Organic Chemisty Demystified - CHEMISTRY PROBLEM
Organic ChemistryDemystified
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Organic ChemistryDemystifiedDANIEL R. BLOCHMcGRAW-HILLNew YorkChicago San Francisco Lisbon LondonMadrid Mexico City Milan New DelhiSan Juan Seoul Singapore Sydney Toronto
Copyright 2006 by The McGraw-Hill Companies, Inc. Inc. All rights reserved. Manufactured in the United States of America.Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed inany form or by any means, or stored in a database or retrieval system, without the prior written permission of the publisher.0-07-148710-7The material in this eBook also appears in the print version of this title: 0-07-145920-0.All trademarks are trademarks of their respective owners. Rather than put a trademark symbol after every occurrence of a trademarked name, we use names in an editorial fashion only, and to the benefit of the trademark owner, with no intention of infringement of the trademark. Where such designations appear in this book, they have been printed with initial caps.McGraw-Hill eBooks are available at special quantity discounts to use as premiums and sales promotions, or for use in corporatetraining programs. For more information, please contact George Hoare, Special Sales, at george hoare@mcgraw-hill.com or (212)904-4069.TERMS OF USEThis is a copyrighted work and The McGraw-Hill Companies, Inc. (“McGraw-Hill”) and its licensors reserve all rights in and to thework. Use of this work is subject to these terms. Except as permitted under the Copyright Act of 1976 and the right to store andretrieve one copy of the work, you may not decompile, disassemble, reverse engineer, reproduce, modify, create derivative worksbased upon, transmit, distribute, disseminate, sell, publish or sublicense the work or any part of it without McGraw-Hill’s prior consent. You may use the work for your own noncommercial and personal use; any other use of the work is strictly prohibited. Yourright to use the work may be terminated if you fail to comply with these terms.THE WORK IS PROVIDED “AS IS.” McGRAW-HILL AND ITS LICENSORS MAKE NO GUARANTEES OR WARRANTIESAS TO THE ACCURACY, ADEQUACY OR COMPLETENESS OF OR RESULTS TO BE OBTAINED FROM USING THEWORK, INCLUDING ANY INFORMATION THAT CAN BE ACCESSED THROUGH THE WORK VIA HYPERLINK OROTHERWISE, AND EXPRESSLY DISCLAIM ANY WARRANTY, EXPRESS OR IMPLIED, INCLUDING BUT NOT LIMITED TO IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. McGraw-Hill andits licensors do not warrant or guarantee that the functions contained in the work will meet your requirements or that its operationwill be uninterrupted or error free. Neither McGraw-Hill nor its licensors shall be liable to you or anyone else for any inaccuracy,error or omission, regardless of cause, in the work or for any damages resulting therefrom. McGraw-Hill has no responsibility forthe content of any information accessed through the work. Under no circumstances shall McGraw-Hill and/or its licensors be liablefor any indirect, incidental, special, punitive, consequential or similar damages that result from the use of or inability to use thework, even if any of them has been advised of the possibility of such damages. This limitation of liability shall apply to any claimor cause whatsoever whether such claim or cause arises in contract, tort or otherwise.DOI: 10.1036/0071459200
To Nan for her assistance, patience, and helpful comments.
