CONTENTS 11-10 Integration of H NMR Absorptions:Proton Counting 370 11-1 Spin-Spin Splitting in H NMR Spectra 112 More Complex Spin-Spin Splitting Patterns 1-13 Uses of H NMR Spectroscopy 3 SOMETHING EXTRA Magnetic Resonance Imaging (MRI) 380 Organohalides:Nucleophilic Substitutions and Eliminations 382 121 Names and Structures of Alkyl Halides 383 12-2 Preparing Alkyl Halides from Alkenes:Allylic Bromination 385 12-3 Preparing Alkyl Halides from Alcohols 390 12-4 Reactions of Alkyl Halides:Grignard Reagents 391 12-5 Organometallic Coupling Reactions 393 12-6 Discovery of the Nucleophilic Substitution Reaction 395 12-7 The SN2 Reaction 3 12-8 Characteristics of the SN2 Reactior 401 12.9 The sNl Reaction 408 12-10 Characteristics of the SN1 Reaction 412 12-11 Biological Substitution Reactions 12-12 Elimination Reactions:Zaitsev's Rule 420 12-13 The E2 Reaction and the Deuterium Isotope Effect 422 12.14 The El and ElcB Reactions 12-15 Biological Elimination Reactions 428 12-16 A Summary of Reactivity:SN1,SN2,E1,EIcB,and E2 429 SoMETHING EXTRA Naturally Occurring Organohalides 430 3 Alcohols,Phenols,and Thiols; Ethers and Sulfides 435 131 Naming Alcohols,Phenols,and Thiols 13-2 Properties of Alcohols,Phenols,and Thiols 4 13-3 Preparing Alcohols from Carbonyl Compounds 43 13.4 Reactions of alcohols 4 13-5 Oxidation of Alcohols and Phenols 456
Contents xi 11-10 integration of 1 h nMR absorptions: proton counting 370 11-11 spin–spin splitting in 1 h nMR spectra 371 11-12 More complex spin–spin splitting patterns 376 11-13 Uses of 1 h nMR spectroscopy 379 soMetHinG eXtra Magnetic Resonance imaging (MRi) 380 12 organohalides: nucleophilic substitutions and eliminations | 382 12-1 names and structures of alkyl halides 383 12-2 preparing alkyl halides from alkenes: allylic Bromination 385 12-3 preparing alkyl halides from alcohols 390 12-4 Reactions of alkyl halides: grignard Reagents 391 12-5 organometallic coupling Reactions 393 12-6 Discovery of the nucleophilic substitution Reaction 395 12-7 the sn2 Reaction 398 12-8 characteristics of the sn2 Reaction 401 12-9 the sn1 Reaction 408 12-10 characteristics of the sn1 Reaction 412 12-11 Biological substitution Reactions 418 12-12 Elimination Reactions: Zaitsev’s Rule 420 12-13 the E2 Reaction and the Deuterium isotope Effect 422 12-14 the E1 and E1cB Reactions 427 12-15 Biological Elimination Reactions 428 12-16 a summary of Reactivity: sn1, sn2, E1, E1cB, and E2 429 soMetHinG eXtra naturally occurring organohalides 430 13 alcohols, Phenols, and thiols; ethers and sulfides | 435 13-1 naming alcohols, phenols, and thiols 437 13-2 properties of alcohols, phenols, and thiols 439 13-3 preparing alcohols from carbonyl compounds 443 13-4 Reactions of alcohols 452 13-5 oxidation of alcohols and phenols 456 42912_00_FM_i-xxiv.indd 11 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
