Instructor's Resource Manual with Test Bank Organic Chemistry

Instructor’s Resource Manual with Test Bank Organic Chemistry: A Short Course Twelfth Edition Harold Hart Michigan State University Leslie E. Craine Central Connecticut State University David J. Hart The Ohio State University Christopher M. Hadad The Ohio State University HOUGHTON MIFFLIN COMPANY Bo...

Instructor’s Resource Manual with Test Bank Organic Chemistry: A Short Course Twelfth Edition Harold Hart Michigan State University Leslie E. Craine Central Connecticut State University David J. Hart The Ohio State University Christopher M. Hadad The Ohio State University HOUGHTON MIFFLIN COMPANY Boston New York Publisher: Charles Hartford Executive Editor: Richard Stratton Sr. Development Editor: Rita Lombard Editorial Associate: Henry Cheek Assistant Editor: Liz Hogan Marketing Manager: Laura McGinn Marketing Assistant: Kris Bishop Copyright © 2007 by Houghton Mifflin Company. All rights reserved. Houghton Mifflin Company hereby grants you permission to reproduce the Houghton Mifflin material contained in this work in classroom quantities, solely for use with the accompanying Houghton Mifflin textbook. All reproductions must include the Houghton Mifflin copyright notice, and no fee may be collected except to cover the cost of duplication. If you wish to make any other use of this material, including reproducing or transmitting the material or portions thereof in any form or by any electronic or mechanical means including any information storage or retrieval system, you must obtain prior written permission from Houghton Mifflin Company, unless such use is expressly permitted by federal copyright law. If you wish to reproduce material acknowledging a rights holder other than Houghton Mifflin Company, you must obtain permission from the rights holder. Address inquiries to College Permissions, Houghton Mifflin Company, 222 Berkeley Street, Boston, MA 02116-3764. ISBN-10: 0-618-59079-X ISBN-13: 978-0-618-59079-7 1 2 3 4 5 6 7 8 9-XX-10 09 08 07 06 Contents Preface v Transition Guide for Instructors Switching from the Eleventh to Twelfth Edition of Organic Chemistry: A Short Course PART I The Text Chapter 1 Chapter 2 Chapter Chapter Chapter Chapter 3 4 5 6 Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter 7 8 9 10 11 12 13 14 15 16 17 18 1 Bonding and Isomerism 6 Alkanes and Cycloalkanes; Conformational and Geometric Isomerism 7 Alkenes and Alkynes 7 Aromatic Compounds 8 Stereoisomerism 9 Organic Halogen Compounds; Substitution and Elimination Reactions 10 Alcohols, Phenols, and Thiols 10 Ethers and Epoxides 11 Aldehydes and Ketones 12 Carboxylic Acids and Their Derivatives 13 Amines and Related Nitrogen Compounds 14 Spectroscopy and Structure Determination 14 Heterocyclic Compounds 15 Synthetic Polymers 15 Lipids and Detergents 16 Carbohydrates 17 Amino Acids, Peptides, and Proteins 17 Nucleotides and Nucleic Acids 18 vi PART II The Study Guide 19 Answers to Synthesis-Type Problems in the Study Guide PART III Test Bank Chapter 1 Chapter 2 Chapter Chapter Chapter Chapter 3 4 5 6 Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter Chapter 7 8 9 10 11 12 13 14 15 16 17 18 19 36 Bonding and Isomerism 36 Alkanes and Cycloalkanes; Conformational and Geometric Isomerism 44 Alkenes and Alkynes 53 Aromatic Compounds 67 Stereoisomerism 80 Organic Halogen Compounds; Substitution and Elimination Reactions 91 Alcohols, Phenols, and Thiols 100 Ethers and Epoxides 107 Aldehydes and Ketones 115 Carboxylic Acids and Their Derivatives 129 Amines and Related Nitrogen Compounds 139 Spectroscopy and Structure Determination 152 Heterocyclic Compounds 163 Synthetic Polymers 174 Lipids and Detergents 185 Carbohydrates 197 Amino Acids, Peptides, and Proteins 212 Nucleotides and Nucleic Acids 224 Preface This three-part instructor’s resource manual (IRM) is written to accompany the twelfth edition of Hart: Organic Chemistry: A Short Course and its accompanying Study Guide and Solutions