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For more information about this title, click hereCONTENTSPrefacexviiAcknowledgmentsxixCHAPTER 1Structure and BondingAtomic StructureAtomic Number and Atomic Mass (Weight)Electron Energy LevelsThe Octet RuleValencesLewis StructuresOrbital ShapesQuantum MechanicsBond FormationValence Bond TheoryMolecular OrbitalsBonding and Antibonding MOsBonding and 3-D Molecular ShapeCurved ArrowsElectronegativity and Bond PolarityDipole MomentsFormal ChargesResonance StructuresIntermolecular ER 2Families and Functional Groups43vii
CONTENTSviiiCHAPTER 3Acids and BasesIntroductionArrhenius DefinitionBrønsted-Lowry DefinitionConjugate Acids and BasesEquilibrium ReactionsWeak Hydrocarbon AcidsLewis Acids and BasesQuiz464647474749535456CHAPTER 4Alkanes and CycloalkanesIntroductionSources of AlkanesAcyclic and Cyclic l IsomersCycloalkanesAlkyl GroupsNomenclature—Naming Compoundsby the IUPAC SystemPhysical PropertiesChemical PropertiesConformations of AlkanesConformations of CylcoalkanesQuiz59596060616262646667CHAPTER 5StereochemistryIsomersChiral CompoundsStereocentersChirality CentersEnantiomersRacemic Mixtures7074757684949999100101102105109
CONTENTSixThe R/S SystemWhen the Lowest Priority Group Is Notin the BackMolecules with Multiple AsymmetricCentersEnantiomersDiastereomersMeso CompoundsFisher ProjectionsRotating Fisher Projections/StructuresCyclic StereoisomersNaming Cyclic StereoisomersProchiral Carbons PTER 6Structure and Properties of AlkenesIntroductionStructureNaming AlkenesCommon NamesCis and Trans IsomersThe E/Z (Easy) SystemDegrees of UnsaturationStability of AlkenesPhysical Properties of AlkenesChemical PropertiesThe Curved APTER 7Reaction ationsStereochemistry145145145148150151113
CONTENTSxCHAPTER 8CHAPTER 9The Hammond PostulateRegiochemical ReactionsThe Markovnikov RuleStereochemistryRearrangement Reactions of CarbocationsQuiz152154155156157159Reactions of AlkenesReaction with Hydrogen Halides in InertSolventsReaction with Hydrogen Halides in ProticSolventsOxymercuration-Demercuration ReactionsHydroboration-ReductionHalogenation in Inert SolventsStereochemistry HalogenationHalogenation in Reactive SolventsRadical BrominationFormation of DiolsDouble Bond lkynesIntroductionStructureNomenclaturePhysical PropertiesChemical PropertiesReactions with Brønsted-Lowry 177178180180181182
CONTENTSxiReactions with HBr and PeroxidesReaction with HalogensHydration ReactionsHydroboration-Oxidation ReactionsHydrogenation/Reduction ReactionsOxidation ReactionsAcidity of AlkynesAlkylation ReactionsPreparation of AlkynesQuiz193195195198199200201202204204CHAPTER oscopyUV SpectroscopyNuclear Magnetic Resonance SpectroscopyNuclear PropertiesNMR Spectrometers1 H NMR Spectroscopy13 C NMR SpectroscopyMass 51CHAPTER reparation of HalidesRadical HalogenationIsomeric ProductsAllylic HalogenationReactions of OrganohalidesQuiz256256256257258258260263265266
CONTENTSxiiCHAPTER 12CHAPTER 13Nucleophilic Substitution andElimination ReactionsIntroductionProperties of NucleophilesProperties of BasesProperties of Substrates/ElectrophilesProperties of Leaving GroupsProperties of SolventsSecond-Order Nucleophilic Substitution(SN 2) ReactionsFirst-Order Nucleophilic Substitution(SN 1) ReactionsSummary of SN 1 and SN 2 ReactionsSecond-Order Elimination (E2)ReactionsFirst-Order Elimination (E1) ReactionsSummary of E1 and E2 ReactionsCompetition between Substitution andElimination ReactionsQuizAlcoholsIntroductionProperties of AlcoholsNomenclatureAcidity and Basicity of AlcoholsReactions with Active MetalsPreparation of AlcoholsOrganometallic CompoundsPreparation of Alcohols UsingOrganometallic ReagentsReactions of AlcoholsConversion of Alcohols to Alkyl HalidesDehydration 91291292295295296297299301301306307310311313313
CONTENTSxiiiCHAPTER ion of EthersReactions of EthersThree-Membered Ether RingsQuiz317317317318319321323327CHAPTER 15Sulfur CompoundsNomenclaturePropertiesReactions of Sulfur CompoundsQuiz330330331333335CHAPTER 16Conjugated SystemsIntroductionStability of DienesElectrophilic Addition to Conjugated DienesAllylic Cations, Radicals, and AnionsDiels-Alder ReactionsQuiz337337337344347349355CHAPTER 17Aromatic Compounds358Introduction358Reactivity of Aromatic Compounds358Nomenclature359Kekulé Structures361Stability of Benzene362The Resonance Model364Molecular Orbital Description of Aromaticity 365Properties of Aromatic, Nonaromatic, andAntiaromatic Compounds369Hückel’s Rule370Heterocyclic Compounds371
CONTENTSxivAromatic IonsPolycyclic Aromatic CompoundsQuiz372374375CHAPTER 18Reactions of Benzene and otherAromatic Compounds378Introduction378Electrophilic Aromatic Substitution379Nucleophilic Aromatic Substitution386More Derivatives of Benzene388Multiple Substitution Reactions392Electrophilic Substitution in DisubstitutedBenzenes399Quiz400CHAPTER 19Aldehydes and KetonesIntroductionNomenclaturePhysical PropertiesChemical PropertiesPreparation of Aldehydes and KetonesHydration of AlkynesReduction of Acid ChloridesReactions of Aldehydes and Ketones withNucleophilesWittig ReactionsOxidation and Reduction ReactionsQuiz404404405408408410412414Carboxylic AcidsIntroductionNomenclatureThree-Dimensional StructureMolecular Orbital (MO) DescriptionPhysical Properties430430431434434435CHAPTER 20418424425427
