loudon 01-table of contents
DESCRIPTION
Organic Chemistry Textbook Part 1TRANSCRIPT
OrganlcChemlstry
FrFTH EDrrloN r
Marc LoudonPurdue University
ROBERTS AND COMPANY PUBLISHERSGreenwood Village, Colorado
1
PrefaceReviewers and ConsultantsAbout the Author
CHEMIGAT BONDING AND CHEMIGAT STRUGTURE
Contents
xxxlxxxvixxxix
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
lntroductionA. 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 Bond
Structures of Covalent GompoundsA. Methods for Determining Molecular GeometryB. Prediction of Molecular Geometry
Resonance StructuresWave Nature of the Electron
Electronic structure of the Hydrogen AtomA. Orbitals, Quantum Numbers, and EnergyB. Spatial Characteristics of OrbitalsC. Summary: Atomic Orbitals of Hydrogen
Electronic Structures of More Complex Atoms
Another 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 Ammonia
11
1
2
33359
1313I4
20
22
23232528
29
323236
373740
vii
1.9
viii coNrENrs
2
Key ldeas in Chapter 1
Additional Problems
ALKANES
4243
46
2.1 Hydrocarbons
2.2 Unbranched Alkanes
2.3 conformations of AlkanesA. Conformation of EthaneB. Conformations of Butane
2.4 Gonstitutional lsomers and NomenclatureA. IsomersB. Organic NomenclatureC. Substitutive Nomenclature of AlkanesD. Highly Condensed StructuresE. Classification of Carbon Substitution
2.5 Cycloalkanes and skeletal structures2.6 Physical Properties of Alkanes
A. Boiling PointsB. Melting PointsC. Other Physical Properties
2.7 Gombustion2.8 occurrence and use of Alkanes
2.9 Functional Groups, Gompound Classes, and the "R" NotationA. Functional Groups and Compound ClassesB. "R" Notation
Key ldeas in Chapter 2Additional Problems
ACIDS AND BASES. THE CURVED.ARROW NOTATION
46
48
505053
575758596466
67
70707374
76
78
3
818182
8383
87
3.1 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 and
Dissociation Reactions
878788
89
4
3.2 Electron-pair oisplacement ReactionsA. Donation of Electrons to Atoms That Are Not Electron-DeficientB. The Curved-Arrow Notation for Electron-Pair Displacement Reactions
3.3 Review of the Curued-Arrow NotationA. Use of the Curved-Arrow Notation to Represent ReactionsB. Use of the Curved-Arrow Notation to Derive Resonance Structures
3.4 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 Reactions
3.5 Free Energy and Chemical Equilibrium3.6 Relationship of Structure to Acidity
A. The Element EffectB. The Charge EffectC. The Polar Effect
Key ldeas in Chapter 3Additional Problems
INTRODUGTION TO AIKENES.STRUCTURE AND REACTIVITY
CONTENTS iX
909091
949494
959698
101103104
106
108108110lll
116117
122
4"1 Structure and Bonding in RfkenesA. Carbon Hybridization in AlkenesB. The n- (Pi) BondC. Double-Bond Stereoisomers
4.2 Nomenclature of AlkenesA. IUPAC Substitutive NomenclatureB. Nomenclature of Double-Bond Stereoisomers: The E,Z Svstem
4.3 Unsaturation Humber4.4 Phy$ical Propefties of Alkenes4.5 Relative $tabilities of Allcene lsomers
A. Heats of FormationB. Relative Stabilities of Alkene Isomers
4.5 Additisn Reactions of Alkenes4"7 Addition of Hydrcgen Halides to nlilrenas
A. Regioselectivity of Hydrogen Halide AdditionB. Carbocation Intermediates in Hydrogen Halide Addition
122r23r25128
131131t34
139
140
141I4Ir44
147
147148r49
CONTENTS
4.8
4.9
C. Structure and Stability of CarbocationsD. Carbocation Rearrangement in Hydrogen Halide Addition
Reaction RatesA. The Transition StateB. The Energy BarrierC. Multistep Reactions and the Rate-Limiting StepD. Hammond's Postulate
catalysisA. Catalytic Hydrogenation of AlkenesB. Hydration of AlkenesC. Enzyme Catalysis
Key ldeas in Chapter 4Additional Problems
151r54
157158160r62r64
166168r69172
172174
1785 ADDITION REACTIONS OF ALKENES
5.1
5.2
5.3
5.4
5.5
5.6
An Overuiew of Electrophilic Addition Reactions
Reactions of Alkenes with HalogensA. Addition of Chlorine and BromineB. Halohydrins
writing organic Reactions
Gonverion of Alkenes into AlcoholsA. Oxymercuration-Reduction of AlkenesB. Hydroboration-Oxidation of AlkenesC. Comparison of Methods for the Synthesis of Alcohols from Alkenes
Ozonolysis of Alkenes
Free-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 Energies
5.7 Polymeni: Free-Radical Polymerization of Alkenes
5.8 Alkenes in the Ghemical lndustry
Key ldeas in Chapter 5Additional Problems
178
181181183
186
187r87190194
196
