Contents 1 Structure and Bonding 2 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 Atomic Structure 3 Atomic Structure: Orbitals 3 Atomic Structure: Electron Configurations 5 Development of Chemical Bonding Theory 6 The Nature of Chemical Bonds 7 Valence Bond Theory 10 Hybridization: Sp3 Orbitals and the Structure of Methane 11 Hybridization: Sp3 Orbitals and the Structure of Ethane 12 Hybridization: Sp2 Orbitals and the Structure of Ethylene 13 Hybridization: sp Orbitals and the Structure of Acetylene 16 Hybridization of Nitrogen and Oxygen 17 Molecular Orbital Theory 19 CHEMISTRY@WORK: CHEMICALS, TOXICITY,AND RISK 20 Summary and KeyWords 21 . Exercises 23 Building Block Questions 28 . InfoTrac College Edition 28 Polar Covalent Bonds; Adds and Bases VI 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 Polar Covalent Bonds: Electronegativity 29 Polar Covalent Bonds: Dipole Moments 32 Formal Charges 34 Resonance 37 Rules for Resonance Forms 39 Drawing Resonance Forms 40 Acids and Bases: The Br0nsted-Lowry Definition 43 Acid and Base Strength 45 Predicting Acid-Base Reactions from pKaValues 46 Organic Acids and Organic Bases 48 Acids and Bases: The Lewis Definition 51 Drawing Chemical Structures 55 Molecular Models 57 CHEMISTRY@WORK: ALKALOIDS: NATURAllY OCCURRING BASES 58 Summary and KeyWords 59 . Exercises 60 BuildingBlockQuestions67 . InfoTracCollegeEdition67
14
Embed
Contents - glib.hcmuns.edu.vn CHEMISTR… · An Example of a Polar Reaction: Addition of HBr to Ethylene 144 Using Curved Arrows in Polar Reaction Mechanisms 147 Describing a Reaction:
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
Contents
1Structure and Bonding
2
1.11.21.31.41.51.61.71.81.91.101.111.12
Atomic Structure 3Atomic Structure: Orbitals 3Atomic Structure: Electron Configurations 5Development of Chemical Bonding Theory 6The Nature of Chemical Bonds 7
Valence Bond Theory 10Hybridization: Sp3 Orbitals and the Structure of Methane 11Hybridization: Sp3 Orbitals and the Structure of Ethane 12Hybridization: Sp2 Orbitals and the Structure of Ethylene 13Hybridization: sp Orbitals and the Structure of Acetylene 16Hybridization of Nitrogen and Oxygen 17Molecular Orbital Theory 19
Polar Covalent Bonds: Electronegativity 29Polar Covalent Bonds: Dipole Moments 32Formal Charges 34Resonance 37Rules for Resonance Forms 39
Drawing Resonance Forms 40Acids and Bases: The Br0nsted-Lowry Definition 43Acid and Base Strength 45Predicting Acid-Base Reactions from pKaValues 46Organic Acids and Organic Bases 48Acids and Bases: The Lewis Definition 51
Industrial Preparation and Use of Alkenes 170Calculating Degree of Unsaturation 171Naming Alkenes 173Electronic Structure of Alkenes 175Cis-Trans Isomerism in Alkenes 176
Sequence Rules: The E,Z Designation 177Stability of Alkenes 181Electrophilic Addition of HXto Alkenes 184Orientation of Electrophilic Addition: Markovnikov's Rule 187Carbocation Structure and Stability 190The Hammond Postulate 192
Evidence for the Mechanism of Electrophilic Addition:Carbocation Rearrangements 195CHEMISTRY@WORK: TERPENES: NATURALLYOCCURRING ALKENES 197
Preparation of Alkenes: A Preview of Elimination Reactions 207Addition of Halogens to Alkenes 208Halohydrin Formation 210Addition of Water to Alkenes: Oxymercuration 212Addition of Water to Alkenes: Hydroboration 215Addition of Carbenes to Alkenes: Cyclopropane Synthesis 219Reduction of Alkenes: Hydrogenation 222Oxidation of Alkenes: Hydroxylation and Cleavage 224Biological Alkene Addition Reactions 227Addition of Radicals to Alkenes: Polymers 228CHEMISTRY@WORK: NATURALRUBBER 233