CONTENTSxvAcidity of Carboxylic AcidsPreparation of Carboxylic AcidsDerivatives of Carboxylic AcidsQuiz437439444444CHAPTER 21Derivatives of Carboxylic AcidsIntroductionCarboxylic Acid HalidesCarboxylic Acid AnhydridesCarboxylic EstersAmidesCyclic 8470CHAPTER 22Alpha-Substitution Reactions inCarbonyl CompoundsIntroductionEnol and Enolate AnionsAlpha Monohalogenation of Aldehydesand Ketonesα,β Unsaturated Ketonesα-Bromination of Carboxylic AcidsAcidity of α-Hydrogen AtomsMalonic Ester SynthesisAcetoacetic Ester SynthesisAdditional Condensation ReactionsQuizCHAPTER 23Carbonyl Condensation ReactionsIntroductionAldol ReactionsDehydration of Aldol CompoundsMixed or Crossed Aldol 1492493
CONTENTSxviIntramolecular Aldol ReactionsClaisen Condensation Reactionsα-Substitution ReactionsQuiz494495499502Final Exam504Quiz and Exam Solutions531Appendix A / Periodic Tableof the Elements537Bibliography539Index541
PREFACEOrganic chemistry is the chemistry of carbon-containing compounds. Everyliving organism, plant and animal, is composed of organic compounds. Anyonewith an interest in life and living things needs to have a basic understanding oforganic chemistry.Articles continue to appear in newspapers and magazines describing thedevelopment of new medicines and diagnostic tests. These new products andtechnologies are results of a better understanding of the structure and functionof DNA, proteins, and other organic biological molecules. The reactions andinteractions of these complex molecules are the same reactions and interactionsthat occur in more simple organic molecules.This text was written to help those who are intimidated by the words organicchemistry. Those who have never had a formal course in organic chemistry andstudents currently taking or planning to take a formal course will find this textan easy-to-read introduction and supplement to other texts.The chapters are written in the same general order as found in most collegetextbooks. It would be helpful, but not necessary, if the reader had a course inintroductory chemistry. The first three chapters cover the background materialtypically covered in general chemistry courses. It is not necessary that chaptersbe read sequentially, but since material tends to build on previous concepts it willbe easier to understand the material if the chapters are read in sequential order.Key terms and concepts are italicized. Be sure you understand these conceptsas they will continue to appear in other sections of this book. Questions (andanswers) are given within each chapter to help you measure your understanding.Each chapter ends with a quiz covering the material presented. Use each quizto check your comprehension and progress. The answers to quizzes are givenin the back of the text. Review those problems (immediately) you did not getcorrect. Be sure you understand the concepts before going to the next chapteras new material often builds upon previous concepts.xviiCopyright 2006 by The McGraw-Hill Companies, Inc. Click here for terms of use.
xviiiPREFACEAs you read each chapter, take frequent breaks (you can munch on the extragum drops used to make models in Chapter 5). The book contains a lot of figuresand diagrams. Follow these as you read the text. It is often easier to understanda reaction mechanism in a diagram than to describe it in words.Yes, there is some memorization. New terms will appear that you probablyhave never heard before. For a series of terms I recommend making a mnemonicand I suggested a few. Reaction mechanisms are not as difficult as they mayappear. You can predict most reactions in that negative species will be attractedto positive species (opposites attract). Atoms with electrons to share will beattracted to species that want more electrons—it is just that simple.There is a multiple-choice final exam at the end of the text. The final examhas more general, but similar, questions than those in the quizzes. Answers aregiven in the back of the book. If you are able to answer 80% of the final examquestions correctly (the first time), you will have a good understanding of thematerial.I hope you will enjoy reading about organic chemistry as much as I haveenjoyed writing about it.Daniel R. Bloch
ACKNOWLEDGMENTSThe author expresses his appreciation to Nan for her assistance, patience, andhelpful comments during the preparation of this book.The following individuals were kind enough to review various chapters inthis book:Vaughn Ausman, Marquette UniversityKate Bichler, University of Wisconsin Center—ManitowocPeter Conigliaro (retired), S.C. JohnsonSheldon Cramer (emeritus), Marquette UniversityTimothy Eckert, Carthage CollegeSharbil Firson, Sigma-AldrichKevin Glaeske, Wisconsin Lutheran CollegeBruce HolmanShashi Jasti, Sigma-AldrichSteven Levsen, Mount Mary CollegeJulie Lukesh, University of Wisconsin—Green BayKevin Morris, Carthage CollegePatt Nylen, University of Wisconsin—MilwaukeeStephen Templin, Cardinal Stritch UniversityA special thanks to Priyanka Negi and Judy Bass who assisted with thetechnical editing of this book.xixCopyright 2006 by The McGraw-Hill Companies, Inc. Click here for terms of use.