20020020r202207zrl
214
216
219220
6 PRINCIPLES OF STEREOCHEMISTRY
CONTENTS xl
226
7
6.1 Enantiomelri, Chirality, and SymmetryA. Enantiomers and ChiralityB. Asymmetric Carbon and StereocentersC. Chirality and Symmetry
6.2 Nomenclature of Enantiomers: The R,S System
6.3 Physical Properties of Enantiomers: Optical ActivityA. Polarized LightB. Optical ActivityC. Optical Activities of Enantiomers
6.4 Racemates
5.5 Stereochemical Correlation
6.6 Diastereomers
6.7 Meso Compounds
6.8 Enantiomeric Resolution
6.9 Ghiral Molecules without Asymmetric Atoms
6.10 Conformational StereoisomersA. Stereoisomers Interconvefied by Internal RotationsB. Asymmetric Nitrogen: Amine Inversion
6,17 Drawing Structures That ContainThree-Dimensional lnformation
6.12 The Postulation of Tetrahedral Carbon
Key ldeas in Chapter 6Additional Problems
cYcHc coMPouNDs.STEREOCHEMISTRY OF REACTIONS
226226229229
231
234235235238
239
241
242
246
249
251
253253255
257
2s9
263253
268
7.1 Relative Stabilities of the Monocyclic Alkanes7.2 Conformations of Gyclohexane
A. The Chair ConformationB. Interconversion of Chair ConformationsC. Boat and Twist-Boat Conformations
268
269269273274
xtl CONTENTS
7.3
7.4
7,5
7.6
7.7
7.8
7.9
INTRODUCTION TO ATKYL HAIIDES, ALCOHOLS,ETHERS, THIOLS, AND SUTFIDES
Monosubstituted Gyclohexalres. Gonformational Rnalysis
Disu bstituted GyclohexanesA. Cis-Trans Isomerism in Disubstituted CyclohexanesB. Conformational AnalysisC. Use of Planar Structures for Cyclic CompoundsD. Stereochemical Consequences of the Chair Interconversion
Gyclopentar€, Gyclobutane, and GyclopropaneA. CyclopentaneB. Cyclobutane and Cyclopropane
Bicyclic and Polycyclic GompoundsA. Classification and NomenclatureB. Cis and Trans Ring FusionC. Trans-Cycloalkenes and Bredt's RuleD. Steroids
Relative Reactivities of StereoisomersA. Relative Reactivities of EnantiomersB. Relative Reactivities of Diastereomers
Reactions That Form StereoisomersA. Reactions of Achiral Compounds That Give Enantiomeric ProductsB. Reactions That Give Diastereomeric Products
Stereochemistry of Ghemical ReactionsA. Stereochemistry of Addition ReactionsB. Stereochemistry of Substitution ReactionsC. Stereochemistry of Bromine AdditionD. Stereochemistry of Hydroboration-OxidationE. Stereochemistry of Other Addition Reactions
Key ldeas in Chapter 7Additional Problems
277
281281283284285
288288289
290290292294296
298298300
301301304
30530s306308312313
314316
323I8.1 Nomenclature
A. Nomenclature of Alkyl HalidesB. Nomenclature of Alcohols and ThiolsC. Nomenclature of Ethers and Sulfides
8.2 Structures
8.3 Effect of Molecular Polarity andHydrogen Bonding on Physical PropertiesA. Boiling Points of Ethers and Alkyl Halides
324324326330
332
333333
CONTENTS XI II
9
B. Boiling Points of AlcoholsC. Hydrogen Bonding
8,4 Solvents in Organic ChemistryA. Classification of SolventsB. Solubility
8,5 Application$ of Solubility and Solvation principle$A. Cell Membranes and Drug SolubilityB. Cation-Binding Molecules
8,6 Acidity of Alcohols and ThiolsA. Formation of Alkoxides and MercaptidesB. Polar Effects on Alcohol AcidityC. Role of the Solvent in Alcohol Acidity
8.7 Bssicity of Alcohols and Ethers
8.8 Grignard and Organolithium ReagentsA. Formation of Grignard and Organolithium ReagentsB. Protonolysis of Grignard and Organolithium Reagents
8.9 Industrial Prepsration and Use ofAlkyl Halides, Alcohols, and EthersA. Free-Radical Halogenation of AlkanesB. Uses of Halogen-Containing CompoundsC. Production and Use of Alcohols and EthersD. Safety Hazards of Ethers
Key ldeas in Chapter Il\dditional Problems
THE CHEMISTRY OF ALKYL HALIDES
335336
339339340
346346351
3S5356358358
359
361361362
3643643653683tl
372373
377
9.1 An Overview of ruucleophilic Substitutionand p-Elimination ReactionsA. Nucleophilic Substitution ReactionsB. B-Elimination ReactionsC. Competition between Nucleophilic Substitution and B-Elimination Reactions
9.2 Equilibria in tUucleophilic Substitution Reactaons
9.3 Reaction RatesA. Definition of Reaction RateB. The Rate LawC. Relationship of the Rate Constant to the Standard Free Energy of Activation
9.4 The S*2 ReactionA. Rate Law and Mechanism of the S*2 Reaction
377377378380
381
382382383384
385386
XIV CONTENTS
