I II J European Patent Office © Publication number: 0 178 184 B1 Office_„. europeen- desj brevets^ » © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 28.04.93 © Int. CI.5: C07C 45/45, C07C 49/76, C07C 51/58 © Application number: 85307320.3 @ Date of filing: 11.10.85 © Preparation of aromatic carbonyl compounds. © Priority: 11.10.84 US 659598 (73) Proprietor: RAYCHEM CORPORATION (a Dela- ware corporation) @ Date of publication of application: 300 Constitution Drive 16.04.86 Bulletin 86/16 Menlo Park, California 94025(US) © Publication of the grant of the patent: @ Inventor: Horner, Patrick James 28.04.93 Bulletin 93/17 139 Buckthorn Way Menlo Park California 94025(US) © Designated Contracting States: Inventor: Jansons, Vlktors AT BE CH DE FR GB IT LI NL SE 123 New York Avenue Los Gatos California 95030(US) References cited: Inventor: Gors, Helnrlch Carl EP-A- 0 024 286 EP-A- 0 069 598 2508 Mardell Way DE-A- 2 014 514 GB-A- 1 420 506 Mountain View California, 94043(US) GB-A- 2 103 604 US-A- 1 874 580 US-A- 3 282 989 Representative: Jay, Anthony William et al Raychem Limited Intellectual Property Law Department Faraday Road Dorcan Swindon Wiltshire (GB) 00 00 00 Note: Within nine months from the publication of the mention of the grant of the European patent, any person ® may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition CL shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee LU has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services (3. 10/3.5x/3.0. 1) EP 0 178 184 B1 Description This invention relates to the preparation of aryl carbonyl compounds, and in particular to para substituted aryl carbonyl compounds. 5 Aryl carbonyl compounds are useful in the preparation of poly(arylene ether ketones). In the preparation of these polymers it is essential that the monomers used be in a highly pure state to prevent undesirable side reactions. Furthermore, the polymers obtained should be stable enough to survive extrusion without undue deleterious effects on their physical properties. The substitution pattern of the monomers used can control the properties of the polymers synthesised, and it is generally recognised that the highest melting io points and glass-rubber transition temperatures are obtained with all para linked polymers. Mixtures of substitution isomers are used when polymers of reduced crystallinity or lowered Tg are required, but the all para substituted polymers are most preferred. When mixtures of monomers are used, known ratios of the different isomers are needed, necessitating the use of pure starting materials. The present invention relates to a process for the preparation of aryl carbonyl compounds that improves outstandingly the degree of 75 purity of the product and/or the degree of para substitution. Aryl carbonyl compounds are also useful as chemicals and chemical intermediates, for example, in the pharmaceutical and agricultural chemicals, dyestuffs and general chemical additives area. Here too it is frequently found that the all para substituted carbonyl compounds are the most useful. Avoidance of concurrent formation of other isomeric by products in the synthesis of such compounds is always beneficial 20 economically and in some instances is essential because some isomeric compounds which are different to remove have been found to be toxic or even carcinogenic. A known method of producing aryl carbonyl compounds by Friedel Crafts condensation using a Lewis acid catalyst is described in GB-A-21 03604. In accordance with the present invention, the Friedel-Crafts condensation of appropriate reactants is 25 controlled to suppress side reaction including alkylation and/or ortho acylation by the addition of a controlling agent, such as a Lewis base, to the reaction medium. Thus the invention provides a process for the preparation of a para-substituted aromatic carbonyl compound which is not an oligomer or polymer, by a Friedel Crafts condensation of (1) an aromatic compound containing at least one activated hydrogen atom with (2) phosgene or an acyl compound in the 30 presence of (3) a Lewis acid, characterised in that any aromatic ring which contains an activated hydrogen atom also contains less than 2 alkoxy groups, and the condensation is controlled by the addition of at least 0.1 equivalents of Lewis base per equivalent of acid, ester of acid halide groups in the reactants, plus an additional equivalent of Lewis acid per equivalent of Lewis base. One aspect of this invention provides a process for the preparation of an aromatic carbonyl compound 35 having the formula (R)sArDCOY, (R)sArDCOBD(R')t, (R)sArDCOBDCOArD(R)s or (R)sArDCODAr(R)s wherein each s and t independently is 1 , 2 or 3 and each R, Ar, B, D, Y and R' independently is as defined 40 below, which comprises reacting a first reactant consisting