Manual. We hope that it will help users of these books with their course planning. Part I of this manual deals with the text, Organic Chemistry: A Short Course. Tables suggest the approximate number of lectures to devote to each chapter and provide a summary of the worked examples and problems. A chapter-by-chapter outline lists those sections that are most important and those that may be skipped or assigned as optional. Part II of this manual provides answers to the review problems on synthesis featured in the Study Guide and Solutions Manual. The study guide itself includes answers to all the text problems and suggestions for solving them. It also includes a summary of each chapter, a summary of reactions and reaction mechanisms introduced in the chapter, and a list of learning objectives for each chapter. Near the end, the study guide also contains a summary of synthetic methods for each major class of compounds and a summary of reaction mechanisms. In addition, it contains review problems on synthesis and 110 sample multiple-choice test questions with an answer key. With this edition we are pleased to offer your students a Study Guide and Solutions Manual and access to materials on the text’s Online Study Center (OSC) located at: http://college.hmco.com/pic/hart12e Resources on the OSC include “A Closer Look” links, dynamic Flashcards, Ace practice quizzes, and visualization animations complete with Practice Questions. Part III of this manual includes a bank of approximately 800 multiple choice test questions. An answer key is also provided. This IRM has customarily contained a section devoted to the Laboratory Manual for Organic Chemistry: A Short Course. This material will now appear in a separate ancillary called the Instructor’s Resource Manual for the Laboratory Manual. Copyright © Houghton Mifflin Company. All rights reserved. v Transition Guide for Instructors Switching from the Eleventh to Twelfth Edition of Organic Chemistry: A Short Course If you used the Eleventh Edition of Organic Chemistry: A Short Course, you will find the Twelfth Edition is a minor revision. There are no changes in section numbers and only a few changes in figure and equation numbers. There are a few changes, however, that you should know about. These focus on improving graphics in a more pedagogically useful manner, and include the following general changes: New ball-and-stick structures have been added throughout the text to help students visualize molecules in three dimensions. Problems have been added that require students to develop their three-dimensional visualization skills. For example, students are given a ball-and-stick structure and asked to name the compound, or assign stereochemistry at a stereogenic center. Electrostatic potential maps have been added in places that should help you discuss acid-base chemistry. The electrostatic potential diagrams are color-coded to show sites of high electron density (red) and relative electron deficiency (blue), which can be used to describe properties of molecules and the nature of intermolecular interactions. Three-dimensional structures have been added to several energy-reaction diagrams to better illustrate the structural changes that occur as reactions proceed from reactants to products. Other changes include increased use of the arrow-pushing formalism to facilitate teaching and understanding of reaction mechanisms. Three new A Closer Look At sections have been added. Activities that include computer manipulations of structures and visualization animations, available for use by students at the Online Student Center, have been updated and expanded. Substantive changes that might affect your lecture plans are noted below on a chapter-by-chapter basis. Chapter 1: vi Figure 1.10 has been added to the text. This figure compares dash-wedge, ball-andstick, space-filling and electrostatic potential map structures of methane. It is an important addition because all of these representations of molecules are