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Organic ChemistryDemystifiedxxiCopyright 2006 by The McGraw-Hill Companies, Inc. Click here for terms of use.
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1CHAPTERStructure andBondingIntroductionThe study of organic chemistry involves the reactions and interactions ofmolecules. Since molecules are composed of atoms, it is necessary to reviewthe structure of atoms and how they contribute to the properties of molecules.Atomic StructureAtoms are composed of a nucleus surrounded by electrons, as shown in Fig. 1-1.The nucleus consists of positively charged protons and neutral neutrons. Although the nucleus consists of other subatomic particles, the proton, neutron,and electron are the only subatomic particles that will be discussed in this text.1Copyright 2006 by The McGraw-Hill Companies, Inc. Click here for terms of use.
CHAPTER 12Structure and BondingNucleus containsprotons and neutrons and isabout 0.0001 angstrom in diameterElectron cloud1ÅdiameterFig. 1-1. Structure of an atom.The atom is extremely small. It has a diameter of about 10 10 m(0.000,000,000,1 m or 0.000,000,004 in.). These small dimensions are usually expressed in angstroms (Å), where 1 Å equals 1 10 10 m, or pm where1 pm equals 1 10 12 m. The nucleus is about 1/10,000th the diameter of theatom, or about 10 4 Å. A key point: most of the volume of an atom is occupiedby the electrons. To put this in terms that are easier to understand, if the atomwas magnified so that the nucleus was the size of a marble, the area occupied bythe electrons would be the size of a football stadium. Take a minute to visualizethat. The area occupied by electrons is huge relative to that of the nucleus. Thearea occupied by electrons is referred to as the electron cloud.MASSES OF ATOMSThe mass of an atom is concentrated in the nucleus. A proton and a neutroneach have a mass of about 1.66 10 24 g. An electron has a mass of 1/1800ththat of a proton. Since these are such very small numbers, it is more convenientto give the mass of a proton and a neutron in atomic mass units (amu). Oneamu is equal to 1.66 10 24 g. The mass of individual atoms is also given ina.m.u. The mass of 1 mole of atoms (a mole is a specific number, approximately6.022 1023 ) is the atomic mass, which we usually call the atomic weight, ofan element. The atomic weight is expressed in grams/mol.ELECTRON CLOUDSStructures of molecules are usually written as shown in Fig. 1-2. Structure 1-2aimplies that atoms are quite far apart, relative to their size. This is certainly truefor the nuclei, but not for the electron clouds. The distance between a hydrogennucleus and a carbon nucleus in a carbon-hydrogen bond is about 1.14 Å. The
CHAPTER 1Structure and Bonding1.14 ÅHHCElectron cloudoverlapHHH1-2aHC3HH1-2bFig. 1-2. Bond formation resulting from electron cloud overlap.radius of the electron cloud of an isolated hydrogen atom is calculated to be 0.79Å and the radius of an isolated carbon atom is calculated to be 0.91 Å. Since thesum of the radii of the two atoms is 1.70 Å and the actual bond length is only1.14 Å, the electron clouds must overlap to form the C H bond. Generally, thegreater the electron cloud overlap, the greater the electron density in the bondand the stronger the bond. The area occupied by the electrons, the electron cloud,is much greater than implied in the structures typically drawn (such as Structure1-2a) in this book and other organic chemistry textbooks. The area occupied byelectrons in a molecule is more accurately represented by Structure 1-2b.Why do we need to be so concerned with electrons and electron clouds?Organic chemistry involves physical interactions and chemical reactions between molecules. Electrons are pri
Organic chemistry is the chemistry of carbon-containing compounds. Every living organism, plant and animal, is composed of organic compounds. Anyone with an interest in life and living things needs to have a basic understanding of organic chemistry. Articles cont
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