Essential Organic Chemistry ( PDF

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1、To The STudenTWelcome to the fascinating world of organic chemistry. You are about to embark on an exciting journey. This book has been written with students like you in mindthose who are encounter-ing the subject for the first time. The books central goal is to make this journey through organic che

2、mistry both stimulating and enjoyable by helping you understand central principles and asking you to apply them as you progress through the pages. You will be reminded about these principles at frequent intervals in references back to sections you have already mastered.You should start by familiariz

3、ing yourself with the book. Inside the front and back covers is information you may want to refer to often during the course. The list of Some Important Things to Remember and the Reaction Summary at each chapters end provide helpful checklists of the concepts you should understand after studying th

4、e chapter. The Glossary at the end of the book can also be a useful study aid. The molecular models and electrostatic potential maps that you will find throughout the book are provided to give you an appreciation of what molecules look like in three dimensions and to show how charge is distributed w

5、ithin a molecule. Think of the margin notes as the authors opportunity to inject personal reminders of ideas and facts that are important to remember. Be sure to read them.Work all the problems within each chapter. These are drill problems that you will find at the end of each section that allow you

6、 to check whether you have mastered the skills and concepts the particular section is teaching before you go on to the next section. Some of these problems are solved for you in the text. Short answers to some of the othersthose marked with a diamondare provided at the end of the book. Do not overlo

7、ok the “Problem-Solving Strategies” that are also sprinkled throughout the text; they provide practical suggestions on the best way to approach important types of problems.In addition to the within-chapter problems, work as many end-of-chapter problems as you can. The more problems you work, the mor

8、e comfortable you will be with the subject matter and the better prepared you will be for the material in subsequent chapters. Do not let any problem frustrate you. If you cannot figure out the answer in a reasonable amount of time, turn to the Study Guide and Solutions Manual to learn how you shoul

9、d have approached the problem. Later on, go back and try to work the problem on your own again. Be sure to visit www.MasteringC, where you can explore study tools, including Exercise Sets, an Interactive Molecular Gallery, and Biographical Sketches of historically important chemists, and where you c

10、an access content on many important topics.The most important advice to remember (and follow) in studying organic chemistry is DO NOT FALL BEHIND! The individual steps to learning organic chemistry are quite simple; each by itself is relatively easy to master. But they are numerous, and the subject

11、can quickly become overwhelming if you do not keep up.Before many of the theories and mechanisms were figured out, organic chemistry was a discipline that could be mastered only through memorization. Fortunately, that is no longer true. You will find many unifying ideas that allow you to use what yo

12、u have learned in one situation to predict what will happen in other situations. So, as you read the book and study your notes, always make sure that you understand why each chemical event or behavior happens. For example, when the reasons behind reac-tivity are understood, most reactions can be pre

13、dicted. Approaching the course with the misconception that to succeed you must memorize hundreds of unrelated reactions could be your downfall. There is simply too much material to memorize. Understanding and reasoning, not memorization, provide the necessary foundation on which to lay subsequent le

14、arning. Nevertheless, from time to time some memo-rization will be required: some fundamental rules will have to be memorized, and you will need to learn the common names of a number of organic compounds. But that should not be a problem; after all, your friends have common names that you have been

15、able to learn and remember.Students who study organic chemistry to gain entrance into professional schools sometimes wonder why these schools pay so much attention to this topic. The importance of organic chemistry is not in the subject matter alone. Mastering organic chemistry requires a thorough u

16、nderstanding of certain fundamental principles and the ability to use those fundamentals to analyze, classify, and predict. Many professions make similar demands.Good luck in your study. I hope you will enjoy studying organic chemistry and learn to appreciate the logic of this fascinating discipline

17、. If you have any comments about the book or any suggestions for improving it, I would love to hear from you. Remember, positive comments are the most fun, but negative comments are the mostuseful.Paula Y urkanis Bruicepybruicechem.ucsb.eduA01_BRUI9034_03_GE_FM.indd 1 03/19/15 11:06 AMRC CHROCR OOCO