i DETAILED CONTENTS 13.6 Protection of Alcohols 13-7 Preparation and Reactions of Thiols 13-8 Ethers and Sulfides 64 13-9 Preparing Ethers 4 13-10 Reactions of Ethers 4 13-11 Crown Ethers and lonophores 472 13.12 Preparation and Reactions of Sulfides 47 13-13 Spectroscopy of Alcohols,Phenols,and Ethers 75 SOMETHING EXTRA Ethanol:Chemical,Drug,Poison 78 A Preview of Carbonyl Chemistry 483 Kinds of Carbonyl Compounds Nature of the Carbonyl Group General Reactions of Carbonyl Compounds Summary 491 4 Aldehydes and Ketones: Nucleophilic Addition Reactions 492 14-1 Naming Aldehydes and Ketones 9 14-2 Preparing Aldehydes and Ketones 14-3 Oxidation of Aldehydes 14.4 Nucleophilic Addition Reactions of Aldehydes and Ketones 497 14-5 Nucleophilic Addition of H2O:Hydration 501 14-6 Nucleophilic Addition of Hydride and Grignard Reagents:Alcohol Formation 14-7 Nucleophilic Addition of Amines:Imine and Enamine Formation 505 14-8 Nucleophilic Addition of Alcohols:Acetal Formation 509 14-9 Nucleophilic Addition of Phosphorus Ylides:The Wittig Reaction 3 14-10 Biological Reductions 14-11 Conjugate Nucleophilic Addition to a,B-Unsaturated Aldehydes and Ketones 518 14.12 Spectroscopy of Aldehydes and Ketones 522 SOMETHING EXTRA Enantioselective Synthesis 526
xii DetaileD Contents 13-6 protection of alcohols 460 13-7 preparation and Reactions of thiols 463 13-8 Ethers and sulfides 464 13-9 preparing Ethers 466 13-10 Reactions of Ethers 467 13-11 crown Ethers and ionophores 472 13-12 preparation and Reactions of sulfides 474 13-13 spectroscopy of alcohols, phenols, and Ethers 475 soMetHinG eXtra Ethanol: chemical, Drug, poison 478 a Preview of Carbonyl Chemistry | 483 i Kinds of carbonyl compounds 483 ii nature of the carbonyl group 485 iii general Reactions of carbonyl compounds 485 iV summary 491 14 aldehydes and Ketones: nucleophilic addition reactions | 492 14-1 naming aldehydes and Ketones 493 14-2 preparing aldehydes and Ketones 495 14-3 oxidation of aldehydes 497 14-4 nucleophilic addition Reactions of aldehydes and Ketones 497 14-5 nucleophilic addition of h2o: hydration 501 14-6 nucleophilic addition of hydride and grignard Reagents: alcohol Formation 503 14-7 nucleophilic addition of amines: imine and Enamine Formation 505 14-8 nucleophilic addition of alcohols: acetal Formation 509 14-9 nucleophilic addition of phosphorus Ylides: the wittig Reaction 513 14-10 Biological Reductions 516 14-11 conjugate nucleophilic addition to a,b-Unsaturated aldehydes and Ketones 518 14-12 spectroscopy of aldehydes and Ketones 522 soMetHinG eXtra Enantioselective synthesis 526 42912_00_FM_i-xxiv.indd 12 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
CONTENTS 5 Carboxylic Acids and Nitriles 530 15.1 Naming Carboxylic Acids and Nitriles 5 15-2 Structure and Properties of Carboxylic Acids 533 153 Biological Acids and the Henderson-Hasselbalch Equation 154 Substituent Effects on Acidity 15-5 Preparing Carboxylic Acids 540 15-6 Reactions of Carboxylic Acids:An Overview 15-7 Chemistry of Nitriles 543 15-8 Spectroscopy of Carboxylic Acids and Nitriles 5 SOMETHING EXTRA Vitamin C 50 16 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions 555 16-1 Naming Carboxylic Acid Derivatives 16-2 Nucleophilic Acyl Substitution Reactions 59 16-3 Reactions of Carboxylic Acids 16-4 Reactions of Acid Halides 90 16-5 Reactions of Acid Anhydrides 576 16-6 Reactions of Esters 167 Reactions of Amides 16-8 Reactions of Thioesters and Acyl Phosphates: Biological Carboxylic Acid Derivatives 587 16-9 Polyamides and Polyesters:Step-Growth Polymers 589 16-10 Spectroscopy of Carboxylic Acid Derivatives 592 SOMETHING EXTRA B-Lactam Antibiotics 594 Carbonyl Alpha-Substitution and Condensation Reactions599 17-1 Keto-Enol Tautomerism %6 17-2 Reactivity of Enols:a-Substitution Reactions 6 17-3 Alpha Bromination of Carboxylic Acids 17-4 Acidity of a Hydrogen Atoms:Enolate lon Formation 607
