STUDENT STUDY GUIDE AND SOLUTIONS MANUAL ORGANIC CHEMISTRY BY DAVID KLEIN 4TH EDITION

Student Study Guide and Solutions Manual, 4e for Organic Chemistry, 4e David Klein Johns Hopkins UniversitySVP, PUBLISHING STRATEGY AND QUALITY: Elizabeth Widdicombe ASSOCIATE PUBLISHER: Sladjana Bruno MARKETING MANAGER: Michael Olsen SENIOR MANAGING EDITOR: Mary Donovan EXECUTIVE MANAGING EDITOR: Valerie Zaborski EDITORIAL ASSISTANT: Samantha Hart COURSE CONTENT DEVELOPER: Andrew Moore SENIOR COURSE PROUCTION OPERATIONS SPECIALIST: Patricia Gutierrez SENIOR MANAGER, COURSE DEVELOPMENT AND PRODUCTION: Svetlana Barskaya ART DIRECTOR/COVER DESIGNER: Wendy Lai Cover: Wiley Cover Images: Abstract geometric texture ©bgblue/Getty Images, Flask – Norm Christiansen, Colorful Paintbrushes © Maartje van Caspel/Getty Images, Honeycomb slice © eli_asenova/Getty Images, Color diffuse © Korolkoff/Getty Images, Rosemary © Tetiana Rostopira/Getty Images 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. 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Upon completion of the review period, please return the evaluation copy to Wiley. Return instructions and a free of charge return shipping label are available at ISBN: 978‐1‐119‐65958‐7 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 The inside back cover will contain printing identification and country of origin if omitted from this page. In addition, if the ISBN on the back cover differs from the ISBN on this page, the one on the back cover is correct.CONTENTS Chapter 1 – Electrons, Bonds, and Molecular Properties 1 Chapter 2 – Molecular Representations 27 Chapter 3 – Acids and Bases 69 Chapter 4 – Alkanes and Cycloalkanes 110 Chapter 5 – Stereoisomerism 141 Chapter 6 – Chemical Reactivity and Mechanisms 173 Chapter 7 – Alkyl Halides: Nucleophilic Substitution and Elimination Reactions 195 Chapter 8 – Addition Reactions of Alkenes 262 Chapter 9 – Alkynes 317 Chapter 10 – Radical Reactions 368 Chapter 11 – Synthesis 409 Chapter 12 – Alcohols and Phenols 449 Chapter 13 – Ethers and Epoxides; Thiols and Sulfides 510 Chapter 14 – Infrared Spectroscopy and Mass Spectrometry 563 Chapter 15 – Nuclear Magnetic Resonance Spectroscopy 593 Chapter 16 – Conjugated Pi Systems and Pericyclic Reactions 639 Chapter 17 – Aromatic Compounds 682 Chapter 18 – Aromatic Substitution Reactions 717 Chapter 19 – Aldehydes and Ketones 790 Chapter 20 – Carboxylic Acids and Their Derivatives 865 Chapter 21 – Alpha Carbon Chemistry: Enols and Enolates 929 Chapter 22 – Amines 1010 Chapter 23 – Introduction to Organometallic Compounds 1071 Chapter 24 – Carbohydrates 1126 Chapter 25 – Amino Acids, Peptides, and Proteins 1154 Chapter 26 – Lipids 1183 Chapter 27 – Synthetic Polymers 1202HOW TO USE THIS BOOK Organic chemistry is much like bicycle riding. You cannot learn how to ride a bike by watching other people ride bikes. Some people might fool themselves into believing that it’s possible to become an expert bike rider without ever getting on a bike. But you know that to be incorrect (and very naïve). In order to learn how to ride a bike, you must be willing to get on the bike, and you must be willing to fall. With time (and dedication), you can quickly train yourself to avoid falling, and to ride the bike with ease and confidence. The same is true of organic chemistry. In order to become proficient at solving problems, you must “ride the bike”. You must try to solve the problems yourself (without the solutions manual open in front of you). Once you have solved the problems, this book will allow you to check your solutions. If, however, you don’t attempt to solve each problem on your own, and instead, you read the problem statement and then immediately read the solution, you are only hurting yourself. You are not learning how to avoid falling. Many students make this mistake every year. They use the solutions manual as a crutch, and then they never really attempt to solve the problems on their own. It really is like believing that you can become an expert bike rider by watching hundreds of people riding bikes. The world doesn’t work that way! The textbook has thousands of problems to solve. Each of these problems should be viewed as an opportunity to develop your problem-solving skills. By reading a problem statement and then reading the solution immediately (without trying to solve the problem yourself), you are robbing yourself of the opportunity provided by the problem. If you repeat that poor study habit too many times, you will not learn how to solve problems on your own, and you will not get the grade that you want. Why do so many students adopt this bad habit (of using the solutions manual too liberally)? The answer is simple. Students often wait until a day or two before the exam, and then they spend all night cramming. Sound familiar? Unfortunately, organic chemistry is the type of course where cramming is insufficient, because you need time in order to ride the bike yourself. You need time to think about each problem until you have developed a solution on your own. For some problems, it might take days before you think of a solution. This process is critical for learning this subject. Make sure to allot time every day for studying organic chemistry, and use this book to check your solutions. This