OrganlcChemlstryFrFTH EDrrloN rMarc LoudonPurdue UniversityROBERTS AND COMPANY PUBLISHERSGreenwood Village, Colorado1PrefaceReviewers and ConsultantsAbout the AuthorCHEMIGAT BONDING AND CHEMIGAT STRUGTUREContentsxxxlxxxvixxxix11.11.21.31.41.51.61.71.8lntroductionA. What Is Organic Chemistry?B. Emergence of Organic ChemistryC. Why Study Organic Chemistry?Classical Theories of Chemical BondingA. Electrons in AtomsB. The Ionic BondC. The Covalent BondD. The Polar Covalent BondStructures of Covalent GompoundsA. Methods for Determining Molecular GeometryB. Prediction of Molecular GeometryResonance StructuresWave Nature of the ElectronElectronic structure of the Hydrogen AtomA. Orbitals, Quantum Numbers, and EnergyB. Spatial Characteristics of OrbitalsC. Summary: Atomic Orbitals of HydrogenElectronic Structures of More Complex AtomsAnother took at the Covalent Bond: Molecular OrbitalsA. Molecular Orbital TheoryB. Molecular Orbital Theory and the Lewis Structure of H,Hybrid OrbitalsA. Bonding in MethaneB. Bonding in Ammonia1112333591313I420222323252829323236373740vii1.9viii coNrENrs2Key ldeas in Chapter 1Additional ProblemsALKANES4243462.1 Hydrocarbons2.2 Unbranched Alkanes2.3 conformations of AlkanesA. Conformation of EthaneB. Conformations of Butane2.4 Gonstitutional lsomers and NomenclatureA. IsomersB. Organic NomenclatureC. Substitutive Nomenclature of AlkanesD. Highly Condensed StructuresE. Classification of Carbon Substitution2.5 Cycloalkanes and skeletal structures2.6 Physical Properties of AlkanesA. Boiling PointsB. Melting PointsC. Other Physical Properties2.7 Gombustion2.8 occurrence and use of Alkanes2.9 Functional Groups, Gompound Classes, and the "R" NotationA. Functional Groups and Compound ClassesB. "R" NotationKey ldeas in Chapter 2Additional ProblemsACIDS AND BASES. THE CURVED.ARROW NOTATION46485050535757585964666770707374767838181828383873.1 Lewis Acid-Base Association ReactionsA. Electron-Deficient CompoundsB. Reactions of Electron-Deficient Compounds with Lewis BasesC. The Curved-Arrow Notation for Lewis Acid-Base Association andDissociation Reactions8787888943.2 Electron-pair oisplacement ReactionsA. Donation of Electrons to Atoms That Are Not Electron-DeficientB. The Curved-Arrow Notation for Electron-Pair Displacement Reactions3.3 Review of the Curued-Arrow NotationA. Use of the Curved-Arrow Notation to Represent ReactionsB. Use of the Curved-Arrow Notation to Derive Resonance Structures3.4 Bronsted-Lowry Acids and BasesA. Definition of Brgnsted Acids and BasesB. Nucleophiles, Electrophiles, and Leaving GroupsC. Strengths of Brpnsted AcidsD. Strengths of Brgnsted BasesE. Equilibria in Acid-Base Reactions3.5 Free Energy and Chemical Equilibrium3.6 Relationship of Structure to AcidityA. The Element EffectB. The Charge EffectC. The Polar EffectKey ldeas in Chapter 3Additional ProblemsINTRODUGTION TO AIKENES.STRUCTURE AND REACTIVITYCONTENTS iX909091949494959698101103104106108108110lll1161171224"1 Structure and Bonding in RfkenesA. Carbon Hybridization in AlkenesB. The n- (Pi) BondC. Double-Bond Stereoisomers4.2 Nomenclature of AlkenesA. IUPAC Substitutive NomenclatureB. Nomenclature of Double-Bond Stereoisomers: The E,Z Svstem4.3 Unsaturation Humber4.4 