THEORY AND PROBLEMS OF Third Edition MEISLICH, Ph.D. HOWARD NECHAMKIN, Ed.D. Professor Emeritus of Chemistry Trenton State College AREFKIN, Ph.D. GEORGE J. HADEMENOS, Ph.D. Visiting Assistant Professor Department of Physics University of Dallas Schaum’s Outline Series McGRAW-HILL New York San Francisco Washington, D.C. Auckland Bogoth Caracas Lisbon London Madrid Mexico City Milan Montreal New Delhi San Juan Singapore Sydney Tokyo Toronto HERBERT MEISLICH holds a B.A. degree from Brooklyn College and an M.A. and Ph.D. from Columbia University. He is a professor emeritus from the City College of CUNY, where he taught Organic and General Chemistry for forty years at both the undergraduate and doctoral levels. He received the Outstanding Teacher award in 1985, and has coauthored eight textbooks, three laboratory manuals in General and Organic Chemistry, and 15 papers on his research interests. HOWARD NECHAMKIN is Professor Emeritus of Chemistry at Trenton State College; for 11 years of his tenure he served as Department Chairman. His Bachelor’s degree is from Brooklyn College, his Master’s from the Polytechnic Institute of Brooklyn and his Doctorate in Science Education from New York University. He is the author or coauthor of 53 papers and 6 books in the areas of inorganic, analytical, and environmental chemistry. JACOB SHAREFKIN is Professor Emeritus of Chemistry at Brooklyn College. After receiving a B.S. from City College of New York, he was awarded an M.A. from Columbia University and a Ph.D. from New York University. His publications and research interest in Qualitative Organic Analysis and organic boron and iodine compounds have been supported by grants from the American Chemical Society, for whom he has also designed national examinations in Organic Chemistry. GEORGE J. HADEMENOS is a Visiting Assistant Professor of Physics at the University of Dallas. He received his B.S. with a combined major of physics and chemistry from Angelo State University, his M.S. and Ph.D. in physics from the University of Texas at Dallas, and completed postdoctoral fellowships in nuclear medicine at the University of Massachusetts Medical Center and in radiological sciences/biomedical physics at UCLA Medical Center. His research interests have involved biophysical and biochemical mechanisms of disease processes, particularly cerebrovascular diseases and stroke. He has published his work in journals such as American Scientist, Physics Today, Neurosurgery, and Stroke. In addition, he has written three books: Physics of Cerebrovascular Diseases: Biophysical Mechanisms of’ Development, Diagnosis, and Therap-y, published by Springer-Verlag; Schaum S Outline of Physics jor Pre-Med, Biolog,v, und Allied Health Students, and Schaum S Outline of Biology, coauthored with George Fried, Ph.D., both published by McGraw-Hill. Among other courses, he teaches general physics for biology and pre-med students. Schaum’s Outline of Theory and Problems of ORGANIC CHEMISTRY Copyright 0 1999, 1991, 1977 by The McGraw-Hill Companies, Inc. All rights reserved. Printed in the United States of America. Except as permitted under the 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. 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 PRS PRS 9 0 2 I 0 9 ISBN 0-07-134165-x Sponsoring Editor: Barbara Gilson Production Supervisor: Shem Souffrance Editing Supervisor: Maureen Walker Project Management: Techset Composition Limited Library of Congress Cataloging-in-Publication Data Schaum’s outline of theory and problems of organic chemistry / Herbert Meislich [et al.]. 