DOCSLIB.ORG

Copyrighted Material

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Copyrighted Material JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm SUBJECT INDEX The vast use of transition metal catalysts in organic chemistry makes the citation of every individual metal impractical, so there are limited citations of individual metals. Palladium is one exception where individual citations are common, in keeping with the widespread use of that metal. However, in most cases, the term metal catalyst, or catalyst, metal is used as a heading, usually representing transition metals. A-SE2 mechanism 893 and the steering wheel model acceleration of Diels-Alder reactions 487 151–152 reactions, high pressure A1 mechanism, acetal hydrolysis and universal NMR database 1038 487 155 hydrogen-bonding 1038 A1,3-strain 196 Cahn-Ingold-Prelog system hydrophobic effect 1038 A2 mechanism, acetal hydrolysis 149–152 in water 1038 487 determination 152 ionic liquids 1038 ab initio calculations 36 D/L nomenclature 149 micellular effects 1038 and acidity 346 Kishi’s NMR method 155 microwave irradiation 1038 and antiaromaticity 71 sequence rules 149–152 phosphate 1039 and nonclassical carbocations absolute hardness 64, 359, 361 solid state 1038 427 table 361 ultracentrifuge 1038 norbornyl carbocation 436 absorbents, chiral 168 ultrasound 1038 ab initio studies 248 absorption, and conjugation 317 zeolites 1038 1,2-alkyl shifts in alkyne anions differential, and diastereomers acceleration, Petasis reaction 1349 168 1202 and cubyl carbocation 413 differential, and resolution 169 acenaphthylene, reaction with and SN2 408–409 abstraction, and vinylic DBr 894 cyclopropane ring opening 907 hydrogenation 852 acenaphthylenes 1285 E2 mechanism 1274 benzylic hydrogens, by radicals acenaphthylene, with DBr 894 transition state for radical 852 acenes, hetero see heteroacenes hydrogen abstraction 849 hydrogen atom, photochemical acenes 61, 85 abnormal Beckmann 330 twisted 85 rearrangement 1326, hydrogen, by radicals, rate 848 zigzag 85 1369, 1377 and carbenes 727 acepentalenes, radical ions 265 abnormal Claisen rearrangement by nitrenes 277 acetal formation, and drying 1419 by radicals, ab initio study agents 1101 abrine esters, as catalysts 310 849 azeotropic distillation 1101 absolute aromaticity 39 by radicals, and mechanism 1102 absolute configuration 149 rearrangements 1346 acetaldehyde, and paraldehyde and biochemical methods 153 by radicals, transition state 1259 and circular dichroism 154 848 rational barrier 193 and GC 153 radical, and stereoelectronic acetals, acid catalyzed hydrolysis and glyceraldehyde 148 effects 853 486 and molar rotation 155 COPYRIGHTEDselectivity by radicals 849 MATERIALand enol ethers 1103 and Mosher’s acid 153 stereoselective 851 and Lewis acids 488 and Mosher’s ester 153 of atoms from radicals 263 and microwaves 1103 and NMR 153 radicals, and alkanes 849 and transacetalization 1103 and optical comparison 153 radicals, and alkenes 852 from alcohols and aldehydes optical rotatory dispersion 154 radicals, transition state 845 1101 and specific rotation 155 abstracts 1614 from aldehydes 1102 the SN2 reaction 153 ABX pattern, NMR 155–156 and ketones 1101 March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Eighth Edition. Michael B. Smith. © 2020 John Wiley & Sons, Inc. Published 2020 by John Wiley & Sons, Inc. 1917 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm 1918 SUBJECT INDEX acetals, acid catalyzed hydrolysis acetylenes, electron density map acidic hydrogen atoms, solvents (Continued) 12 1171 and Eosin Y 1102 excited state 319 acidic Lewis ionic liquids 395 photochemistry 1102 triplet 269 acidity see acid strength from alkynes 918 acetylenic