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Chapter1 Introduction 0011.1 The Development of Organic Chemistry 0011.2 The Structural Theory of Organic Chemistry 0011.2.1 Atomic orbitals 0021.2.2 Ionic bonding 0021.2.3 Covalent bonding 0031.2.4 Hybridization 0031.2.5 Polar covalent bond, electronegativity and dipole moment 0071.3 Acid-Base Theory in Organic Chemistry 0081.3.1 Brnsted-Lowry acids and bases 0081.3.2 Lewis acids and bases 0091.4 Function Groups and Classify of Organic Chemical Compounds 010Extending reading: Linus Pauling 012Chapter1 Introduction 0011.1 The Development of Organic Chemistry 0011.2 The Structural Theory of Organic Chemistry 0011.2.1 Atomic orbitals 0021.2.2 Ionic bonding 0021.2.3 Covalent bonding 0031.2.4 Hybridization 0031.2.5 Polar covalent bond, electronegativity and dipole moment 0071.3 Acid-Base Theory in Organic Chemistry 0081.3.1 Brnsted-Lowry acids and bases 0081.3.2 Lewis acids and bases 0091.4 Function Groups and Classify of Organic Chemical Compounds 010Extending reading: Linus Pauling 012Problems 016 Chapter2 Alkanes 0172.1 Introduction 0172.2 Nomenclature of Alkanes 0182.2.1 Nomenclature of unbranched alkyl groups 0202.2.2 Nomenclature of branched-chain alkanes 0202.2.3 Nomenclature of branched alkyl groups 0222.2.4 Classification of hydrogen atoms 0232.3 Structure and Conformations of Alkanes 0232.3.1 Structure of methane 0232.3.2 Structure of ethane 0242.3.3 Free rotation, conformations, torsional strain of the carbon-carbon single bond 0252.3.4 Propane and the butane 0272.3.5 Conformations of n-butane: van der Waals repulsion 0282.4 Physical Properties of Alkanes 0292.4.1 Boiling point 0292.4.2 Melting point 0302.4.3 Solubility in water 0312.5 Chemical Properties of Alkanes 0322.5.1 Combustion of alkanes 0322.5.2 Pyrolysis of alkanes: Cracking 0342.5.3 Halogenation of alkanes 0352.6 Occurrence and Uses of Alkanes 0442.6.1 Sources of alkanes: petroleum 0442.6.2 Petroleum refining 0452.6.3 Cracking 045Extending reading: Jacobus Henricus van’t Hoff 045Problems 047 Chapter3 Alkenes 0493.1 Structure of Alkenes 0493.2 Nomenclature and Geometric Isomerism of Alkenes 0503.2.1 Nomenclature of alkenes 0503.2.2 Geometric isomerism of alkenes and its nomenclature 0513.3 Physical Properties of Alkenes 0523.4 Preparation and Uses of Alkenes 0533.4.1 Dehydration 0533.4.2 Dehydrohalogenation 0543.4.3 Cracking 0553.4.4 Use of alkenes 0553.5 Chemical Properties of Alkenes 0553.5.1 Catalytic hydrogenation reaction 0553.5.2 Electrophilic addition to alkenes 0563.5.3 HBr free radical addition 0603.5.4 Addition of diboranes 0613.5.5 Reactions of alkenes with oxygen electrophiles 0623.5.6 The reaction of α-H 0663.6 Polymer and Plastics 067Extending reading: Synthesis of Palytoxin 069Problems 070 Chapter4 Dienes and Conjugation 0724.1 Nomenclature of Dienes 0724.2 Structure and Stability of Conjugated Dienes 0734.2.1 Conjugative effect 0734.2.2 Molecular orbital (MO) of 1,3-butadiene 0744.3 Chemical Properties of Conjugative Dienes 0754.3.1 Electrophile addition 0754.3.2 Diels-Alder reaction 0764.4 Rubber 078Extending reading 1: Otto Paul Hermann Diels 080Extending reading 2: Kurt Alder 080Problems 081 Chapter5 Cycloalkanes 0835.1 Nomenclature of Cycloalkanes 0835.1.1 Nomenclature of monocycloalkanes 0835.1.2 Nomenclature of polycycloalkanes 