B. Comparison of the Rates of S*2 Reactions and Bronsted Acid-Base ReactionsC. Stereochemistry of the S*2 ReactionD. Effect of Alkyl Halide Structure on the S0.2 ReactionE. Nucleophilicity in the S*2 ReactionF. Leaving-Group Effects in the S*2 ReactionG. Summary of the S*2 Reaction
9.5 The E2 ReactionA. Rate Law and Mechanism of theE2 ReactionB. Why theE2 Reaction Is ConcertedC. Leaving-Group Effects on the E2 ReactionD. Deuterium Isotope Effects in the E2 ReactionE. Stereochemistry of the E2 ReactionF. Regioselectivity of the E2 ReactionG. Competition between theE2 and S,o2 Reactions: A Closer LookH. Summary of the E2 Reaction
9.5 The S*1 and El ReactionsA. Rate Law and Mechanism of S*1 and El ReactionsB. Rate-Limiting and Product-Determining StepsC. Reactivity and Product Distributions in S*1-E1 ReactionsD. Stereochemistry of the S"l ReactionE. Summary of the S*l and El Reactions
9.7 Summary of Substitution and EliminationReactions of Alkyl Halides
9.8 Carbenes and CarbenoidsA. a-Elimination ReactionsB. The Simmons-Smith Reaction
Key ldeas in Chapter 9Additional Problems
10 THE CHEMISTRY OF AICOHOIS AND THIOTS
388388390392398399
4004004004024024044064074tl
4124124t44t6418420
429
424424426
428429
436
10.1 Dehydration of Alcohols
1O.2 Reactions of Alcohols with Hydrogen Halides
10.3 Sulfonate and Inorganic Ester Derivatives of AlcoholsA. Sulfonate Ester Derivatives of AlcoholsB. Alkylating AgentsC. Ester Derivatives of Strong Inorganic AcidsD. Reactions of Alcohols with Thionyl Chloride and Phosphorus Tribromide
1O.4 Conversion of Alcohols intoAlkyl Halides: Summary
435
440
443443447448449
450
11
10.5 Oxidation and Reduction in Organic GhemistryA. Half-Reactions and Oxidation NumbersB. Oxidizing and Reducing Agents
10.6 Oxidation of AlcoholsA. Oxidation to Aldehydes and KetonesB. Oxidation to Carboxylic Acids
1O"7 Biological Oxidation of Ethanol
10.8 Chemlcal and Stereochemical Grcup RelationshipsA. Chemical Equivalence and NonequivalenceB. Stereochemistry of the Alcohol Dehydrogenase Reaction
10.9 Oxidation of Thiols
1O.1O $ynthesis of Alcohols
10.11 Desigil of Organic Synthesis
Key ldeas in Chapter 10Additional Problems
THE CHEMISTRY OF ETHERS, EPOXIDES,GLYGOLS, AND SULFIDES
CONTENTS XV
452452156
45945946r
462
465465469
471
474
474
476477
482
11.'l Synthesis of Ethers and SulfidesA. Williamson Ether SynthesisB. Alkoxymercuration-Reduction of AlkenesC. Ethers from Alcohol Dehydration and Alkene Addition
11,2 Synthesis of EpoxidesA. Oxidation of Alkenes with Peroxycarboxylic AcidsB. Cyclization of Halohydrins
11.3 Gleavage of Ethers
11.4 Nucleophilic Substitutioil Reactisns of EpoxidesA. Ring-Opening Reactions under Basic ConditionsB. Ring-Opening Reactions under Acidic ConditionsC. Reaction of Epoxides with Organometallic Reagents
11.5 Preparation and Oxldative Cleavage of GlycolsA. Preparation of GlycolsB. Oxidative Cleavage of Glycols
11.5 oxonium and sulfonium saltsA. Reactions of Oxonium and Sulfonium SaltsB. S-Adenosylmethionine: Nature's Methylating Agent
482482484485
48848849r
492
495495497500
503503s06
508508509
xvl CONTENTS
11.7 tntramolecular Reactlons and the Proximity EffectA. Neighboring-Group ParticipationB. The Proximity Effect and Effective MolarityC. Stereochemical Consequences of Neighboring-Group Participation
11.8 Oxidation of Ethers and Sulfides
11.9 The Three Fundamental Operations of Organic Synthesis11.10 Synthesis of Enantiomerically pure Compounds:
Asymmetric Epoxidation
Key ldeas in chapter 11Additional Problems
ITUTRODUCTION TO SPECTROSCOPY. INFRAREDSPECTROSCOPY AND MASS SPECTROMETRY12
5r05r05135r6
518
520
5e2
5?7s?8
s36
12,1 Introduction to SpectroscopyA. Electromagnetic RadiationB. Absorption Spectroscopy
12.2 lnfrared SpectroscopyA. The Inf-rared SpectrumB. Physical Basis of IR Spectroscopy
12.3 lnfrared Absorption and Chemical StructureA. Factors That Determine IR Absorption PositionB. Factors That Determine IR Absorption Intensity
12.4 Functional-Group Infrared AbsorptionsA. IR Spectra of AlkanesB. IR Spectra of Alkyl HalidesC. IR Spectra of AlkenesD. IR Spectra of Alcohols and Ethers
12.5 Obtaining an Infrared Spectrum12.6 lntroduction to Mass Spectrometry
A. Electron-Impact Mass SpectraB. Isotopic PeaksC. FragmentationD. The Molecular Ion. Chemical-Ionization Mass SpectraE. The Mass Spectrometer
Key ldeas in Chapter 12Additional Problems
536536538
54054054?