sulfoxides, with acidity scales, and alcohols 353 from amides 720 cuprates 962 and amides 353 from Grignard reagents 570 acetylide ion, with alkyl halides and basic solvents 353 from ketones 1102 596 and calorimetric measurements from ortho esters 570, 1103, with epoxides 596 354 1574 with sulfates 596 and carbon acids 353 from oxidation of hydroxy with sulfonate esters 596 and indicators 353 ethers 866 aci form of nitro compounds, and acidity, solvent see solvent acidity hydrolysis 486 tautomerism 102 acidity, amides versus amines 364 and Brønsted coefficient nitro compounds 1099 acidity, and carborane acids 351 487 nitro compounds, and the Nef and carboxylic acids 21 and SN1 mechanisms 486 reaction 1099 and chloromethylation 656 and isotope labeling 486 acid base reactions, and and conformation 368 rate determining step 487 organometallics 732 and cyclopentadiene 64 ketene see ketene acetals acid catalysis, general 356 and electronegativity 365 labeling 486 alkenes with alcohols 917 and entropy 368, 372 N, Se 924 for the Schmidt reaction 1373 and face strain 366 silyl enol see enol silyl acetals acid catalyzed addition of alkenes and five-membered rings 64 silyl ketene 586, 1180 to alkenes 942 and free energy 373 transetherification 496 addition of water to carbonyls and hybridization 368 with allylic silanes 570 1095 and hydrogen bonding 106, 366 with hydride reagents 1574 aldol condensation 1178 and indicators 352 with silyl enol ethers 570 hydration of aldehydes and and ionic liquids 352 with trialkyl phosphites 501 ketones 1096 and ionic strength 373 acetanilide, nitration 632 hydrocarboxylation 984 and IR 352 acetanilides see anilines, acyl hydrocarboxylation of alkenes and Meldrum’s acid 368 acetate, allylic, with keto acids, 982 and organolithium reagents 247 metal catalyzed 887 hydrolysis 383 and periodic table 365 acetate, as a base 340 Knoevenagel reaction 1187 and phenalene 61 acetate, enol see enol acetates reaction with diketones 1103 and proton transfer 350 acetic acid, cis conformation 192 rearrangement of and resonance 365 dimeric 106 hydrazobenzenes 1422 and s character 368 acetic anhydride, and acyl acid derivatives, with amides and solvent 347, 372 fluoroborate 1025 1248 and solvent effects 371 and dehydration of oximes to acid forms 102 and steric effects 366 nitriles 1325 acid solutions, and the tetrahedral and the Hammett reaction and nitration of aromatic mechanism 1090 constant 372 compounds 631 acid strength 238, 340–345 and the medium 370 conjugate addition 979 and solvent 341–345 benzoic acids, and substituents acetoacetamide, enol content 98 crystallographic scale 346 363 acetoacetic esters, and enol definition 340 carboxylic acids 355 content 98 field effects 362 diketones 368 enol 99 Lewis acids 359 diprotic acids, and statistical enol content and solvent 100 mineral acids 346 effects 366 synthesis 577 resonance effects 363 dithianes 1110 acetohydroxamate buffers 1282 acid–base catalysis 355 esters versus ethers 364 acetolysis see solvolysis acid–base equilibrium 339 F strain 366 rates, table 433 acid–base reaction, formation of gas phase 371 acetone, tautomerism, and homoenolates 242 of alcohols 372 bromination 304 and solvents 576 Hammett acidity function 352 acetoxy ketones, from enols 871 free energy 356 hydrocarbon 238 acetoxy sulfides, by Pummerer HCl and acetate 340 -I effect 362 rearrangement 1603 s rate constant 355 inductive and field effects 21 hydrolysis to aldehydes 1603 acid–base, carbanions + proton intrinsic 372 acetoxy ketones, from ketones 249 kinetic 238 871 acid catalysis, alcohol dehydration Lewis acid, and solvents 372 acetoxylation, of alkenes 1025 495 of active methylene compounds acetyl carbocation 230 