0845.2 Stabilities of Cycloalkanes 0865.3 Structures and Conformation of Cycloalkanes 0875.3.1 Structures and conformation of cyclopropane and cyclobutane 0875.3.2 Structures and conformation of cyclopentane 0895.3.3 Structures and conformation of cyclohexane 0895.3.4 Conformations of higher cycloalkanes 0915.3.5 Substituted cyclohexanes: axial and equatorial hydrogen atoms 0925.4 Chemical Properties of Cycloalkanes 096Extending reading: Derek Harold Richard Barton 097Problems 098 Chapter6 Alkynes 1016.1 Structure of Alkynes 1016.2 Nomenclature of Alkynes 1026.3 Physical Properties of Alkynes 1036.4 Preparation and Uses of Alkynes 1036.4.1 Preparation of ethyne (HC≡CH) 1036.4.2 By elimination reaction 1036.5 Chemical Properties of Alkynes 1046.5.1 Acidity of terminal alkynes 1046.5.2 Addition by electrophilic reagents 1066.5.3 Hydroboration/oxidation of alkynes 1086.5.4 Reduction of alkynes 1086.5.5 Oxidation of alkynes 1096.5.6 Alkynes anions as nucleophiles 110Extending reading: Discovery of Acetylene 110Problems 111 Chapter7 Stereochemistry 1137.1 Enantiomerism and Chirality 1137.2 Plane Polarized Light, Optical Activity and Specific Rotation 1167.3 Fischer Projection 1177.4 Configuration Representation Method, Configuration Labeling and Isomer Naming 1187.4.1 R/S absolute configuration representation 1197.4.2 D/L Relative configuration representation 1197.5 Diastereomers 1207.6 Resolution of Racemates 121Extending reading: The Critical Role of Stereochemistry in Organic Chemistry — Insights from the Thalidomide Tragedy 122Problems 123 Chapter8 Alkyl Halides 1258.1 Classification and Nomenclature of Halogenated Hydrocarbons 1258.2 Structure of Halides 1268.3 Physical Properties of Halides 1268.4 Chemical Properties of Halogenated Hydrocarbons 1278.4.1 Nucleophilic substitution reaction 1278.4.2 Elimination reactions of alkyl halides 1328.4.3 Organometallic compounds and their reactions 1338.5 Reaction Mechanism and Influencing Factors of Nucleophilic Substitution Reaction 1358.5.1 The mechanism for SN2 reaction 1358.5.2 The mechanism for SN1 reaction 1378.5.3 Factors affecting the rates of SN1 and SN2 reactions 1408.6 Mechanisms of Dehydrohalogenation 1478.6.1 Bimolecular elimination reaction: E2 reaction 1478.6.2 Unimolecular elimination reaction: E1 reaction 1488.7 Substitution versus Elimination 1498.7.1 SN2 versus E2 1508.7.2 Tertiary halides: SN1 versus E1 1518.8 Halogenated Alkenes 1528.8.1 Vinyl halogenated alkenes 1528.8.2 Allyl halide alkenes 1538.9 Commonly Halogenated Hydrocarbons 154Extending reading: Paul Walden 155Problems 156 Chapter9 Benzene and Aromatic Chemistry 1589.1 Structure of Benzene and Aromaticity 1599.1.1 Kekulé and the structure of benzene 1599.1.2 A resonance of bonding in benzene 1599.1.3 The stability of benzene 1619.1.4 The molecular orbitals of benzene 1629.2 Nomenclature of Benzene Derivatives 1639.3 Physical Properties of Benzene Derivatives 1649.4 Chemical Properties of Benzene Derivatives 1659.4.1 Reduction 1659.4.2 Oxidation of alkyl side-chains 1659.4.3 Free-radical halogenation of alkylbenzenes 1669.5 Electrophilic Aromatic Substitution Reactions of Substituted Benzenes 1679.5.1 Ortho, para-directing groups 1739.5.2 Meta-directing groups 1789.6 Polycyclic Aromatic Compounds 1819.6.1 Non-fused polycyclic aromatic hydrocarbons 