book has also been designed to serve as a study guide, as described below. WHAT’S IN THIS BOOK This book contains more than just solutions to all of the problems in the textbook. Each chapter of this book also contains a series of exercises that will help you review the concepts, skills and reactions presented in the corresponding chapter of the textbook. These exercises are designed to serve as study tools that can help you identify your weak areas. Each chapter of this solutions manual/study guide has the following parts:• Review of Concepts. These exercises are designed to help you identify which concepts are the least familiar to you. Each section contains sentences with missing words (blanks). Your job is to fill in the blanks, demonstrating mastery of the concepts. To verify that your answers are correct, you can open your textbook to the end of the corresponding chapter, where you will find a section entitled Review of Concepts and Vocabulary. In that section, you will find each of the sentences, verbatim. • Review of Skills. These exercises are designed to help you identify which skills are the least familiar to you. Each section contains exercises in which you must demonstrate mastery of the skills developed in the SkillBuilders of the corresponding textbook chapter. To verify that your answers are correct, you can open your textbook to the end of the corresponding chapter, where you will find a section entitled SkillBuilder Review. In that section, you will find the answers to each of these exercises. • Review of Reactions. These exercises are designed to help you identify which reagents are not at your fingertips. Each section contains exercises in which you must demonstrate familiarity with the reactions covered in the textbook. Your job is to fill in the reagents necessary to achieve each reaction. To verify that your answers are correct, you can open your textbook to the end of the corresponding chapter, where you will find a section entitled Review of Reactions. In that section, you will find the answers to each of these exercises. • Review of Mechanisms. These exercises are designed to help you practice drawing the mechanisms. To verify that you have drawn the mechanism correctly, you can open your textbook to the corresponding chapter, where you will find the mechanisms appearing in numbered boxes throughout the chapter. In those numbered boxes, you will find the answers to each of these exercises. • Common Mistakes to Avoid. This is a new feature to this edition. The most common student mistakes are described, so that you can avoid them when solving problems. • A List of Useful Reagents. This is a new feature to this edition. This list provides a review of the reagents that appear in each chapter, as well as a description of how each reagent is used. • Solutions. At the end of each chapter, you’ll find detailed solutions to all problems in the textbook, including all SkillBuilders, conceptual checkpoints, additional problems, integrated problems, and challenge problems. The sections described above have been designed to serve as useful tools as you study and learn organic chemistry. Good luck! David Klein Johns Hopkins UniversityChapter 1 A Review of General Chemistry: Electrons, Bonds and Molecular Properties Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of Chapter 1. Each of the sentences below appears verbatim in the section entitled Review of Concepts and Vocabulary.  _____________ isomers share the same molecular formula but have different connectivity of atoms and different physical properties.  Second-row elements generally obey the _______ rule, bonding to achieve noble gas electron configuration.  A pair of unshared electrons is called a ______________.  A formal charge occurs when atoms do not exhibit the appropriate number of ___________________________.  An atomic orbital is a region of space associated with ____________________, while a molecular orbital is associated with _______________________.  Methane’s tetrahedral geometry can be explained using four degenerate _____-hybridized orbitals to achieve its four single bonds.  Ethylene’s planar geometry can be explained using three degenerate _____-hybridized orbitals.  Acetylene’s linear geometry is achieved via _____-hybridized carbon atoms.  The geometry of small compounds can be predicted using valence shell electron pair repulsion (VSEPR) theory, which focuses on the number of  bonds and _______________ exhibited by each atom.  The physical properties of compounds are determined by __________________ forces, the attractive forces between molecules.  