acid, normal, definition 350 364, 575 acetylene see ethyne acid, sulfuric see sulfuric acid of ketones or aldehydes 1110 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm SUBJECT INDEX 1919 of PCC 1448 sulfonyl, reduction with metals alkylation 575 of protons, and solvent acidity 1270 and the Knoevenagel reaction 352 acids, superacids 225, 229–230, 1187 of solvents 352 346–347, 698 arylation 575, 819–820 phenols 355 and alkenes 724 and radicals 820 pKa of acid types 341–345 and arenium ions 611 enantioselective 820 protons α- to a heteroatom and benzenonium ions 611 structural variations 820 590 and carbocations 226–227, as nucleophiles 566 solvent 355 410, 439, 1345, 1398 conversion to diazo compounds spectrophotometric and diazonium salts 467 712 measurement 352 and hydration of alkynes 914 functional groups 575 statistical effects 366 ionization 414 with acyl halides 1252 substituent effects 362 and nonclassical carbocations with aryldiazonium salts 710 thermodynamic 238 435 with tosyl azides 712 acids see Brønsted-Lowry acids, and oxocarbenium ions 1381 activity, of radicals 856 Lewis acids, solvent acidity cleavage of alkanes 759 acyals, from anhydrides 1104 acids, amino see amino acids coupling of alkenes 724 acyclic compounds, conformation acids, Brønsted-Lowry see sulfur dioxide 226 188 Brønsted-Lowry acids acids, table, delocalization 753 acyclic molecules, and entropy acids, carboxylic see carboxylic type, table of pKa 341–345 284 acids very weak acids 346 acyl addition see addition acids, fatty see fatty acids acoustic cavitation see cavitation acyl addition intramolecular 981 acids, glycidic see glycidic acoustic cavitation, and Grignard reagents 1129 acids, Lewis see Lewis acid sonochemistry 331 organolithium reagents 1129 acids, sulfinic see sulfonic acids acridinium photooxidant 920 syn or anti 1088 acids, sulfonic see sulfonic acids acrolein, canonical forms 47 water 1095 acids, acid strength 341–345 acrylic acids, from with nucleophiles 1087 activity of proton 352 tosylhydrazones 1161 acylals, and silanes 1105 and hydrogen exchange, actinometer, and photochemical formation of, reagents
Load more

Recommended publications
  • 69-4845 BEGLAND, Robert Walter, 1941
    This dissertation has been microfilmed exactly as received 69-4845 BEGLAND, Robert Walter, 1941- PARTICIPATION AND STERIC EFFECTS OF NEIGHBORING DIVALENT OXYGEN. The Ohio State University, Ph.D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan PARTICIPATION AND STEPJ.C EFFECTS OF NEIGHBORING DIVALENT OXYGEN DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Robert Walter Beglnnd, B.S., M.S. * it * * it it * The Ohio State University 1968 Approved by Adviser \J Departmeirt of Chemistry DEDICATION This dissertation is dedicated to my w ife June, ny con Michael Brian and my son Douglas Samuel. i i ACKNOWLEDGMENT The author wishes to express his appreciation to Dr. L. A. Paquette for his guidance, encouragement and considerable time spent in the course of this research. The author also wishes to express his appreciation to his parents, Mr. and Mrs. Walter C. Bcgland, for their assistance and encouragement throughout his college training, and to lir. and Mrs. Lester Berndt. i i i VITA July 23, 1941 Born - Oak Park, Illinois 1963 B.S. in Education, The Ohio State University Columbus, Ohio 1965 M.S., The Ohio State University Columbus, Ohio 1968 Ph.D., The Ohio State University Columbus, Ohio PUBLICATIONS 1. Transannular Participation of Ether Oxygen in the Hydrolysis of a Mesocyclic Dienamine, J. Am. Chen. Soc. 87, 3784 (1965). 2. Stabilized Derivatives of cis,cis,cis-1,3.5-Cyclodecatricne Keto-Enol Tautomerism in 2,3-DicarboiEeth.oxy-cis,c is -3,5~ cyclodecadienones and c.is-3-Cycloalkenones.