of a substituted or unsubstituted aromatic compound containing at least one activated hydrogen atom of the formula (R)sArDH 45 with a second reactant consisting of phosgene or a mono-functional acyl compound of the general formula YCOBD(R'), or 0(COBD(R'),)2 50 or a di-functional acyl compound of the general formula YCOBDCOY in a reaction medium comprising: 55 A) a Lewis acid in an amount of one equivalent per equivalent of carbonyl or other basic species in the reactants plus one equivalent per equivalent of Lewis base plus an amount effective to act as a catalyst for the reaction; 2 EP 0 178 184 B1 B) a Lewis base in an amount of from 0.1 to 4 equivalents per equivalent of acid, ester or acid halide group in the reactants; and C) a non-protic diluent in an amount from about 20 to about 93% by weight, based on the weight of the total reaction mixture, 5 wherein: (a) Ar is a homo or hetero-aromatic mono-, di- or tri- cyclic moiety or a fused homo-aromatic ring system containing less than 20 aromatic carbon atoms or a hetero-aromatic system containing less than 8 nitrogen atoms; (b) D is -(ZAr)n-(ZAr)m-(ZAr)p- io wherein n, m, and p are each independently 0, 1, 2 or 3, provided that n + m + p is less than 4, and Z -CO- or -SO2- when linking two Ar moieties which are both 4-phenoxyphenyl, or Z is -CO-CgH^-CO-, -0- (CF2)qO-, or V, provided that when n + m + p > 0 any Ar group comprising an activated hydrogen atom is also linked to a V group, where V Is a divalent radical of the formula 15 -0-, -S-, -N = N-, -(CF2)q-, -(CH2)q- or -C(CH3)2- wherein q is 1 to 20; (c) B is independently a divalent substituted or unsubstituted aliphatic or cycloaliphatic group or Ar; 20 (d) R and R' which may be the same or different are H, Br, CI or F atom or a hydroxy, alkoxy, alkyl, aralkyl, unsubstituted or mono- or disubstituted amino, nitro, ester, acid, or acid halide, amide or imide group; and (e) Y represents a Br, CI or F atom or a hydroxy or alkoxy group; subject to the proviso that any aromatic ring which contains an activated hydrogen atom also contains less than 2 alkoxy groups, and 25 the resulting aromatic carbonyl compound contains less than 2 identical directly linked sequences containing at least one -CO- or -S02 -group and at least one -V-group. Pendant substitutents which can be present on B or Ar groups include, for example, lower alkyl, cyano, halogen, nitro, benzoyl or any other atom or group which will not interfere with the reaction by virtue of either its chemical nature or its location in the reactant from which the B group is derived. 30 The term "activated hydrogen atom" refers to a hydrogen atom displaceable under the electrophilic (Friedel-Crafts) reaction conditions employed in the reaction. Aromatic compounds suitable for acylation according to the process of the instant invention exhibit carbon-13 nuclear magnetic resonance (C-13 NMR) chemical shifts at the ring site where acylation is desired at least 2.1, preferably at least 2.4 and most preferably at least 2.8 parts per million (ppm) less than 35 that exhibited by benzene. For a listing of C-13 NMR chemical shifts of monosubstituted benzenes see M. Mishima et al (Memoirs of the Faculty of Science, Kyusuu Un., Ser. C, Vol. 11 No. 1, 1978). Table 2 of this reference lists C-13 NMR chemical shifts of a variety of mono-substituted benzenes measured in solution in carbon tetrachloride. Benzene in this solvent is stated to have a chemical shift of 128.04 ppm. The aromatic compounds useful in the instant invention may, but preferably do not, form additional complexes with Lewis 40 acid under the reaction conditions. Those skilled in the art will readily recognize that when an addition complex is formed, it should not substantially deactivate the molecule to acylation. Thus such complexes, for example, should still exhibit C-13 NMR chemical shifts which are at least 2.1 ppm less than that of benzene or sufficient uncomplexed aromatic compound is present to enable the reaction to proceed at the desired rate. 45 Illustrative aromatic compounds of the general formulas (R)sArDh are: toluene, ethyl benzene, fluorobenzene, anisole, ethoxy benzene, 3-chloroanisole, naphthalene, anth- racene, and compounds of the formulas 50 55 3 EP 0 178 184 B1 0~0 0-*0 000 0^> o-~o-!-o--o O-O-fO-O O^C o*o*o Illustrative mono or di-acyl compounds of the general formula YC0BD(R'),,0(C0BD(R')t)2 or YCOBDCOY are: acetic anhydride, acetyl chloride, adipoyl dichloride, benzoyl chloride, 4-fluorobenzoyl chloride, 4- chlorobenzoyl chloride, 3-nitrobenzoyl chloride, phthaloyl chloride, pthalic anhydride, naphthoyl chloride, tetrabromophthaloyl chloride, and compounds of the following formulas EP 0 178 184 B1 ' II II 0 0 o 0 20 25 30 35 wherein each V is independently as defined above, a is 0, 1 or 2 and Z is as defined above.