1819.6.2 Fused polycyclic aromatic hydrocarbons 1819.7 Non-Benzene Aromatic Hydrocarbons 1859.7.1 Hückel rule 1859.7.2 Cyclobutadiene and cyclooctatetraene 1879.7.3 Annulene 1879.7.4 Cyclopentadiene and cycloheptatriene 188Extending reading: Discovery of Benzene and the Theory of Molecular Structure of Benzene 188Problems 189 Chapter10 Alcohols, Phenols and Ethers 19210.1 Structure of Alcohols, Phenols and Ethers 19210.1.1 Structure of alcohols 19210.1.2 Structure of phenols 19210.1.3 Structure of ethers 19310.2 Nomenclature of Alcohols, Phenols and Ethers 19310.2.1 Nomenclature of alcohols 19310.2.2 Nomenclature of phenols 19410.2.3 Nomenclature of ethers 19510.3 Physical Properties of Alcohols, Phenols and Ethers 19510.3.1 Physical properties of alcohols 19510.3.2 Physical properties of phenols 19610.3.3 Physical properties of ethers 19710.4 Preparation and Uses of Alcohols 19710.4.1 Synthesis of alcohols by hydration of alkenes 19710.4.2 Synthesis of alcohols by addition to carbonyl groups 19910.4.3 Synthesis of alcohols by reduction of carbonyl-containing compounds 20010.5 Chemical Properties of Alcohols 20110.5.1 Acidity of alcohols 20110.5.2 Conversion to alkyl halides 20210.5.3 Dehydration of alcohols 20310.5.4 Esterification of alcohols 20410.5.5 Oxidation of alcohols 20610.6 Preparation and Uses of Phenols 20710.6.1 Laboratory synthesis 20710.6.2 Industrial synthesis 20710.7 Chemical Properties of Phenols 20810.7.1 Acidity of phenols 20810.7.2 Other reaction of the OH group of phenols 20910.7.3 Reaction of the benzene ring of phenols 21110.8 Preparation of Ethers 21310.9 Chemical Properties of Ethers 21410.9.1 The formation of oxonium salts 21410.9.2 Acid-catalyzed cleavage of ethers 21410.9.3 Autoxidation of ethers 21510.10 Thiols, Sulfides and Disulfides 215Extending reading: Victor Grignard 217Problems 218 Chapter11 Nuclear Magnetic Resonance Spectroscopy 21911.1 Principles of Nuclear Magnetic Resonance 21911.1.1 Discovery of nuclear magnetic resonance 21911.1.2 Spin phenomenon of atomic nucleus 21911.1.3 The reasons of nuclear magnetic resonance 21911.2 Chemical Shift 22111.2.1 Definition of chemical shift 22111.2.2 Shielding effect 22111.2.3 Practical representation of chemical shift 22211.2.4 Factors affecting chemical shift 22311.3 Chemical Shifts of Characteristic Protons in 1H-NMR 22511.4 Integration Curves and Peak Areas 22811.5 Spin Coupling 22811.5.1 The causes of spin coupling 22811.5.2 Coupling constant (J) 23011.5.3 The law of coupling and splitting 23011.5.4 Spectrum analysis 23111.6 NMR Instrument 23311.7 Carbon Spectrum (13C-NMR) 234Extended reading: Paul Lauterbur 235Problems 237 Chapter12 Infrared Spectroscopy 24112.1 Theoretical Background 24112.1.1 Introduction 24112.1.2 Generation conditions of infrared absorption spectra 24212.1.3 Molecular vibration 24312.1.4 Vibrational forms of molecules 24412.2 The Infrared Spectrometer 24512.3 Characteristic Absorption of Functional Groups 24712.3.1 The functional group and fingerprint regions 24712.3.2 Characteristic infrared absorption bands 24812.3.3 The intensity of absorption bands 24912.3.4 The infrared spectra of alkane, haloalkane, alkene, benzene and alcohol 24912.4 Identifying Infrared Spectra 251Extended reading: Kirchhoff and Bunsen on Spectroscopy 253Problems 254 Chapter13 Aldehydes and Ketones 