    [Show full text]
  • Chapter 1 Tropone and Tropolone
    School of Molecular and Life Sciences New Routes to Troponoid Natural Products Jason Matthew Wells This thesis is presented for the Degree of Doctor of Philosophy of Curtin University November 2018 Declaration To the best of my knowledge and belief this thesis contains no material previously pub- lished by any other person except where due acknowledgement has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any other university. Signature: Date: i Abstract Malaria is an infectious disease found in humans and other animals, it is caused by a single-cell parasite of the Plasmodium genus with many different substrains. Of these, P. falciparum is the most deadly to humans causing the majority of deaths. Although research into the area of antimalarial compounds is wide spread, few have been devel- oped with new structural features. Cordytropolone 37 is a natural product isolated in 2001 from the insect pathogenic fungus Cordyceps sp. BCC 1681 and has been shown to have antimalarial activity against P. falciparum. It has a structure unrelated to antimalarial com- pounds currently used in therapy. It does not contain a peroxide bridge as with artemisinin 25 or quinoline rings as with chloroquine 22. This unique structure indicates that it could possibly interact with the malaria parasite in a fashion unlike current treatments. In order for cordytropolone to be further developed as a potential treatment, it must first be synthe- sised in a laboratory environment. This study attempts to develop the first total synthesis of cordytropolone. H HO O N O O N O N H H H O O Cl HO O 22 25 37 Figure 0.0.1: Cordytropolone 37 has a unique structure compared to the current common malaria treatments The first method investigated towards the total synthesis of cordytropolone involved an intramolecular Buchner ring expansion.
    [Show full text]
  • Alkyl Halides Work Best; Secondary Alkyl Halides Give Lower Yields
    CHAPTER 21 ESTER ENOLATES ou have already had considerable experience with carbanionic compounds and their applications in synthetic organic chemistry. The first was acetylide ion in YChapter 9, followed in Chapter 14 by organometallic compounds—Grignard reagents, for example—that act as sources of negatively polarized carbon. In Chapter 18 you learned that enolate ions—reactive intermediates generated from aldehydes and ketones—are nucleophilic, and that this property can be used to advantage as a method for carbon–carbon bond formation. The present chapter extends our study of carbanions to the enolate ions derived from esters. Ester enolates are important reagents in synthetic organic chemistry. The stabilized enolates derived from ␤-keto esters are particularly useful. OO C ␣ C ␤ R CH2 ORЈ ␤-Keto ester: a ketone carbonyl is ␤ to the carbonyl group of the ester. A proton attached to the ␣-carbon atom of a ␤-keto ester is relatively acidic. Typical Ϫ11 acid dissociation constants Ka for ␤-keto esters are Ϸ10 (pKa 11). Because the ␣- carbon atom is flanked by two electron-withdrawing carbonyl groups, a carbanion formed at this site is highly stabilized. The electron delocalization in the anion of a ␤-keto ester is represented by the resonance structures 831 832 CHAPTER TWENTY-ONE Ester Enolates Ϫ Ϫ O O O O O O C C C C C C R C ORЈ R ϪC ORЈ R C ORЈ H H H Principal resonance structures of the anion of a ␤-keto ester We’ll begin by describing the preparation and properties of ␤-keto esters, proceed to a discussion of their synthetic applications, continue to an examination of related species, and conclude by exploring some recent developments in the active field of synthetic car- banion chemistry.