Electronic Structure of Alkynes 246Naming Alkynes 247Preparation of Alkynes: Elimination Reactions of Dihalides 248Reactions of Alkynes: Addition of HXand X2 249Hydration of Alkynes 250Reduction of Alkynes 254Oxidative Cleavage of Alkynes 256Alkyne Acidity: Formation of Acetylide Anions 257Alkylation of Acetylide Anions 258An Introduction to Organic Synthesis 260
CHEMISTRY@WORK:THEARTOFORGANICSYNTHESIS 265
Summary and Key Words 266 .Summary of Reactions 266 . Exercises 268
Building Block Questions 274 . InfoTrac College Edition 274
-Enantiomers and the Tetrahedral Carbon 275
The Reason for Handedness in Molecules: Chirality 277Optical Activity 280Pasteur's Discovery of Enantiomers 281Sequence Rules for Specification of Configuration 282Diastereomers 287
Meso Compounds 288Molecules with More than TwoChirality Centers 290Physical Properties of Stereoisomers 291Racemic Mixtures and Their Resolution 291A Brief Review of Isomerism 293
Stereochemistry of Reactions: Addition of HBrto Alkenes 295Stereochemistry of Reactions: Addition of Br2to Alkenes 296Stereochemistry of Reactions: Addition of HBrto a Chiral Alkene 298Chirality at Atoms Other Than Carbon 299Chirality in Nature 300Prochirality 301
Naming Alkyl Halides 317Structure of AlkylHalides 319Preparing AlkylHalides 319Radical Halogenation of Alkanes 320Allylic Bromination of Alkenes 323Stability of the Allyl Radical: Resonance Revisited 325Preparing AlkylHalides from Alcohols 327Reactions of Organohalides: Grignard Reagents 329Organometallic Coupling Reactions 330Oxidation and Reduction in Organic Chemistry 332
Summary and Key Words 336 . Summary of Reactions 336 . Exercises 338
Building Block Questions 342 . InfoTracCollege Edition 342
Reactions of AlkylHalides: NucleophilicSubstitutions andEliminations
11.1 The Discovery of the Walden Inversion 34311.2 Stereochemistry of Nucleophilic Substitution 34411.3 Kinetics of Nucleophilic Substitution 34611.4 The SN2Reaction 34711.5 Characteristics of the SN2Reaction 34911.6 The SNlReaction 35611.7 Kinetics of the SNlReaction 35711.8 Stereochemistry of the SNlReaction 35911.9 Characteristics of the SNlReaction 36111.10 Elimination Reactions of Alkyl Halides: Zaitsev's Rule 36711.11 The E2 Reaction 369
11.12 Elimination Reactions and Cyclohexane Conformation 37211.13 The Deuterium Isotope Effect 37411.14 The El Reaction 374
11.15 Summary of Reactivity: SN1,SN2,El, E2 37611.16 Substitution Reactions in Synthesis 378
CHEMISTRY@WORK: SUBSTITUTION REACTIONS IN LIVING ORGANISMS 380
Summary and Key Words 381 . Summary of Reactions 382 . Exercises 383Building Block Questions 392 . InfoTrac College Edition 392
12
Contents xi
Structure Determination:
Mass Spectrometry andInfrared Spectroscopy
13Structure Determination:
Nuclear MagneticResonanceSpectroscopy
14
12.112.212.312.412.512.612.7
12.812.9
13.1
13.213.313.413.5
13.613.713.813.913.1013.11
13.1213.13
Mass Spectrometry 394
Interpreting Mass Spectra 396Interpreting Mass-Spectral Fragmentation Patterns 397Mass-Spectral Behavior of Some Common Functional Groups 400Spectroscopy and the Electromagnetic Spectrum 403Infrared Spectroscopy of Organic Molecules 406Interpreting Infrared Spectra 407Infrared Spectra of Hydrocarbons 411Infrared Spectra of Some Common Functional Groups 412
Summary and Key Words 417 . Exercises 417Building Block Questions 423 . InfoTrac College Edition 423
-Nuclear Magnetic Resonance Spectroscopy 424
The Nature of NMR Absorptions 426Chemical Shifts 429
