THE STORY OF ALCHEMY AND THE BEGINNINGS OF CHEMISTRY

By KAREN SMITH

CONTENTS PART ONE FUNDAMENTALS OF ORGANIC CHEMISTRY STRUCTURES OF ORGANIC COMPOUNDS ORGANIC CHEMISTRY STRUCTURES AND PROPERTIES OF MOLECULES ISOMERISM NOMENCLATURE OF ORGANIC COMPOUNDS STRUCTURAL THEORY INTRODUCTION THE CHEMICAL BOND BEFORE 1926 QUANTUM MECHANICS SHAPES OF ATOMIC ORBITALS ELECTRONIC CONFIGURATION PAULI EXCLUSION PRINCIPLE MOLECULAR ORBITALS THE COVALENT BOND TYPES OF MOS HYBRIDIZATION OF ORBITALS HYBRIDIZATION AND OVERLAP ENERGIES OF HYBRIDIZATION PARAMETERS OF MOLECULAR GEOMETRY BOND ENERGY AND BOND DISSOCIATION ENERGY 3D-STRUCTURE OF CSP3 COMPOUNDS INTRAMOLECULAR FORCES POLARITY OF BONDS POLARITY OF MOLECULES STRUCTURE AND PHYSICAL PROPERTIES MELTING POINT INTERMOLECULAR FORCES BOILING POINT SOLUBILITY SYMMETRY OF ORGANIC MOLECULES (MOLECULAR DISSYMMETRY) SYMMETRY ELEMENTS POINT GROUPS DETERMINING THE POINT GROUP OF ORGANIC MOLECULES STEREOGENICITY ACHIRAL STEREOGENICITY STEREOHETEROTOPICITY TYPES OF REACTIONS OF ORGANIC COMPOUNDS REACTION MECHANISM ELECTRON DELOCALIZATION FORMATION OF REACTION INTERMEDIATES TRANSITION STATE TYPES OF REAGENTS TYPES OF ORGANIC REACTIONS ACIDS AND BASES HARD AND SOFT ACIDS AND BASES (HSAB CONCEPT) THERMODYNAMICS OF ORGANIC REACTIONS KINETICS OF ORGANIC REACTIONS THERMODYNAMIC AND KINETIC CONTROL OF REACTIONS EFFECT OF CATALYST ON THE KINETICS OF A REACTION LINEAR FREE ENERGY RELATIONSHIPS (THE HAMMETT EQUATION) CURVED HAMMETT DIAGRAMS SEPARATION OF POLAR, RESONANCE, AND STERIC EFFECTS OF SUBSTITUENT CONSTANTS (S AND S) VALUES THE TAFT EQUATION SECONDARY BONDING AND ROLE OF SOLVENT ALKANES, CYCLOALKANES AND AROMATIC HYDROCARBONS CLASSIFICATION OF HYDROCARBONS ALKANES: STRUCTURE OF METHANE CLASSIFICATION BY STRUCTURE: THE FAMILY STRUCTURE OF ETHANE FREE ROTATION ABOUT THE CARBON–CARBON SINGLE BOND CONFORMATIONS TORSIONAL STRAIN PROPANE AND THE BUTANES CONFORMATIONS OF N-BUTANE VAN DER WAALS REPULSION HIGHER ALKANES THE HOMOLOGOUS SERIES NOMENCLATURE 5AI 10 ALKYL GROUPS 5AI 11 COMMON NAMES OF ALKANES 5AI 12 IUPAC NAMES OF ALKANES 5AI 13 CLASSES OF CARBON ATOMS AND HYDROGEN ATOMS 5AI 14 PHYSICAL PROPERTIES 5AI 15 INDUSTRIAL SOURCE 5AI 16 INDUSTRIAL SOURCE VS LABORATORY PREPARATION 5AI 17 PREPARATION 5AI 18 THE GRIGNARD REAGENT: AN ORGANOMETALLIC COMPOUND 5AI 19 COUPLING OF ALKYL HALIDES WITH ORGANOMETALLIC COMPOUNDS 5AI 20 REACTIONS 5AI 21 HALOGENATION 5AI 22 MECHANISM OF HALOGENATION 5AI 23 ORIENTATION OF HALOGENATION 5AI 24 RELATIVE REACTIVITIES OF ALKANES TOWARD HALOGENATION 5AI 25 EASE OF ABSTRACTION OF HYDROGEN ATOMS ENERGY OF ACTIVATION 5AI 26 