    [Show full text]
  • Knoevenagel Condensation
    Knoevenagel condensation The Knoevenagel condensation (pronounced [ˈknøːvənaːɡl̩ ]) Knoevenagel condensation reaction is an organic reaction named after Emil Knoevenagel. It is a Named after Emil Knoevenagel modification of the aldol condensation.[1][2] Reaction type Coupling reaction A Knoevenagel condensation is a nucleophilic addition of an active Identifiers hydrogen compound to a carbonyl group followed by a dehydration reaction in which a molecule of water is eliminated (hence Organic knoevenagel- condensation). The product is often an α,β-unsaturated ketone (a Chemistry condensation conjugated enone). Portal RSC ontology RXNO:0000044 ID In this reaction the carbonyl group is an aldehyde or a ketone. The catalyst is usually a weakly basic amine. The active hydrogen component has the form[3] Z–CH2-Z or Z–CHR–Z for instance diethyl malonate, Meldrum's acid, ethyl acetoacetate or malonic acid, or cyanoacetic acid.[4] Z–CHR1R2 for instance nitromethane. where Z is an electron withdrawing functional group. Z must be powerful enough to facilitate deprotonation to the enolate ion even with a mild base. Using a strong base in this reaction would induce self-condensation of the aldehyde or ketone. The Hantzsch pyridine synthesis, the Gewald reaction and the Feist–Benary furan synthesis all contain a Knoevenagel reaction step. The reaction also led to the discovery of CS gas. Contents Doebner modification Scope Weiss–Cook reaction See also References Doebner modification The Doebner modification of the Knoevenagel condensation. Acrolein and malonic acid react in pyridine to give trans-2,4-pentadienoic acid with the loss of carbon dioxide. With malonic compounds the reaction product can lose a molecule of carbon dioxide in a subsequent step.
    [Show full text]
  • Stereoselective Transformations Starting with Chiral (Aikoxy)Methyl-Substituted Organosilicon Compounds
    AWARDS 1996 (NSCS) . PREISTRAGER 1996 (NSCG) 133 CHIMIA 5/ (1997) Nr. 4lApriIJ A a 1996 ( rager•• Chimia 51 (/997) 133-139 © Neue Schweizerische Chemische Gesellschaft ISSN 0009-4293 Stereoselective Transformations Starting with Chiral (AIkoxy)methyl-Substituted Organosilicon Compounds Stefan Bienz* Stefan Bienz was born on Januar 17, 1958, in (Werner Prize 1996 of the NSCS) Lucerne (CH). He is citizen ofWolhusen (LU) and Lucerne, Switzerland. Academic Background: 1977-1983: Studies Abstract. The following short review summarizes the results we achieved with the in Chemistry at the Phi losophical Faculty II of investigation of chiral silicon groups as auxiliaries for the enantioselective synthesis. the University of Zurich, Switzerland. Gradu- (Alkoxy)methyl-substituted silicon compounds with 'Si-centered chirality', which ate research under the supervision of Prof. Dr. were prepared in optically active form by application of a bioreduction, have been M. Hesse at the Institute of Organic Chemistry towards the diploma (May 5, 1983; thesis: efficiently used as starting materials for a number of stereoselective reactions. Acylsi- 'Contribution to the Transformation of Car- lanes of this type upon treatment with organometallic reagents gave rise to 1,2-addition bocycIes to Lactams by Ring Enlargement products with high degrees of stereoselectivities. The respective a-hydroxysilanes Reaction') and 1983-1987 towards the Ph.D. could be stereospecifically desilylated to chiral secondary alcohols, or, depending on (December 18, 1987; thesis: 'Synthesis of the substitution pattern, further used as starting compounds for stereocontrolled Macrocyc\ic Natural Products by Ring En- oxidation, Cope- or Claisen-type rearrangement reactions. Chiral a-metallated vinyl- largement Reactions', distinguished for its silanes were converted to a-silyl-substituted allylic alcohols and to a-silyl-substituted excellence).