Contents xiii 15 Carboxylic acids and nitriles | 530 15-1 naming carboxylic acids and nitriles 531 15-2 structure and properties of carboxylic acids 533 15-3 Biological acids and the henderson–hasselbalch Equation 537 15-4 substituent Effects on acidity 538 15-5 preparing carboxylic acids 540 15-6 Reactions of carboxylic acids: an overview 543 15-7 chemistry of nitriles 543 15-8 spectroscopy of carboxylic acids and nitriles 548 soMetHinG eXtra Vitamin c 550 16 Carboxylic acid Derivatives: nucleophilic acyl substitution reactions | 555 16-1 naming carboxylic acid Derivatives 556 16-2 nucleophilic acyl substitution Reactions 559 16-3 Reactions of carboxylic acids 564 16-4 Reactions of acid halides 570 16-5 Reactions of acid anhydrides 576 16-6 Reactions of Esters 578 16-7 Reactions of amides 584 16-8 Reactions of thioesters and acyl phosphates: Biological carboxylic acid Derivatives 587 16-9 polyamides and polyesters: step-growth polymers 589 16-10 spectroscopy of carboxylic acid Derivatives 592 soMetHinG eXtra b-lactam antibiotics 594 17 Carbonyl alpha-substitution and Condensation reactions | 599 17-1 Keto–Enol tautomerism 600 17-2 Reactivity of Enols: a-substitution Reactions 603 17-3 alpha Bromination of carboxylic acids 606 17-4 acidity of a hydrogen atoms: Enolate ion Formation 607 42912_00_FM_i-xxiv.indd 13 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
xiv DETAILED CONTENTS 17.5 Alkylation of Enolate lons 17.6 Carbonyl Condensations:The Aldol Reaction 620 17-7 Dehydration of Aldol Products 623 17-8 Intramolecular Aldol Reactions 17-9 The Claisen Condensation Reaction 62 17-10 Intramolecular Claisen Condensations:The Dieckmann Cyclization 9 17.11 Conjugate Carbonyl Additions:The Michael Reaction 17-12 Carbonyl Condensations with Enamines:The Stork Reactior 634 17-13 Biological Carbonyl Condensation Reactions 637 SOMETHING EXTRA Barbiturates 63g 8 Amines and Heterocycles 644 18-1 Naming Amines 18-2 Properties of Amines 18-3 Basicity of Amines 649 18-4 Basicity of Arylamines 18-5 Biological Amines and the Henderson-Hasselbalch Equation 18-6 Synthesis of Amines 6 18-7 Reactions of Amines 18-8 Heterocyclic Amines 65 18-9 Fused-Ring Heterocycles 18-10 Spectroscopy of Amines SOMETHING EXTRA Green Chemistry 614 19 Biomolecules:Amino Acids. Peptides,and Proteins 678 19-1 Structures of Amino Acids 679 19-2 Amino Acids and the Henderson-Hasselbalch Equation: Isoelectric Points 6 193 Synthesis of Amino Acids 6 19.4 Peptides and Proteins 195 Amino Acid Analysis of Peptides 691 19-6 Peptide Sequencing:The Edman Degradation 693 19-7 Peptide Synthesis 696