used throughout the text, particularly when stereochemical issues are discussed. We encourage you to take time to discuss these representations with your students and compare them with representations of methane (and other molecules) that do not provide stereochemical information. Copyright © Houghton Mifflin Company. All rights reserved. Chapter 2: An electrostatic potential map, added to Figure 2.2, is intended to help with a discussion of hydrogen bonding within the context of the structure of water. Ball-and-stick and space-filling models have been added to Figure 2.4 to help students visualize the molecular surfaces involved in intermolecular interactions. New ball-and-stick structures have been introduced throughout Section 2.9 (cycloalkanes). Problems 2.33 and 2.35 will encourage students to develop three-dimensional visualization skills. Chapter 3: Electrostatic potential maps added to Figures 3.1 and 3.7 (ethylene), Equation 3.34 (allylic carbocation), and Figure 3.17 (acetylene), illustrate pi-electron distribution in three important structures. Ball-and-stick models have been added to help illustrate the process of alkene isomerization (Equation 3.2) and the addition of HBr to ethylene (Figure 3.11). Problems 3.34, 3.41 and 3.58 will encourage students to develop three-dimensional visualization skills. Chapter 4: Electrostatic potential maps that illustrate the pi-electron distribution in benzene (Figure 4.4 and 4.6), toluene (Figure 4.6) and nitrobenzene (Figure 4.6) should help a discussion of electrophilic aromatic substitution reactions. Ball-and-stick structures illustrate the structure of intermediates in the electrophilic aromatic substitution reactions (Figure 4.5). Problems 4.41 require students to develop three-dimensional visualization skills. Chapter 5: Problems 5.28, 5.31, 5.36, 5.37 and 5.51 require students to develop threedimensional visualization skills. Chapter 6: Ball-and-stick structures have been added to illustrate structural changes that occur in energy-reaction diagrams describing the SN 2 and SN1 reactions (Figures 6.1 and 6.2). Space-filling models and ball-and-stick structures are used to illustrate the difference in base size between ethoxide and t-butoxide. Problems 6.7, 6.20, 6.23 and 6.25 require students to develop three-dimensional visualization skills. Copyright © Houghton Mifflin Company. All rights reserved. vii Chapter 7: An electrostatic potential map of 1-propanol (Figure 7.1) can be used in a discussion of hydrogen-bonding properties of alcohols. Probems 7.1, 7.14, 7.16, 7.28, 7.46, 7.50 and 7.51 require students to develop threedimensional visualization skills. Chapter 8: Electrostatic potential maps of dimethyl ether and ethylene oxide (Figure 8.1) illustrate the basic nature of the oxygen in ethers. Ball-and-stick structures are used in Section 8.9 to illustrate the three-dimensional structures of cyclic ethers (tetrahydrofuran, tetrahydropyran and 1,4-dioxane). Problems 8.17 and 8.22 require students to develop three-dimensional visualization skills. Chapter 9: An electrostatic potential map illustrates the polar nature of the carbonyl group (Figure 9.2). Ball-and-stick structures are used throughout the chapter. Structures of the macrocyclic ketone civetone (page 253) and the cyclic hemiacetal form of glucose (page 263) are notable. Problems 9.2, 9.15, 9.20, 9.30, 9.36 and 9.49 require students to develop threedimensional visualization skills. Example 9.7 serves the same purpose. Chapter 10: An electrostatic potential map is used to illustrate intermolecular hydrogen bonding between two carboxylic acids on page 290. This map can be revisited when the A-T and G-C base-pairing is discussed in Chapter 18 (Figure 18.5). Electrostatic potential maps are used in Figure 10.1 to illustrate the difference between a delocalized carboxylate anion and localized alkoxide anion. Space-filling models, electrostatic potential maps and ball-and-stick structures illustrate the similarities and