Francis A Carey I Robert M Giuliano I Neil T Allison I Susan L Bane Elev ent h Edition ORGANIC CHEMIS R e Cl ~~~ /\ Page i THE PRINCIPAL FUNCTIONAL GROU PS OF ORGANIC CHEMISTRY Acceptable Name( ) of Example Characteristic Reaction Type Alkanes Ethane Free-radical substitution of hydrogen by halogen Alkenes Ethene or ethylene Electrophilic addjtion to double bond Example Hydrocarbons Alkynes HC - CH Ethyne or acetylene Electrophilic addjtion to triple bond Dienes H 2C = CHCH= CH 1,3-Butaruene Arenes Electrophilk addjtion to double bonds Benzene Electrophilic aromatic ubstitution Chloroethane or ethyl chloride NucleophiJjc substitution; elimination Alkenyl halides Chloroethene or vinyl chloride Electrophilic addition to double bond; elimination Ary! halides Chlorobenzene Electrophilic aromatic ubstitution; nucleophilic aromatic substitution Alcohols Ethanol or ethyl alcohol Dehydration; conversion to alkyl halides; esterification Phenols Phenol Electrophilic aromatic ubstitution Ethers Ethoxyethane or dfothyl ether Cleavage by hydrogen haJjdes Epoxides Epoxyethane or ethylene oxide or oxuane Nucleophilic ring operung Aldehydes Ethanal or acetaldehyde Nucleophilic addition to carbonyl group Ketones 2-Propanone or acetone Nucleophilic addjtion to car bony I group Carboxylic acids Ethanoic acid or Ionization of car boxy 1; Halogen-st1bstituted derivatives of hydrocarbons Alkyl haljdes CR3CH 2Cl Oxygen-containing organic compounds aceoc ac10 0 - o a 0 D esreru1canon - Page ii THE PRINCIPAL FUNCTIONAL GROU PS OF ORGANIC CHEMISTRY &:ample Acceptable Name(s) of Example Characteristic Reaction Type Ethanoyl chloride or acetyl chloride Nucleophilic acyl substitution Ethanoic anhydride or acetic anhydride Nucleophilic acyl substitution Ethyl ethanoate or ethyl acetate Nucleophilic acyl substitution N-Methylethanarnide or N- methy lacetantide Nucleophilic acyl substitution Ethanamine or ethylamine Nitrogen acts as a base or as a nucleophile Ethanenitrile or acetoni lri le Nucleophilic addition to carbo11-nitrogen triple bond itrobenzene Reduction of nitro group to amine Car boxylic acid der ivatives Acy! halides II CH3CCI Acid anhydrides Esters II CH 3COCH CH3 Amides II CH 3CNHCH3 Nitrogen-containing organic compot1nds Amines CH 3CH 2NH itriles itro compounds Sulfm - contain i ng organic compounds Thiols Sulfides CH3CH SH Ethanethiol Oxidation to a sulfenic, sulfin ic, or sulfonic acid or to a disulfide Diethyl sulfide Alkylation to a suJfonium salt; oxidation to a sulfoxide or sulfone Page iii Organic Chemistry ELEVENTH EDITION Francis A Carey University of Virginia Robert M Giuliano Villanova University Neil T Allison University of Arkansas Susan L Bane Binghamton University Page iv ORGANIC CHEMISTRY, ELEVENTH EDITION Published by McGraw-Hill Education, Penn Plaza, New York, NY 10121 Copyright © 2020 by McGraw-Hill Education All rights reserved Printed in the United States of America Previous editions © 2017, 2014, and 2011 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 consent of McGraw-Hill Education, including, but not limited to, in any network or other electronic storage or transmission, or broadcast for distance learning Some ancillaries, including electronic and print components, may not be available to customers outside the United States This book is printed on acid-free paper LWI 21 20 19 ISBN 978-1-260-14892-3 MHID 1-260-14892-0 Portfolio Manager: Michelle Hentz Product Developers: Mary E Hurley & Megan Platt Marketing Manager: Tamara Hodge Content Project Managers: Laura Bies, Rachael Hillebrand & Sandra Schnee Buyer: Sandy Ludovissy Design: Daivd W Hash Content Licensing Specialists: Lorraine Buczek Cover Image: ©Ella Maru Studio Compositor: Aptara, Inc All credits appearing on page or at the end of the book are considered to be an extension of the copyright page Library of Congress Cataloging-in-Publication Data Names: Carey, Francis A., 1937- author | Giuliano, Robert M., 1954- author | Allison, Neil T (Neil Thomas), 1953- author | Tuttle, Susan L Bane, author Title: Organic chemistry / Francis A Carey (University of Virginia), Robert M Giuliano (Villanova University), Neil T Allison (University of Arkansas), Susan L Bane Tuttle (Binghamton University) Description: Eleventh edition | New York, NY: McGraw-Hill Education, 2018 | Includes index Identifiers: LCCN 2018024902| ISBN 9781260148923 (alk paper) | ISBN 1260148920 (alk paper) Subjects: LCSH: Chemistry, Organic | Chemistry, Organic—Textbooks Classification: LCC QD251.3 C37 2018 | DDC 547—dc23 LC record available at https://lccn.loc.gov/2018024902 The Internet addresses listed in the text were accurate at the time of publication The inclusion of a website does not indicate an endorsement by the authors or