Thiocyanate Pyridine Complexes
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Synthesis of Densely Substituted Pyridine Derivatives from Nitriles by a Non-Classical [4+2] Cycloaddition/1,5-Hydrogen Shift Strategy
Synthesis of densely substituted pyridine derivatives from nitriles by a non-classical [4+2] cycloaddition/1,5-hydrogen shift strategy Wanqing Wu ( [email protected] ) South China University of Technology https://orcid.org/0000-0001-5151-7788 Dandan He South China University of Technology Kanghui Duan South China University of Technology Yang Zhou South China University of Technology Meng Li South China University of Technology Huanfeng Jiang South China University of Technology Article Keywords: pyridine derivatives, organic synthesis, medicinal chemistry. Posted Date: March 3rd, 2021 DOI: https://doi.org/10.21203/rs.3.rs-258126/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Page 1/18 Abstract A novel strategy has been established to assemble an array of densely substituted pyridine derivatives from nitriles and o-substituted aryl alkynes or 1-methyl-1,3-enynes via a non-classical [4 + 2] cycloaddition along with 1,5-hydrogen shift process. The well-balanced anities of two different alkali metal salts enable the C(sp3)-H bond activation as well as the excellent chemo- and regioselectivities. This protocol offers a new guide to construct pyridine frameworks from nitriles with sp3-carbon pronucleophiles, and shows potential applications in organic synthesis and medicinal chemistry. Introduction Compounds containing pyridine core structures, not only widely exist in natural products, pharmaceuticals, and functional materials,1–7 but also serve as useful and valuable building blocks for metal ligands.8,9 For instance, pyridine derivative Actos I10 is a famous drug for the treatment of type 2 diabetes; Bi-(or tri-)pyridines II11–15 are often used as ligands in metal-catalyzed reactions; Kv1.5 antagonist III16 and alkaloid papaverine IV17 are two representative isoquinolines as a promising atrial- selective agent and a smooth muscle relaxant, respectively (Fig. -
TR-470: Pyridine (CASRN 110-86-1) in F344/N Rats, Wistar Rats, And
NTP TECHNICAL REPORT ON THE TOXICOLOGY AND CARCINOGENESIS STUDIES OF PYRIDINE (CAS NO. 110-86-1) IN F344/N RATS, WISTAR RATS, AND B6C3F1 MICE (DRINKING WATER STUDIES) NATIONAL TOXICOLOGY PROGRAM P.O. Box 12233 Research Triangle Park, NC 27709 March 2000 NTP TR 470 NIH Publication No. 00-3960 U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service National Institutes of Health FOREWORD The National Toxicology Program (NTP) is made up of four charter agencies of the U.S. Department of Health and Human Services (DHHS): the National Cancer Institute (NCI), National Institutes of Health; the National Institute of Environmental Health Sciences (NIEHS), National Institutes of Health; the National Center for Toxicological Research (NCTR), Food and Drug Administration; and the National Institute for Occupational Safety and Health (NIOSH), Centers for Disease Control and Prevention. In July 1981, the Carcinogenesis Bioassay Testing Program, NCI, was transferred to the NIEHS. The NTP coordinates the relevant programs, staff, and resources from these Public Health Service agencies relating to basic and applied research and to biological assay development and validation. The NTP develops, evaluates, and disseminates scientific information about potentially toxic and hazardous chemicals. This knowledge is used for protecting the health of the American people and for the primary prevention of disease. The studies described in this Technical Report were performed under the direction of the NIEHS and were conducted in compliance with NTP laboratory health and safety requirements and must meet or exceed all applicable federal, state, and local health and safety regulations. Animal care and use were in accordance with the Public Health Service Policy on Humane Care and Use of Animals. -
Heats of Formation of Certain Nickel-Pyridine Complex Salts