13CNMR Spectroscopy: Signal Averaging and FT-NMR 431Characteristics of 13CNMR Spectroscopy 432DEPT13CNMR Spectroscopy 434Uses of 13CNMR Spectroscopy 437lH NMR Spectroscopy and Proton Equivalence 438Chemical Shifts in lH NMR Spectroscopy 440Integration of lH NMR Absorptions: Proton Counting 443Spin-Spin Splitting in lH NMR Spectra 443
More Complex Spin-Spin Splitting Patterns 448Uses oflH NMR Spectroscopy 451
CHEMISTRY@WORK:MAGNETICRESONANCEIMAGING(MRI) 452
Summary and Key Words 452 . Exercises 453Building Block Questions 463 . InfoTrac College Edition 463
Conjugated Dienes andUltraviolet Spectroscopy
14.114.214.314.414.514.614.7
Preparation and Stability of Conjugated Dienes 465Molecular Orbital Description of 1,3-Butadiene 467Electrophilic Additions to Conjugated Dienes: Allylic Carbocations 469Kinetic versus Thermodynamic Control of Reactions 472The Diels-Alder Cycloaddition Reaction 474Characteristics of the Diels-Alder Reaction 475
Diene Polymers: Natural and Synthetic Rubbers 480
xii Contents
15
14.8
14.914.1014.11
Structure Determination in Conjugated Systems:Ultraviolet Spectroscopy 482Ultraviolet Spectrum of 1,3-Butadiene 483Interpreting Ultraviolet Spectra: The Effect of Conjugation 485Conjugation, Color, and the Chemistry of Vision 486
CHEMISTRY@WORK: PHOTOLITHOGRAPHY 488
Summary and KeyWords489 . Summary of Reactions 490 .Exercises 490
Building BlockQuestions 497 . InfoTracCollege Edition 497
Benzene and Aromaticlty
;;,~~
16
15.115.215.315.415.515.615.715.815.915.10
Sources of Aromatic Hydrocarbons 499Naming Aromatic Compounds 500Structure and Stability of Benzene 502Molecular Orbital Description of Benzene 504Aromaticity and the HUckel4n + 2 Rule 505Aromatic Ions 507
Aromatic Heterocycles: Pyridine and Pyrrole 510Why 4n + 2? 512Polycyclic Aromatic Compounds: Naphthalene 514Spectroscopy of Aromatic Compounds 515
CHEMISTRY@WORK: ASPIRIN, NSAlDs, AND COX-2 INHIBITORS 519
NamingAlcohols and Phenols 588Propertiesof Alcohols and Phenols:HydrogenBonding 590Propertiesof Alcohols and Phenols:Acidity and Basicity 591Preparationof Alcohols: A Review 596Alcohols from Reductionof CarbonylCompounds 598Alcohols from Reactionof CarbonylCompoundswith Grignard Reagents 601SomeReactionsof Alcohols 605Oxidation of Alcohols 611Protectionof Alcohols 613Preparationand Usesof Phenols 615Reactionsof Phenols 618
Spectroscopyof Alcohols and Phenols 619
CHEMISTRY@WORK: ETHANOL:CHEMICAL, DRUG, AND POISON 623
Summary and KeyWords 624 .Summaryof Reactions625 .Exercises628Building BlockQuestions638 .InfoTracCollegeEdition638
Naming Aldehydes and Ketones 683Preparation of Aldehydes and Ketones 685Oxidation of Aldehydes and Ketones 687Nucleophilic Addition Reactions of Aldehydes and Ketones 688Relative Reactivity of Aldehydes and Ketones 690
Nucleophilic Addition of H2O:Hydration 691Nucleophilic Addition of HCN: Cyanohydrin Formation 693Nucleophilic Addition of Grignard Reagents and Hydride Reagents:Alcohol Formation 695
Nucleophilic Addition of Amines: Imine and Enamine Formation 696
Nucleophilic Addition of Hydrazine: The Wolff-Kishner Reaction 700Nucleophilic Addition of Alcohols: Acetal Formation 702Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction 706The Cannizzaro Reaction: Biological Reductions 709Conjugate Nucleophilic Addition to a,f3-UnsaturatedAldehydes and Ketones 711Some Biological Nucleophilic Addition Reactions 715Spectroscopy of Aldehydes and Ketones 716
CHEMISTRY@WORK:ENANTIOSELECTIVESYNTHESIS 720