25913.1 Structure and Nomenclature of Aldehydes and Ketones 25913.1.1 Structure and bonding of carbonyl group 25913.1.2 Nomenclature of aldehydes and ketones 26013.1.3 Physical properties 26113.2 Preparation of Aldehydes and Ketones 26113.2.1 Oxidation of alcohols (dehydrogenation) 26113.2.2 Oxidation of alkenes (ozonolysis) 26313.2.3 Hydrolysis of gem-dihalides 26313.2.4 Hydration of alkynes 26313.2.5 Friedel-Crafts acylation 26313.2.6 Hydroformylation of the linear α-olefins 26413.2.7 Oxidation of side chain of arenes 26413.3 Reactions of Aldehydes and Ketones 26513.3.1 Nucleophilic addition 26513.3.2 The activity of α-hydrogen in aldehydes and ketones 27013.3.3 Oxidation reactions 27513.3.4 Reduction 27613.4 α,β-Unsaturated Carbonyl Compounds 277Extended reading: Organic Chemist Huang Minglong 278Problems 279 Chapter14 Carboxylic Acids and Acid Derivatives 28114.1 Nomenclature of Carboxylic Acids and Their Derivatives 28114.1.1 Nomencalture of carboxylic acids 28114.1.2 Nomenclature of carboxylic acid derivatives 28414.2 Structure and Physical Properties of Carboxylic Acids and Their Derivatives 28714.2.1 Structure of carboxylic acids and their derivatives 28714.2.2 Physical properties of carboxylic acids and their derivatives 29014.3 Preparation of Carboxylic Acids 29114.3.1 Oxidation reaction 29114.3.2 Hydrolysis of carboxylic acid derivatives 29314.3.3 Reaction of organometallic compounds with carbon dioxide 29314.3.4 Other methods 29414.4 Acidity of Carboxylic Acids 29514.5 Formation of Acid Halides and Anhydrides 29814.5.1 Formation of acid halides 29814.5.2 Formation of acid anhydrides 29914.6 Hydrolysis of Carboxylic Acid Derivatives 30114.6.1 Hydrolysis reaction 30114.6.2 Hydrolysis reaction mechanism 30214.7 Alcoholysis of Carboxylic Acid Derivatives 30414.7.1 Acylation 30414.7.2 Transesterification 30614.7.3 Esterification reaction mechanism 30614.8 Aminolysis of Carboxylic Acid Derivatives 30814.8.1 Reaction of carboxylic acid derivatives with amines 30814.8.2 Nucleophilic substitution reaction mechanism of amines 31014.9 Reaction of Carboxylic Acid Derivatives with Metal Reagents 31014.9.1 Reaction with metal magnesium reagents 31014.9.2 Reaction with metal lithium reagents 31114.9.3 Reaction with metal copper-lithium reagents 31114.9.4 Reaction with metal cadmium reagents 31214.10 Reductions of Carboxylic Acids and Their Derivatives 31214.10.1 Reduction of carboxylic acids 31214.10.2 Reduction of acid halides 31314.10.3 Reduction of esters 31414.10.4 Reduction of amides 31414.10.5 Reduction of nitriles 31514.11 Other Reactions of Carboxylic Acids and Their Derivatives 31614.11.1 Decarboxylation reaction 31614.11.2 α-Substituted carboxylic acids and their derivatives 31814.11.3 Elimination reaction of esters 31914.11.4 Hoffmann degradation reaction of amides 32014.12 Lactones 32014.13 Lipids and Waxes 32214.14 Carbonic Acid Derivatives 32314.15 Surfactants and Soaps 324Extended reading 1: August Wilhelm von Hofmann 326Extended reading 2: Aspirin (acetylsalicylic acid) 327Problems 327 Chapter15 Difunctional Compounds 33315.1 Introduction 33315.2 Hydroxy Aldehydes and Ketones 33415.2.1 Properties 33415.2.2 Preparation 33415.2.3 Reactions 33515.3 Hydroxy Acids 33515.3.1 Properties 33515.3.2 Preparation 33515.3.3 Dehydration of hydroxy acid 33615.4 Dicarboxylic