544545548
5525s2552553556
557
558558560563566569
571571
CONTENTS XVI I
13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 578
13.1 An Overview of Proton NMR Spectroscopy
13.2 physlcal Basls of NMR spectroscopy
13.3 The NMR Spectrum: Ghemlcal Shift and htegralA. Chemical ShiftB. Chemical Shift ScalesC. Relationship of Chemical Shift to StructureD. The Number of Absorptions in an NMR SpectrumE. Counting Protons with the IntegralF. Using the Chemical Shift and Integral to Determine Unknown Structures
13.4 The NMR Spectrum: spin-spln spllttingA. The n * 1 Splitting RuleB. Why Splitting OccursC. Solving Unknown Structures with NMR Spectra Involving Splitting
13.5 Complex NMR SpecffaA. Multiplicative SplittingB. Breakdown of the n * I Rule
13.6 Use of Deuterlum in Proton NMR
13.7 Characterlstic Functlonal-Group NMR AbsorptionsA. NMR SPectra of AlkenesB. NMR Spectra of Alkanes and CycloalkanesC. NMR Spectra of Alkyl Halides and EthersD. NMR SPectra of Alcohols
13.8 NMR Spectroscopy of Dynamic Systems
13.9 Carbon NMR
13.10 Solving Structure Problems with Spectroscopy
13.11 The NMR Spectrometer
13.12 Other Uses of NMR
Key ldeas in ChaPter 13Additional Problems
14 THE CHEMISTRV OF ATKYNES
578
581
s83583585586589592593
59S596599601
603603607
611
6',12
612614616616
619
629
6e9
639
634
63563S
644
14.1 Nomenclature of AlkYnes
t{.e $tructure and Bonding in Alltynes
644
646
XViii CONTENTS
14.3
14.4
14.5
14.6
14.7
14.9
14.9
14.10
Physical Properties of RlkynesA. Boiling Points and SolubilitiesB. IR Spectroscopy of AlkynesC. NMR Spectroscopy of Alkynes
Introduction to Addition Reactions of the Triple Bond
Conversion of Alkynes into Aldehydes and KetonesA. Hydration of AlkynesB. Hydroboration-Oxidation of Alkynes
Reduction of AlkynesA. Catalytic Hydrogenation of AlkynesB. Reduction of Alkynes with Sodium in Liquid Ammonia
Acidity of l-AlkynesA. Acetylenic AnionsB. Acetylenic Anions as Nucleophiles
Organic Synthesis Using AlkynesPheromones
Occurrence and Use of Alkynes
Key ldeas in Chapter 14Additional Problems
6496496496s0
5s2
654654657
659659660
662662665
666
668
574
57 1
671
67615 DIENES, RESONANCE, AND AROMATICITY
15.1 Structure and Stability of DienesA. Stability of Conjugated Dienes. Molecular OrbitalsB. Structure of Conjugated DienesC. Structure and Stability of Cumulared Dienes
15.2 Ultraviolet-Visible SpectroscopyA. The UV-Vis SpectrumB. Physical Basis of UV-Vis SpectroscopyC. UV-Vis Spectroscopy of Conjugated Alkenes
15.3 The Diels-Alder ReactionA. Reaction of conjugated Dienes with AlkenesB. Effect of Diene Conformation on the Diels-Alder ReactionC. Stereochemistry of the Diels-Alder Reaction
15.4 Addition of Hydrogen Halides to conjugated DienesA. 1,2- and 1,4-AdditionsB. Allylic Carbocations. The Connection between Resonance and StabilitvC. Kinetic and Thermodynamic Control
677677680682
684684686687
690690694696
700700702705
CONTENTS XIX
15,5 Diene Polymers
15.6 ResonanceA. Drawing Resonance StructuresB. Relative Importance of Resonance StructuresC. Use of Resonance Structures
15.7 Introduction to Aromatic Compound$A. Benzene, aPuzzling 'Alkene"B. Structure of BenzeneC. Stability of BenzeneD. Aromaticity and the Hiickel an | 2 RuleE. Antiaromatic Compounds
Key ldeas in Chapter 15Additional Problems
708
7497t07Ir714
716l1771872172r728
730731
16 THE CHEMISTRY OF BENZENE AND ITS DERIVATIVES 74O
16.1 Nomenclature of Benzene Derivatives
16.2 Physical troperties of Benzene Derivatives
16.3 Spectroscopy of Benzene DerivativesA. IR SPectroscoPyB. NMR Spectroscopyc. r3C NMR spectroscopyD. UV Spectroscopy
16.4 Electrophilic Aromatic Substitution Reactions of BenzeneA. Halogenation of BenzeneB. Electrophilic Aromatic SubstitutionC. Nitration of BenzeneD. Sulfonation of BenzeneE. Friedel-Crafts Alkylation of BenzeneF. Friedel-Crafts Acylation of Benzene