Load more

Recommended publications
  • 5 Phosphorus Oxychloride1 Acute Exposure Guideline Levels
    Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 10 Committee on Acute Exposure Guideline Levels Committee on Toxicology Board on Environmental Studies and Toxicology Division on Earth and Life Studies Copyright © National Academy of Sciences. All rights reserved. Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 10 THE NATIONAL ACADEMIES PRESS 500 FIFTH STREET, NW WASHINGTON, DC 20001 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Insti- tute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. This project was supported by Contract No. W81K04-06-D-0023 and EP-W-09-007 be- tween the National Academy of Sciences and the U.S. Department of Defense and the U.S. Environmental Protection Agency. Any opinions, findings, conclusions, or recom- mendations expressed in this publication are those of the author(s) and do not necessarily reflect the view of the organizations or agencies that provided support for this project. International Standard Book Number-13: 978-0-309-21987-7 International Standard Book Number-10: 0-309-21987-6 Additional copies of this report are available from The National Academies Press 500 Fifth Street, NW Box 285 Washington, DC 20055 800-624-6242 202-334-3313 (in the Washington metropolitan area) http://www.nap.edu Copyright 2011 by the National Academy of Sciences.
    [Show full text]
  • Psilocybin † † † ‡ Haden A
    Review pubs.acs.org/chemneuro DARK Classics in Chemical Neuroscience: Psilocybin † † † ‡ Haden A. Geiger, Madeline G. Wurst, and R. Nathan Daniels*, , † Department of Pharmaceutical Sciences, Lipscomb University College of Pharmacy and Health Sciences, Nashville, Tennessee 37204, United States ‡ Department of Pharmacology, Vanderbilt University Medical Center, Nashville, Tennessee 37232-6600, United States ABSTRACT: Psilocybin is found in a family of mushrooms commonly known as “magic mushrooms” that have been used throughout history to induce hallucinations. In the late 1950s Albert Hofmann, of Sandoz Laboratories, identified and synthesized the psychoactive compounds psilocybin and psilocin which are found in psilocybe mushrooms. Psilocybin was marketed by Sandoz as Indocybin for basic psychopharmacological and therapeutic clinical research. Psilocybin saw a rapid rise in popularity during the 1960s and was classed as a Schedule I drug in 1970. This led to a significant decrease in psilocybin research. Recently, however, preliminary studies with psilocybin have shown promise as potential for the treatment of obsessive compulsive disorder, alcohol addiction, tobacco addiction, and major depressive disorder, and the treatment of depression in terminally ill cancer patients. This review describes in detail the synthesis, metabolism, pharmacology, adverse drug reactions, and importance of psilocybin to neuroscience in the past and present. KEYWORDS: Psilocybin, psilocin, indolealkylamine, hallucinogen, psychedelic, magic mushrooms, mushrooms, O-acetylpsilocin, indocybin I. INTRODUCTION The structure of psilocybin, and other indolealkylamine Psilocybin (1, Figure 1), a tryptamine alkaloid, is found in a hallucinogens, is similar to that of the endogenous neuro- family of mushroom-forming fungi that when ingested can transmitter serotonin (3), the hormone melatonin (4), and the hypothesized endogenous psychedelic, N,N-dimethyltrypt- cause hallucinations.
