Investigations of the Reactivity of Pyridine Carboxylic Acids with Diazodiphenylmethane in Protic and Aprotic Solvents. Part I
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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. -
APPENDIX G Acid Dissociation Constants
harxxxxx_App-G.qxd 3/8/10 1:34 PM Page AP11 APPENDIX G Acid Dissociation Constants § ϭ 0.1 M 0 ؍ (Ionic strength ( † ‡ † Name Structure* pKa Ka pKa ϫ Ϫ5 Acetic acid CH3CO2H 4.756 1.75 10 4.56 (ethanoic acid) N ϩ H3 ϫ Ϫ3 Alanine CHCH3 2.344 (CO2H) 4.53 10 2.33 ϫ Ϫ10 9.868 (NH3) 1.36 10 9.71 CO2H ϩ Ϫ5 Aminobenzene NH3 4.601 2.51 ϫ 10 4.64 (aniline) ϪO SNϩ Ϫ4 4-Aminobenzenesulfonic acid 3 H3 3.232 5.86 ϫ 10 3.01 (sulfanilic acid) ϩ NH3 ϫ Ϫ3 2-Aminobenzoic acid 2.08 (CO2H) 8.3 10 2.01 ϫ Ϫ5 (anthranilic acid) 4.96 (NH3) 1.10 10 4.78 CO2H ϩ 2-Aminoethanethiol HSCH2CH2NH3 —— 8.21 (SH) (2-mercaptoethylamine) —— 10.73 (NH3) ϩ ϫ Ϫ10 2-Aminoethanol HOCH2CH2NH3 9.498 3.18 10 9.52 (ethanolamine) O H ϫ Ϫ5 4.70 (NH3) (20°) 2.0 10 4.74 2-Aminophenol Ϫ 9.97 (OH) (20°) 1.05 ϫ 10 10 9.87 ϩ NH3 ϩ ϫ Ϫ10 Ammonia NH4 9.245 5.69 10 9.26 N ϩ H3 N ϩ H2 ϫ Ϫ2 1.823 (CO2H) 1.50 10 2.03 CHCH CH CH NHC ϫ Ϫ9 Arginine 2 2 2 8.991 (NH3) 1.02 10 9.00 NH —— (NH2) —— (12.1) CO2H 2 O Ϫ 2.24 5.8 ϫ 10 3 2.15 Ϫ Arsenic acid HO As OH 6.96 1.10 ϫ 10 7 6.65 Ϫ (hydrogen arsenate) (11.50) 3.2 ϫ 10 12 (11.18) OH ϫ Ϫ10 Arsenious acid As(OH)3 9.29 5.1 10 9.14 (hydrogen arsenite) N ϩ O H3 Asparagine CHCH2CNH2 —— —— 2.16 (CO2H) —— —— 8.73 (NH3) CO2H *Each acid is written in its protonated form. -
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. -
Nomenclature of Carboxylic Acids • Select the Longest Carbon Chain Containing the Carboxyl Group
Chapter 5 Carboxylic Acids and Esters Carboxylic Acids • Carboxylic acids are weak organic acids which Chapter 5 contain the carboxyl group (RCO2H): Carboxylic Acids and Esters O C O H O RCOOH RCO2H Chapter Objectives: O condensed ways of • Learn to recognize the carboxylic acid, ester, and related functional groups. RCOH writing the carboxyl • Learn the IUPAC system for naming carboxylic acids and esters. group a carboxylic acid C H • Learn the important physical properties of the carboxylic acids and esters. • Learn the major chemical reaction of carboxylic acids and esters, and learn how to O predict the products of ester synthesis and hydrolysis reactions. the carboxyl group • Learn some of the important properties of condensation polymers, especially the polyesters. Mr. Kevin A. Boudreaux • The tart flavor of sour-tasting foods is often caused Angelo State University CHEM 2353 Fundamentals of Organic Chemistry by the presence of carboxylic acids. Organic and Biochemistry for Today (Seager & Slabaugh) www.angelo.edu/faculty/kboudrea 2 Nomenclature of Carboxylic Acids • Select the longest carbon chain containing the carboxyl group. The -e ending of the parent alkane name is replaced by the suffix -oic acid. • The carboxyl carbon is always numbered “1” but the number is not included in the name. • Name the substituents attached to the chain in the Nomenclature of usual way. • Aromatic carboxylic acids (i.e., with a CO2H Carboxylic Acids directly connected to a benzene ring) are named after the parent compound, benzoic acid. O C OH 3 -
Ester Synthesis Lab (Student Handout)
Name: ________________________ Lab Partner: ____________________ Date: __________________________ Class Period: ____________________ Ester Synthesis Lab (Student Handout) Lab Report Components: The following must be included in your lab book in order to receive full credit. 1. Purpose 2. Hypothesis 3. Procedure 4. Observation/Data Table 5. Results 6. Mechanism (In class) 7. Conclusion Introduction The compounds you will be making are also naturally occurring compounds; the chemical structure of these compounds is already known from other investigations. Esters are organic molecules of the general form: where R1 and R2 are any carbon chain. Esters are unique in that they often have strong, pleasant odors. As such, they are often used in fragrances, and many artificial flavorings are in fact esters. Esters are produced by the reaction between alcohols and carboxylic acids. For example, reacting ethanol with acetic acid to give ethyl acetate is shown below. + → + In the case of ethyl acetate, R1 is a CH3 group and R2 is a CH3CH2 group. Naming esters systematically requires naming the functional groups on both sides of the bridging oxygen. In the example above, the right side of the ester as shown is a CH3CH2 1 group, or ethyl group. The left side is CH3C=O, or acetate. The name of the ester is therefore ethyl acetate. Deriving the names of the side from the carboxylic acid merely requires replacing the suffix –ic with –ate. Materials • Alcohol • Carboxylic Acid o 1 o A o 2 o B o 3 o C o 4 Observation Parameters: • Record the combination of carboxylic acid and alcohol • Observe each reactant • Observe each product Procedure 1. -
