Multicomponent Reactions for the Synthesis of Pyrroles
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Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides
Proceedings of the Iowa Academy of Science Volume 61 Annual Issue Article 26 1954 Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides B. R. Bluestein Coe College Albert Hybl Coe College Yoshimi Al Nishioka Coe College Let us know how access to this document benefits ouy Copyright ©1954 Iowa Academy of Science, Inc. Follow this and additional works at: https://scholarworks.uni.edu/pias Recommended Citation Bluestein, B. R.; Hybl, Albert; and Nishioka, Yoshimi Al (1954) "Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides," Proceedings of the Iowa Academy of Science, 61(1), 225-232. Available at: https://scholarworks.uni.edu/pias/vol61/iss1/26 This Research is brought to you for free and open access by the Iowa Academy of Science at UNI ScholarWorks. It has been accepted for inclusion in Proceedings of the Iowa Academy of Science by an authorized editor of UNI ScholarWorks. For more information, please contact [email protected]. Bluestein et al.: Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlor Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides By B. R. BLUESTEIN, ALBERT HYBL* AND YosHIMI AL NISHIOKA INTRODUCTION The reaction kinetics of the alcoholysis of substituted benzoyl chlorides was studied. The mechanism of the alcoholysis reaction, which is most generally accepted ( 1), shows that the overall re action should be second-order and that the reaction should be first-order with respect to the acid chloride and first-order with respect to the alcohol. This rate study was carried out using a large excess of alcohol as the solvent, thus obtaining pseudo-first order rate constants, first-order with respect to the acid chloride only. -
The Multicomponent Synthesis of Pyrroles from Cylcopropane S Using a One Pot Pd(0) Catalyzed Dehydrocarbonylation Protocol
Western University Scholarship@Western Electronic Thesis and Dissertation Repository 7-27-2012 12:00 AM The Multicomponent Synthesis of Pyrroles from Cylcopropane S Using a One Pot Pd(0) Catalyzed Dehydrocarbonylation Protocol William J. Humenny The University of Western Ontario Supervisor Dr. Michael Kerr The University of Western Ontario Graduate Program in Chemistry A thesis submitted in partial fulfillment of the equirr ements for the degree in Master of Science © William J. Humenny 2012 Follow this and additional works at: https://ir.lib.uwo.ca/etd Part of the Organic Chemistry Commons Recommended Citation Humenny, William J., "The Multicomponent Synthesis of Pyrroles from Cylcopropane S Using a One Pot Pd(0) Catalyzed Dehydrocarbonylation Protocol" (2012). Electronic Thesis and Dissertation Repository. 695. https://ir.lib.uwo.ca/etd/695 This Dissertation/Thesis is brought to you for free and open access by Scholarship@Western. It has been accepted for inclusion in Electronic Thesis and Dissertation Repository by an authorized administrator of Scholarship@Western. For more information, please contact [email protected]. THE MULTICOMPONENT SYNTHESIS OF PYRROLES FROM CYLCOPROPANES USING A ONE POT Pd(II) CATALYZED DEHYDROCARBONYLATION PROTOCOL (Synthetic Methodology: Application Towards Pyrroles) (Thesis format: Monograph) by William John Humenny Graduate Program in Chemistry A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science The School of Graduate and Postdoctoral Studies The University of Western Ontario London, Ontario, Canada © William John Humenny 2012 THE UNIVERSITY OF WESTERN ONTARIO School of Graduate and Postdoctoral Studies CERTIFICATE OF EXAMINATION Supervisor Examiners ______________________________ ______________________________ Dr. Michael Kerr Dr. James Wisner Supervisory Committee ______________________________ Dr. -
Regioselective Addition of 1,3-Dicarbonyl Dianion to N-Sulfonyl Aldimines: an Expedient Route to N-Sulfonyl Piperidines and N-Sulfonyl Azetidines