18、OPR OOCRNOHOCR ClOCR OROCROCROCROCC XOHAlkyl halideAlcoholRRNH2HRNHRN R 2NH2CH X R XRCH OH RRRRRCO HRRRNRRRAmineAmideR NH RRprimary secondary tertiaryX = F, Cl, Br, or ICH2CH2RCH3 AlkaneAlkeneAlkyneNitrileEtherThiolRC CRRC NRORSHCC CC H2RCH2internal terminalinternal terminalDisulfide RSSRSulfide RSR

19、Sulfonium ionR REpoxideONH2AnilineBenzenePyridineAcyl phosphateAcyl adenylate(Ad = adenosyl)PhenolCarboxylic acidAcyl chlorideOHAcid anhydrideEsterR SROCThioesterAldehydeKetoneCommon Functional GroupsRS+RROOOPR OOCA d OAcyl pyrophosphateOOPR OOCOOOPOA01_BRUI9034_03_GE_FM.indd 2 03/19/15 11:06 AMAppr

20、oximate pKaValuescarboxylic acidsprotonated anilineprotonated carbonyl groupsprotonated alcoholsprotonated water+OH+ROHH+HOHH 0+ArNH35a-carbon (aldehyde)a-carbon (ketone)a-carbon (ester)20protonated aminesphenol ArOH10+RNH3aminesalkanes4025RNH2RCH360H2Oalcoholswater15ROHR OHOCR OHCOROCOCRRCHOCHHRCHH

21、RCHHATPAdaaB0applied magnetic fieldDebye; a measure of dipole momentDdGGHSpartial or chemical shiftheatfree energy of activationGibbs standard free energy changechange in enthalpychange in entropydimethylformamidedimethyl sulfoxideDMFDMSOE entgegen (opposite sides in E,Z nomenclature) Eaenergy of ac

22、tivationflavin adenine dinucleotide FADH2CrO4chromic acidinfraredhypochlorous acid HOClIRk rate constantKaacid dissociation constantKeqequilibrium constantCommon Symbols and AbbreviationsLiAlH4lithium aluminum hydridemass spectroscopy MSm dipole momentNAD+nicotinamide adeninedinucleotideNaOCl sodium

23、 hypochloritenanometers nmnuclear magnetic resonanceparts per million (of the applied field)measure of the acidity of a solution (= log H+) NMRppmpyridoxal phosphate PLPpHpKameasure of the strength of an acid (= log Ka) alkyl group; group derived from a hydrocarbonRR,S configuration about an asymmet

24、ric centerBu butyltetrahydrofuran or tetrahydrofolatetetramethylsilane, (CH3)4Siultraviolet/visiblehalogen atomthiamine pyrophosphateTHFTMSTPPUV/VisXZ zusammen (same side in E,Z nomenclature) adenosylspecific rotationobserved rotationadenosine triphosphateethyldiethyl etherEtEt2ONaBH4sodium borohydr

25、ideisoelectric point pIA01_BRUI9034_03_GE_FM.indd 3 03/19/15 11:06 AMA01_BRUI9034_03_GE_FM.indd 4 03/19/15 11:06 AMThis page intentionally left blankEssential Organic ChemistryTHIRD EDITIONglObal EDITIONPaula Yurkanis BruiceUNIVERSITY OF CALIFORNIA SANTA BARBARAA01_BRUI9034_03_GE_FM.indd 5 03/19/15

26、11:06 AMEditor-in-Chief: Jeanne ZaleskyMarketing Manager: Will MooreProgram Managers: Coleen Morrison / Sarah ShefvelandTeam Lead, Project Management Biology, Chemistry, Environmental Science, and Geo Science: David ZielonkaProject Manager: Beth SweetenPublishing Administrator and Business Analyst,

27、Global Edition: Shokhi Shah KhandelwalAssistant Acquisitions Editor, Global Edition: Murchana BorthakurAssitant Project Editor, Global Edition: Sinjita BasuSenior Manufacturing Controller, Production, Global Edition: Trudy KimberOperations Specialist: Maura Zaldivar-GarciaText Permissions Manager: W