HEATS OF FORFATION OF CERTAIN NICKEL-PYRIDINE COLPLEX SALTS DAVID CLAIR BUSH A THESIS submitted to OREGON STATE COLLEGE in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE June l9O [4CKNOWLEDGMENT The writer wishes to acknowledge his indebtedness and gratitude to Dr. [4. V. Logan for his help and encour- agement during this investigation. The writer also wishes to express his appreciation to Dr. E. C. Gilbert for helpful suggestions on the con- struction of the calortheter, and to Lee F. Tiller for his excellent drafting and photostating of the figures and graphs. APPROVED: In Charge of ?ajor Head of Department of Chemistry Chairrian of School Graduate Comrittee Dean of Graduate School Date thesis is presented /11 ' Typed by Norma Bush TABLE OF CONTENTS HISTORICAL BACKGROUND i INTRODUCTION 2 EXPERIMENTAL 5 Preparation of the Compounds 5 Analyses of the Compounds 7 The Calorimeter Determination of the Heat Capacity 19 Determination of the Heat of Formation 22 DISCUSSION 39 41 LITERATURE CITED 42 TABLES I Analyses of the Compounds 8 II Heat Capacity of the Calorimeter 23 III Heat of Reaction of Pyridine 26 IV Sample Run and Calculation 27 V Heat of Reaction of Nickel Cyanate 30 VI Heat of Reaction of Nickel Thiocyanate 31 VII Heat of Reaction of Hexapyridinated Nickel Cyanate 32 VIII Heat of Reaction of Tetrapyridinated Nickel Thiocyanate 33 IX Heat of Formation of the Pyridine Complexes 34 FI GURES i The Calorimeter 10 2 Sample Ijector (solids) 14 2A Sample Ejector (liquids) 15 3 Heater Circuit Wiring Diagram 17 4 heat Capacity of the Calorimeter 24 5 Heat of Reaction of Pyridine 28 6 Heat of Reaction of Hexapyridinated Nickel Cyanate 35 7 Heat of Reaction of Tetrapyridinated Nickel Thiocyanate 36 8 Heat of Reaction of Nickel Cyanate 37 9 Heat of Reaction of Nickel Thiocyanate 38 HEATS OF FOW ATION OF CERTAIN NICKEL-PYRIDINE COMPLEX SALTS HISTORICAL BACKGROUND Compounds of pyridine with inorganic salts have been prepared since 1970. -
United States Patent Office Patented Jan
3,071,593 United States Patent Office Patented Jan. 1, 1963 2 3,071,593 O PREPARATION OF AELKENE SULFES Paul F. Warner, Philips, Tex., assignor to Philips Petroleum Company, a corporation of Delaware wherein each R is selected from the group consisting of No Drawing. Filed July 27, 1959, Ser. No. 829,518 5 hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl 8 Claims. (C. 260-327) groups having 1 to 8 carbon atoms, the combined R groups having up to 12 carbon atoms. Examples of Suit This invention relates to a method of preparing alkene able compounds are ethylene oxide, propylene oxide, iso sulfides. Another aspect relates to a method of convert butylene oxide, a-amylene oxide, styrene oxide, isopropyl ing an alkene oxide to the corresponding sulfide at rela O ethylene oxide, methylethylethylene oxide, 3-phenyl-1, tively high yields without refrigeration. 2-propylene oxide, (3-methylphenyl) ethylene oxide, By the term "alkene sulfide' as used in this specifica cyclohexylethylene oxide, 1-phenyl-3,4-epoxyhexane, and tion and in the claims, I mean to include not only un the like. substituted alkene sulfides such as ethylene sulfide, propyl The salts of thiocyanic acid which I prefer to use are ene sulfide, isobutylene sulfide, and the like, but also 5 the salts of the alkali metals or ammonium. I especially hydrocarbon-substituted alkene sulfides such as styrene prefer ammonium thiocyanate, sodium thiocyanate, and oxide, and in general all compounds conforming to the potassium thiocyanate. These compounds can be reacted formula with ethylene oxide in a cycloparaffin diluent to produce 20 substantial yields of ethylene sulfide and with little or S no polymer formation. -
Robert Burns Woodward
The Life and Achievements of Robert Burns Woodward Long Literature Seminar July 13, 2009 Erika A. Crane “The structure known, but not yet accessible by synthesis, is to the chemist what the unclimbed mountain, the uncharted sea, the untilled field, the unreached planet, are to other men. The achievement of the objective in itself cannot but thrill all chemists, who even before they know the details of the journey can apprehend from their own experience the joys and elations, the disappointments and false hopes, the obstacles overcome, the frustrations subdued, which they experienced who traversed a road to the goal. The unique challenge which chemical synthesis provides for the creative imagination and the skilled hand ensures that it will endure as long as men write books, paint pictures, and fashion things which are beautiful, or practical, or both.” “Art and Science in the Synthesis of Organic Compounds: Retrospect and Prospect,” in Pointers and Pathways in