xiv DetaileD Contents 17-5 alkylation of Enolate ions 610 17-6 carbonyl condensations: the aldol Reaction 620 17-7 Dehydration of aldol products 623 17-8 intramolecular aldol Reactions 626 17-9 the claisen condensation Reaction 627 17-10 intramolecular claisen condensations: the Dieckmann cyclization 629 17-11 conjugate carbonyl additions: the Michael Reaction 632 17-12 carbonyl condensations with Enamines: the stork Reaction 634 17-13 Biological carbonyl condensation Reactions 637 soMetHinG eXtra Barbiturates 639 18 amines and Heterocycles | 644 18-1 naming amines 645 18-2 properties of amines 647 18-3 Basicity of amines 649 18-4 Basicity of arylamines 652 18-5 Biological amines and the henderson–hasselbalch Equation 653 18-6 synthesis of amines 654 18-7 Reactions of amines 659 18-8 heterocyclic amines 665 18-9 Fused-Ring heterocycles 669 18-10 spectroscopy of amines 672 soMetHinG eXtra green chemistry 674 19 Biomolecules: amino acids, Peptides, and Proteins | 678 19-1 structures of amino acids 679 19-2 amino acids and the henderson–hasselbalch Equation: isoelectric points 684 19-3 synthesis of amino acids 687 19-4 peptides and proteins 689 19-5 amino acid analysis of peptides 691 19-6 peptide sequencing: the Edman Degradation 693 19-7 peptide synthesis 696 42912_00_FM_i-xxiv.indd 14 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
CONTENTS 19-8 Protein Structure 7 19-9 Enzymes and Coenzymes 19.10 1 How Do Enzymes Work?Citrate Synthase 707 SOMETHING EXTRA The Protein Data Bank 。 20 Amino Acid Metabolism714 20-1 An Overview of Metabolism and Biochemical Energy 715 20-2 Catabolism of Amino Acids:Deamination 719 20-3 The urea cycle 3 20-4 Catabolism of Amino Acids:The Carbon Chains 7 20-5 Biosynthesis of Amino Acids 731 SOMETHING EXTRA Visualizing Enzyme Structures 735 Biomolecules:Carbohydrates 738 2 Classifying Carbohydrates 739 -2 Representing Carbohydrate Stereochemistry:Fischer Projections 21-3 D,L Sugars 1 21-4 Configurations of the Aldoses 21-5 Cyclic Structures of Monosaccharides:Anomers 21-6 Reactions of Monosaccharides 753 21-7 The Eight Essential Monosaccharides 21-8 Disaccharides 7 21-9 Polysaccharides and Their Synthesis 765 21-10 Some Other Important Carbohydrates SOMETHING EXTRA Sweetness Carbohydrate Metabolism 773 22-1 Hydrolysis of Complex Carbohydrates 4 22-2 Catabolism of Glucose:Glycolysis 776 22-3 Conversion of Pyruvate to Acetyl CoA
Contents xv 19-8 protein structure 700 19-9 Enzymes and coenzymes 703 19-10 how Do Enzymes work? citrate synthase 707 soMetHinG eXtra the protein Data Bank 710 20 amino acid Metabolism | 714 20-1 an overview of Metabolism and Biochemical Energy 715 20-2 catabolism of amino acids: Deamination 719 20-3 the Urea cycle 723 20-4 catabolism of amino acids: the carbon chains 728 20-5 Biosynthesis of amino acids 731 soMetHinG eXtra Visualizing Enzyme structures 735 21 Biomolecules: Carbohydrates | 738 21-1 classifying carbohydrates 739 21-2 Representing carbohydrate stereochemistry: Fischer projections 740 21-3 d,l sugars 745 21-4 configurations of the aldoses 746 21-5 cyclic structures of Monosaccharides: anomers 750 21-6 Reactions of Monosaccharides 753 21-7 the Eight Essential Monosaccharides 761 21-8 Disaccharides 762 21-9 polysaccharides and their synthesis 765 21-10 some other important carbohydrates 768 soMetHinG eXtra sweetness 770 22 Carbohydrate Metabolism | 773 22-1 hydrolysis of complex carbohydrates 774 22-2 catabolism of glucose: glycolysis 776 22-3 conversion of pyruvate to acetyl coa 783 42912_00_FM_i-xxiv.indd 15 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it