Tetrahedron 63 (2007) 4779–4787 Regioselective addition of 1,3-dicarbonyl dianion to N-sulfonyl aldimines: an expedient route to N-sulfonyl piperidines and N-sulfonyl azetidines Manas K. Ghorai,* Amit Kumar and Sandipan Halder Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India Received 26 June 2006; revised 23 February 2007; accepted 15 March 2007 Available online 18 March 2007 Abstract—A simple route for the synthesis of d-amino-b-keto esters and d-amino-b-diketones is reported. This involves regioselective addition of 1,3-dianions derived from ethyl acetoacetate and acetyl acetone to N-sulfonyl aldimines. The d-amino-b-keto ester derivatives were further converted into the corresponding N-sulfonyl piperidines and N-sulfonyl azetidines. Ó 2007 Elsevier Ltd. All rights reserved. 1. Introduction In continuation of our research on enolate chemistry and also supported by the related literature on the reactivity of 1,3-di- 1,3-Dicarbonyl dianions have been used extensively in or- carbonyl dianions, it was envisaged that dianions derived ganic synthesis for building ring systems. The anion on the from suitable precursors could be regioselectively added to terminal carbon of the dianion can be regioselectively reacted aldimines to give an easy access to d-amino-b-keto esters18 with 1 equiv of an electrophile resulting in an enolate ion, and their diketone analogues. These compounds could easily which can be trapped by the addition of a second electrophile be converted into various piperidine and azetidine deriva- -
United States Patent Office 3,321,512 Patiented May 23, 1967 2 3,321,512 Peroxide Can Be Prepared in Any Convenient Manner
United States Patent Office 3,321,512 Patiented May 23, 1967 2 3,321,512 peroxide can be prepared in any convenient manner. It MANUFACTURE OF PERBENZOIC ACDS is preferred, however, to produce the suspension by dis David James Cooper and Tony Nicholas Gibson, both of tributing the corresponding benzoyl chloride in finely di Whitley Bay, Northumberiand, England, assignors to vided form in an aqueous alkaline solution of hydrogen Thecorporation Procter of & OhioGamble Company, Cincinnati, Cilio, a peroxide having a pH of not less than 10. The benzoyl No Drawing. Fified Jan. 22, 1964, Ser. No. 339,323 chloride reacts with the hydrogen peroxide solution pro Ciains priority, application (Great Britaia, Jan. 31, 1963, ducing the benzoyl peroxide which is obtained in the form 4,012/63 of a fine suspension. This can be achieved by introducing 2. Ciaisas. (C. 260-502) the benzoyl chloride at the periphery of a high speed agi IO tator (for example, an agitator of at least 2 inches in This invention relates to an improved process for the diameter rotating at 1500 to 2000 rp.m.) which is located manufacture of perbenzoic acids. in the solution. Alternatively, the benzoyl chloride can The conventional method of preparing aromatic percar be introduced into the throat of a Venturi mixer through boxylic acids is a two stage process in which the diacyl which the aqueous alkaline solution is passing. peroxide is prepared by reacting the aromatic acyl chlo 15 As stated above, the alkaline solution of hydrogen per ride (e.g., benzoyl chloride) with alkaline hydrogen per oxide must have a pH of at least 10. -
Development of New Domino Reactions of Alkylidene Meldrum's
Development of New Domino Reactions of Alkylidene Meldrum’s Acids Involving Friedel-Crafts Chemistry and Catalytic Conjugate Allylation of Alkylidene Meldrum’s Acids by Aaron Michael Dumas A thesis presented to the University of Waterloo in fulfilment of the thesis requirement for the degree of Doctor of Philosophy in Chemistry Waterloo, Ontario, Canada, 2009 © Aaron Michael Dumas 2009 I hereby declare that I am the sole author of this thesis. This is a true copy of my thesis, including any required final revisions, as accepted by my examiners. I understand that my thesis may be made electronically available to the public. ii Abstract