Slideshare - 3 files

download Slideshare - 3 files

If you can't read please download the document

  • date post

    20-Aug-2015
  • Category

    Documents

  • view

    680
  • download

    3

Embed Size (px)

Transcript of Slideshare - 3 files

  1. 1. f o u r t h e d i t i o n ORGANIC CHEMISTRY Francis A. Carey University of Virginia Boston Burr Ridge, IL Dubuque, IA Madison, WI New York San Francisco St. Louis Bangkok Bogot Caracas Lisbon London Madrid Mexico City Milan New Delhi Seoul Singapore Sydney Taipei Toronto | | | | v v e-Text Main Menu Textbook Table of Contents Study Guide Table of Contents
  2. 2. ORGANIC CHEMISTRY, FOURTH EDITION Copyright 2000, 1996, 1992, 1987 by The McGraw-Hill Companies, Inc. All rights reserved. Printed 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 data base or retrieval system, without the prior written permission of the publisher. This book is printed on acid-free paper. 1 2 3 4 5 7 8 9 0 VNH/VNH 9 0 9 8 7 6 5 4 3 2 1 0 9 ISBN 0-07-290501-8 Vice president and editorial director: Kevin T. Kane Publisher: James M. Smith Sponsoring editor: Kent A. Peterson Developmental editor: Terrance Stanton Editorial assistant: Jennifer Bensink Senior marketing manager: Martin J. Lange Senior marketing assistant: Tami Petsche Senior project manager: Peggy J. Selle Senior production supervisor: Sandra Hahn Designer: K. Wayne Harms Photo research coordinator: John C. Leland Senior supplement coordinator: David A. Welsh Compositor: GTS Graphics, Inc. Typeface: 10/12 Times Roman Printer: Von Hoffmann Press, Inc. Cover/interior designer: Jamie ONeal Photo research: Mary Reeg Photo Research The credits section for this book begins on page C-1 and is considered an extension of the copyright page. Library of Congress Cataloging-in-Publication Data Carey, Francis A. Organic chemistry / Francis A. Carey. 4th ed. p. cm. Includes index. ISBN 0-07-290501-8 ISBN 0-07-117499-0 (ISE) 1. Chemistry, Organic. I. Title. QD251.2.C364 2000 547dc21 99-045791 CIP INTERNATIONAL EDITION ISBN 0-07-117499-0 Copyright 2000. Exclusive rights by The McGraw-Hill Companies, Inc. for manufacture and export. This book cannot be re-exported from the country to which it is consigned by McGraw-Hill. The International Edition is not available in North America. www. mhhe.com McGraw-Hill Higher Education A Division of The McGraw-Hill Companies | | | | v v e-Text Main Menu Textbook Table of Contents Study Guide Table of Contents
  3. 3. A B O U T T H E A U T H O R Francis A. Carey is a native of Pennsylvania, educated in the public schools of Philadelphia, at Drexel Univer- sity (B.S. in chemistry, 1959), and at Penn State (Ph.D. 1963). Following postdoctoral work at Harvard and mil- itary service, he joined the chemistry faculty of the Uni- versity of Virginia in 1966. With his students, Professor Carey has published over 40 research papers in synthetic and mechanistic organic chemistry. He is coauthor (with Richard J. Sund- berg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and advanced undergraduates, and (with Robert C. Atkins) of Organic Chemistry: A Brief Course, an introductory text for the one-semester organic course. Since 1993, Professor Carey has been a member of the Committee of Examiners of the Graduate Record Examination in Chemistry. Not only does he get to par- ticipate in writing the Chemistry GRE, but the annual working meetings provide a stimulating environment for sharing ideas about what should (and should not) be taught in college chemistry courses. Professor Careys main interest shifted from research to undergraduate education in the early 1980s. He regularly teaches both general chemistry and organic chemistry to classes of over 300 students. He enthusi- astically embraces applications of electronic media to chemistry teaching and sees multimedia presentations as the wave of the present. Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of three grown sons and the grandparents of Riyad and Ava. | | | | v v e-Text Main Menu Textbook Table of Contents Study Guide Table of Contents
  4. 4. ix B R I E F C O N T E N T S Preface xxv Introduction 1 1 CHEMICAL BONDING 7 2 ALKANES 53 3 CONFORMATIONS OF ALKANES AND CYCLOALKANES 89 4 ALCOHOLS AND ALKYL HALIDES 126 5 STRUCTURE AND PREPARATION OF ALKENES: ELIMINATION REACTIONS 167 6 REACTIONS OF ALKENES: ADDITION REACTIONS 208 7 STEREOCHEMISTRY 259 8 NUCLEOPHILIC SUBSTITUTION 302 9 ALKYNES 339 10 CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS 365 11 ARENES AND AROMATICITY 398 12 REACTIONS OF ARENES: ELECTROPHILIC AROMATIC SUBSTITUTION 443 13 SPECTROSCOPY 487 14 ORGANOMETALLIC COMPOUNDS 546 15 ALCOHOLS, DIOLS, AND THIOLS 579 16 ETHERS, EPOXIDES, AND SULFIDES 619 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 654 18 ENOLS AND ENOLATES 701 19 CARBOXYLIC ACIDS 736 20 CARBOXYLIC ACID DERIVATIVES: NUCLEOPHILIC ACYL SUBSTITUTION 774 21 ESTER ENOLATES 831 22 AMINES 858 23 ARYL HALIDES 917 24 PHENOLS 939 25 CARBOHYDRATES 972 26 LIPIDS 1015 27 AMINO ACIDS, PEPTIDES, AND PROTEINS. NUCLEIC ACIDS 1051 APPENDIX 1 PHYSICAL PROPERTIES A-1 APPENDIX 2 ANSWERS TO IN-TEXT PROBLEMS A-9 APPENDIX 3 LEARNING CHEMISTRY WITH MOLECULAR MODELS: Using SpartanBuild and SpartanView A-64 GLOSSARY G-1 CREDITS C-1 INDEX I-1 | | | | v v e-Text Main Menu Textbook Table of Contents Study Guide Table of Contents