STABILITY OF FREE RADICALS 5AI 27 EASE OF FORMATION OF FREE RADICALS 5AI 28 TRANSITION STATE FOR HALOGENATION 5AI 29 ORIENTATION AND REACTIVITY 5AI 30 REACTIVITY AND SELECTIVITY 5AI 31 NON-REARRANGEMENT OF FREE RADICALS ISOTOPIC TRACERS 5AI 32 COMBUSTION 5AI 33 THE GREENHOUSE EFFECT 5AI 34 PYROLYSIS: CRACKING 5AI 35 DETERMINATION OF STRUCTURE STEREOISOMERISM ENANTIOMERISM PLANE-POLARIZED LIGHT POLARIMETER SPECIFIC ROTATION OPTICAL ACTIVITY: HOW DOES IT ARISE? PROJECTION STRUCTURES OF STEREOISOMERS PROPERTIES OF ENANTIOMERS RACEMIC MODIFICATION AND RESOLUTION 5AII 10 OPTICAL ACTIVITY: A CLOSER LOOK 5AII 11 ASSIGNMENT OF CONFIGURATION 5AII 12 SPECIFICATION OF CONFIGURATION: R AND S 5AII 13 SEQUENCE RULES 5AII 14 DIASTEREOMERS 5AII 15 MESO STRUCTURES 5AII 16 SPECIFICATION OF CONFIGURATION: MORE THAN ONE CHIRAL CENTER 5AII 17 CONFORMATIONAL ISOMERS 5AII 18 REACTIONS INVOLVING STEREOISOMERS 5AII 19 GENERATION OF A CHIRAL CENTER SYNTHESIS AND OPTICAL ACTIVITY 5AII 20 REACTIONS OF CHIRAL MOLECULES BOND-BREAKING 5AII 21 REACTIONS OF CHIRAL MOLECULES RELATING CONFIGURATIONS 5AII 22 OPTICAL PURITY 5AII 23 REACTIONS OF CHIRAL MOLECULES GENERATION OF A SECOND CHIRAL CENTER 5AII 24 TOPICITY OF LIGANDS (PROCHIRALITY) OPEN-CHAIN AND CYCLIC COMPOUNDS INDUSTRIAL SOURCE PREPARATION REACTIONS REACTIONS OF SMALL-RING COMPOUNDS CYCLOPROPANE AND CYCLOBUTANE BAEYER STRAIN THEORY HEATS OF COMBUSTION AND RELATIVE STABILITIES OF THE CYCLOALKANES ORBITAL PICTURE OF ANGLE STRAIN FACTORS AFFECTING STABILITY OF CONFORMATIONS CONFORMATIONS OF CYCLOALKANES EQUATORIAL AND AXIAL BONDS IN CYCLOHEXANE PREPARATION OF CYCLOPROPANE RINGS BY -INSERTION REACTION OF CARBENES STEREOISOMERISM OF CYCLOALKANES AND THEIR DERIVATIVES: CONFIGURATIONAL ISOMERISM OF CYCLIC COMPOUNDS GEOMETRIC ISOMERISM OF ALKENES CONFORMATIONAL ANALYSIS ALIPHATIC AND AROMATIC COMPOUNDS STRUCTURE OF BENZENE MOLECULAR FORMULA ISOMER NUMBER KEKULÉ STRUCTURE STABILITY OF THE BENZENE RING REACTIONS OF BENZENE STABILITY OF THE BENZENE RING HEATS OF HYDROGENATION AND COMBUSTION CARBON–CARBON BOND LENGTHS IN BENZENE RESONANCE STRUCTURE OF BENZENE ORBITAL PICTURE OF BENZENE REPRESENTATION OF THE BENZENE RING AROMATIC CHARACTER THE HÜCKEL 4N 2 RULE NOMENCLATURE OF BENZENE DERIVATIVES POLYNUCLEAR AROMATIC HYDROCARBONS NAPHTHALENE ELECTROPHILIC AROMATIC SUBSTITUTION EFFECT OF SUBSTITUENT GROUPS DETERMINATION OF ORIENTATION REGIOSELECTIVITY OF ELECTROPHILIC AROMATIC SUBSTITUTIONS: RELATIVE REACTIVITY OF MONOSUBSTITUTED BENZENES CLASSIFICATION OF SUBSTITUENT GROUPS ORIENTATION IN DISUBSTITUTED BENZENES MECHANISM OF ELECTROPHILIC AROMATIC SUBSTITUTION: THE TWO STEPS REACTIVITY AND ORIENTATION THEORY OF REACTIVITY THEORY OF ORIENTATION ELECTRON RELEASE VIA RESONANCE EFFECT OF HALOGEN ON ELECTROPHILIC AROMATIC SUBSTITUTION ELECTROPHILIC SUBSTITUTION IN NAPHTHALENE PART TWO CHEMISTRY OF FUNCTIONAL GROUPS ALKENES CLASSES OF ORGANIC COMPOUNDS HAVING ONE OR MORE FUNCTIONAL GROUP(S) UNSATURATED HYDROCARBONS STRUCTURE OF ETHYLENE THE CARBON–CARBON DOUBLE BOND PROPYLENE HYBRIDIZATION AND ORBITAL SIZE THE BUTYLENES HIGHER ALKENES NAMES OF ALKENES PHYSICAL PROPERTIES THE ORGANIC CHEMISTRY OF VISION DEHYDROHALOGENATION OF ALKYL HALIDES: 1,2-ELIMINATION KINETICS OF DEHYDROHALOGENATION DUALITY OF MECHANISM THE E2 MECHANISM EVIDENCE FOR THE E2 MECHANISM KINETICS AND ABSENCE OF REARRANGEMENTS EVIDENCE FOR THE E2 MECHANISM ISOTOPE EFFECTS EVIDENCE FOR THE E2 MECHANISM ABSENCE OF HYDROGEN EXCHANGE EVIDENCE FOR THE E2 MECHANISM THE ELEMENT EFFECT THE E2 REACTION: ORIENTATION AND REACTIVITY THE E1 MECHANISM EVIDENCE FOR THE E1 MECHANISM THE E1 REACTION: ORIENTATION STEREOCHEMISTRY OF ELIMINATION FROM ALICYCLIC COMPOUNDS ELIMINATION: E2 VS E1 DEHYDRATION OF ALCOHOLS CONVERSION OF ALDEHYDES AND KETONES TO ALKENES REACTIONS OF THE CARBON–CARBON DOUBLE BOND OF ALKENES ADDITION REACTIONS: ELECTROPHILIC ADDITIONS HYDROGENATION HEAT OF HYDROGENATION HEAT OF HYDROGENATION AND STABILITY OF ALKENES ADDITION OF HYDROGEN HALIDES MARKOVNIKOV’S RULE REGIOSELECTIVE REACTIONS ADDITION OF HYDROGEN BROMIDE PEROXIDE EFFECT ADDITION OF SULFURIC ACID ADDITION OF WATER HYDRATION MECHANISM OF ELECTROPHILIC ADDITION REACTIONS ELECTROPHILIC 1,2-SHIFT DURING ELECTROPHILIC ADDITIONS REACTIVITY AND REGIOSELECTIVITY IN ELECTROPHILIC ADDITIONS ADDITION OF HALOGENS MECHANISM OF ADDITION OF HALOGENS (STEREOSELECTIVITY OF THE REACTION) HALOHYDRIN FORMATION: ADDITION OF THE ELEMENTS OF HYPOHALOUS ACIDS ADDITION OF ALKENES DIMERIZATION ADDITION OF ALKANES ALKYLATION OXYMERCURATION–DEMERCURATION HYDROBORATION–OXIDATION MECHANISM OF HYDROBORATION (REGIO- AND STEREOSELECTIVITY OF THE REACTION) FREE-RADICAL ADDITION MECHANISM OF THE PEROXIDE-INITIATED ADDITION OF HBR REGIOSELECTIVITY OF FREE-RADICAL ADDITION FREE-RADICAL POLYMERIZATION OF ALKENES HYDROXYLATION FORMATION OF 1,2-DIOLS CLEAVAGE: DETERMINATION OF STRUCTURE BY DEGRADATION OZONOLYSIS (1,3-DIPOLAR CYCLOADDITION) THE CARBON–CARBON DOUBLE BOND AS A SUBSTITUENT FREE-RADICAL HALOGENATION OF ALKENES: SUBSTITUTION VS ADDITION FREE-RADICAL SUBSTITUTION IN ALKENES: ORIENTATION AND REACTIVITY FREE-RADICAL SUBSTITUTION IN ALKENES: ALLYLIC REARRANGEMENT THE THEORY OF RESONANCE THE ALLYL RADICAL AS A RESONANCE HYBRID