Research (Bombay:CIBA of India, 1963). Robert Burns Woodward • Graduated from MIT with his Ph.D. in chemistry at the age of 20 Woodward taught by example and captivated • A tenured professor at Harvard by the age of 29 the young... “Woodward largely taught principles and values. He showed us by • Published 196 papers before his death at age example and precept that if anything is worth 62 doing, it should be done intelligently, intensely • Received 24 honorary degrees and passionately.” • Received 26 medals & awards including the -Daniel Kemp National Medal of Science in 1964, the Nobel Prize in 1965, and he was one of the first recipients of the Arthur C. -
Toxicological Profile for Pyridine
TOXICOLOGICAL PROFILE FOR PYRIDINE Agency for Toxic Substances and Disease Registry U.S. Public Health Service September 1992 ii DISCLAIMER The use of company or product name(s) is for identification only and does not imply endorsement by the Agency for Toxic Substances and Disease Registry. 1 1. PUBLIC HEALTH STATEMENT This Statement was prepared to give you information about pyridine and to emphasize the human health effects that may result from exposure to it. The Environmental Protection Agency (EPA) has identified 1,177 sites on its National Priorities List (NPL). Pyridine has been found at 4 of these sites. However, we do not know how many of the 1,177 NPL sites have been evaluated for pyridine. As EPA evaluates more sites, the number of sites at which pyridine is found may change. This information is important for you to know because pyridine may cause harmful health effects and because these sites are potential or actual sources of human exposure to pyridine. When a chemical is released from a large area, such as an industrial plant, or from a container, such as a drum or bottle, it enters the environment as a chemical emission. This emission, which is also called a release, does not always lead to exposure. You can be exposed to a chemical only when you come into contact with the chemical. You may be exposed to it in the environment by breathing, eating, or drinking substances containing the chemical or from skin contact with it. If you are exposed to a hazardous chemical such as pyridine, several factors will determine whether harmful health effects will occur and what the type and severity of those health effects will be. -
House Fly Attractants and Arrestante: Screening of Chemicals Possessing Cyanide, Thiocyanate, Or Isothiocyanate Radicals
House Fly Attractants and Arrestante: Screening of Chemicals Possessing Cyanide, Thiocyanate, or Isothiocyanate Radicals Agriculture Handbook No. 403 Agricultural Research Service UNITED STATES DEPARTMENT OF AGRICULTURE Contents Page Methods 1 Results and discussion 3 Thiocyanic acid esters 8 Straight-chain nitriles 10 Propionitrile derivatives 10 Conclusions 24 Summary 25 Literature cited 26 This publication reports research involving pesticides. It does not contain recommendations for their use, nor does it imply that the uses discussed here have been registered. All uses of pesticides must be registered by appropriate State and Federal agencies before they can be recommended. CAUTION: Pesticides can be injurious to humans, domestic animals, desirable plants, and fish or other wildlife—if they are not handled or applied properly. Use all pesticides selectively and carefully. Follow recommended practices for the disposal of surplus pesticides and pesticide containers. ¿/áepé4áaUÁí^a¡eé —' ■ -"" TMK LABIL Mention of a proprietary product in this publication does not constitute a guarantee or warranty by the U.S. Department of Agriculture over other products not mentioned. Washington, D.C. Issued July 1971 For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 - Price 25 cents House Fly Attractants and Arrestants: Screening of Chemicals Possessing Cyanide, Thiocyanate, or Isothiocyanate Radicals BY M. S. MAYER, Entomology Research Division, Agricultural Research Service ^ Few chemicals possessing cyanide (-CN), thio- cyanate was slightly attractive to Musca domes- eyanate (-SCN), or isothiocyanate (~NCS) radi- tica, but it was considered to be one of the better cals have been tested as attractants for the house repellents for Phormia regina (Meigen). -
Efficient Synthesis of Novel Pyridine-Based Derivatives Via