    [Show full text]
  • Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts
    Organic Process Research & Development 2010, 14, 1501–1505 Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts Heiner Eckert* and Johann Auerweck Department of Chemistry, Technische UniVersitaet Muenchen, Lichtenbergstr. 4, Garching 85747, Germany Abstract: Scheme 1. Decomposition of triphosgene (1a) into carbon tetrachloride, carbon dioxide, and 1 equiv of phosgene (3) Phosgene is quantitatively formed from solid triphosgene in a solvent-free and safe process without any reaction heat, catalyzed by planar N-heterocycles with deactivated imino functions. The rate of phosgene generation is adjustable to the rate of phosgene consumption in the subsequent phosgenation reaction by thermal control, catalyst concentration, and in some cases, specific proper- ties of selected metal phthalocyanines. A thermal runaway reaction of this process is impossible. phosgene in most reactions, yet several phosgenation reactions are advantageously carried out with phosgene, that is, when excessive triphosgene is difficult to remove during the reaction Introduction workup because of its high boiling point of over 200 °C. Its Phosgene (3) is a highly useful and versatile chemical in excess can be destroyed by hydrolysis, when phosgenation performing syntheses.1a Although consisting of only four atoms, products are not sensitive to moisture as are carbonates, four important transformations can be carried out with it in carbamates, ureas, diarylketones, alkylhalides, cyanides, and organic
    [Show full text]
  • Beitrag Zur Chemie Des Galliums the Synthesis and Some Properties of Gallium Ethoxide
    52 4 R. REINMANN UND A. TANNER Beitrag zur Chemie des Galliums The Synthesis and some Properties of Gallium Ethoxide R . R e in m a n n u n d A . T anner Forschungsinstitut der Schweizerischen Aluminium A.G., Neuhausen am Rheinfall/Schweiz (Z. Naturforsdig. 20 b, 524—525 [1965] ; eingegangen am 6. März 1965) Experimental amounts in the range of 50 g each of gallium triethoxide have been prepared by reacting gallium trichloride with freshly prepared sodium ethoxide in absolute alcohol. Chloride, always present in the raw product, can be eliminated by precipitation with silver nitrate. Gallium triethoxide crystallizes in colourless needles, melting at 144.5 °C. The density of the very hygro­ scopic product is 1.23 g/cc. It is volatile at elevated temperature in vacuum. By alcohol interchange, the ethoxide can easily be transformed to the isopropoxide. Although many of the various alkoxides are Sodium metal is carefully freed from its superficial described in the literature, those of gallium were crust in a glove box under dry nitrogen, weighed, and lacking until recently. dissolved in ethanol under reflux. The stoichiometric amount of gallium trichloride, dissolved in cooled etha­ The purpose of this investigation was to find a nol, is added dropwise to the sodium ethoxide solution. suitable method for the preparation of gallium The mixture is finally heated to ebullition for about ethoxide, and to evaluate also some properties of 30 minutes. After cooling, when the NaCl and the the new compound. major part of the Gallium ethoxide are precipitated, benzene is added to about 30 — 40% of the final When writing this manuscript, we came across the mixture.