McGraw-Hill Education, and McGraw-Hill Education does not guarantee the accuracy of the information presented at these sites mheducation.com/highered Page v Each of the eleven editions of this text has benefited from the individual and collective contributions of the staff at McGraw-Hill They are the ones who make it all possible We appreciate their professionalism and thank them for their continuing support Page vii About the Authors Before Frank Carey retired in 2000, his career teaching chemistry was spent entirely at the University of Virginia In addition to this text, he is coauthor (with Robert C Atkins) of Organic Chemistry: A Brief Course and (with Richard J Sundberg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and advanced undergraduates Frank and his wife Jill are the parents of Andy, Bob, and Bill and the grandparents of Riyad, Ava, Juliana, Miles, Wynne, and Sawyer Robert M Giuliano was born in Altoona, Pennsylvania, and attended Penn State (B.S in chemistry) and the University of Virginia (Ph.D., under the direction of Francis Carey) Following postdoctoral studies with Bert FraserReid at the University of Maryland, he joined the chemistry department faculty of Villanova University in 1982, where he is currently Professor His research interests are in synthetic organic and carbohydrate chemistry Bob and his wife Margot, an elementary school teacher he met while attending UVa, are the parents of Michael, Ellen, and Christopher and the grandparents of Carina, Aurelia, Serafina, Lucia, and Francesca Neil T Allison was born in Athens, Georgia, and attended Georgia College (B.S., 1975, in chemistry) and the University of Florida (Ph.D., 1978, under the direction of W M Jones) Following postdoctoral studies with Emanuel Vogel at the University of Cologne, Germany, and Peter Vollhardt at the University of California, Berkeley, he joined the faculty of the Department of Chemistry and Biochemistry, University of Arkansas in 1980 His research interests are in physical organometallic chemistry and physical organic chemistry Neil and his wife Amelia met while attending GC, and are the parents of Betsy, Joseph, and Alyse and the grandparents of Beau Susan L Bane was raised in Spartanburg, South Carolina, and attended Davidson College (B.S., 1980, in chemistry) and Vanderbilt University (Ph.D., 1983, in biochemistry under the direction of J David Puett and Robley C Williams, Jr.) Following postdoctoral studies in bioorganic chemistry with Timothy L Macdonald at the University of Virginia, she joined the faculty of the Department of Chemistry of Binghamton University, State University of New York, in 1985 She is currently Professor of Chemistry and director of the Biochemistry Program Her research interests are in bioorganic and biophysical chemistry Susan is married to David Tuttle and is the mother of Bryant, Lauren, and Lesley Page viii Brief Contents List of Important Features xix Preface xxiii Acknowledgements xxx 1 Structure Determines Properties 2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons 54 3 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 98 4 Chirality 134 5 Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms 172 6 Nucleophilic Substitution 210 7 Structure and Preparation of Alkenes: Elimination Reactions 244 8 Addition Reactions of Alkenes 288 9 Alkynes 330 10 Introduction to Free Radicals 356 11 Conjugation in Alkadienes and Allylic Systems 384 12 Arenes and Aromaticity 426 13 Electrophilic and Nucleophilic Aromatic Substitution 476 14 Spectroscopy 532 15 Organometallic Compounds 600 16 Alcohols, Diols, and Thiols 638 17 Ethers, Epoxides, and Sulfides 676 18 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 714 19 Carboxylic Acids 764 20 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 800 21 Enols and Enolates 850 22 Amines 890 23 Carbohydrates 946 24 Lipids 996 25 Amino Acids, Peptides, and Proteins 1036 26 Nucleosides, Nucleotides, and Nucleic Acids 1098 27 Synthetic Polymers 1140 Appendix: Summary of Methods Used to Synthesize a Particular Functional Group A-1 Glossary G-1 Index I-1 Page ix Contents List of Important Features xix Preface xxiii Acknowledgements xxx CHAPTER Structure Determines Properties 1.1 Atoms, Electrons, and Orbitals Organic Chemistry: The Early Days 1.2 Ionic Bonds 1.3 Covalent Bonds, Lewis Formulas, and the Octet Rule 1.4 Polar Covalent Bonds, Electronegativity, and Bond Dipoles 11 Electrostatic Potential Maps 13 1.5 Formal Charge 14 1.6 Structural Formulas of Organic Molecules: Isomers 16 1.7 Resonance and Curved Arrows 20 1.8 Sulfur and Phosphorus-Containing Organic Compounds and the Octet Rule 24 1.9 Molecular Geometries 25 Molecular Models and Modeling 27 1.10 Molecular Dipole Moments 28 1.11 