Acids 33715.4.1 Property and reactions 33715.4.2 Acidity of dicarboxylic acids 33815.5 Dicarbonyl Compounds 33815.5.1 Acidity of β-dicarbonyl compounds and stability of enol anion 33815.5.2 Diethyl malonate 33915.5.3 Ethyl acetoacetate 34015.5.4 Michael addition reaction 34115.6 Summary 342Extended reading: Possible Substitutes for White Pollution—Lactic Acid Polymer 344Problems 344 Chapter16 Amines and Other Nitrogen-Containing Compounds 34816.1 Amines 34816.1.1 Nomenclature 34816.1.2 Structure and physical properties 35016.1.3 Preparation 35116.1.4 Chemical properties 35416.1.5 Reactions of diazonium ions 36116.2 Nitro Compounds 36316.3 Nitriles 36516.3.1 Nomenclature 36516.3.2 Physical properties 36516.3.3 Preparation 36516.3.4 Reactions of nitriles 365Extended reading: The Development of Nitroglycerin 366Problems 368 Chapter17 Heterocyclic Compounds 37017.1 Heterocyclic System 37017.2 Classification and Nomenclature of Heterocycles 37117.3 Structure and Aromaticity of Heterocycles 37217.4 Five-Membered Unsaturated Heterocycles 37317.4.1 Furan 37317.4.2 Thiophene 37517.4.3 Pyrrole 37517.4.4 Indole 37617.5 Six-Membered Unsaturated Heterocycles 37817.6 Quinoline and Isoquinoline 38017.6.1 Quinoline 38017.6.2 Isoquinoline 381Extended reading: Tu Youyou and Artemisinin 382Problems 383 Chapter18 Carbohydrates and Nucleic Acids 38618.1 Stereochemistry of Sugars 38618.1.1 The D and L notation 38618.1.2 Configurations of aldoses 38718.1.3 Configurations of ketoses 38918.2 Structure of Glucose 38918.3 Reactions of Monosaccharides 39218.3.1 Reduction 39218.3.2 Oxidation 39318.3.3 Osazone formation 39418.3.4 Ester formation 39518.3.5 Chain elongation 39518.3.6 Chain shortening 39618.4 Disaccharides 39618.5 Polysaccharides 399Extended reading: Hermann Emil Fischer 401Problems 403 Chapter19 Amino Acids, Peptides, Proteins and Nucleic Acids 40519.1 Amino Acids 40519.1.1 Nomenclature of amino acids 40519.1.2 Physical properties of amino acids 40719.1.3 The acidity and alkalinity of amino acids 40719.1.4 Amino acid reaction 41019.1.5 Amino acid synthesis 41219.2 Peptides and Proteins 41319.2.1 Peptide nomenclature 41419.2.2 Synthesis of peptides and proteins 41419.2.3 Determination of polypeptide structure 41919.2.4 Protein hierarchy 42419.3 Enzyme 42719.4 Nucleic Acid 428Extended reading: Human Genome Project 431Problems 432 Chapter20 Organometallic Compounds 43420.1 Preparation of Organometallic Compounds 43420.1.1 Preparation of organolithium compounds 43420.1.2 Preparation of organomagnesium compounds 43520.1.3 Preparation of organocopper compounds 43520.1.4 Preparation of organozinc compounds 43620.2 Main Reactions of Organometallic Compounds 43620.2.1 Organometallic compounds as Brnsted bases 43620.2.2 Organometallic compounds as nucleophilic reagents 437Extended reading: Karl Ziegler 440Problems 440 Chapter21 Orbitals and Organic Chemistry: Pericyclic Reactions 44321.1 Introduction 44321.1.1 Evolution of the theory of concerted reactions 44321.1.2 A review of π molecular orbitals 44421.1.3 Interactions between molecular orbitals 44521.2 Electrocyclic Reaction 44521.3 Cycloaddition Reaction 44721.3.1 Photochemical dimerization of alkenes 44721.3.2 Diels-Alder reaction 44821.4 Sigmatropic Rearrangements 448Extended reading: Robert Burns Woodward 449Problems 450Reference 452