differences between carboxylic acids, acid chlorides, anhydrides, esters and amides. Problems 10.4, 10.14, 10.19, 10.38, 10.49 and 10.62 require students to develop three-dimensional visualization skills. Chapter 11: viii Electrostatic potential maps of aniline and cyclohexylamine illustrate the similarities and differences between these important organic bases (Figure 11.2). Copyright © Houghton Mifflin Company. All rights reserved. The sterochemical information present in ball-and-stick structures of choline and muscarine can be contrasted with line formulas that lack stereochemical detail on page 343. Problems 11.11, 11.22, 11.25 and 11.37 require students to develop threedimensional visualization skills. Chapters 12: Visualization animations of numerous IR stretching and bending modes are now available at the Online Study Center. Closer Look At: Mass Spectrometry and Carbon Dating has been added to Section 12.6. Problem 12.26 requires students to develop three-dimensional visualization skills. A problem that requires analysis of multiple spectra has been added (12.48). Chapter 13: Electrostatic potential maps of benzene (Figure 13.1), pyridine (Figure 13.1), furan (Figure 13.2), pyrrole (Figure 13.3) and imidazole (Figure 13.4) are useful for discussing electron distribution in these aromatic compounds. The structure of imidazole nicely illustrates the different properties of the two nitrogen atoms in this important heterocyclic base. Problem 13.23 requires students to sharpen their three-dimensional visualization skills. Chapter 14: Ball-and-stick structures are used to illustrate polymer tacticity in Figure 14.1. Chapter 15: An electrostatic potential map of sodium stearate (Figure 15.3) illustrates the ambiphilic nature of this soap. The color of micelle structure illustrations has been improved in Figure 15.5. Problem 15.26 challenges students to develop three-dimensional visualization skills. Chapter 16: A ball-and-stick structure of sucrose, accompanied by an electrostatic potential map, illustrates the polar nature of the surface of this molecule imposed by the presence of multiple hydroxyl groups (Figure 16.3). Problem 16.24 requires students to develop three-dimensional visualization skills. Copyright © Houghton Mifflin Company. All rights reserved. ix Chapter 17: Electrostatic potential maps have been added to structures that accompany the titration curve of alanine (Figure 17.2). These nicely demonstrate how the charge distribution in an amino acid changes with the pH of its environment. The presentation of the Merrifield solid phase synthesis of peptides has been streamlined in Figure 17.7. The mechanism of DCC-mediated formation of an amide from an acid and an amine is clarified in Figure 17.8. Closer Look At: Nobel Laureates and Protein Chemistry has been added to Section 17.15. Chapter 18: Electrostatic potential maps of A-T and G-C base pairs illustrate the acid-base nature of these intermolecular interactions (Figure 18.5). Closer Look At: The Polymerase Chain Reaction (PCR) has been added to Section 18.9. This section will be useful to those who want to supplement the brief treatment of this topic in the text. Problem 18.31 requires students to extract acid-base information from an electrostatic potential map. We hope you find this Instructor’s Resource Manual useful and that you and your students enjoy using our text and ancillaries. If you have any suggestions or comments, please write us. Harold Hart Department of Chemistry Michigan State University East Lansing, Michigan 48842 Leslie E. Craine Department of Chemistry Central Connecticut State University 1615 Stanley Street New Britain, Connecticut 06050 David J. Hart Department of Chemistry The Ohio State University 100 West 18 th Avenue Columbus, Ohio 43210 Christopher M. Hadad Department of Chemistry The Ohio State University 100 W. 18 th Avenue Columbus, Ohio 43210 x Copyright © Houghton Mifflin Company. All rights reserved. Part III Test Bank Chapter 1 