    [Show full text]
  • Recent Syntheses of Steroidal Oxazoles, Oxazolines and Oxazolidines
    A Platinum Open Access Journal Review for Organic Chemistry Free to Authors and Readers DOAJ Seal Arkivoc 2021, part i, 471-490 Recent syntheses of steroidal oxazoles, oxazolines and oxazolidines Besma Bendif,a,b Malika Ibrahim-Ouali,*a and Frédéric Dumur c aAix Marseille Univ, CNRS, Centrale Marseille, iSm2, F-13397 Marseille, France bLaboratoire de Chimie Appliquée, Faculté des Sciences, Université du 08 mai 1945 Guelma, Algeria cAix Marseille Univ, CNRS, ICR, UMR 72 73, F-13397 Marseille, France Email: [email protected] Received 03-15-2021 Accepted 04-11-2021 Published on line 05-08-2021 Abstract It was found that the introduction of heterocycles to steroids often leads in a change of their physiological activity and the appearance of new interesting biological precursors. Recent developments in the syntheses of steroidal oxazoles, oxazolines, and oxazolidines are described herein. The biological activities of those steroidal derivatives for which data are available are given. Keywords: Steroids, oxazoles, oxazolines, oxazolidines DOI: https://doi.org/10.24820/ark.5550190.p011.512 Page 471 ©AUTHOR(S) Arkivoc 2021, i, 471-490 Bendif, B. et al. Table of Contents 1. Introduction 2. Synthesis of Steroidal Oxazoles 3. Synthesis of Steroidal Oxazolines 4. Synthesis of Steroidal Oxazolidines 5. Conclusions Acknowledgements References 1. Introduction Steroids constitute an extensive and important class of biologically active polycyclic compounds that are widely used for therapeutic purposes.1-3 Even after decades of research, the total synthesis of steroid nuclei by improved strategies continues to receive considerable attention. Numerous methods have been exploited for the total synthesis of steroids which are widely distributed in nature and which possess practical medical importance.
    [Show full text]
  • DEVELOPMENT of NOVEL METHODOLOGIES UTILIZING QUATERNARY AMMONIUM SALTS AS CATALYSTS by LINDSEY RAE CULLEN DISSERTATION Submitted
    DEVELOPMENT OF NOVEL METHODOLOGIES UTILIZING QUATERNARY AMMONIUM SALTS AS CATALYSTS BY LINDSEY RAE CULLEN DISSERTATION Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate College of the University of Illinois at Urbana-Champaign, 2015 Urbana, Illinois Doctoral Committee: Professor Scott E. Denmark, Chair Professor Martin D. Burke Professor Scott K. Silverman Professor Steven C. Zimmerman ii Abstract The first half of this thesis (Chapter 2) described the development of a fluoride-promoted conjugate addition of sulfur-stabilized carbanion nucleophiles to α,β-unsaturated ketones and esters. This reaction was achieved using a substoichiometric amount of TBAF, resulting in high yields on the desired 1,4-addition product. The addition of 1,3-dithianes was given particular focus as a novel method for the preparation of differentially protect 1,4-dicarbonyl compounds. Observation by 13C NMR spectroscopy provided evidence that the reaction proceeds through an ion pair, and attempts to extend this reaction to asymmetric additions using a chiral counterion are presented in detail. The second half of this thesis (Chapter 3) details development of a phase transfer catalyzed [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds. Initial investigation focused on identifying viable substrate classes that would undergo selective [2,3]-rearrangement under phase transfer conditions. Under certain conditions, the [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds takes place in the presence of a phase transfer agent, providing a rare example of a phase transfer catalyzed unimolecular reaction. In the course of this investigation it was found that catalysis is dependent on several variables including base concentration, catalyst structure, and substrate lipophilicity.