3rd ed. p. cm. (Schaum’s outline series) Includes index. ISBN 0-07-134165-X 1. Chemistry, Organic Problems, exercises, etc. 2. Chemistry, Organic Outlines, syllabi, etc. I. Meislich, Herbert. 11. Title: Theory and problems of organic chemistry. 111. Title: Organic Chemistry, QD257.M44 1999 547 dc2 1 99-2858 1 PID Lll McGraw - Hill E A Division of The McGmw-HiU Companies To Amy Nechamkin, Belle D. Sharefkin, John 6. Sharefkin, Kelly Hademenos, and Alexandra Hademenos The beginning student in Organic Chemistry is often overwhelmed by facts, concepts, and new language. Each year, textbooks of Organic Chemistry grow in quantity of subject matter and in level of sophistication. This Schaum’s Outline was undertaken to give a clear view of first-year Organic Chemistry through the careful detailed solution of illustrative problems. Such problems make up over 80% of the book, the remainder being a concise presentation of the material. Our goal is for students to learn by thinking and solving problems rather than by merely being told. This book can be used in support of a standard text, as a supplement to a good set of lecture notes, as a review for taking professional examinations, and as a vehicle for self-instruction. The second edition has been reorganized by combining chapters to emphasize the similarities of fhctional groups and reaction types as well as the differences. Thus, polynuclear hydrocarbons are combined with benzene and aromaticity. Nucleophilic aromatic displacement is merged with aromatic substitution. Sulfonic acids are in the same chapter with carboxylic acids and their derivatives, and carbanion condensations are in a separate new chapter. Sulfur compounds are discussed with their oxygen analogs. This edition has also been brought up to date by including solvent effects, CMR spectroscopy, an elaboration of polymer chemistry, and newer concepts of stereochemistry, among other material. HERBERTMEISLICH HOWARDNECHAMKIN JACOB SHAREFKIN GEORGE J. HADEMENOS 1 CHAPTER 9. CHAPTER 2 CHAPTER 3 CHAPTER 4 STRUCTURE AND PROPERTIES OF ORGANIC COMPOUNDS 1.1 1.2 I .3 1.4 1.5 Carbon Compounds 1 Lewis Structural Formulas 2 Types of Bonds 6 Functional Groups 6 Formal Charge 7 BONDING AND MOLECULAR STRUCTURE 13 2.1 Atomic Orbitals 13 2.2 Covalent Bond Formation-Molecular Orbital (MO) Method 14 2.3 Hybridization of Atomic Orbitals 17 2.4 Electronegativity and Polarity 21 2.5 Oxidation Number 21 2.6 Intermolecular Forces 22 2.7 Solvents 22 2.8 Resonance and Delocalized n Electrons 23 CHEMICAL REACTIVITY AND ORGANIC REACTIONS 31 3.1 Reaction Mechanism 31 3.2 Carbon-Containing Intermediates 31 3.3 Types of Organic Reactions 33 3.4 Electrophilic and Nucleophilic Reagents 35 3.5 Thermodynamics 36 3.6 Bond-Dissociation Energies 37 3.7 Chemical Equilibrium 37 3.8 Rates of Reactions 39 3.9 Transition-State Theory and Enthalpy Diagrams 39 3.10 Bronsted Acids and Bases 42 3.1 1 Basicity (Acidity) and Structure 43 3.12 Lewis Acids and Bases 44 ALKANES 50 4.1 Definition 50 4.2 Nomenclature of Alkanes 54 4.3 Preparation of Alkanes 56 4.4 Chemical Properties of Alkanes 58 4.5 Summary of Alkane Chemistry 62 CONTENTS CHAPTER 5 CHAPTER 6 CHAPTER 7 CHAPTER $ CHAPTER 9 STEREOC H EM ISTRY 69 5.1 Stereoisomerism 69 5.2 Optical Isomerism 70 5.3 Relative and Absolute Configuration 72 5.4 Molecules with More Than One Chiral Center 77 5.5 Synthesis and Optical Activity 79 ALKENES 87 6.1 Nomenclature and Structure 87 6.2 Geometric (cis-tram) Isomerism 88 6.3 Preparation of Alkenes 91 6.4 Chemical Properties of Alkenes 95 6.5 Substitution Reactions at the Allylic Position 105 6.6 Summary of Alkene Chemistry ALKYL HALIDES 7.1 Introduction 7.2 Synthesis of RX 7.3 Chemical Properties 7.4 Summary of Alkyl Halide Chemistry