16.5 Electrophilicaromatic Substitution Reactionsof Substituted BenzenesA. Directing Effects of SubstituentsB. Activating and Deactivating Effects of SubstituentsC. Use of Electrophilic Aromatic Substitution in Organic Synthesis
16.6 Hydrogenation of Benzene Derivatives
15.7 source and lndustrial Use of Aromatic ttydrocarbons
rey ldeas in ChaPter t6Additional Problems
744
743
743143744748748
75075r753754755756759
762762768772
776
777
780780
XX CO NTE NTS
17 ALTYLIG AND BENZYLIG REAGTIVITY 788
17.1 Reactions tnvolvlng Allylic and Benzyllc Carbocations17.2 Reactions lnvolvlng Allyllc and Benzylic Radicals17.3 Reactions tnvolvlng Allylic and Benzyllc Anions
A. Allylic Grignard ReagentsB. E2 Eliminations Involving Allylic or Benzylic Hydrogens
17.4 Allyllc and Benzylic Sn2 Reactions
17.s Allyllc and Benzylic OxidationA. Oxidation of Allylic and Benzylic AlcoholsB. Benzylic Oxidation of Alkylbenzenes
17.6 TerpenesA. The Isoprene RuleB. Biosynthesis of Terpenes
Key ldeas in chapter 17Additional Problems
789
793
798799801
802
803803805
807807810
813814
18 THE CHEM|STRY OF ARYL HAL|DES, VtNyLtc HALIDES,AND PHENOLS. TRANSITION.METAL CATALYSIS 822
18.1 Lack of Reactivity of vinylic and Aryl Halidesunder SNz Gonditlons
18.2 Elimination Reactions of vinylic Halides
18.3 Lack of Reactivlty of Vinylic andAryl Halldes under SNI Gonditions
18.4 NucleophilicAromatic substitutionReactions of Aryl Halides
18,5 Introduction to Transition-Metal Catalyzed ReactionsA. Transition Metals and Their ComplexesB. Oxidation StateC. The d'NotationD. Electron Counting: The 16- and lS-Electron RulesE. Fundamental Reactions of Transition-Metal Complexes
18-6 Examples ofTransition-Metal-Catalyzed ReactionsA. The Heck ReactionB. The Suzuki Coupling
8?3
825
826
828
831832835836836839
845845848
19
C. Alkene MetathesisD. Other Examples of Transition-Metal-Catalyzed Reactions
18.7 Acidity of PhenolsA. Resonance and Polar Effects on the Acidity of PhenolsB. Formation and Use of Phenoxides
18.8 Oxidation of Phenols to Quinones
18.9 Electrophillc eromatic Substitution Reactions of Phenols
18.10 Reactivity of the Aryl-oxygen BondA. Lack of Reactivity of the Aryl-Oxygen Bond in S*l and S*2 ReactionsB. Substitution at the Aryl-Oxygen Bond: The Stille Reaction
18.11 hdustrial Preparation and Use of Phenol
Key ldeas in Chapter 18Additional Problems
THE GHEMISTRY OF ALDEHYDES AND KETONES.CARBONYT.ADDITION REACTIONS
CONTENTS XXi
852857
858858861
862
867
870870872
874
875876
888
19.1 Nomenclature of Aldehydes and KetonesA. Common NomenclatureB. Substitutive Nomenclature
19.2 Physical Properties of Aldehydes and Ketones
19.3 Spectroscopy of Aldehydes and KetonesA. IR SpectroscopyB. Proton NMR SpectroscopyC. Carbon NMR SpectroscopyD. UV SpectroscopyE. Mass Spectrometry
19.4 Synthesis of Aldehydes and Ketones
19.5 htroduction to Aldehyde and Ketone Reactions
19.6 Basicity of Aldehydes and Ketones
19.7 Reversible Rddition Reactions of Aldehydes and KetonesA. Mechanisms of Carbonyl-Addition ReactionsB. Equilibria in Carbonyl-Addition ReactionsC. Rates of Carbonyl-Addition Reactions
19.8 Reduction of Aldehydes and Ketones to Alcohols
890890892
894
895895897898899901
903
903
904
997907910913
914
xxii coNrENrs
1g.g
19.10
19.11
19,12
19.13
19,14
19.15
Reactions of Aldehydes and Ketones withGrignard and Related Reagents
Acetals and Their Use as Protecting GroupsA. Preparation and Hydrolysis of AcetalsB. Protecting Groups
Reactions of Aldehydes and Ketones with AminesA. Reaction with Primary Amines and Other Monosubstituted
Derivatives of AmmoniaB. Reaction with Secondary Amines
Reduction of carbonyl Groups to Methylene Groups
The Wittig Alkene SynthesisOxidation of Aldehydes to Carboxylic AcidsManufacture and use of Aldehydes and Ketones
Key ldeas in Chapter 19Additional Problems
918
921921925
926
926929
931
933
936
938
93e940
94820 THE CHEMISTRY OF CARBOXYLIC ACIDS
20.1
20.2
20.3
2A,4
20.5
20,6
20.7
20.9