    [Show full text]
  • Deoxydehydration of Vicinal Diols by Homogeneous Catalysts: a Mechanistic Overview
    Deoxydehydration of vicinal diols by homogeneous royalsocietypublishing.org/journal/rsos catalysts: a mechanistic overview Review Cite this article: DeNike KA, Kilyanek SM. 2019 Kayla A. DeNike and Stefan M. Kilyanek Deoxydehydration of vicinal diols by homogeneous catalysts: a mechanistic overview. Department of Chemistry and Biochemistry, University of Arkansas, 1 University of Arkansas, Fayetteville, AR 727001, USA R. Soc. open sci. 6: 191165. http://dx.doi.org/10.1098/rsos.191165 SMK, 0000-0002-6179-2510 Received: 4 July 2019 Deoxydehydration (DODH) is an important reaction for the Accepted: 4 October 2019 upconversion of biomass-derived polyols to commodity chemicals such as alkenes and dienes. DODH can be performed Subject Category: by a variety of early metal-oxo catalysts incorporating Re, Mo and V. The varying reduction methods used in the DODH Chemistry catalytic cycle impact the product distribution, reaction Subject Areas: mechanism and the overall yield of the reaction. This review surveys the reduction methods commonly used in homogeneous inorganic chemistry/organometallic chemistry/ DODH catalyst systems and their impacts on yield and reaction green chemistry conditions. Keywords: deoxydehydration, catalysis, biomass upconversion, early metal-oxo 1. Introduction Due to the long-term implications for the climate of continuing to Author for correspondence: consume non-renewable carbon resources, such as oil, the Stefan M. Kilyanek decarbonization of the economy has become the topic of e-mail: [email protected] significant public and scientific concern [1,2]. As a result, the development of processes to produce valuable carbon-based commodity chemicals from renewable carbon feedstocks has become an important field of study [3].
    [Show full text]
  • Nickel-Catalyzed Cyanation of Benzylic and Allylic Pivalates
    Nickel-Catalyzed Cyanation of Benzylic and Allylic Pivalates by Alexandria Daria Maria Jeanneret A thesis submitted in conformity with the requirements for the degree of Master of Science Department of Chemistry University of Toronto © Copyright by Alexandria Daria Maria Jeanneret 2018 Nickel-Catalyzed Cyanation of Benzylic and Allylic Pivalates Alexandria Daria Maria Jeanneret Master of Science Department of Chemistry University of Toronto 2018 Abstract Nitriles are considered very versatile functional groups due to their ability to easily be transformed into a variety of other functional groups in one or two steps. In particular, the synthesis of α-arylnitriles is of interest to organic chemists due to their presence in pharmaceuticals and their value as synthetic intermediates. Taking advantage of nickel’s unique ability to insert into a C‒O bond, the focus of this thesis is on the nickel-catalyzed cyanation of benzylic and allylic pivalates, exploring the use of inorganic and organic cyanide sources for this transformation. The substrate scope for the synthesis of benzylic and allylic nitriles will be presented as well as studies examining the functional group tolerance of this cyanation reaction, which led to further insights into the mechanism and applicability of this chemistry. ii Acknowledgments First and foremost, I would like to thank Professor Sophie Rousseaux for the opportunity to work to work in her lab over the last year. Her passion for chemistry is beyond contagious and her guidance has been invaluable. I would also like to thank Professor Mark Taylor for his help with this thesis. Secondly, I would like to thank all the staff at the NMR and AIMS facility for all their hard-work and dedication to ensuring the instruments run smoothly and for always taking the time to answer questions.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 5,342,985 Herrmann Et Al
    USOO5342985A United States Patent (19) 11 Patent Number: 5,342,985 Herrmann et al. (45. Date of Patent: Aug. 30, 1994 54) ORGANIC DERIVATIVES OF RHENIUM 58 Field of Search ................ 556/482, 485; 560/130, OXDES AND THER PREPARATION AND 560/219, 221, 205; 568/626, 627, 630, 655, 685, USE FOR THE METATHESS OF OLEFENS 687; 570/135, 136; 585/510,520 75 Inventors: Wolfgang A. Herrmann, Freising: Primary Examiner-Paul F. Shaver Werner Wagner, Munich; Ursula Attorney, Agent, or Firm-Connolly & Hutz Volkhardt, Freising, all of Fed. Rep. of Germany 57 ABSTRACT 73) Assignee: Hoechst AG, Frankfurt am Main, The invention relates to a process for the metathesis of Fed. Rep. of Germany olefins which comprises reacting an olefin of the for mula YCZ=CZ-(CX2),R2 (II) wherein 21 Appl. No.: 569,614 n is an integer from 1 to 28, 22 Filed: Aug. 20, 1990 X represents H or F, Y represents H or alkyl having from 1 to 10 carbon Related U.S. Application Data atoms and 63 Continuation-in-part of Ser. No. 320,404, Mar. 8, 1989, Z represents Hor a non-aromatic hydrocarbon group abandoned. having from 1 to 6 carbon atoms and R2 represents a H, alkyl, halogen, COOR3 or OR', wherein R3and 30 Foreign Application Priority Data R4 represent alkyl having from 1 to 15 carbon Dec. 10, 1988 DE Fed. Rep. of Germany ....... 384,733 atoms or phenyl which is unsubstituted or contains Jan. 31, 1989 IDE Fed. Rep. of Germany ....... 3902787 from 1 to 3 substituents or wherein R is trialkylsi Mar.