ALKYNES AND DIENES 8.1 Alkynes 8.2 Chemical Properties of Acetylenes 8.3 Alkadienes 8.4 MO Theory and Delocalized n: Systems 8.5 Addition Reactions of Conjugated Dienes 8.6 Polymerization of Dienes 8.7 C ycloaddition 8.8 Summary of Alkyne Chemistry 8.9 Summary of Diene Chemistry CYCLIC HYDROCARBONS 9.1 Nomenclature and Structure 9.2 Geometric Isomerism and Chirality 9.3 Conformations of Cycloalkanes 9.4 Synthesis 9.5 Chemistry 9.6 MO Theory of Pericyclic Reactions 9.7 Terpenes and the Isoprene Rule 107 118 118 119 121 132 140 140 143 146 147 149 153 154 154 154 162 162 163 166 173 175 177 181 CONTENTS CHAPTER 10 BENZENE AND POLYNUCLEAR AROMATIC COMPOUNDS 189 10.1 Introduction 189 10.2 Aromaticity and Huckel’s Rule 193 10.3 Antiaromaticity 194 10.4 Polynuclear Aromatic Compounds 197 1 0.5 Nomenclature 198 10.6 Chemical Reactions 199 10.7 Synthesis 202 CHAPTER 12 AROMATIC SUBSTITUTION. ARENES 205 1 1.1 Aromatic Substitution by Electrophiles (Lewis Acids, E+ or E) 205 1 1.2 Electrophilic Substitutions in Syntheses of Benzene Derivatives 214 1 1.3 Nucleophilic Aromatic Substitutions 215 11.4 Arenes 218 11.5 Summary of Arene and Aryl Halide Chemistry 223 CHAPTER 12 SPECTROSCOPY AND STRUCTURE 230 1 2.1 Introduction 230 12.2 Ultraviolet and Visible Spectroscopy 23 1 12.3 Infrared Spectroscopy 233 12.4 Nuclear Magnetic Resonance (Proton, PMR) 236 12.5 13C NMR (CMR) 245 12.6 Mass Spectroscopy 247 CHAPTER 13 ALCOHOLS AND THIOLS 256 A. Alcohols 256 1 3.1 Nomenclature and H-Bonding 256 13.2 Preparation 258 13.3 Reactions 262 13.4 Summary of Alcohol Chemistry 266 B. Thiols 267 13.5 General 267 13.6 Summary of Thiol Chemistry 268 CHAPTER 24 ETHERS, EPOXIDES, GLYCOLS, AND THIOETHERS 278 A. Ethers 278 14.1 Introduction and Nomenclature 278 CONTENTS 14.2 Preparation 279 14.3 Chemical Properties 282 14.4 Cyclic Ethers 285 14.5 Summary of Ether Chemistry 286 B. Epoxides 287 14.6 Introduction 287 14.7 Synthesis 287 14.8 Chemistry 288 14.9 Summary of Epoxide Chemistry 290 C. Glycols 29 1 14.10 Preparation of 1,2-Glycols 29 1 14.11 Unique Reactions of Glycols 292 14.12 Summary of Glycol Chemistry 294 D. Thioethers 294 14.13 Introduction 294 14.14 Preparation 295 14.15 Chemistry 295 CHAPTER 15 CARBONYL COMPOUNDS: ALDEHYDES AND KETONE 302 15.1 Introduction and Nomenclature 302 15.2 Preparation 305 15.3 Oxidation and Reduction \ 3 10 15.4 Addition Reactions of Nucleophiles to ,C=O 313 15.5 Addition of Alcohols: Acetal and Ketal Formation 317 15.6 Attack by Ylides; Wittig Reaction 319 15.7 Miscellaneous Reactions 321 15.8 Summary of Aldehyde Chemistry 323 15.9 Summary of Ketone Chemistry 324 CHAPTER 16 CARBOXYLIC ACIDS AND THEIR DERIVATIVES 331 16.1 Introduction and Nomenclature 33 1 16.2 Preparation of Carboxylic Acids 334 16.3 Reactions of Carboxylic Acids 336 16.4 Summary of Carboxylic Acid Chemistry 342 16.5 Polyfunctional Carboxylic Acids 342 1 6.6 Transacylation; Interconversion of Acid Derivatives 346 16.7 More Chemistry of Acid Derivatives 349 16.8 Summary of Carboxylic Acid Derivative Chemistry 356 16.9 Analytical Detection of Acids and Derivatives 356 16.10 Carbonic Acid Derivatives 358 16.1 1 Summary of Carbonic Acid Derivative Chemistry 359 16.12 Synthetic Condensation Polymers 360 16.13 Derivatives of Sulfonic Acids 361 CONTENTS CARBANION-ENOLATES AND ENOLS 373 17.1 Acidity of H’s a to C=O; Tautomerism 373 17.2 Alkylation of Simple Carbanion-Enolates 377 17.3 Alkylation of Stable Carbanion-Enolates 380 1 7.4 Nucleophilic Addition to Conjugated Carbonyl Compounds: Michael 3’4-Addition 385 17.5 Condensations 386 400 18.1 Nomenclature and Physical Properties 400 18.2 Preparation 402 18.3 Chemical Properties 407 