molecules Article Efficient Synthesis of Novel Pyridine-Based Derivatives via Suzuki Cross-Coupling Reaction of Commercially Available 5-Bromo-2-methylpyridin-3-amine: Quantum Mechanical Investigations and Biological Activities Gulraiz Ahmad 1, Nasir Rasool 1,*, Hafiz Mansoor Ikram 1, Samreen Gul Khan 1, Tariq Mahmood 2, Khurshid Ayub 2, Muhammad Zubair 1, Eman Al-Zahrani 3, Usman Ali Rana 4, Muhammad Nadeem Akhtar 5 and Noorjahan Banu Alitheen 6,* 1 Department of Chemistry, Government College University Faisalabad, Faisalabad 38000, Pakistan; [email protected] (G.A.); [email protected] (H.M.I.); [email protected] (S.G.K.); [email protected] (M.Z.) 2 Department of Chemistry, COMSATS Institute of Information Technology, University Road, Tobe Camp, 22060 Abbottabad, Pakistan; [email protected] (T.M.); [email protected] (K.A.) 3 Chemistry Department, Faculty of Science, Taif University, 888-Taif, Saudi Arabia; [email protected] 4 Sustainable Energy Technologies Center, College of Engineering, P.O. Box 800, King Saud University, Riyadh 11421, Saudi Arabia; [email protected] 5 Faculty of Industrial Sciences & Technology, University Malaysia Pahang, Lebuhraya Tun, Razak 26300, Kuantan Pahang, Malaysia; [email protected] 6 Faculty of Biotechnology and Biomolecular Sciences, University Putra Malaysia, Serdang, Selangor Darul Ehsan 43400, Malaysia * Correspondence: [email protected] (N.R.); [email protected] (N.B.A.); Tel.: +92-332-7491790 (N.R.); +60-3-8946-7471 (N.B.A.); Fax: +92-41-9201032 (N.R.); +60-3-8946-7510 (N.B.A.) Academic Editor: Diego Muñoz-Torrero Received: 20 November 2016; Accepted: 6 January 2017; Published: 27 January 2017 Abstract: The present study describes palladium-catalyzed one pot Suzuki cross-coupling reaction to synthesize a series of novel pyridine derivatives 2a–2i, 4a–4i. -
Heterocyclic Chemistrychemistry
HeterocyclicHeterocyclic ChemistryChemistry Professor J. Stephen Clark Room C4-04 Email: [email protected] 2011 –2012 1 http://www.chem.gla.ac.uk/staff/stephenc/UndergraduateTeaching.html Recommended Reading • Heterocyclic Chemistry – J. A. Joule, K. Mills and G. F. Smith • Heterocyclic Chemistry (Oxford Primer Series) – T. Gilchrist • Aromatic Heterocyclic Chemistry – D. T. Davies 2 Course Summary Introduction • Definition of terms and classification of heterocycles • Functional group chemistry: imines, enamines, acetals, enols, and sulfur-containing groups Intermediates used for the construction of aromatic heterocycles • Synthesis of aromatic heterocycles • Carbon–heteroatom bond formation and choice of oxidation state • Examples of commonly used strategies for heterocycle synthesis Pyridines • General properties, electronic structure • Synthesis of pyridines • Electrophilic substitution of pyridines • Nucleophilic substitution of pyridines • Metallation of pyridines Pyridine derivatives • Structure and reactivity of oxy-pyridines, alkyl pyridines, pyridinium salts, and pyridine N-oxides Quinolines and isoquinolines • General properties and reactivity compared to pyridine • Electrophilic and nucleophilic substitution quinolines and isoquinolines 3 • General methods used for the synthesis of quinolines and isoquinolines Course Summary (cont) Five-membered aromatic heterocycles • General properties, structure and reactivity of pyrroles, furans and thiophenes • Methods and strategies for the synthesis of five-membered heteroaromatics -
The Mechanism of Pyridine Hydrogenolysis on Molybdenum-Containing Catalysts III
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Universiteit Twente Repository JOURNAL OF CATALYSIS 34, 215-229 (1974) The Mechanism of Pyridine Hydrogenolysis on Molybdenum-Containing Catalysts III. Cracking, Hydrocracking, Dehydrogenation and Disproportionation of Pentylamine J. SONNEMANS” AND P. MARS l’wente University of Technology, Enschede, The Netherlands Received October 30, 1973 The conversion of pentylamine on a MoOrA1203 catalyst was studied between 250 and 350°C at various hydrogen pressures. The reactions observed were cracking to pentene and ammonia, hydrocracking to pentane and ammonia, dehydrogenation to pentanimine and butylcarbonitrile, and disproportionation to ammonia and dipentylamine. The equilibrium between pentylamine, dipentylamine and ammonia appeared to be established under most of the experimental conditions. The equilibrium constant is about 9 at 250°C and about 5 at 320°C. The disproportionation