In This Handout, All of Our Functional Groups Are Presented As Condensed Line Formulas, 2D and 3D Formulas and with Nomenclature Prefixes and Suffixes (If Present)
In this handout, all of our functional groups are presented as condensed line formulas, 2D and 3D formulas and with nomenclature prefixes and suffixes (if present). Organic names are built on a foundation of alkanes, alkenes and alkynes. Those examples are presented first and you need to know those rules. The strategies can be found in Chapter 4 of our textbook (alkanes: pages 93-98, cycloalkanes 102-104, alkenes: pages 104-110, alkynes: pages 112-113 and combinations of all of them 113-115). After introducing examples of alkanes, alkenes, alkynes and combinations of them, the functional groups are presented in order of priority. A few nomenclature examples are provided for each of the functional groups. Examples of the various functional groups are presented on pages 115-135 in the textbook. Two overview pages are on pages 136-137. Some functional groups have a suffix name when they are the highest priority functional group and a prefix name when they are not the highest priority group, and these are added to the skeletal names with identifying numbers and stereochemistry terms (E and Z for alkenes, R and S for chiral centers and cis and trans for rings). Several low priority functional groups only have a prefix name. A few additional special patterns are shown on pages 98-102. The only way to learn this topic is practice (over and over). The best practice approach is to actually write out the names (on an extra piece of paper or on a white board, and then do it again). The same functional groups are used throughout the entire course. -
Thiocyanate Pyridine Complexes
W&M ScholarWorks Undergraduate Honors Theses Theses, Dissertations, & Master Projects 5-2017 Structural Comparison of Copper(II) Thiocyanate Pyridine Complexes Joseph V. Handy College of WIlliam & Mary Follow this and additional works at: https://scholarworks.wm.edu/honorstheses Part of the Inorganic Chemistry Commons Recommended Citation Handy, Joseph V., "Structural Comparison of Copper(II) Thiocyanate Pyridine Complexes" (2017). Undergraduate Honors Theses. Paper 1100. https://scholarworks.wm.edu/honorstheses/1100 This Honors Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Undergraduate Honors Theses by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. Structural Comparison of Copper(II) Thiocyanate Pyridine Complexes A thesis submitted in partial fulfillment of the requirement for the degree of Bachelor of Science in Chemistry from The College of William & Mary by Joseph Viau Handy Accepted for ____________________________ ________________________________ Professor Robert D. Pike ________________________________ Professor Deborah C. Bebout ________________________________ Professor David F. Grandis ________________________________ Professor William R. McNamara Williamsburg, VA May 3, 2017 1 Table of Contents Table of Contents…………………………………………………...……………………………2 List of Figures, Tables, and Charts………………………………………...…………………...4 Acknowledgements….…………………...………………………………………………………6 -
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 -
Potentially Explosive Chemicals*
Potentially Explosive Chemicals* Chemical Name CAS # Not 1,1’-Diazoaminonaphthalene Assigned 1,1-Dinitroethane 000600-40-8 1,2,4-Butanetriol trinitrate 006659-60-5 1,2-Diazidoethane 000629-13-0 1,3,5-trimethyl-2,4,6-trinitrobenzene 000602-96-0 1,3-Diazopropane 005239-06-5 Not 1,3-Dinitro-4,5-dinitrosobenzene Assigned Not 1,3-dinitro-5,5-dimethyl hydantoin Assigned Not 1,4-Dinitro-1,1,4,4-tetramethylolbutanetetranitrate Assigned Not 1,7-Octadiene-3,5-Diyne-1,8-Dimethoxy-9-Octadecynoic acid Assigned 1,8 –dihydroxy 2,4,5,7-tetranitroanthraquinone 000517-92-0 Not 1,9-Dinitroxy pentamethylene-2,4,6,8-tetramine Assigned 1-Bromo-3-nitrobenzene 000585-79-5 Not 2,2',4,4',6,6'-Hexanitro-3,3'-dihydroxyazobenzene Assigned 2,2-di-(4,4,-di-tert-butylperoxycyclohexyl)propane 001705-60-8 2,2-Dinitrostilbene 006275-02-1 2,3,4,6- tetranitrophenol 000641-16-7 Not 2,3,4,6-tetranitrophenyl methyl nitramine Assigned Not 2,3,4,6-tetranitrophenyl nitramine Assigned Not 2,3,5,6- tetranitroso nitrobenzene Assigned Not 2,3,5,6- tetranitroso-1,4-dinitrobenzene Assigned 2,4,6-Trinitro-1,3,5-triazo benzene 029306-57-8 Not 2,4,6-trinitro-1,3-diazabenzene Assigned Not 2,4,6-Trinitrophenyl trimethylol methyl nitramine trinitrate Assigned Not 2,4,6-Trinitroso-3-methyl nitraminoanisole Assigned 2,4-Dinitro-1,3,5-trimethyl-benzene 000608-50-4 2,4-Dinitrophenylhydrazine 000119-26-6 2,4-Dinitroresorcinol 000519-44-8 2,5-dimethyl-2,5-diydroperoxy hexane 2-Nitro-2-methylpropanol nitrate 024884-69-3 3,5-Dinitrosalicylic acid 000609-99-4 Not 3-Azido-1,2-propylene glycol dinitrate