Curved Arrows, Arrow Pushing, and Chemical Reactions 29 1.12 Acids and Bases: The Brønsted–Lowry View 31 1.13 How Structure Affects Acid Strength 36 1.14 Acid–Base Equilibria 41 1.15 Acids and Bases: The Lewis View 44 1.16 Summary 45 Problems 48 Descriptive Passage and Interpretive Problems 1: Amide Lewis Structural Formulas 53 CHAPTER Alkanes and Cycloalkanes: Introduction to Hydrocarbons 54 2.1 Classes of Hydrocarbons 55 H, ~ :p· Hco~ + H H ·'o - H :0 Water I :0 + H Acetic acid Hyclronium ion pKa =0 stronger acid pKa = 4.7 weaker acid :o~ Acetate ion Here, the weaker acid (acetic acid) is on the left and the stronger acid (hydronium ion) is on the right The equilibrium constant position of equilibrium lies far to the left Keg = 10 7, and the Problem 39 What is the equilibrium constant for the following acid-base reactions? (a) ammonia and acetic acid (b) fl uoride ion and acetic acid (c) ethanol and hydrobromic acid Sample Solution (a) Always start with an equation for an acid-base reaction Ammonia is a Brnmsted base and accepts a proton from the -OH group of acetic acid Ammonia is converted to its conjugate acid, and acetic acid to its conjugate base H H :N/'°"+ I H Ammonia :0 H {}?~ Acetic acid pKa = 4.7 stronger acid ~ H H \+ - N- H I H Ammonium ion pKa = 9.3 weaker acid :Q + :o~ Acetate ion From their respective pKa's, we see that acetic acid is a much stronger acid than ammonium ion Therefore, the equilibrium lies to the right The equilibrium constant for the process is K eq 10-pK, of acetic acid (reactant) 10-4 = - - - - - - - - - - - = - -9= 10 46 · 10- pK, of ammonium ion (product) 10- -3 An unexpected fact emerges by working through this exercise We see that although acetic acid is a weak acid and ammonia is a weak base, the acid-base reaction between them is virtually complete Two important points come from using relative p.Ka's to analyze acid-base equilibria: Page43 They permit clear-cut distinctions between strong and weak acids and bases A strong acid is one that is stronger than H30+ Conversely, a weak acid is one that is weaker than H3O+ Example: The pKa's for the first and second ionizations of sulfuric acid are - 4.8 and 2.0, respectively Sulfuric acid (HOSO2OH) is a strong acid; hydrogen sulfate ion (HOSO2◊-) is a weak acid A strong base is one that is stronger than HO- Example: A common misconception is that the conjugate base of a weak acid is strong This is sometimes, but not always, tme It is tme, for example, for ammonia, which is a very weak acid (pKa 36) Its conj ugate base amide ion (H2NJ is a much stronger base than HO- It is not true, however, for acetic acid; both acetic acid and its conj ugate base acetate ion are weak The conjugate base of a weak acid will be strong only when the acid is a weaker acid than water The strongest acid present in significant amounts at equilibrium after a strong acid is dissolved in water is H3O+ The strongest acid present in significant amounts when a weak acid is dissolved in water is the weak acid itself Example: (H3O7 = 1.0 Min a 1.0 M aqueous solution ofHBr The concentration of undissociated HBr molecules is near zero (H3OJ = 0.004 M in a 1.0 M aqueous solution of acetic acid The concentration of undissociated acetic acid molecules is near 1.0 M Likewise, HO- is the strongest base that can be present in significant quantities in aqueous solution Problem 1.40 Rank the following in order of decreasing concentration in a solution prepared by dissolving 1.0 mol of sulfuric acid in enough water to give 1.0 L of solution (It is not necessary to any calculations.) H2S04, HS04- , S042-, H30+ Analyzing aci~ase reactions according to the Br0nsted-Lowry picture provides yet another benefit Tah]e ) 8, which lists acids according to their strength in descending order along with their conjugate bases, can be used to predict the direction of proton transfer Acid-base reactions in which a proton is transferred from an acid to a base that lies below it in the table have favorable equilibrium constants Proton transfers from an acid to a base that lies above it in the table are unfavorable Thus, the equilibrium constant for proton transfer from phenol to hydroxide ion is greater than 1, but that for proton transfer from phenol to hydrogen carbonate ion is less than H K>1 \ : Q -H Phenol Phenoxide ion Hydrox ide ion Water H K- ') )>- ')-N: + H- O : ~ ~ + H-C = CH N: ~ Each of the following acid-base reactions involves substances found in Table Use the pKa data in the table to help you predict the products of the reactions Use curved arrows to show electron flow Predict whether the equilibrium lies to the left or to the right and calculate the equilibrium constant for each reaction (a) HC- CH + -=NH2 (b) HC= CH + (c) -= q