Nomenclature of Carboxylic RcidsA. Common NomenclatureB. Substitutive Nomenclature
Structure and Physical Properties of Carboxylic Rcids
Spectroscopy of Carboxylic RcidsA. IR SpectroscopyB. NMR Spectroscopy
Acid-Base Properties of Garboxylic RcidsA. Acidity of Carboxylic and Sulfonic AcidsB. Basicity of Carboxylic Acids
Fatty Acids, Soaps, and DetergentsSynthesis of Carboxylic Rcids
lntroduction to carboxylic Rcid Reactions
Gonversion of carboxylic Rcids into EstersA. Acid-Cataly zed Esterifi cationB. Esterification by Alkylation
948948951
953
955955955
957957960
960
963
964
965965968
20.9 Gonversion of Carboxylic Acids into AcidChlorides and AnhydridesA. Synthesis of Acid ChloridesB. Synthesis of Anhydrides
20.10 Reduction of Garboxylic Acids to Primary Alcohols
2O.11 Decarboxylation of Garboxylic Acids
Key ldeas in Chapter 20Additional Problems
CONTENTS XXI I I
9IO970972
974
976
978979
21 THE CHEMISTRY OF GARBOXYTIC AGID DERIVATIVES 986
21.1 Nomenclature and Glassificationof Carboxylic Acid DerivativesA. Esters and LactonesB. Acid HalidesC. AnhydridesD. NitrilesE. Amides, Lactams, and ImidesF. Nomenclature of Substituent GroupsG. Carbonic Acid Derivatives
21.2 Structures of Carboxylic Acid Derivatives
21.3 Physical Propefties of Carboxylic Acid DerivativesA. EstersB. Anhvdrides and Acid ChloridesC. NitrilesD. Amides
21.4 Spectroscopy of Carboxylic Rcid DerivativesA. IR SpectroscopyB. NMR Spectroscopy
21.5 Basicity of Garboxylic Acid Derivatives
21.6 Introduction to the Reactions of carboxylic Acid
21,7 llydrolysis of Carboxylic Acid Derivatives
Derivatives 1003
98698698898898998999r99r
992
99499499499599s
996996997
1000
10041004I 008r 0091011101 1
A. Hydrolysis of EstersB. Hydrolysis of AmidesC. Hydrolysis of NitrilesD. Hydrolysis of Acid Chlorides and AnhydridesE. Mechanisms and Reactivity in Nucleophilic Acyl Substitution Reactions
XX|V CoNTENTS
22
21.8 Reactions of Carboxylic ncidDerivatives with NucleophilesA. Reactions of Acid Chlorides with NucleophilesB. Reactions of Anhydrides with NucleophilesC. Reactions of Esters with Nucleophiles
21.9 Reduction of Garboxylic Acid DerivativesA. Reduction of Esters to Primary AlcoholsB. Reduction of Amides to Amines
s ftt*:ti:t :i xt#nffiT?:*il'ffT*'/
E. Relative Reactivities of Carbonyl Compounds
21 10 ffifiit?ll ""ff:[3fr]['il:#?$,3"'iva*vesA. Reaction of Esters with Grignard ReagentsB. Reaction of Acid Chlorides with Lithium Dialkylcuprates
21.11 Synthesis of Carboxylic Acid Derivatives21 12
Hi':11 lfilll'ffi "'**iTlox'r i c
A. Nylon and PolyestersB. Waxes, Fats, and Phospholipids
ffi1,iff::,.;':[il;T"
THE CHEMISTRY OF ENOTATE IONS, ENOLS,AND a,B-UNSATURATED CARBONYL GOMPOUNDS
101610161019I 020
1022t0221 023I 025t02l1 028
'1o29r029103 l
1032
10341 031l 036
1 0371 038
1047
22.1 Acidity of Garbonyl CompoundsA. Formation of Enolate AnionsB. Introduction to Reactions of Enolate Ions
22.2 Enolization of Carbonyl Compounds
22.3 orHalogenation of Carbonyl CompoundsA. Acid-Catalyzed a-HalogenationB. Halogenation of Aldehydes and Ketones in Base: The Haloform ReactionC. a-Bromination of Carboxylic AcidsD. Reactions of a-Halo Carbonyl Compounds
22.4 Aldol Addition and Aldol GondensationA. Base-Catalyzed Aldol ReactionsB. Acid-Catalyzed Aldol CondensationC. Special Types of Aldol ReactionsD. Synthesis with the Aldol Condensation
1048r 048105 1
1053
1057l 0571 0591060r062
1063I 0631066r067I 070
CONTENTS XXV
23
22.5 Gondensation Reactions |nvolving Ester Enolate lonsA. Claisen CondensationB. Dieckmann CondensationC. Crossed Claisen CondensationD. Synthesis with the Claisen Condensation
22.6 Biosynthesis of Fatty Acids
22,7 Alkylation of Ester Enolate lonsA. Malonic Ester SynthesisB. Direct Alkylation of Enolate Ions Derived from MonoestersC. Acetoacetic Ester Synthesis
22.8 Conjugate-Addition ReactionsA. Conjugate Addition to a,B-Unsaturated Carbonyl CompoundsB. Conjugate Addition Reactions versus Carbonyl-Group ReactionsC. Conjugate Addition of Enolate Ions