Bonding and Isomerism Valence, Bonding, and Lewis Structures 1.1. What is the most electropositive element? *a. Li 1.2. b. Be b. B b. CO b. N2 *b. N2 b. 2 b. S c. F2 *d. NF3 e. NaF c. BCl3 d. HF e. CCl4 *c. 3 d. 4 e. 5 c. Se d. Te e. Po b. 1.54Å *c. 1.76Å d. 1.98Å e. 3.52Å F 4.0 Cl 3.0 O 3.5 C 2.5 H 2.1 b. C–Cl c. C–O d. C–H e. C–C The most electronegative elements in the periodic table are generally found a. *b. c. d. e. 36 e. NF3 Given the following electronegativity values, predict the most polar covalent bond below: *a. C–F 1.10. d. Br2 If the Cl–Cl bond length is 1.98Å and the C–C bond length is 1.54Å, what would you expect the bond length of Cl–C to be? a. 0.74Å 1.9. c. ICl Which of the following elements is the most electronegative? *a. O 1.8. *e. P The number of electrons in the valence shell of aluminum is: a. 1 1.7. d. F Which molecule has nonpolar covalent bonds? a. NO 1.6. c. S Which of the following would you expect to have polar covalent bonds? a. MgF2 1.5. e. N Which of the following would you expect to have ionic bonds? *a. MgF2 1.4. d. C Which of the following elements has 5 electrons in the valence (outer) shell? a. C 1.3. c. B toward the left in a horizontal row and toward the top in a column. toward the right in a horizontal row and toward the top in a column. toward the left in a horizontal row and toward the bottom in a column. toward the right in a horizontal row and toward the bottom in a column. distributed randomly throughout the table. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 1.11. In which of the following electron-dot formulas is the Formal Charge incorrectly assigned? + _ *b. H C N _ + a. H C N _ + d. H C N. H C c. N e. H C N Structural Isomers 1.12. Which of the following molecules are structural isomers? OH. CH3CH2CH2OH. O CH3CH2OCH3 CH3CHCH3 CH3CCH3 2 3 4 1.. a. 1, 2, and 4 1.13. 1.14. c. 1, 3, and 4 d. 2, 3, and 4 e. 3 and 4 Which of the following abbreviated structural formulas is NOT an isomer of the others? a. b. *d. e. c. The number of possible acyclic hydrocarbons with the molecular formula C4 H6 is a. 2 1.15. *b. 1, 2, and 3 b. 3 *c. 4 d. 5 e. 6 Which of the following structural formulas represents a structural isomer of CH3CH2CH2CH2CH3?. a. CH3CH2CH2 b. CH3CH2CHCH3 CH2CH3 *d. CH3CH2CH(CH3)2 CH2CH3 e. CH2CH2CH3 CH3. Copyright © Houghton Mifflin Company. All rights reserved. c. (CH3)2CHCH3. 37 38 PART III 1.16. Which of the following molecules are structural isomers?. CH2CH2CH2CH3 CH2CH2CH2CH3 CH2CH3 CH3 CH2CH3 2 1 CH2CH2CH2CH3 (CH3)2CH CH2CH2OH. 3 CH(CH3)2 5 4. a. 1, 2 and 3 *d. 1, 3 and 5 1.17. CH3CH2 CHCH3 b. 1, 3 and 4 e. 2 and 3 c. 2, 3 and 5 Which of the following abbreviated structural formulas represents a structural isomer of CH3CH2CH2CH2CH3? a. *b. d. e. c. Structural Formulas 1.18. The structural formula for (CH3 )2C(CH2CH3 )2 is. a. c. H2 C H3C C H3C e. b. CH3CH3CCH2CH3CH2CH3 C H2 CH3CH2CH3 H3C CH3 *d. CH3 CH3CH2CH3. CH2CH3 C H3C CH2CH3 C7H16. 1.19. The structural formula has the molecular formula a. C6 H10 *b. C8 H14 c. C8 H16 d. C8 H18 e. C8 H20 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 1.20. Which of the following structural formulas does not have the molecular formula C6 H14?. b. a. (CH3)2CHCH2CH3 *d. 1.21. c. e. Which of the following structural formulas has the molecular formula C6 H12? 2 1 a. 2 and 3 1.22. (CH3)3CCH2CH3 b. 1 and 4 5 4 3 *c. 1, 4, and 5 d. 1 and 2 e. 4 and 5 The structural formula for (CH3CH2 )2CHCH2CH(CH3)2 is CH3 a. *b. C9H20 CH3CH2CHCH2CHCH3 CH2CH3 CH3 c. CH3CH2 d. CH3CH2CH2CHCHCH3 CHCH CH3CH2 CH2CH3 CH3 CH3 CH3 e. CH3CH2CH2CH2CH2CH2CH CH3 1.23. The structural formula has the molecular formula a. C7H16 b. C6H14 *c. C7H14 Copyright © Houghton Mifflin Company. All rights reserved. d. C6H12 e. C7H12 39 40 PART III 1.24. The structural formula CH3 H3C C CH2 has the molecular formula *a. C10H16 b. C9H18 c. C10H22 d. C6H14 e. C10H18 Formal Charge, Resonance, and Curved-Arrow Formalism 1.25. For carbon monoxide, a. +1 1.26. For carbon monoxide, *a. 1.27. +1 C O , C has a formal charge of: *b. –1 C c. 0 d. –2 e. +2 O , O has a formal charge of: b. –1 c. 0 d. –2 e. +2 What is the formal charge of N in HNO3 , as seen below? O H O N O *a. +1 1.28. b. +2 c. 0 d. –1 e. –2 The formal charges in the perchlorate ion are. O. Cl O O O. *a. b. c. d. e. –1 on each O and +3 on the Cl. 0 on each O and –1 on the Cl. –1 on each O and +4 on the Cl. –1/4 on each O and 0 on the Cl. +1 on each O and –1 on the Cl. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 1.29. Which of the following structures is a resonance structure of _ O.. C + H3C. CH3.. a. H2C CHOH H2C b. H2C CH2 H2C O H3C O d. H C O *c. C CH3. O e. CH2CH3 H3C HC CH2. 1.30. The formal charges in the complex. H H H B N H H H. are *a. b. c. d. e. 1.31. 0 on each H, +1 on N, and –1 on B. +1 on each H, +1 on N, and –1 on B. 0 on each H, –1 on N, and +1 on B. 0 on each H, 0 on N, and 0 on B. –1 on each H, +3 on N, and +3 on B. The curved arrows in the resonance structure for the acetate ion shown below O H3C C O _ indicate the following alternative resonance structure for the acetate ion: O a. H3C O C b. O _ O d. H3C C H3C _ *c. C O _ O e. H3C O Copyright © Houghton Mifflin Company. All rights reserved. O C O _ H3C C O _ 41 42 PART III Electronic Structure and Molecular Geometry 1.32. What is the percent s character in an sp3 hybridized orbital? *a. 25% 1.33. b. 33% *b. 2 e. 75% c. 3 d. 4 e. 5 d. 120° e. 180° d. 120o e. 180o The approximate H–C–H bond angle in methane is: a. 60° 1.35. d. 67% The maximum number of electrons that a molecular orbital can contain is: a. 1 1.34. c. 50% b. 90° *c. 109.5° The Lewis structure of methane is H H C H H. The approximate H–C–H bond angle in methane is a. 60o b. 90o *c. 109.5o Classification of Organic Compounds 1.36. Which of the following molecules is carbocyclic? a. CH3CH2CH3 *b. c. CH3CHCH3. CH3 d. 1.37. e. CH3OCH2CH3 Which of the following molecules contain the same functional group? CH3 OH CH3OCH3 CH3CH2 OH 1 2 3 a. 1, 2 and 3 *b. 1, 3 and 4 c. 1 and 2 CH3CH(OH)CH3 4 d. 2 and 4 e. 3 and 4 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 1.38. Which of the following molecules is acyclic?. OH a. *b.. c. O d. 1.39. e. Which of the following molecules is heterocyclic?. OH *a. c. b. N d. 1.40. e. Which of the following molecules contain the same functional group?. OCH3 CH3CHCH3 CH3CH2CH2OH OH 1 2 a. 1, 2 and 3 *d. 1 and 2 CH3CH2CH2SH 3 b. 1, 2 and 4 e. 1 and 3 Copyright © Houghton Mifflin Company. All rights reserved. 4 c. 2 and 4. 43 Chapter 2 Alkanes and Cycloalkanes; Conformational and Geometric Isomerism Alkane Nomenclature and Structural Formulas 2.1. What is the molecular formula of an alkane that has fourteen carbon atoms? a. C14H28 2.2. *b. C14H30 b. C5H12 e. C14H26 c. C5H14 d. C5H8 e. C5H5 What is the name of the alkane that has two carbon atoms? a. methane 2.4. d. C14H34 What is the molecular formula of a cycloalkane that has five carbon atoms? *a. C5H10 2.3. c. C14H32 *b. ethane c. propane d. butane e. isobutane The correct IUPAC name for the following molecule is: CH3 CH3CH2CHCHCH2CHCH3 CH3 CH2CH3 a. 6-ethyl-3,4,-dimethylheptane *c. 3,4,6-trimethyloctane e. none of these 2.5. b. 2-ethyl-4,5-dimethylheptane d. 3,5,6-trimethyloctane What is the common name for the following molecule?.. CH3CHCH2Br. CH3. *a. isobutyl bromide d. sec-butyl bromide 2.6. c. butyl bromide The name of the alkyl group that contains two carbons is: a. methyl d. isopropyl 44 b. tert-butyl bromide e. bromo-sec-butane *b. ethyl e. none of these c. propyl Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 2.7. 45 Which of the following structures is 2-methylpentane?. a. CH3CH2CH2CH2CH3 CH3CHCH2CH2CH3 *b. c. CH3CCH3 CH3 d. CH3 CH3 CH3CH2CHCH3 e.. CH3. 