Alkylidene Meldrum’s acids are very reactive acceptors in conjugate additions, and are known to be significantly more electrophilic than other α,β-unsaturated carbonyl electrophiles. They also offer advantages in terms of ease of preparation, purification and storage. Despite this, they are relatively underused in organic synthesis, and have been treated as something of a curiousity in the literature. The goal of my research was to demonstrate the utility of these molecules in new reactions that are not readily available to other electrophiles. To facilitate this work, new conditions for the Knoevenagel condensation of aldehydes with Meldrum’s acid were developed. This allowed access to a broader range of monosubstituted alkylidenes than was previously possible from any single method. In a reaction that exploits the acylating ability of Meldrum’s acid, a domino addition of phenols to alkylidene Meldrum’s acids was developed. Here, Yb(OTf)3 catalyzed the addition of a phenol to the alkylidene as well as acylation through activation of the electrophile. -
Benzoyl Peroxide
BENZOYL PEROXIDE Prepared at the 63rd JECFA (2004), published in FNP 52 Add 12 (2004) superseding specifications prepared at the 55th JECFA (2000) and published in FNP 52 Add 8 (2000). Treatment of whey with benzoyl peroxide at a maximum concentration of 100 mg/kg does not pose a safety concern (63rd JECFA, 2004). SYNONYMS Benzoyl superoxide, INS No. 928 DEFINITION Benzoyl peroxide is manufactured by the reaction of benzoyl chloride, sodium hydroxide and hydrogen peroxide. Chemical name Dibenzoyl peroxide C.A.S. number 94-36-0 Chemical formula C14H10O4 Structural formula Formula weight 242.23 Assay Not less than 96.0% DESCRIPTION Colourless, crystalline solid having a faint odour of benzaldehyde. Caution: Benzoyl peroxide, especially in the dry form, is a dangerous, highly reactive, oxidizing material and has been known to explode spontaneously FUNCTIONAL USES Bleaching agent CHARACTERISTICS IDENTIFICATION Solubility (Vol. 4) Insoluble in water, slightly soluble in ethanol and soluble in ether. Melting range (Vol. 4) 103 - 106° with decomposition Decomposition to benzoic To 0.5 g of the sample add 50 ml of 0.5 N ethanolic potassium hydroxide, heat acid gradually to boiling and continue boiling for 15 min. Cool and dilute with 200 ml of water. Add sufficient 0.5 N hydrochloric acid to make strongly acidic and extract with ether. Dry the ether solution over anhydrous sodium sulfate, and then evaporate to dryness on a steam bath. The benzoic acid so obtained melts between 121° and 123°. PURITY Lead (Vol. 4) Not more than 2 mg/kg Determine using an atomic absorption technique appropriate to the specified level. -
Determination of Solvent Effects on Ketoðenol Equilibria of 1,3-Dicarbonyl Compounds Using NMR: Revisiting a Classic Physical C
In the Laboratory Determination of Solvent Effects on Keto–Enol Equilibria W of 1,3-Dicarbonyl Compounds Using NMR Revisiting a Classic Physical Chemistry Experiment Gilbert Cook* and Paul M. Feltman Department of Chemistry, Valparaiso University, Valparaiso, IN 46383; *[email protected] “The influence of solvents on chemical equilibria was discovered in 1896, simultaneously with the discovery of keto–enol tautomerism in 1,3-dicarbonyl compounds” (1). The solvents were divided into two groups according to their ability to isomerize compounds. The study of the keto–enol tautomerism of β-diketones and β-ketoesters in a variety of solvents using proton NMR has been utilized as a physical Figure 1. The β-dicarbonyl compounds studied in the experiment. chemistry experiment for many years (2, 3). The first reported use of NMR keto–enol equilibria determination was by Reeves (4). This technique has been described in detail in an experiment by Garland, Nibler, and Shoemaker (2). panded (i) to give an in-depth analysis of factors influencing The most commonly used β-diketone for these experi- solvent effects in tautomeric