22.9 Reduction of n,F-Unsaturated Carbonyl Gompounds
22.10 Reactions of c,F-Unsaturated GarbonylCompounds with Organometallic ReagentsA. Addition of Organolithium Reagents to the Carbonyl GroupB. Conjugate Addition of Lithium Dialkylcuprate Reagents
22.11 Organic Synthesis with Conjugate-Addition Reactions
Key ldeas in Chapter 22Additional Problems
THE CHEMISTRY OF AMINES
10721012r07 6r07 61 078
1081
1084I 0841 086I 089
1492r092I 095t091
1 100
1 1011101I 102
1 103
1 1051146
1116
23.1 Nomenclature of AminesA. Common NomenclatureB. Substitutive Nomenclature
23.2 Structure of Amines
23.3 Physical Properties of Amines
23.4 Spectroscopy of AminesA. IR SpectroscopyB. NMR Spectroscopy
23.5 Basicity and Acidity of AminesA. Basicity of AminesB. Substituent Effects on Amine BasicityC. Separations Using Amine BasicityD. Acidity of AminesE. Summary of Aciditv and Basicity
1117IttTtln
1119
1124
1127ttzlttzl
1122tt22tt231 t271 128rr29
XXVI CoNTENTS
24
23.6 Quaternary Ammonium and Phosphonium Salts
23.7 Alltylation and Acylation Reactions of RminesA. Direct Alkvlation of AminesB. Reductive AminationC. Acylation of Amines
23.8 Hofmann Elimination of Quaternary Ammonium Hydroxides 1136
23.9 Aromatic Substitution Reactions of Aniline Derivatives23.10 Diazotization; Reactions of Diazonium lons
A. Formation and Substitution Reactions of Diazonium SaltsB. Aromatic Substitution with Diazonium IonsC. Reactions of Secondary and Tertiary Amines with Nitrous Acid
23.11 Synthesis of AminesA. Gabriel Synthesis of Primary AminesB. Reduction of Nitro CompoundsC. Amination of Aryl Halides and Aryl TriflatesD. Curtius and Hofmann RearrangementsE. Synthesis of Amines: Summary
23.12 Use and Occurrence of AminesA. Industrial Use of Amines and AmmoniaB. Naturally Occurring Amines
Key ldeas in Chapter 23Additional Problems
CARBOHYDRATES
1 138
11391 139Ir42II44
1145tr45t146tr47I 150lt54
11551 155I 155
11571158
1156
1129
113111311 1331 135
24,1 Glassification and Properties of Carbohydrates24.2 FischerProiections24.3 Structures of the Monosaccharides
A. Stereochemistry and Confi gurationB. Cyclic Structures of the Monosaccharides
24.4 Mutarotation of Garbohydrates
24.5 Base-Catalyzed lsomerization of Aldoses and Ketoses
24.6 Glycosides
24.7 Ether and Ester Derivatives of Garbohydrates24.8 Oxidation and Reduction Reactions of Carbohydrates
A. Oxidation to Aldonic Acids
1167
1168
1173tt731178
1183
1186
1188
1191
1193tt94
B. Oxidation to Aldaric AcidsC. Periodate OxidationD. Reduction to Alditols
24.9 Kiliani-Fischer Synthesis
24.10 Proof of Glucose StereochemistryA. Which Diastereomer? The Fischer ProofB. Which Enantiomer? The Absolute Configuration of n-(+)-Glucose
24.11 Disaccharides and Polysaf,charidesA. DisaccharidesB. Polysaccharides
Key ldeas in Chapter 24Additional Problems
CONTENTS XXVI I
1 1951 196rr97
r 198
11991199r203
12051205r209
12121213
25 THE CHEMISTRY OF THE AROMATIC HETEROGYCTES 1220
25.1 Nomenclature and Structure of the Aromatic HeterocyclesA. NomenclatureB. Structure and Aromaticity
25.2 Sasicity and Acidity of the Nitrogen HeterocyclesA. Basicity of the Nitrogen HeterocyclesB. Acidity of Pyrrole and Indole
25.3 The Chemistry of Furan, Pyrrolq and ThiopheneA. Electrophilic Aromatic SubstitutionB. Addition Reactions of FuranC. Side-Chain Reactions
25.4 The chemistry of eyridineA. Electrophilic Aromatic SubstitutionB. Nucleophilic Aromatic SubstitutionC. N-Alkylpyridinium Salts and Their ReactionsD. Side-Chain Reactions of Pyridine DerivativesE. Pyridinium Ions in Biology: Pyridoxal Phosphate
25.5 tuucleosides, Nucleotides, and Nucleic AcidsA. Nucleosides and NucleotidesB. The Structures of DNA and RNAC. DNA Modification and Chemical Carcinogenesis
25.6 Other Biologically lmportant Heterocyclic Compounds
Key ldeas in Chapter 25Additional Problem$
1220r220r22l
12241224r226
1226t226r229r230