    [Show full text]
  • S.T.E.T.Women's College, Mannargudi Semester Iii Ii M
    S.T.E.T.WOMEN’S COLLEGE, MANNARGUDI SEMESTER III II M.Sc., CHEMISTRY ORGANIC CHEMISTRY - II – P16CH31 UNIT I Aliphatic nucleophilic substitution – mechanisms – SN1, SN2, SNi – ion-pair in SN1 mechanisms – neighbouring group participation, non-classical carbocations – substitutions at allylic and vinylic carbons. Reactivity – effect of structure, nucleophile, leaving group and stereochemical factors – correlation of structure with reactivity – solvent effects – rearrangements involving carbocations – Wagner-Meerwein and dienone-phenol rearrangements. Aromatic nucleophilic substitutions – SN1, SNAr, Benzyne mechanism – reactivity orientation – Ullmann, Sandmeyer and Chichibabin reaction – rearrangements involving nucleophilic substitution – Stevens – Sommelet Hauser and von-Richter rearrangements. NUCLEOPHILIC SUBSTITUTION Mechanism of Aliphatic Nucleophilic Substitution. Aliphatic nucleophilic substitution clearly involves the donation of a lone pair from the nucleophile to the tetrahedral, electrophilic carbon bonded to a halogen. For that reason, it attracts to nucleophile In organic chemistry and inorganic chemistry, nucleophilic substitution is a fundamental class of reactions in which a leaving group(nucleophile) is replaced by an electron rich compound(nucleophile). The whole molecular entity of which the electrophile and the leaving group are part is usually called the substrate. The nucleophile essentially attempts to replace the leaving group as the primary substituent in the reaction itself, as a part of another molecule. The most general form of the reaction may be given as the following: Nuc: + R-LG → R-Nuc + LG: The electron pair (:) from the nucleophile(Nuc) attacks the substrate (R-LG) forming a new 1 bond, while the leaving group (LG) departs with an electron pair. The principal product in this case is R-Nuc. The nucleophile may be electrically neutral or negatively charged, whereas the substrate is typically neutral or positively charged.
    [Show full text]
  • Xarox University Microfilms
    INFORMATION TO USERS Thil material was produced from a microfilm copy of the original documant. While the moat advanced technological meant to photograph and reproduce this documant have been used, the quality is heavily dependant upon the quality of the original submitted. The following explanation o f techniques is provided to help you understand markings or patterns which m ay appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Misting Page(s)". If it was possible to obtain the misting page(s) or section, th a y era spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pagae to insure you complete continuity. 2. Whan an image on th e film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus causa a blurred image. You will find a good image of the pnga in the adjacent frame. 3. Whan a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It ie customary to begin photoing at the upper left hand comer of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row end continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation.
    [Show full text]