equilibria and (ii) to illustrate ments is acetylacetone (Scheme I). Use of proton NMR is a the use of molecular modeling in determining the origin of viable method for measuring this equilibrium because the a molecule’s polarity. The experiment’s original benefits of tautomeric keto–enol equilibrium is slow on the NMR time using proton NMR as a noninvasive method of evaluating scale, but enol (2a)–enol (2b) tautomerism is fast on this scale equilibrium are maintained. (5). It has been observed that acyclic β-diketones and β- Experimental Procedure ketoesters follow Meyer’s rule of a shift in the tautomeric equi- librium toward the keto tautomer with increasing solvent Observations of the solvent effects for three other 1,3- polarity (6). -
Organic Chemistry II / CHEM 252 Chapter 19 – Synthesis And
Organic Chemistry II / CHEM 252 Chapter 19 – Synthesis and Reactions of β-Dicarbonyl Compounds Bela Torok Department of Chemistry University of Massachusetts Boston Boston, MA 1 Introduction β-Dicarbonyl compounds have two carbonyl groups separated by a carbon • Protons on the α-carbon of β-dicarbonyl compounds are acidic (pKa = 9-10) – The acidity can be explained by resonance stabilization of the corresponding enolate by two carbonyl groups 2 Synthesis Claisen condensation • The acetoacetic ester and malonic acid syntheses use β-dicarbonyl compounds for carbon-carbon bond forming reactions • The acetoacetic ester and malonic ester syntheses usually conclude with decarboxylation of a β-keto acid 3 Synthesis • The Claisen Condensation: Synthesis of β-Keto Esters • Ethyl acetate undergoes a Claisen condensation when treated with sodium ethoxide – The product is commonly called an acetoacetic ester • Ethyl pentanoate undergoes an analogous reaction 4 Synthesis • The overall reaction involves loss of an α hydrogen from one ester and loss of ethoxide from another • The mechanism is an example of the general process of nucleophilic addition-elimination at an ester carbonyl 5 Synthesis 6 Synthesis • The alkoxide base must have the same alkyl group as the alkoxyl group of the ester – The use of a different alkoxide would result in formation of some transesterification products • Esters with only one α hydrogen do not undergo Claisen condensation – A second hydrogen on the α carbon is necessary so that it can be deprotonated in Step 3 – This deprotonation -
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 -
Friedel and Crafts' Reaction-The Preparation of Orthobenzoyl-Benzoic Acid and Benzophenone
732 C. R. RUBIDGE AND N. C. QUA. two and five-tenths grams of cyanimidocaxbonic ethyl ester, prepared from bromocyanogen, potassium cyanide, and alcohol1 were added to the suspended alcoholate. Heat was developed, the solution became yellow, and sodium cyanide was precipitated. The reaction mixture was heated for two hours in a flask connected with a reflux condenser, and enough water was added to dissolve the sodium cyanide. After the water solution had been extracted with ether several times, the ether was dried with calcium chloride. Thus, 32 g. of a light yellow oil, possessing a strong basic odor, were obtained when the ether was evaporated. Even at a pressure of 25 mm. the compound could not be distilled without consid- erable decomposition. Therefore, no analysis of the substance was at- tempted. Its identity was established by converting it into the corre- sponding oximido derivative. Preqaration of Oximidocarbonic Ethyl Isoamyl Ester, CZHS@-C~C~HII,- II NOH Eight and four-tenths grams of hydroxylamine, dissolved in a small amount of water, were added to 20 g. of the imido ester dissolved'in 20 cc. of ether. The mixture was shaken thirty minutes, the water layer was drawn off, extracted several times with ether, and the ether dried with sodium sulfate. Twenty grams of a reddish yellow oil were obtained when the ether evaporated. When cooled to -15', white crystals ap- peared which melted when they were spread out on a cold clay plate. 0.1754 g. gave 12.8 cc. Nz at 24.5' and 742 mm. Calc. for CsH1703N: N, 7.99. -