1231I23Tt2341238r239r240
1245t245t248t253
r 255
1?571 258
xxviii coNrENrs
26 AMINO ACIDS, PEPTIDES, AND PROTEINS 1255
26.1 Nomenclature of Amino Acids and PeptidesA. Nomenclature of Amino AcidsB. Nomenclature of Peptides
26.2 Stereochemistry of the rAffiiro Acids
26.3 Acid-Base Properties of Amino Acids and PeptidesA. Zwitterionic Structures of Amino Acids and PeptidesB. Isoelectric Points of Amino Acids and PeptidesC. Separations of Amino Acids and Peptides Using Acid-Base Properties
26.4 Synthesis and Enantiomeric Resolution of a-Ami]ro AcidsA. Alkylation of AmmoniaB. Alkylation of Aminomalonate DerivativesC. Strecker SynthesisD. Enantiomeric Resolution of a-Amino Acids
26.5 Acylation and Esterification Reactions of Amino Acids
26.6 Solid-PhasePeptideSynthesis26.7 Hydrolysis of Peptides
A. Complete Hydrolysis and Amino Acid AnalysisB. Enzyme-C ataly zed Peptide Hydrolysis
26.8 Primary Structure of Peptides and ProteinsA. Peptide Sequencing by Mass SpectrometryB. Peptide Sequencing by the Edman DegradationC. Protein SequencingD. Posttranslational Modification of Proteins
26.9 Higher-Order Structures of ProteinsA. Secondary StructureB. Tertiary and Quaternary Structure
26.10 Enzymes: Biological CatalystsA. The Catalytic Action of EnzymesB. Enzymes as Drug Targets: Enzyme Inhibition
Key ldeas in Chapter 26Additional Problems
PERICYCLIC REACTIONS
1266r266t267
1270
1271r27 |t273r271
127912791279I 280128 I
1282
r 283
129?^r2921295
1296r299I 303I 3051 305
1 308I 3081310
131 513151318
1 3231324
133327
27.1 Molecular Orbitals of Gonjugated rrElectron SystemsA. Molecular Orbitals of Conjugated Alkenes
1 336I 336
B. Molecular Orbitals of Conjugated Ions and RadicalsC. Excited States
27.2 Electrocyclic ReactionsA. Ground-State (Thermal) Electrocyclic ReactionsB. Excited-State (Photochemical) Electrocyclic ReactionsC. Selection Rules and Microscopic Reversibility
27.3 Cycloaddition Reactions
27.4 Thermal Sigmatropic Reaction$A. Classiflcation and StereochemistryB. Thermal [3,3] Sigmatropic ReactionsC. Summary: Selection Rules for Thermal Sigmatropic Reactions
27.5 Fluxional Molecules
27.6 Biological Pericyclic Reactions:The Formation of Vitamin D
Key ldeas in Chapter 27Additional Prohlems
coNrENrs xxix
I 3401343
13431343r346t317
1349
1 3S31353I 360t362
1364
1365
13671 368
A-1APPENDIGES
Appendix l.Appendix ll.
Appendix lll.
APPENDIX IV.
ITPPENDIX V.
Substitutive Nomenclature of Organic Gompounds
lnfrared Absorptions of Organic Compounds
Proton NMR Chemical Shifts in Organic CompoundsA. Protons within Functional GroupsB. Protons Adjacent to Functional Groups
t3C NMR Chemical Shifts in Organic GompoundsA. Chemical Shifts of Carbons within Functional GroupsB. Chemical Shifts of Carbons Adjacent to Functional Groups
Summary of Synthetic Method$A. Synthesis of Alkanes and Aromatic HydrocarbonsB. Synthesis of AlkenesC. Synthesis of AlkynesD. Synthesis of Alkyl, Aryl, and Vinylic HalidesE. Synthesis of Grignard Reagents and Related Organometallic CompoundsF. Synthesis of Alcohols and PhenolsG. Synthesis of GlycolsH. Synthesis of Ethers, Acetals, and SulfidesI. Synthesis of EpoxidesJ. Synthesis of Disulfides
A-1
A-2
A'5A-5A-5
A-7A-lA-1
A-gA-8A-9A-9A-9A-9
A-10A-10A- 10A-10A-10
xxx loNrENrs
K. Synthesis of AldehydesL. Synthesis of KetonesM. Synthesis of Sulfoxides and SulfonesN. Synthesis of Carboxylic and Sulfonic AcidsO. Synthesis of EstersP. Synthesis of AnhydridesQ. Synthesis of Acid ChloridesR. Synthesis of AmidesS. Synthesis of NitrilesT. Synthesis of AminesU. Synthesis of Nimo Compounds
Reactions Used to Form Garbon-Carbon Bonds
A. Acidities of Groups That Ionize to Give Anionic Conjugate BasesB. Basicities of Groups That Protonate to Give Cationic Conjugate Acids
CreditsIndex
A-11A-11A-11A-11A-T2A-T2A-t2A-12A-t2A.T2A-13
A-13APPENDIXVI.
APPENDIXVII. Typlcal Aclditles and Baslcltles of OGanlc Functlonal Groups A-14A-14A-15
c-1l-1