Tài liệu Organic Chemistry Demystified - Daniel Bloch, 2006

Organic Chemistry Demystified Demystified Series Accounting Demystified Advanced Statistics Demystified Algebra Demystified Anatomy Demystified asp.net 2.0 Demystified Astronomy Demystified Biology Demystified Biotechnology Demystified Business Calculus Demystified Business Math Demystified Business Statistics Demystified C++ Demystified Calculus Demystified Chemistry Demystified College Algebra Demystified Corporate Finance Demystified Databases Demystified Data Structures Demystified Differential Equations Demystified Digital Electronics Demystified Earth Science Demystified Electricity Demystified Electronics Demystified Environmental Science Demystified Everyday Math Demystified Forensics Demystified Genetics Demystified Geometry Demystified Home Networking Demystified Investing Demystified Java Demystified JavaScript Demystified Linear Algebra Demystified Macroeconomics Demystified Management Accounting Demystified Math Proofs Demystified Math Word Problems Demystified Medical Terminology Demystified Meteorology Demystified Microbiology Demystified Microeconomics Demystified Nanotechnology Demystified OOP Demystified Options Demystified Organic Chemistry Demystified Personal Computing Demystified Pharmacology Demystified Physics Demystified Physiology Demystified Pre-Algebra Demystified Precalculus Demystified Probability Demystified Project Management Demystified Psychology Demystified Quality Management Demystified Quantum Mechanics Demystified Relativity Demystified Robotics Demystified Six Sigma Demystified sql Demystified Statistics Demystified Technical Math Demystified Trigonometry Demystified uml Demystified Visual Basic 2005 Demystified Visual C# 2005 Demystified xml Demystified Organic Chemistry Demystified DANIEL R. BLOCH McGRAW-HILL New York Chicago San Francisco Lisbon London Madrid Mexico City Milan New Delhi San Juan Seoul Singapore Sydney Toronto Copyright © 2006 by The McGraw-Hill Companies, Inc. Inc. All rights reserved. Manufactured in the United States of America. Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without the prior written permission of the publisher. 0-07-148710-7 The material in this eBook also appears in the print version of this title: 0-07-145920-0. All trademarks are trademarks of their respective owners. Rather than put a trademark symbol after every occurrence of a trademarked name, we use names in an editorial fashion only, and to the benefit of the trademark owner, with no intention of infringement of the trademark. Where such designations appear in this book, they have been printed with initial caps. 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This page intentionally left blank For more information about this title, click here CONTENTS Preface xvii Acknowledgments xix CHAPTER 1 Structure and Bonding Atomic Structure Atomic Number and Atomic Mass (Weight) Electron Energy Levels The Octet Rule Valences Lewis Structures Orbital Shapes Quantum Mechanics Bond Formation Valence Bond Theory Molecular Orbitals Bonding and Antibonding MOs Bonding and 3-D Molecular Shape Curved Arrows Electronegativity and Bond Polarity Dipole Moments Formal Charges Resonance Structures Intermolecular Forces Quiz 1 1 3 4 7 8 9 15 15 18 20 21 21 23 30 31 33 34 36 37 39 CHAPTER 2 Families and Functional Groups 43 vii CONTENTS viii CHAPTER 3 Acids and Bases Introduction Arrhenius Definition Brønsted-Lowry Definition Conjugate Acids and Bases Equilibrium Reactions Weak Hydrocarbon Acids Lewis Acids and Bases Quiz 46 46 47 47 47 49 53 54 56 CHAPTER 4 Alkanes and Cycloalkanes Introduction Sources of Alkanes Acyclic and Cyclic Alkanes Nomenclature Formulas Structures Constitutional Isomers Cycloalkanes Alkyl Groups Nomenclature—Naming Compounds by the IUPAC System Physical Properties Chemical Properties Conformations of Alkanes Conformations of Cylcoalkanes Quiz 59 59 60 60 61 62 62 64 66 67 CHAPTER 5 Stereochemistry Isomers Chiral Compounds Stereocenters Chirality Centers Enantiomers Racemic Mixtures 70 74 75 76 84 94 99 99 100 101 102 105 109 CONTENTS ix The R/S System When the Lowest Priority Group Is Not in the Back Molecules with Multiple Asymmetric Centers Enantiomers Diastereomers Meso Compounds Fisher Projections Rotating Fisher Projections/Structures Cyclic Stereoisomers Naming Cyclic Stereoisomers Prochiral Carbons (Wanabees) Quiz 110 115 116 116 117 119 120 122 125 126 126 CHAPTER 6 Structure and Properties of Alkenes Introduction Structure Naming Alkenes Common Names Cis and Trans Isomers The E/Z (Easy) System Degrees of Unsaturation Stability of Alkenes Physical Properties of Alkenes Chemical Properties The Curved Arrow Quiz 129 129 130 132 134 134 135 136 140 141 141 142 142 CHAPTER 7 Reaction Mechanisms Introduction Thermodynamics Kinetics