Material Safety Data Sheet HCS Risk Phrases HCS CLASS: Corrosive Liquid
Material Safety Data Sheet HCS Risk Phrases HCS CLASS: Corrosive liquid. HCS CLASS: Combustible liquid IIIA having a flash point between 60.0°C (140°F) and 93.3°C (200°F) Section I. Chemical Product and Company Identification Common Name/ Benzoyl Chloride In Case of Trade Name Emergency In the continental U.S.A. call CHEMTREC 800-424-9300 (24 hours) Outside the continental U.S.A. call CHEMTREC 703-527-3887 (24 hours) Supplier Velsicol Chemical Corporation Manufacturer Velsicol Chemical Corporation 10400 W. Higgins Road 10400 W. Higgins Road Rosemont, IL 60018 U.S.A. Rosemont, IL 60018 U.S.A. Phone: 847-298-9000 Phone: 847-298-9000 Fax: 847-298-9015 Fax: 847-298-9015 Synonym Benzenecarbonyl Chloride Material Uses Agricultural Industry: Chloramber Chemical Name Benzoyl Chloride (herbicide). Intermediate for pesticides. Chemical Family Acyl Halide Industrial Applications: Acylation. Chemical C7 H5 CL 0 Polymerization initiator of benzophenone. Formula Intermediate for stabilizers. Acetic anhydride production. Textile Industry: Cellulosic yarn treatment agent. Fastness improver. Other Non-Specified Industry: Organic analysis. Dyes. Perfumes. Section II. Composition and Information on Ingredients Name CAS# % by Weight TLV/PEL OSHA Hazardous Ingredients 1) Benzoyl Chloride 98-88-4 >99.5 STEL: 2.8 (mg/m3) from Yes ACGIH (TLV) 2) Benzotrichloride 98-07-7 <0.02 STEL: 0.1 ppm from Yes ACGIH; Skin designation. 3) Benzyl Alcohol 100-44-7 <0.01 TWA: 1 (ppm) from Yes ACGIH (TLV) Section III. Hazards Identification Emergency Overview Clear. Liquid. Pungent. Acrid odor. DANGER! CAUSES SEVERE EYE, SKIN AND RESPIRATORY TRACT BURNS. MAY CAUSE BLINDNESS. -
Synthesis and Functionalization of 1,4-Polyketones and Enantioselective Polyester Catalyst Development Using Molecular Lego Scaffolds
SYNTHESIS AND FUNCTIONALIZATION OF 1,4-POLYKETONES AND ENANTIOSELECTIVE POLYESTER CATALYST DEVELOPMENT USING MOLECULAR LEGO SCAFFOLDS A Dissertation Submitted to the Temple University Graduate Board In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY by Evan M. Samples May 2019 Examining Committee Members: Graham E. Dobereiner, Ph.D, Dissertation Supervisor, Temple University Ann M. Valentine, Ph.D., Temple University Stephanie L. Wunder, Ph.D., Temple University Deanna L. Zubris, Ph.D., External Member, Villanova University © Copyright 2019 by Evan M. Samples All Rights Reserved ii ABSTRACT Objectives of the present study are aimed towards improving upon alternating copolymerization techniques for polyketones and aliphatic polyesters, and the majority of this work focused on post-polymerization modifications to alternating polyketones. These materials are currently understudied in the literature, but the aptly spaced, repeating carbonyl functionality creates an easily functionalized material. Complementary work described herein relates to efforts currently underway to prepare highly enantioselective catalysts for the alternating copolymerization of epoxides with cyclic anhydrides. Aliphatic polyesters currently suffer from a lack of chemical diversity, and, with greener chemistries on the forefront of research efforts, polyesters made from environmentally benign and/or renewable materials are desirable. Additional limitations of aliphatic polyesters include difficulty obtaining stereoregular polyesters. In collaboration with the Schafmeister laboratory we are developing catalysts for the alternating copolymerization of polyesters to address these limitations. The model catalysts are carefully designed scaffolds of spiroligomers encasing a Lewis acidic transition metal at its center ([spiro]MX). The spiroligomer bulk around the metal center imparts significant chirality onto the catalyst thereby controlling which enantiomer of a given monomer is polymerized leading to stereoregular polyesters.