London dispersion forces result from the interaction between transient __________________ and are stronger for larger alkanes due to their larger surface area and ability to accommodate more interactions. Review of Skills Fill in the blanks and empty boxes below. To verify that your answers are correct, look in your textbook at the end of Chapter 1. The answers appear in the section entitled SkillBuilder Review. SkillBuilder 1.1 Drawing Constitutional Isomers of Small Molecules SkillBuilder 1.2 Drawing the Lewis Structure of a Small Molecule2 CHAPTER 1 SkillBuilder 1.3 Calculating Formal Charge SkillBuilder 1.4 Locating Partial Charges Resulting from Induction SkillBuilder 1.5 Reading Bond-Line Structures SkillBuilder 1.6 Identifying Electron Configurations 1s 2s 2p 1s 2s 2p Nitrogen Step 1 In the energy diagram shown here, draw the electron configuration of nitrogen (using arrows to represent electrons). Step 2 Fill in the boxes below with the numbers that correctly describe the electron configuration of nitrogen. SkillBuilder 1.7 Identifying Hybridization StatesCHAPTER 1 3 SkillBuilder 1.8 Predicting Geometry SkillBuilder 1.9 Identifying the Presence of Molecular Dipole Moments SkillBuilder 1.10 Predicting Physical Properties H C O H H H C H H C C O H H H H H H C C H H H H H C H H H C C H H H H H C C H H H H H C H H H3C C CH3 CH2 H3C C CH3 O Circle the compound below that is expected to have the higher boiling point. Dipole-Dipole Interactions Circle the compound below that is expected to have the higher boiling point. Hydrogen-Bonding Interactions Circle the compound below that is expected to have the higher boiling point. Carbon Skeleton A Common Mistake to Avoid When drawing a structure, don’t forget to draw formal charges, as forgetting to do so is a common error. If a formal charge is present, it MUST be drawn. For example, in the following case, the nitrogen atom bears a positive charge, so the charge must be drawn: As we progress though the course, we will see structures of increasing complexity. If formal charges are present, failure to draw them constitutes an error, and must be scrupulously avoided. If you have trouble drawing formal charges, go back and master that skill. You can’t go on without it. Don’t make the mistake of underestimating the importance of being able to draw formal charges with confidence.4 CHAPTER 1 Solutions 1.1. (a) Begin by determining the valency of each atom that appears in the molecular formula. The carbon atoms are tetravalent, while the chlorine atom and hydrogen atoms are all monovalent. The atoms with more than one bond (in this case, the three carbon atoms) should be drawn in the center of the compound. Then, the chlorine atom can be placed in either of two locations: i) connected to the central carbon atom, or ii) connected to one of the other two (equivalent) carbon atoms. The hydrogen atoms are then placed at the periphery (ensuring that each carbon atom has a total of four bonds). The formula C3H7Cl has two constitutional isomers. (b) Begin by determining the valency of each atom that appears in the molecular formula. The carbon atoms are tetravalent, while the hydrogen atoms are all monovalent. The atoms with more than one bond (in this case, the four carbon atoms) should be drawn in the center of the compound. There are two different ways to connect four carbon atoms. They can either be arranged in a linear fashion or in a branched fashion: We then place the hydrogen atoms at the periphery (ensuring that each carbon atom has a total of four bonds). The formula C4H10 has two constitutional isomers: (c) Begin by determining the valency of each atom that appears in the molecular formula. The carbon atoms are tetravalent, while the hydrogen atoms are all monovalent. The atoms with more than one bond (in this case, the five carbon atoms) should be drawn in the center of the compound. So we must explore all of the different ways to connect five carbon atoms. First, we can connect all five carbon atoms in a linear fashion: Alternatively, we can draw four carbon atoms in a linear fashion, and then draw the fifth carbon atom on a branch. There are many ways to draw this possibility: Finally, we can draw three carbon atoms in a linear fashion, and then draw the remaining two carbon atoms on separate branches. Note that we cannot draw a unique carbon skeleton (a unique arrangement of carbon atoms) simply by placing the last two carbon atoms together as one branch, because that possibility has already been drawn earlier (a linear chain of four carbon atoms with a single branch): In summary, there are three different ways to connect five carbon atoms: We then place the hydrogen atoms at the periphery (ensuring that each carbon atom has a total of four bonds). The formula C5H12 has three constitutional isomers: (d) Begin by determining the valency of each atom that appears in the molecular formula. The carbon atoms are tetravalent, the oxygen atom is divalent, and the hydrogen atoms are all monovalent. Any atoms with more than one bond (in this case, the four carbon atoms and the one oxygen atom) should be drawn in the center of the compound, with the hydrogen atoms at the periphery. There are several different ways to connect four carbon atoms and one oxygen atom. Let’s begin with the four carbon atoms. There are two different ways to connect four carbon atoms. They can either be arranged in a linear fashion or in a branched fashion.CHAPTER 1 5 Next, the oxygen atom must be inserted. For each of the two skeletons above (linear or branched), there are several different locations to insert the oxygen atom. The linear skeleton has four possibilities, shown here: C CC 1 2 3 C4 C CC 1 2 3 C4 O CC 1 2 3 C4 O O C C CO 1 2 3 C4 C and the branched skeleton has three possibilities shown here: Finally, we complete all of the structures by drawing the bonds to hydrogen atoms (ensuring that each carbon atom has four bonds, and each oxygen atoms has two bonds).