    [Show full text]
  • The Synthesis and Characterization of Novel Group 13 Nanostructured Building Block Heterogeneous Silicate Catalysts
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 8-2012 The Synthesis and Characterization of Novel Group 13 Nanostructured Building Block Heterogeneous Silicate Catalysts Joshua G. Abbott Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Catalysis and Reaction Engineering Commons, Inorganic Chemistry Commons, and the Materials Chemistry Commons Recommended Citation Abbott, Joshua G., "The Synthesis and Characterization of Novel Group 13 Nanostructured Building Block Heterogeneous Silicate Catalysts. " PhD diss., University of Tennessee, 2012. https://trace.tennessee.edu/utk_graddiss/1430 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Joshua G. Abbott entitled "The Synthesis and Characterization of Novel Group 13 Nanostructured Building Block Heterogeneous Silicate Catalysts." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Craig E. Barnes, Major Professor We have read this dissertation and recommend its acceptance: Craig E. Barnes, Zi-ling Xue, Michael Best, Joseph J. Bozell Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) The Synthesis and Characterization of Novel Group 13 Nanostructured Building Block Heterogeneous Silicate Catalysts A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Josh G.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 5,677,453 Cramm Et Al
    US005677453A United States Patent (19) 11 Patent Number: 5,677,453 Cramm et al. 45 Date of Patent: Oct. 14, 1997 54 PROCESS FOR THE PREPARATION OF 46 R. Hull, A New Sythesis of 4:6-dihydroxypyrimidines-J. DCHLOROPYRIMDINES Chem. Soc. (1951) p. 2214. Contribution a la synthese de la dichloro-4-6 pyrimidine, 75 Inventors: Ginther Cramm; Wolker Kiss, both Hennart et al., Bull. de la Soc. Chim. France, (1959) pp. of Leverkusen; Guido Stefan, 741-742. Odenthal, all of Germany Experiments on the Synthesis of Purine Nucleosides. Part IV. Kenner et al., J. Chem. Soc. (1943), pp. 574-575. 73) Assignee: Bayer Aktiengesellschaft, Leverkusen, A New Synthesis of 4:6-Dihydroxpyrimidines, Hull, J. Germany Chem. Soc. (1951), p. 2214. Synthesis of 21 Appl. No.: 699,812 4-(p-Aminobenzenesulfonamido)-6-Methoxypyrimidine, 22 Filed: Aug. 19, 1996 Zasosov et al., Translated from Khimiko-Farmatsevticheskii Zhurnal, vol. 8, No. 12, pp. 28–31, Dec., 1974. Original 30 Foreign Application Priority Data article submitted Dec. 6, 1973. Aug. 25, 1995 DEl Germany ........................ 19531 299.6 Primary Examiner-John M. Ford Attorney, Agent, or Firm-Sprung Horn Kramer & Woods (51) Int. Cl. ... C07D 239/30 52 U.S. Cl. ..................... ... 544/334 57 ABSTRACT 58) Field of Search ............................................. 544/334 4,6-Dichloropyrimidines are obtained by the reaction of (56) References Cited 4,6-dihydroxypyrimidines with excess phosphoryl chloride in a particularly advantageous manner when no base is FOREIGN PATENT DOCUMENTS added, during and/or after the reaction 0.75 to 1.5 mol of O 251 246A1 1A1988 European Pat. Off.. phosphorus trichloride and 0.7 to 1.3 mol of chlorine are O 697 406A1 2/1996 European Pat.
    [Show full text]
  • Safety Data Sheet
    SAFETY DATA SHEET Creation Date 16-May-2011 Revision Date 18-Jan-2021 Revision Number 2 SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1. Product identifier Product Description: Gallium(III) chloride, ultra dry Cat No. : 45026 CAS-No 13450-90-3 EC-No. 236-610-0 Molecular Formula GaCl3 Reach Registration Number - 1.2. Relevant identified uses of the substance or mixture and uses advised against Recommended Use Laboratory chemicals. Uses advised against No Information available 1.3. Details of the supplier of the safety data sheet Company Alfa Aesar . Avocado Research Chemicals, Ltd. Shore Road Port of Heysham Industrial Park Heysham, Lancashire LA3 2XY United Kingdom Office Tel: +44 (0) 1524 850506 Office Fax: +44 (0) 1524 850608 E-mail address [email protected] www.alfa.com Product Safety Department 1.4. Emergency telephone number Call Carechem 24 at +44 (0) 1865 407333 (English only); +44 (0) 1235 239670 (Multi-language) SECTION 2: HAZARDS IDENTIFICATION 2.1. Classification of the substance or mixture CLP Classification - Regulation (EC) No 1272/2008 Physical hazards Based on available data, the classification criteria are not met Health hazards ______________________________________________________________________________________________ ALFAA45026 Page 1 / 10 SAFETY DATA SHEET Gallium(III) chloride, ultra dry Revision Date 18-Jan-2021 ______________________________________________________________________________________________ Skin Corrosion/Irritation Category 1 B (H314) Serious Eye Damage/Eye Irritation Category 1 (H318) Environmental hazards Based on available data, the classification criteria are not met Full text of Hazard Statements: see section 16 2.2. Label elements Signal Word Danger Hazard Statements H314 - Causes severe skin burns and eye damage EUH014 - Reacts violently with water Precautionary Statements P280 - Wear protective gloves/protective clothing/eye protection/face protection P301 + P330 + P331 - IF SWALLOWED: Rinse mouth.