  5. 5. P R E F A C E xxv PHILOSOPHY From its rst edition through this, its fourth, Organic Chemistry has been designed to meet the needs of the mainstream, two-semester, undergraduate organic chemistry course. It has evolved as those needs have changed, but its philosophy remains the same. The over- arching theme is that organic chemistry is not only an interesting subject, but also a logical one. It is logical because its topics can be connected in a steady pro- gression from simple to complex. Our approach has been to reveal the logic of organic chemistry by being selective in the topics we cover, as well as thorough and patient in developing them. Teaching at all levels is undergoing rapid change, especially in applying powerful tools that exploit the graphics capability of personal computers. Organic chemistry has always been the most graphical of the chemical sciences and is well positioned to benet sig- nicantly from these tools. Consistent with our philoso- phy, this edition uses computer graphics to enhance the core material, to make it more visual, and more under- standable, but in a way that increases neither the amount of material nor its level. ORGANIZATION The central message of chemistry is that the properties of a substance come from its structure. What is less obvious, but very powerful, is the corollary. Someone with training in chemistry can look at the structure of a substance and tell you a lot about its properties. Organic chemistry has always been, and continues to be, the branch of chemistry that best connects structure with properties. This text has a strong bias toward structure, and this edition benets from the availability of versa- tile new tools to help us understand that structure. The text is organized to ow logically and step by step from structure to properties and back again. As the list of chapter titles reveals, the organization is accord- ing to functional groupsstructural units within a mol- ecule most responsible for a particular property because that is the approach that permits most students to grasp the material most readily. Students retain the material best, however, if they understand how organic reactions take place. Thus, reaction mechanisms are stressed early and often, but within a functional group framework. A closer examination of the chapter titles reveals the close link between a functional group class (Chapter 20, Carboxylic Acid Derivatives) and a reaction type (Nucleophilic Acyl Substitution), for example. It is very satisfying to see students who entered the course believing they needed to memorize everything progress to the point of thinking and reasoning mechanistically. Some of the important stages in this approach are as follows: The rst mechanism the students encounter (Chap- ter 4) describes the conversion of alcohols to alkyl halides. Not only is this a useful functional-group transformation, but its rst step proceeds by the simplest mechanism of allproton transfer. The overall mechanism provides for an early rein- forcement of acid-base chemistry and an early introduction to carbocations and nucleophilic sub- stitution. Chapter 5 continues the chemistry of alcohols and alkyl halides by showing how they can be used to prepare alkenes by elimination reactions. Here, the students see a second example of the formation of carbocation intermediates from alcohols, but in this case, the carbocation travels a different path- way to a different destination. The alkenes prepared in Chapter 5 are studied again in Chapter 6, this time with an eye toward their own chemical reactivity. What the students learned about carbocations in Chapters 4 and 5 serves them well in understanding the mechanisms of the reactions of alkenes in Chapter 6. Likewise, the mechanism of nucleophilic addition to the carbonyl group of aldehydes and ketones described in Chapter 17 sets the stage for aldol con- densation in Chapter 18, esterication of carboxylic acids in Chapter 19, nucleophilic acyl substitution in Chapter 20, and ester condensation in Chapter 21. | | | | v v e-Text Main Menu Textbook Table of Contents Study Guide Table of Contents
  6. 6. xxvi PREFACE THE SPARTAN INTEGRATION The third edition of this text broke new ground with its emphasis on molecular modeling, including the addition of more than 100 exercises of the model-building type. This, the fourth edition, moves to the next level of mod- eling. Gwendolyn and Alan Shustermans 1997 Journal of Chemical Education article Teaching Chemistry with Electron Density Models described how models show- ing the results of mole