28、illiam OpaluchCompositor: Lumina Datamatics, Inc.Cover Designer: Lumina Datamatics, Inc.Cover Photo Source: Shutterstock Cover Printer: PrintpackPearson Education LimitedEdinburgh GateHarlowEssex CM20 2JEEnglandand Associated Companies throughout the worldVisit us on the World Wide Web at: Pearson E

29、ducation Limited 2016The rights of Paula Yurkanis Bruice to be identified as the author of this work have been asserted by her in accordance with the Copyright, Designs and Patents Act 1988.Authorized adaptation from the United States edition, entitled Essential Organic Chemistry, 3rd edition, ISBN

30、978-0-321-93771-1, by Paula Yurkanis Bruice, published by Pearson Education 2016.All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, withouteither t

31、he prior written permission of the publisher or a license permitting restricted copying in the United Kingdom issued by the Copyright Licensing Agency Ltd, Saffron House, 610 Kirby Street, London EC1N 8TS.All trademarks used herein are the property of their respective owners.The use of any trademark

32、 in this text does not vest in the author or publisher any trademark ownership rights in such trademarks, nor does the use of such trademarks imply any affiliation with or endorsement of this book by such owners.ISBN 10: 1-292-08903-2ISBN 13: 978-1-292-08903-4British Library Cataloguing-in-Publicati

33、on DataA catalogue record for this book is available from the British Library.10 9 8 7 6 5 4 3 2 114 13 12 11 10Typeset in Times LT Std 10.5/12 by Lumina Datamatics, Inc.Printed and bound in Malaysia.A01_BRUI9034_03_GE_FM.indd 6 03/20/15 11:39 AM 7Preface 19About the Author 23CHapTER 1 Remembering G

34、eneral Chemistry: ElectronicStructure andBonding 29CHapTER 2 Acids and Bases: Central to Understanding Organic Chemistry 68TUTORIal Acids and Bases 93CHapTER 3 An Introduction to Organic Compounds 101CHapTER 4 Isomers: The Arrangement of Atoms inSpace 144CHapTER 5 Alkenes 176TUTORIal An Exercise in

35、Drawing Curved Arrows: Pushing Electrons 202CHapTER 6 The Reactions of Alkenes and Alkynes 210CHapTER 7 Delocalized Electrons and Their Effect on Stability, pKa, and the Products of a Reaction Aromaticity and the Reactions ofBenzene 242TUTORIal Drawing Resonance Contributors 283CHapTER 8 Substitutio

36、n and Elimination Reactions of Alkyl Halides 291CHapTER 9 Reactions of Alcohols, Ethers, Epoxides, Amines, and Thiols 331CHapTER 10 Determining the Structure of Organic Compounds 367CHapTER 11 Reactions of Carboxylic Acids and Carboxylic Acid Derivatives 421CHapTER 12 Reactions of Aldehydes and Keto

37、nes More Reactions of Carboxylic Acid Derivatives 459CHapTER 13 Reactions at the a-Carbon of Carbonyl Compounds 489CHapTER 14 Radicals 513CHapTER 15 Synthetic Polymers 527CHapTER 16 The Organic Chemistry of Carbohydrates 553CHapTER 17 The Organic Chemistry of Amino Acids, Peptides, and Proteins 577C

38、HapTER 18 How Enzymes Catalyze Reactions The Organic Chemistry of the Vitamins available on -lineCHapTER 19 The Organic Chemistry of the Metabolic Pathways 609CHapTER 20 The Organic Chemistry of Lipids 634CHapTER 21 The Chemistry of the Nucleic Acids 650app ENDICEs I Physical Properties of Organic C

39、ompounds available on -lineappENDICEs II Spectroscopy Tables available on -line Answers to Selected Problems A-1 Glossary G-1 Photo Credits P-1 Index I-1Brief Table of ContentsA01_BRUI9034_03_GE_FM.indd 7 03/19/15 11:06 AM8 1 Remembering General Chemistry: electronic Structure andBonding 29Natural O