Carbocations Stereochemistry 145 145 145 148 150 151 113 CONTENTS x CHAPTER 8 CHAPTER 9 The Hammond Postulate Regiochemical Reactions The Markovnikov Rule Stereochemistry Rearrangement Reactions of Carbocations Quiz 152 154 155 156 157 159 Reactions of Alkenes Reaction with Hydrogen Halides in Inert Solvents Reaction with Hydrogen Halides in Protic Solvents Oxymercuration-Demercuration Reactions Hydroboration-Reduction Halogenation in Inert Solvents Stereochemistry Halogenation Halogenation in Reactive Solvents Radical Bromination Formation of Diols Double Bond Cleavage Hydrogenation Epoxides Cyclopropanes Quiz 161 Alkynes Introduction Structure Nomenclature Physical Properties Chemical Properties Reactions with Brønsted-Lowry Acids 185 185 185 186 188 188 189 161 162 165 167 171 173 174 175 177 178 180 180 181 182 CONTENTS xi Reactions with HBr and Peroxides Reaction with Halogens Hydration Reactions Hydroboration-Oxidation Reactions Hydrogenation/Reduction Reactions Oxidation Reactions Acidity of Alkynes Alkylation Reactions Preparation of Alkynes Quiz 193 195 195 198 199 200 201 202 204 204 CHAPTER 10 Characterization Introduction Chromatography Spectroscopy UV Spectroscopy Nuclear Magnetic Resonance Spectroscopy Nuclear Properties NMR Spectrometers 1 H NMR Spectroscopy 13 C NMR Spectroscopy Mass Spectrometry Quiz 207 207 207 212 222 226 226 228 230 243 246 251 CHAPTER 11 Organohalides Introduction Nomenclature Properties Preparation of Halides Radical Halogenation Isomeric Products Allylic Halogenation Reactions of Organohalides Quiz 256 256 256 257 258 258 260 263 265 266 CONTENTS xii CHAPTER 12 CHAPTER 13 Nucleophilic Substitution and Elimination Reactions Introduction Properties of Nucleophiles Properties of Bases Properties of Substrates/Electrophiles Properties of Leaving Groups Properties of Solvents Second-Order Nucleophilic Substitution (SN 2) Reactions First-Order Nucleophilic Substitution (SN 1) Reactions Summary of SN 1 and SN 2 Reactions Second-Order Elimination (E2) Reactions First-Order Elimination (E1) Reactions Summary of E1 and E2 Reactions Competition between Substitution and Elimination Reactions Quiz Alcohols Introduction Properties of Alcohols Nomenclature Acidity and Basicity of Alcohols Reactions with Active Metals Preparation of Alcohols Organometallic Compounds Preparation of Alcohols Using Organometallic Reagents Reactions of Alcohols Conversion of Alcohols to Alkyl Halides Dehydration Reactions Quiz 269 269 270 271 272 272 273 276 279 284 284 289 291 291 292 295 295 296 297 299 301 301 306 307 310 311 313 313 CONTENTS xiii CHAPTER 14 Ethers Introduction Nomenclature Properties Preparation of Ethers Reactions of Ethers Three-Membered Ether Rings Quiz 317 317 317 318 319 321 323 327 CHAPTER 15 Sulfur Compounds Nomenclature Properties Reactions of Sulfur Compounds Quiz 330 330 331 333 335 CHAPTER 16 Conjugated Systems Introduction Stability of Dienes Electrophilic Addition to Conjugated Dienes Allylic Cations, Radicals, and Anions Diels-Alder Reactions Quiz 337 337 337 344 347 349 355 CHAPTER 17 Aromatic Compounds 358 Introduction 358 Reactivity of Aromatic Compounds 358 Nomenclature 359 Kekulé Structures 361 Stability of Benzene 362 The Resonance Model 364 Molecular Orbital Description of Aromaticity 365 Properties of Aromatic, Nonaromatic, and Antiaromatic Compounds 369 Hückel’s Rule 370 Heterocyclic Compounds 371 CONTENTS xiv Aromatic Ions Polycyclic Aromatic Compounds Quiz 372 374 375 CHAPTER 18 Reactions of Benzene and other Aromatic Compounds 378 Introduction 378 Electrophilic Aromatic Substitution 379 Nucleophilic Aromatic Substitution 386 More Derivatives of Benzene 388 Multiple Substitution Reactions 392 Electrophilic Substitution in Disubstituted Benzenes 399 Quiz 400 CHAPTER 19 Aldehydes and Ketones Introduction Nomenclature Physical Properties Chemical Properties Preparation of Aldehydes and Ketones Hydration of Alkynes Reduction of Acid Chlorides Reactions of Aldehydes and Ketones with Nucleophiles Wittig Reactions Oxidation and Reduction Reactions Quiz 404 404 405 408 408 410 412 414 Carboxylic Acids Introduction Nomenclature Three-Dimensional Structure Molecular Orbital (MO) Description Physical Properties 430 430 431 434 434 435 CHAPTER 20 418 424 425 427 CONTENTS xv Acidity of Carboxylic Acids Preparation of Carboxylic Acids Derivatives of Carboxylic Acids Quiz 437 439 444 444 CHAPTER 21 Derivatives of Carboxylic Acids Introduction Carboxylic Acid Halides Carboxylic Acid Anhydrides Carboxylic Esters Amides Cyclic Amides Imides Nitriles Quiz 447 447 450 454 458 463 466 467 468 470 CHAPTER 22 Alpha-Substitution Reactions in Carbonyl Compounds Introduction Enol and Enolate Anions Alpha Monohalogenation of Aldehydes and Ketones α,β Unsaturated Ketones α-Bromination of Carboxylic Acids Acidity of α-Hydrogen Atoms