STABILITY OF THE ALLYL RADICAL ORBITAL PICTURE OF THE ALLYL RADICAL USING THE RESONANCE THEORY RESONANCE STABILIZATION OF ALKYL RADICALS HYPERCONJUGATION THE ALLYL CATION AS A RESONANCE HYBRID DIENES: STRUCTURE AND PROPERTIES STABILITY OF CONJUGATED DIENES RESONANCE IN CONJUGATED DIENES EASE OF FORMATION OF CONJUGATED DIENES: ORIENTATION OF ELIMINATION ELECTROPHILIC ADDITION TO CONJUGATED DIENES 1,4-ADDITION 1,2- VS 1,4-ADDITION RATE VS EQUILIBRIUM(KINETICALLY AND THERMODYNAMICALLY CONTROLLED REACTIONS) FREE-RADICAL POLYMERIZATION OF DIENES RUBBER AND RUBBER SUBSTITUTES ALKYNES STRUCTURE OF ACETYLENE THE CARBON–CARBON TRIPLE BOND HIGHER ALKYNES NOMENCLATURE PHYSICAL PROPERTIES OF ALKYNES INDUSTRIAL SOURCE OF ACETYLENE PREPARATION OF ALKYNES REACTIONS OF ALKYNES REDUCTION TO ALKENES MECHANISM OF ELECTROPHILIC ADDITION TO ALKYNES ACIDITY OF ALKYNES VERY WEAK ACIDS REACTIONS OF METAL ACETYLIDES SYNTHESIS OF ALKYNES ANALYSIS OF ALKYNES ALKYL HALIDES NUCLEOPHILIC SUBSTITUTIONS, SN REACTIONS FUNCTIONAL GROUPS CLASSIFICATION AND NOMENCLATURE REACTIONS NUCLEOPHILIC ALIPHATIC SUBSTITUTION NUCLEOPHILIC ALIPHATIC SUBSTITUTION NUCLEOPHILES AND LEAVING GROUPS IN SN REACTIONS KINETICS OF SN REACTIONS KINETICS OF NUCLEOPHILIC ALIPHATIC SUBSTITUTION SECOND-ORDER AND FIRST-ORDER REACTIONS NUCLEOPHILIC ALIPHATIC SUBSTITUTION: DUALITY OF MECHANISM MECHANISM OF SN2 REACTIONS STEREOCHEMISTRY OF SN2 REACTIONS: WALDEN INVERSION THE SN2 REACTION: STRUCTURE OF THE SUBSTRATE AND REACTIVITY MECHANISM OF SN1 REACTIONS CARBOCATIONS STABILIZATION OF CARBOCATIONS ACCOMMODATION OF CHARGE POLAR EFFECTS STABILITY OF CARBOCATION AND ITS EASE OF FORMATION: SN1 REACTIVITY STEREOCHEMISTRY OF SN1 REACTIONS REARRANGEMENT OF CARBOCATIONS SN2 VS SN1 ELIMINATION VS SUBSTITUTION THE SN1 REACTION: ROLE OF THE SOLVENT ION–DIPOLE BONDS THE SN2 REACTION: ROLE OF THE SOLVENT PROTIC AND APROTIC SOLVENTS THE SN2 REACTION: PHASE-TRANSFER CATALYSIS SN2 VS SN1: EFFECT OF THE SOLVENT SOLVOLYSIS NUCLEOPHILIC ASSISTANCE BY THE SOLVENT ARYL HALIDES NUCLEOPHILIC AROMATIC SUBSTITUTION (SNAR REACTIONS) STRUCTURE LOW REACTIVITY OF ARYL AND VINYL HALIDES STUCTURE OF ARYL AND VINYL HALIDES NUCLEOPHILIC AROMATIC SUBSTITUTION: BIMOLECULAR DISPLACEMENT BIMOLECULAR DISPLACEMENT MECHANISM FOR NUCLEOPHILIC AROMATIC SUBSTITUTION REACTIVITY IN NUCLEOPHILIC AROMATIC SUBSTITUTION ORIENTATION IN NUCLEOPHILIC AROMATIC SUBSTITUTION ELECTRON WITHDRAWAL BY RESONANCE EVIDENCE FOR THE TWO STEPS IN BIMOLECULAR DISPLACEMENT NUCLEOPHILIC SUBSTITUTION: ALIPHATIC AND AROMATIC ELIMINATION–ADDITION MECHANISM FOR NUCLEOPHILIC AROMATIC SUBSTITUTION BENZYNE