Organic Chemistry as a Second Language: Second Semester Topics

366 Pages·2011·6.429 MB·

by  Klein D.R.

This page intentionally left blank
ORGANIC CHEMISTRY
AS A SECOND
LANGUAGE, 3e
This page intentionally left blank
ORGANIC CHEMISTRY
AS A SECOND
LANGUAGE, 3e
Second Semester Topics
DAVID KLEIN
Johns Hopkins University
JOHN WILEY & SONS, INC.
ASSOCIATE PUBLISHER Petra Recter
EDITORIAL ASSISTANT Lauren Stauber
MARKETING MANAGER Kristine Ruff
SENIOR PRODUCTION EDITOR Sujin Hong; Production Management Services
provided by Prepare, Inc.
CREATIVE DIRECTOR Harry Nolan
SENIOR COVER DESIGNER Wendy Lai
COVER CREDITS Background: ©William Hopkins/iStockphoto
Test tube: Untitled X-Ray/Nick Veasey/
Getty Images, Inc.
Bicycle: Igor Shikov/Shutterstock
This book was set in 9/11 Times Roman by Prepare, Inc. and printed and bound by
Courier Westford. The cover was printed by Courier Westford.
This book is printed on acid-free paper. (cid:2)
Founded in 1807, John Wiley & Sons, Inc. has been a valued source of knowledge and
understanding for more than 200 years, helping people around the world meet their needs
and fulfill their aspirations. Our company is built on a foundation of principles that include
responsibility to the communities we serve and where we live and work. In 2008, we
launched a Corporate Citizenship Initiative, a global effort to address the environmental,
social, economic, and ethical challenges we face in our business. Among the issues we are
addressing are carbon impact, paper specifications and procurement, ethical conduct within
our business and among our vendors, and community and charitable support. For more
information, please visit our website: www.wiley.com/go/citizenship.
Copyright ©2012, 2006, 2005 John Wiley & Sons, Inc. 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, scanning or
otherwise, except as permitted under Section 107 or 108 of the 1976 United States
Copyright Act, without either the prior written permission of the Publisher or authorization
through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc.,
222 Rosewood Drive, Danvers, MA 01923, website www.copyright.com. Requests to
the Publisher for permission should be addressed to the Permissions Department,
John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030-5774, [phone],
fax [phone], website www.wiley.com/go/permissions.
Evaluation copies are provided to qualified academics and professionals for review purposes
only, foruse in their courses during the next academic year. These copies are licensed and
may not be soldor transferred to a third party. Upon completion of the review period, please
return the evaluation copy to Wiley. Return instructions and a free of charge return mailing
label are available at www.wiley.com/go/returnlabel. If you have chosen to adopt this
textbook for use in your course, please accept this book as your complimentary desk copy.
Outside of the United States, please contact your local sales representative.
ISBN 978-1-118-14434-3
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
CONTENTS
CHAPTER 1 IR SPECTROSCOPY 1
1.1 Vibrational Excitation 2
1.2 IR Spectra 3
1.3 Wavenumber 4
1.4 Signal Intensity 9
1.5 Signal Shape 11
1.6 Analyzing an IR Spectrum 19
CHAPTER 2 NMR SPECTROSCOPY 26
2.1 Chemical Equivalence 26
2.2 Chemical Shift (Benchmark Values) 30
2.3 Integration 35
2.4 Multiplicity 39
2.5 Pattern Recognition 41
2.6 Complex Splitting 43
2.7 No Splitting 44
2.8 Hydrogen Deficiency Index (Degrees of Unsaturation) 46
2.9 Analyzing a Proton NMR Spectrum 49
2.10 13C NMR Spectroscopy 53
CHAPTER 3 ELECTROPHILIC AROMATIC SUBSTITUTION 56
3.1 Halogenation and the Role of Lewis Acids 57
3.2 Nitration 61
3.3 Friedel-Crafts Alkylation and Acylation 64
3.4 Sulfonation 72
3.5 Activation and Deactivation 76
3.6 Directing Effects 78
3.7 Identifying Activators and Deactivators 88
3.8 Predicting and Exploiting Steric Effects 98
3.9 Synthesis Strategies 106
v
vi CONTENTS
CHAPTER 4 NUCLEOPHILIC AROMATIC SUBSTITUTION 112
4.1 Criteria for Nucleophilic Aromatic Substitution 112
4.2 SNAr Mechanism 115
4.3 Elimination-Addition 121
4.4 Mechanism Strategies 126
CHAPTER 5 KETONES AND ALDEHYDES 129
5.1 Preparation of Ketones and Aldehydes 129
5.2 Stability and Reactivity of C¨O Bonds 133
5.3 H-Nucleophiles 135
5.4 O-Nucleophiles 140
5.5 S-Nucleophiles 153
5.6 N-Nucleophiles 155
5.7 C-Nucleophiles 165
5.8 Some Important Exceptions to the Rule 175
5.9 How to Approach Synthesis Problems 180
CHAPTER 6 CARBOXYLIC ACID DERIVATIVES 187
6.1 Reactivity of Carboxylic Acid Derivatives 187
6.2 General Rules 188
6.3 Acid Halides 192
6.4 Acid Anhydrides 201
6.5 Esters 203
6.6 Amides and Nitriles 213
6.7 Synthesis Problems 222
CHAPTER 7 ENOLS AND ENOLATES 231
7.1 Alpha Protons 231
7.2 Keto-Enol Tautomerism 233
7.3 Reactions Involving Enols 238
7.4 Making Enolates 241
7.5 Haloform Reaction 244
7.6 Alkylation of Enolates 247
7.7 Aldol Reactions 252
7.8 Claisen Condensation 259
7.9 Decarboxylation 266
7.10 Michael Reactions 273
CONTENTS vii
CHAPTER 8 AMINES 281
8.1 Nucleophilicity and Basicity of Amines 281
8.2 Preparation of Amines through SN2 Reactions 283
8.3 Preparation of Amines through Reductive Amination 287
8.4 Acylation of Amines 291
8.5 Reactions of Amines with Nitrous Acid 295
8.6 Aromatic Diazonium Salts 298
Answer Key 301
Index 345
This page intentionally left blank