Summary and KeyWords 721 . Summary of Reactions 722 . Exercises 725Building BlockQuestions736 . InfoTrac College Edition 736
Carboxylic Addsand Nitriles
~J
19.919.1019.1119.1219.1319.14
19.1519.16
20.120.220.320.420.520.620.720.820.920.10
Naming Carboxylic Acids and Nitriles 738Structure and Physical Properties of Carboxylic Acids 740Dissociation of Carboxylic Acids 741Substituent Effects on Acidity 743Substituent Effects in Substituted Benzoic Acids 745
Preparation of Carboxylic Acids 746Reactions of Carboxylic Acids: An Overview 749Reduction of Carboxylic Acids 749Chemistry of Nitriles 750Spectroscopy of Carboxylic Acids and Nitriles 755
Naming Carboxylic Acid Derivatives 771Nucleophilic AcylSubstitution Reactions 774Nucleophilic AcylSubstitution Reactions of Carboxylic Acids 779Chemistry of Acid Halides 783Chemistry of Acid Anhydrides 788Chemistry of Esters 789Chemistry of Amides 795Thioesters and AcylPhosphates:Biological Carboxylic Acid Derivatives 798Polyamides and Polyesters: Step-Growth Polymers 799Spectroscopy of Carboxylic Acid Derivatives 802
CHEMISTRY@WORK:P-LACTAMANTIBIOTICS 804
Summary and Key Words 805 .Summary of Reactions 806 . Exercises 809
Building Block Questions 819 . InfoTrac College Edition 819
-Keto-Enol Tautomerism 821
Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions 824Alpha Halogenation of Aldehydes and Ketones 824Alpha Bromination of Carboxylic Acids:The Hell-Volhard-Zelinskii Reaction 827
Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation 828Reactivity of Enolate Ions 832Halogenation of Enolate Ions: The Haloform Reaction 833Alkylation of Enolate Ions 834CHEMISTRY@WORK:UNUSUAL ELEMENTSIN ORGANICCHEMISTRY 842
Summary and Key Words 844 . Summary of Reactions 844 .Exercises 846
Building BlockQuestions 853 . InfoTracCollege Edition 853
Carbonyl CondensationReactions
23.123.223.3
23.423.523.623.723.823.923.10
Mechanism of Carbonyl Condensation Reactions 854Condensations of Aldehydes and Ketones: The Aldol Reaction 855Carbonyl Condensation Reactionsversus Alpha-Substitution Reactions 858Dehydration of Aldol Products: Synthesis of Enones 859Using Aldol Reactions in Synthesis 861Mixed Aldol Reactions 862Intramolecular Aldol Reactions 864The Claisen Condensation Reaction 865Mixed Claisen Condensations 867
Intramolecular Claisen Condensations: The Dieckmann Cyclization 869
28.1 Five-Membered Unsaturated Heterocycles 106128.2 Structures of Pyrrole, Furan, and Thiophene 106228.3 ElectrophilicSubstitution Reactions of Pyrrole, Furan,and Thiophene 106328.4 Pyridine, a Six-Membered Heterocycle 106428.5 Electrophilic Substitution of Pyridine 106528.6 Nucleophilic Substitution of Pyridine 106628.7 Fused-Ring Heterocycles 106728.8 Nucleic Acids and Nucleotides 106928.9 Structure of Nucleic Acids 1071
28.10 Base Pairing in DNA:The Watson-Crick Model 107228.11 Nucleic Acids and Heredity 107428.12 Replication of DNA 107528.13 Structure and Synthesis of RNA:Transcription 107728.14 RNAand Protein Biosynthesis: Translation 107828.15 DNASequencing 108128.16 DNASynthesis 108328.17 The Polymerase Chain Reaction 1086
CHEMISTRY@WORK: DNA FINGERPRINTING 1087
Summary and KeyWords 1088 .Summary of Reactions 1089Exercises 1090 . Building Block Questions 1093InfoTracCollege Edition 1093
The Organic Chemistryof Metabolic Pathways
29.129.229.329.429.529.629.729.829.9
An Overview of Metabolism and Biochemical Energy 1094Catabolism of Fats: f3-0xidation 1098Catabolism of Carbohydrates: Glycolysis 1104The Conversion of Pyruvate to Acetyl CoA 1110The CitricAcid Cycle 1113Catabolism of Proteins: Transamination 1116