Phy$ical Propefties of Alkenes4.5 Relative $tabilities of Allcene lsomersA. Heats of FormationB. Relative Stabilities of Alkene Isomers4.5 Additisn Reactions of Alkenes4"7 Addition of Hydrcgen Halides to nlilrenasA. Regioselectivity of Hydrogen Halide AdditionB. Carbocation Intermediates in Hydrogen Halide Addition122r23r25128131131t34139140141I4Ir44147147148r49CONTENTS4.84.9C. Structure and Stability of CarbocationsD. Carbocation Rearrangement in Hydrogen Halide AdditionReaction RatesA. The Transition StateB. The Energy BarrierC. Multistep Reactions and the Rate-Limiting StepD. Hammond's PostulatecatalysisA. Catalytic Hydrogenation of AlkenesB. Hydration of AlkenesC. Enzyme CatalysisKey ldeas in Chapter 4Additional Problems151r54157158160r62r64166168r691721721741785ADDITION REACTIONS OF ALKENES5.15.25.35.45.55.6An Overuiew of Electrophilic Addition ReactionsReactions of Alkenes with HalogensA. Addition of Chlorine and BromineB. Halohydrinswriting organic ReactionsGonverion of Alkenes into AlcoholsA. Oxymercuration-Reduction of AlkenesB. Hydroboration-Oxidation of AlkenesC. Comparison of Methods for the Synthesis of Alcohols from AlkenesOzonolysis of AlkenesFree-Radical Addition of Hydrogen Bromide to RlkenesA. The Peroxide EffectB. Free Radicals and the "Fishhook" NotationC. Free-Radical Chain ReactionsD. Explanation of the Peroxide EffectE. Bond Dissociation Energies5.7 Polymeni: Free-Radical Polymerization of Alkenes5.8 Alkenes in the Ghemical lndustryKey ldeas in Chapter 5Additional Problems178181181183186187r8719019419620020020r202207zrl2142162192206 PRINCIPLES OF STEREOCHEMISTRYCONTENTSxl22676.1 Enantiomelri, Chirality, and SymmetryA. Enantiomers and ChiralityB. Asymmetric Carbon and StereocentersC. Chirality and Symmetry6.2 Nomenclature of Enantiomers: The R,S System6.3 Physical Properties of Enantiomers: Optical ActivityA. Polarized LightB. Optical ActivityC. Optical Activities of Enantiomers6.4 Racemates5.5 Stereochemical Correlation6.6 Diastereomers6.7 Meso Compounds6.8 Enantiomeric Resolution6.9 Ghiral Molecules without Asymmetric Atoms6.10 Conformational StereoisomersA. Stereoisomers Interconvefied by Internal RotationsB. Asymmetric Nitrogen: Amine Inversion6,17 Drawing Structures That ContainThree-Dimensional lnformation6.12 The Postulation of Tetrahedral CarbonKey ldeas in Chapter 6Additional ProblemscYcHc coMPouNDs.STEREOCHEMISTRY OF REACTIONS2262262292292312342352352382392412422462492512532532552572s92632532687.1 Relative Stabilities of the Monocyclic Alkanes7.2 Conformations of GyclohexaneA. The Chair ConformationB. Interconversion of Chair ConformationsC. Boat and Twist-Boat Conformations268269269273274xtl CONTENTS7.37.47,57.67.77.87.9INTRODUCTION TO ATKYL HAIIDES, ALCOHOLS,ETHERS, THIOLS, AND SUTFIDESMonosubstituted Gyclohexalres. Gonformational RnalysisDisu bstituted GyclohexanesA. Cis-Trans Isomerism in Disubstituted CyclohexanesB. Conformational AnalysisC. Use of Planar Structures for Cyclic CompoundsD. Stereochemical Consequences of the Chair InterconversionGyclopentar€, Gyclobutane, and GyclopropaneA. CyclopentaneB. Cyclobutane and CyclopropaneBicyclic and Polycyclic GompoundsA. Classification and NomenclatureB. Cis and Trans Ring FusionC.