    [Show full text]
  • Phosphonate–Phosphonochloridate Conversion Bogdan Iorga, Duncan Carmichael, Philippe Savignac
    Phosphonate–phosphonochloridate conversion Bogdan Iorga, Duncan Carmichael, Philippe Savignac To cite this version: Bogdan Iorga, Duncan Carmichael, Philippe Savignac. Phosphonate–phosphonochloridate conversion. Comptes rendus de l’Académie des sciences. Série IIc, Chimie, Elsevier, 2000, 3 (11-12), pp.821-829. 10.1016/s1387-1609(00)01207-x. hal-03161486 HAL Id: hal-03161486 https://hal.archives-ouvertes.fr/hal-03161486 Submitted on 10 Mar 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Phosphonate-Phosphonochloridate Conversion Bogdan Iorga, Duncan Carmichael, Philippe Savignac Laboratoire Hétéroéléments et Coordination, UMR CNRS 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau Cedex, France; E-mail : [email protected] __________________________________________________________________________________________ Abstract - This review deals with the phosphonate-phosphonochloridate conversion. The different phosphorus-chlorine bond forming reagents (COCl2, (COCl)2, SOCl2, PCl5, POCl3, Ph3PCl2, trichloro(o-phenylenedioxy)phosphorane)
    [Show full text]
  • Searching for New Biologically Active Compounds Derived from Isoquinoline Alkaloids †
    Proceeding Paper Searching for New Biologically Active Compounds Derived from Isoquinoline Alkaloids † Anna Kmieciak 1, Marta Ćwiklińska 1, Karolina Jeżak 1, Afef Shili 2 and Marek P. Krzemiński 1,* 1 Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Toruń, Poland; [email protected] (A.K.); [email protected] (M.Ć.); [email protected] (K.J.) 2 Chemistry Department, Faculty of Sciences of Sfax, University of Sfax, Sfax 3029, Tunisia; [email protected] * Correspondence: [email protected] † Presented at the 24th International Electronic Conference on Synthetic Organic Chemistry, 15 November–15 December 2020; Available online: https://ecsoc-24.sciforum.net/. Abstract: Many isoquinoline alkaloids are biologically active compounds and successfully used as pharmaceuticals. Compounds belonging to the isoquinolines and tetrahydroisoquinolines (TIQs) can be used as anesthetics, antihypertensive drugs, antiviral agents, and vasodilators. In the presented studies, the search for new compounds and synthesis of tetrahydroisoquinoline alkaloid derivatives was undertaken. Several dihydroisoquinolines were synthesized by Bishler–Napieralski reaction from the corresponding amides. Dihydroisoquinolines were reduced with sodium borohydride to obtain racemic tetrahydroisoquinolines. Asymmetric reduction of selected 3,4-dihydroisoquinolines was attempted with borane in the presence of chiral terpene spiroboranes. Keywords: isoquinoline; alkaloids; biologically active compound Citation: Kmieciak, A.; Ćwiklińska, M.; Jeżak, K.; Shili, A.; Krzemiński, M.P. Searching for New Biologically 1. Introduction Active Compounds Derived from Isoquinoline Alkaloids. Chem. Proc. Isoquinoline and its derivatives are used as starting materials in the synthesis of 2021, 3, 97. https://doi.org/10.3390/ dyes, insecticides, and pharmaceuticals. Tetrahydroisoquinoline (TIQ) is one of many ecsoc-24-08417 representatives of N-heterocyclic compounds.