18.4 Reactions of Quaternary Ammonium Salts 413 18.5 Ring Reactions of Aromatic Arnines 414 18.6 Spectral Properties 416 18.7 Reactions of Aryl Diazonium Salts 416 18.8 Summary of Amine chemistry 419 PHENOLIC COMPOUNDS 430 19.1 1 9.2 19.3 19.4 19.5 19.6 Introduction 430 Preparation 43 1 Chemical Properties 433 Analytical Detection of Phenols 440 Summary of Phenolic Chemistry 44 1 Summary of Phenolic Ethers and Esters 44 1 2 AROMATIC H ETEROCY CLIC CO M POU N DS 448 ~~~~~~~ 20.1 Five-Membered Aromatic Heterocycles with One Heteroatom 448 20.2 Six-Membered Heterocycles with One Heteroatom 454 20.3 Compounds with Two Heteroatoms 458 20.4 Condensed Ring Systems 458 INDEX 465 !- Structure and Properties of Organic Compounds ON COMPOUNDS Orgatuc chemistry is the study of carbon (C) compounds, all of which have covalent bonds. Carbon atoms can bond to each other to form open-chain compounds, Fig. l-l(u), or cyclic (ring) compounds, Fig. 1-1 (c). Both types can also have branches of C atoms, Fig. 1 - 1 (b) and (6). Saturated compounds have C’s bonded to each other by single bonds, C-C; unsaturated compounds have C’s joined by multiple bonds. Examples with double bonds and triple bonds are shown in Fig. I-l(e). Cyclic compounds having at least one atom in the ring other than C (a heteroatom) are called heterocyclics, Fig. 1-10 The heteroatoms are usually oxygen (0), nitrogen (N), or sulhr (S). I aroblem 1.1 Why are there so many compounds that contain carbon? 4 Bonds between C’s are covalent and strong, so that C’s can form long chains and rings, both of which may have branches. C’s can bond to almost every element in the periodic table. Also, the number of isomers increases as the oreanic molecules become more complex. I 3roblem 1.2 CC 5mpare and contrast the properties of ionic and covalent compounds. 4 Ionic compou nds are generally inorganic; have high melting and boiling points due to the strong electrostatic .~ forces attracting the oppositely charged ions; are soluble in water and insoluble in organic solvents; are hard to bum; involve reactions that are rapid and simple; also bonds between like elements are rare, with isomerism being unusual. Covalent compounds, on the other hand, are commonly organic; have relatively low melting and boiling points because of weak intermolecular forces; are soluble in organic solvents and insoluble in water; bum readily and are thus susceptible to oxidation because they are less stable to heat, usually decomposing at temperatures above 700°C; involve reactions that are slow and complex, often needing higher temperatures and/or catalysts, yielding mixtures of products; also, honds between carbon atoms are typical, with isomerism being common. 1 [...]... [H3NOH]+ There are 25 valence electrons, 21 from three Cl’s and 4 from C The Lewis dot formula shows 26 electrons It has a charge of 25 - 26 = - 1 and is the trichloromethide anion, :CCl, + 6 STRUCTURE AND PROPERTIES OF ORGANIC COMPOUNDS [CHAP 1 1.3 TYPES OF BONDS Covalent bonds, the mainstays of organic compounds, are formed by the sharing of pairs of electrons Sharing can OCCLU in two ways: (1) A* B +... should equal the sum of all the valence electrons of the individual atoms in the molecule Each bond represents a shared pair of electrons (a) N needs three covalent bonds, and H needs one Each N is bonded to the other N and to two H’s: H H I H-N-N-H I (b) C is bonded to 0 and to each C1 To satisfy the tetravalence of C and the divalence of 0, a double bond is placed between C and 0 :0: II cl( c1: ... bonded to one of the 0 atoms and a double bond is placed between the N and the other 0 (Convince yourself that bonding the