40、rgaNic cOmpOuNds Versus s yNthetic OrgaNic cOmpOuNds 301.1 The Structure of an Atom 311.2 How the Electrons in an Atom Are Distributed 321.3 Ionic and Covalent Bonds 341.4 How the Structure of a Compound Is Represented 40prOBlem-sOl ViNg strategy 421.5 Atomic Orbitals 451.6 How Atoms Form Covalent B

41、onds 461.7 How Single Bonds Are Formed in Organic Compounds 471.8 How a Double Bond Is Formed: The Bonds in Ethene 50diamONd, graphite, grapheNe, aNd FullereNes: suBstaNces that cONtaiN ONly c arBON atOms 521.9 How a Triple Bond Is Formed: The Bonds in Ethyne 521.10 The Bonds in the Methyl Cation, t

42、he Methyl Radical, and the Methyl Anion 541.11 The Bonds in Ammonia and in the Ammonium Ion 561.12 The Bonds in Water 57Watera cOmpOuNd ceNtral t O liFe 581.13 The Bond in a Hydrogen Halide 581.14 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles 60prOBlem-sOl ViNg strategy 621.1

43、5 The Dipole Moments of Molecules 63SOME IMPORTANT THINGS TO REMEMBER 64 PROBLEMS 65 2 Acids and Bases: Central to understanding organic Chemistry 682.1 An Introduction to Acids and Bases 682.2 pKa and pH 70acid raiN 722.3 Organic Acids and Bases 72pOisONOus amiNes 73prOBlem-sOl ViNg strategy 752.4

44、How to Predict the Outcome of an AcidBase Reaction 762.5 How to Determine the Position of Equilibrium 762.6 How the Structure of an Acid Affects Its pKa Value 772.7 How Substituents Affect the Strength of an Acid 81prOBlem-sOl ViNg strategy 822.8 An Introduction to Delocalized Electrons 83FOsamax pr

45、eVeNts BONes FrOm BeiNg NiBBled aWay 842.9 A Summary of the Factors that Determine Acid Strength 852.10 How pH Affects the Structure of an Organic Compound 86prOBlem-sOl ViNg strategy 87aspiriN must Be iN its Basic FOrm t O Be physiOl Ogically a ctiVe 88ContentsNew chapter on Acid/Base Chemistry rei

46、nforces fundamental concepts and foundational skills needed for future topics in organic chemistry. for Organic ChemistryMasteringChemistry tutorials guide you through topics in chemistry with self-paced tutorials that provide individualized coaching. These assignable, in-depth tutorials are designe

47、d to coach you with hints and feedback specific to your individual needs. For additional practice on Acids and Bases, go to MasteringChemistry where the following tutorials are available: Acids and Bases: Base Strength and the Effect of pH on Structure Acids and Bases: Factors that Influence Acid St

48、rength Acids and Bases: Predicting the Position of Equilibrium Acids and Bases: DefinitionsA01_BRUI9034_03_GE_FM.indd 8 03/19/15 11:06 AM2.11 Buffer Solutions 89Bl OOd: a BuFFered sOlutiON 89SOME IMPORTANT THINGS TO REMEMBER 90 PROBLEMS 91ACidS And BASeS 93 3 An introduction to organic Compounds 101

49、3.1 How Alkyl Substituents Are Named 104Bad-smelliNg cOmpOuNds 1053.2 The Nomenclature of Alkanes 108hOW is the OctaNe NumBer OF gasOliNe determiNed? 1103.3 The Nomenclature of Cycloalkanes Skeletal Structures 111prOBlem-sOl ViNg strategy 1123.4 The Nomenclature of Alkyl Halides 114prOBlem-sOl ViNg

50、strategy 1143.5 The Classification of Alkyl Halides, Alcohols, and Amines 115NitrOsamiNes aNd caNcer 1153.6 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines 1163.7 Noncovalent Interactions 118prOBlem-sOl ViNg strategy 121drugs BiNd t O their recept Ors 1223.8 Factors that Affect the Sol


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