    [Show full text]
  • List of Lists
    United States Office of Solid Waste EPA 550-B-10-001 Environmental Protection and Emergency Response May 2010 Agency www.epa.gov/emergencies LIST OF LISTS Consolidated List of Chemicals Subject to the Emergency Planning and Community Right- To-Know Act (EPCRA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the Clean Air Act • EPCRA Section 302 Extremely Hazardous Substances • CERCLA Hazardous Substances • EPCRA Section 313 Toxic Chemicals • CAA 112(r) Regulated Chemicals For Accidental Release Prevention Office of Emergency Management This page intentionally left blank. TABLE OF CONTENTS Page Introduction................................................................................................................................................ i List of Lists – Conslidated List of Chemicals (by CAS #) Subject to the Emergency Planning and Community Right-to-Know Act (EPCRA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the Clean Air Act ................................................. 1 Appendix A: Alphabetical Listing of Consolidated List ..................................................................... A-1 Appendix B: Radionuclides Listed Under CERCLA .......................................................................... B-1 Appendix C: RCRA Waste Streams and Unlisted Hazardous Wastes................................................ C-1 This page intentionally left blank. LIST OF LISTS Consolidated List of Chemicals
    [Show full text]
  • Gallium in 2017 (PDF)
    2017 Minerals Yearbook GALLIUM [ADVANCE RELEASE] U.S. Department of the Interior April 2020 U.S. Geological Survey Gallium By Brian W. Jaskula Domestic survey data and tables were prepared by Wanda G. Wooten, statistical assistant. Low-grade primary gallium was recovered globally as a gallium production was 5% from 2007 through 2017. World byproduct of processing bauxite and zinc ores. No domestic high-grade secondary refined gallium production increased at a low-grade primary gallium was recovered in 2017. Imports CAGR of 7%. World gallium consumption, which increased at of gallium metal and gallium arsenide (GaAs) wafers plus a CAGR of 6% from 2007 through 2017, was estimated to have domestically refined and recycled gallium continued to account been 355 t in 2017. for all U.S. gallium consumption (metal and gallium in GaAs). Metal imports were 93% higher than those in 2016 (table 1). Production The leading sources of imported gallium metal were, in No domestic production of low-grade primary gallium was descending order, China (including Hong Kong), the United reported in 2017. Neo Performance Materials Inc. (Canada) Kingdom, France, Ukraine, Russia, and the Republic of Korea recovered gallium from new scrap materials, predominantly (table 4). A significant portion of imports was thought to be those generated during the production of GaAs ingots and low-grade gallium that was refined in the United States and wafers. Neo’s facility in Blanding, UT, had the capability to shipped to other countries. Data on refined gallium exports, produce about 50 metric tons per year of high-grade gallium. however, were not available.
    [Show full text]
  • Searching for New Biologically Active Compounds Derived from Isoquinoline Alkaloids †
    Proceedings Searching for New Biologically Active Compounds Derived from Isoquinoline Alkaloids † Anna Kmieciak 1, Marta Ćwiklińska 1, Karolina Jeżak 1, Afef Shili 2 and Marek P. Krzemiński 1 1 Faculty of Chemistry, Nicolaus Copernicus University, Toruń, Poland 2 Chemistry Department, Faculty of Sciences of Sfax, University of Sfax, Tunisia † Presented at the 24th International Electronic Conference on Synthetic Organic Chemistry, 15 November– 15 December 2020; Available online: https://ecsoc-24.sciforum.net/. Received: date; Accepted: date; Published: date Abstract: Many isoquinoline alkaloids are biologically active compounds and are successfully used as pharmaceuticals. Compounds belonging to isoquinolines and tetrahydroisoquinolines (TIQs) can be used as anesthetics, antihypertensive drugs, antiviral agents, and vasodilators. In the presented studies, the search for new compounds and synthesis of tetrahydroisoquinoline alkaloid derivatives was undertaken. Several dihydroisoquinolines were synthesized by Bishler-Napieralski reaction from the corresponding amides. Dihydroisoquinolines were reduced with sodium borohydride to obtain racemic tetrahydroisoquinolines. Asymmetric reduction of selected 3,4-dihydroisoquinolines was attempted with borane in the presence of chiral terpene spiroboranes. Keywords: isoquinoline; alkaloids; biologically active compound 1. Introduction Isoquinoline and its derivatives are used as starting materials in the synthesis of dyes, insecticides, and pharmaceuticals. Tetrahydroisoquinoline (TIQ) is one of
    [Show full text]