H to the N would not lead to a viable structure.) STRUCTURE AND PROPERTIES OF ORGANIC COMPOUNDS CHAP 11 5 Problem 1.6 Why is none of the following Lewis structures for COCl, correct? (h) :CI-C=O-Cl: ( a ) :Cl-C=6-Cl: ((.) :C+C=ij-.CI: (6) :Cl=C=O-C1: 4 The total number of valence... is planar, and ethyne, which is linear, the structures in Fig 1- 1 are all three-dimensional Organic compounds show a widespread occurrence of isomers, which are compounds having the same molecular formula but different structural formulas, and therefore possessing different properties This T phenomenon of isomerism is exemplified by isobutane and n-butane [Fig 1-l(a) and (b)] he number of isomers... chemical properties and often exhibiting a regular gradation in physical properties with increasing molecular weight Problem 1.11 Methane, CH,; ethane, C2H6; and propane, C3H, are the first three members of the alkane homologous series By what structural unit does each member differ from its predecessor? 4 CHAP 11 7 STRUCTURE AND PROPERTIES OF ORGANIC COMPOUNDS These members differ by a C and two H’s; the... Asterisk indicates antibonding Head-to-head overlap of AO’s gives a sigma (a) MO-the bonds are called a bonds, Fig 2-2(a) The corresponding antibonding MO* is designated a*,Fig 2-2(b) The imaginary line joining the nuclei of the bonding atoms is the bond axis, whose length is the bond length a and S 0 and S and P P ( a ) o Bonding 0 8 and ’ i and S and P P O*@P) ( 6 )o*Antibonding Fig 2-2 Two parallel... (plane of zero electronic density) perpendicular to the crosssectional plane of the n bond Single bonds are 0 bonds A double bond is one 0 and one n bond A triple bond is one a and two n bonds (a n, and a ny, if the triple bond is taken along the x-axis) Although MO’s encompass the entire molecule, it is best to visualize most of them as being localized between pairs of bonding atoms This description of. .. bonding is called linear combination of atomic orbitals (LCAO) P Y ( a ) TI Bonding pv PY (h) n*Antibond ing Fig 2-3 16 BONDING AND MOLECULAR STRUCTURE Problem 2.2 What type of MO results from side-to-side overlap of an s and a p orbital? [CHAP 2 4 The overlap is depicted in Fig 2-4 The bonding strength generated from the overlap between the +s A 0 and the and the portion of the p The MO is nonbonding (n);... number of a and n bonds between two atoms; i.e., 1 for a single bond, 2 for a double bond, 3 for a triple bond Problem 2.6 The MO’s formed when the two sets of the three 2p orbitals overlap are 712p,.”2p~a2px71~~~n~p:a~px (the n and n* pairs are degenerate) (a) Show how MO theory predicts the paramagnetism of 02.6) What is the bond ( order in O,? 4 The valence sequence of MO’s formed from overlap of the... effect does hybridization have on the stability of bonds? 4 Hybrid orbitals can ( a ) overlap better and (b)provide greater bond angles, thereby minimizing the repulsion between pairs of electrons and making for great stability By use of the generalization that each unshared and a-bonded pair of electrons needs a hybrid orbital, but 7t bonds do not, the number of hybrid orbitals (HON) needed by C or any . Chemistry, Organic Problems, exercises, etc. 2. Chemistry, Organic Outlines, syllabi, etc. I. Meislich, Herbert. 11. Title: Theory and problems of organic chemistry. 111. Title: Organic. THEORY AND PROBLEMS OF Third Edition MEISLICH, Ph.D. HOWARD NECHAMKIN, Ed.D. Professor Emeritus of Chemistry Trenton State College AREFKIN,. Among other courses, he teaches general physics for biology and pre-med students. Schaum’s Outline of Theory and Problems of ORGANIC CHEMISTRY Copyright 0 1999, 1991, 1977 by The McGraw-Hill