Malonic Ester Synthesis Acetoacetic Ester Synthesis Additional Condensation Reactions Quiz CHAPTER 23 Carbonyl Condensation Reactions Introduction Aldol Reactions Dehydration of Aldol Compounds Mixed or Crossed Aldol Reactions 474 474 475 477 479 479 479 483 485 486 488 490 490 491 492 493 CONTENTS xvi Intramolecular Aldol Reactions Claisen Condensation Reactions α-Substitution Reactions Quiz 494 495 499 502 Final Exam 504 Quiz and Exam Solutions 531 Appendix A / Periodic Table of the Elements 537 Bibliography 539 Index 541 PREFACE Organic chemistry is the chemistry of carbon-containing compounds. Every living organism, plant and animal, is composed of organic compounds. Anyone with an interest in life and living things needs to have a basic understanding of organic chemistry. Articles continue to appear in newspapers and magazines describing the development of new medicines and diagnostic tests. These new products and technologies are results of a better understanding of the structure and function of DNA, proteins, and other organic biological molecules. The reactions and interactions of these complex molecules are the same reactions and interactions that occur in more simple organic molecules. This text was written to help those who are intimidated by the words organic chemistry. Those who have never had a formal course in organic chemistry and students currently taking or planning to take a formal course will find this text an easy-to-read introduction and supplement to other texts. The chapters are written in the same general order as found in most college textbooks. It would be helpful, but not necessary, if the reader had a course in introductory chemistry. The first three chapters cover the background material typically covered in general chemistry courses. It is not necessary that chapters be read sequentially, but since material tends to build on previous concepts it will be easier to understand the material if the chapters are read in sequential order. Key terms and concepts are italicized. Be sure you understand these concepts as they will continue to appear in other sections of this book. Questions (and answers) are given within each chapter to help you measure your understanding. Each chapter ends with a quiz covering the material presented. Use each quiz to check your comprehension and progress. The answers to quizzes are given in the back of the text. Review those problems (immediately) you did not get correct. Be sure you understand the concepts before going to the next chapter as new material often builds upon previous concepts. xvii Copyright © 2006 by The McGraw-Hill Companies, Inc. Click here for terms of use. xviii PREFACE As you read each chapter, take frequent breaks (you can munch on the extra gum drops used to make models in Chapter 5). The book contains a lot of figures and diagrams. Follow these as you read the text. It is often easier to understand a reaction mechanism in a diagram than to describe it in words. Yes, there is some memorization. New terms will appear that you probably have never heard before. For a series of terms I recommend making a mnemonic and I suggested a few. Reaction mechanisms are not as difficult as they may appear. You can predict most reactions in that negative species will be attracted to positive species (opposites attract). Atoms with electrons to share will be attracted to species that want more electrons—it is just that simple. There is a multiple-choice final exam at the end of the text. The final exam has more general, but similar, questions than those in the quizzes. Answers are given in the back of the book. If you are able to answer 80% of the final exam questions correctly (the first time), you will have a good understanding of the material. I hope you will enjoy reading about organic chemistry as much as I have enjoyed writing about it. Daniel R. Bloch ACKNOWLEDGMENTS The author expresses his appreciation to Nan for her assistance, patience, and helpful comments during the preparation of this book. The following individuals were kind enough to review various chapters in this book: Vaughn Ausman, Marquette University Kate Bichler, University of Wisconsin Center—Manitowoc Peter Conigliaro (retired), S.C. Johnson Sheldon Cramer (emeritus), Marquette University Timothy Eckert, Carthage College Sharbil Firson, Sigma-Aldrich Kevin Glaeske, Wisconsin Lutheran College Bruce Holman Shashi Jasti, Sigma-Aldrich Steven Levsen, Mount Mary College Julie Lukesh, University of Wisconsin—Green Bay Kevin Morris, Carthage College Patt Nylen, University of Wisconsin—Milwaukee Stephen Templin, Cardinal Stritch University A special thanks to Priyanka Negi and Judy Bass who assisted with the technical editing of this book. xix Copyright © 2006 by The McGraw-Hill Companies, Inc. Click here for terms of use.