reaction is zero order in hydrogen and of -1 order in the initial pentylamine pressure. Dehydrogenation was observed at low hydrogen pressures, and especially at higher temperatures; the reaction is first order in pentylamine. Both cracking and hydrocracking take place, mainly above 300°C. Hydrocracking appears to be half order in hydrogen; the rate of cracking is almost independent of the hydrogen pressure. The hydrocarbon formation is of zero order in pentyl- amine or dipentylamine. The same type of reactions (except hydrocracking) take place on alumina, but with a far lower reaction rate. INTRODUCTION catalysts at hydrogen pressures of about One of the intermediates formed in the 60 atm (Z-4). They reported a high rate hydrogenolysis of pyridine is pentylamine of ammonia formation from the primary (1). -
Investigations of the Reactivity of Pyridine Carboxylic Acids with Diazodiphenylmethane in Protic and Aprotic Solvents. Part I
J. Serb. Chem. Soc. 70 (4) 557–567 (2005) UDC 547.821+547.595:543.878 JSCS – 3288 Original scientific paper Investigations of the reactivity of pyridine carboxylic acids with diazodiphenylmethane in protic and aprotic solvents. Part I. Pyridine mono-carboxylic acids ALEKSANDAR D. MARINKOVI]*#, SA[A @. DRMANI]#, BRATISLAV @. JOVANOVI]# and MILICA MI[I]-VUKOVI]# Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P. O. Box 3503, 11120 Belgrade, Serbia and Montenegro (e-mail: [email protected]) (Received 14 May, revised 26 July 2004) Abstract: Rate constants for the reaction of diazodiphenylmethane with isomeric pyridine carboxylic acids were determined in chosen protic and aprotic solvents at 30 °C, using the well known UV spectrophotometric method. The values of the rate constants of the investigated acids in protic solvents were higher than those in aprotic solvents. The second order rate constants were correlated with solvent pa- rameters using the Kamlet-Taft solvatochromic equation in the form: log k =logk0 + sp*+aa + bb. The correlation of the obtained kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The signs of the equation coefficients were in agreement with the postulated reaction mechanism. The mode of the influence of the solvent on the reaction rate in all the investigated acids are discussed on the basis of the correlation results. Keywords: pyridine carboxylic acids, diazodiphenylmethane, rate constants, solvent parameters, protic and aprotic solvents. INTRODUCTION The relationship between the structure of carboxylic acids and their reactivity with diazodiphenylmethane (DDM) has been studied by many authors,1,2 with particular regard to the influence of the solvent. -
Preparation and Properties of Pyridine Pyridine
Preparation and Properties of Pyridine Pyridine • Pyridine is the most important of the heterocyclic ring systems. It occurs along with pyrrole in bone oil and in the light oil fraction of coal tar (boiling point up to 170 C). • It can be isolated from the latter by extracting it with dilute sulphuric acid. This removes pyridine and other bases in the acid layer as soluble sulphates. • The acid layer is then treated with sodium hydroxide when a dark brown liquid separates. Pyridine is obtained from this oily liquid by fractional distillation. Preparation Methods (1) By passing a mixture of acetylene and hydrogen cyanide through a red- hot tube. (2) By dehydrogenation of piperidine with concentrated sulphuric acid at 300°C or with nitrobenzene at 260°C. (3) By heating tetrahydrofurfuryl alcohol with ammonia in the presence of aluminium oxide at 500°C. (Commercial Method of Preparation). Physical properties of Pyridine Pyridine is a colourless liquid, bp 115C°. It has a very characteristic pungent and disgusting odour. Pyridine is miscible with water and most organic solvents. Almost all classes of organic compounds are soluble in pyridine, even many of the high melting solids which scarcely dissolve in solvents such as ethanol and benzene. It is consequently used as a solvent. It is very hygroscopic. Chemical properties of Pyridine (1) Basic Character: Pyridine behaves as a base. It reacts with acids to form fairly stable salts.. (2) Electrophilic Substitution: Pyridine, however, does undergo electrophilic substitution reactions when extremely vigorous reaction conditions are used. Substitution occurs almost exclusively at C-3 (β-Position).