2.8. The name of the alkyl group below is: CH3CH CH3 a. ethyl 2.9. b. propyl *c. isopropyl d. butyl e. isobutyl What is the IUPAC name for the following compound?. Br CH3CH2CHCHCH3.. CH3. a. isohexyl bromide c. 1-bromopropylpropane e. 2-methyl-3-bromopentane 2.10. b. 3-bromo-4-methylpentane *d. 3-bromo-2-methylpentane The IUPAC name for the following molecule is:.. CH3CH2CHClC(CH3)3.. a. 3-chloroheptane c. t-butylpropyl chloride *e. 3-chloro-2,2-dimethylpentane 2.11. b. 2-chloro-1,1,1-trimethylbutane d. 3-chloro-1-dimethylpentane Which of the following structures is tert-butyl iodide? a. CH3CH2CH2CH2I. b. CH3CCH3 CH3 e. CH3CH CH3. Copyright © Houghton Mifflin Company. All rights reserved. c. CH3CHCH2CH3 I CH3 I *d. CH3CHCH2CH2I I. 46 PART III 2.12. What is a correct name for the following molecule?. Cl Cl... a. 2,2-dichlorocyclopropane c. 1,1-dichloropropane *e. 1,1-dichlorocyclopropane 2.13. b. 1,1-dichlorocyclopentane d. trans-1,1-dichlorocyclopropane Trans-1-bromo-3-methylcyclobutane is represented by which structure below? Br Br a. b. Br CH3 H3C d. H3C CH3 Br e. H3C Br 2.14. *c. What is the correct name for the following cycloalkane?. Br CH2CH3 H H. a. bromoethylcyclohexane c. cis-3-bromo-1-ethylhexane *e. cis-1-bromo-3-ethylcyclohexane 2.15. b. trans-1-ethyl-3-bromocyclohexane d. 1-bromo-3-ethylcyclohexane The correct IUPAC name for (CH3 )2CHCH(CH3 )(CH2 )3CH(CH3 )2 is a. diisopropylpentane. b. 1,1,2,6,6-pentamethylhexane. c. 2,5-diisopropylpentane. *d. 2,3,7-trimethyloctane. e. 1,4-diisopropylpentane. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 2.16. The correct IUPAC name for. CH3 CH3 H3C H. is a. b. c. *d. e. 2.17. 1,3,3-trimethylcyclobutane. cis-1,3,3-trimethylcyclobutane. trans-1,3,3-trimethylcyclobutane. 1,1,3-trimethylcyclobutane. 2,2,4-trimethylcyclobutane. The structural formula for 2,2,3-trimethylhexane is. a. b... c.. (CH3)2CCH2CH3 *d.. CH3.. e.. (CH3)3CCHCH3. CH3. Alkane Properties 2.18. Which of the following would exhibit hydrogen bonding? a. CH3Cl 2.19. c. CH4 d. CH2Cl2 e. CH3CH3 Which of the following alkanes would have the highest boiling point? a. pentane *d. hexane 2.20. *b. CH3OH b. isopentane e. isohexane c. neopentane What statement does NOT apply to the boiling points of alkanes? a. The boiling point increases as the length of the carbon chain increases. b. Straight chain alkanes have a higher boiling point than their branched isomers. c. Because they are nonpolar, alkanes have lower boiling points than other organic compounds of similar molar mass. d. The boiling points are affected by Van der Waals attractions. *e. The boiling points are influenced by hydrogen bonding. Copyright © Houghton Mifflin Company. All rights reserved. 47 48 PART III 2.21. Which cycloalkane has the highest boiling point? a. cyclopropane d. cyclohexane 2.22. b. cyclobutane *e. cyclooctane c. cyclopentane The boiling points of normal alkanes a. rise as the length of the carbon chain increases. b. rise as the length of the carbon chain decreases. c. are higher than the boiling points of branched alkanes with the same molecular formula. *d. a and c e. b and c Conformations of Alkanes 2.23. The most stable conformation of propane is: *a. staggered 2.24 b. chair d. eclipsed e. boat *d. eclipsed e. boat The least stable conformation of propane is: a. staggered 2.25. c. planar b. chair c. planar The preferred conformation of butane is given by which of the following Newman projection formulas?. H *a. H3C H H H CH2CH3 H H H H H H CH3 H d. b. CH3 CH3 e. H H3C CH3 H H CH3 H CH3 c. H H CH3 H. H CH3. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 2.26. 49 The least stable conformation of butane is given by which of the following Newman projections? H a. H3C H H H b. H CH3 CH3 H CH3 d. H H CH3 H H CH3 e. H H H3C CH3 *c. CH3 H H H H CH2CH3 H H H H Conformations of Cycloalkanes 2.27. The preferred conformation of cis-3-tert-butyl-1-methylcyclohexane is the one in which: a. b. *c. d. e. 2.28. the t-butyl group is axial and the methyl group is equatorial both groups are axial both groups are equatorial the methyl group is axial and the t-butyl group is equatorial molecule exists in a boat conformation The bond angle of a normal, tetrahedral, sp3 hybridized carbon is 109.5°. What is the C–C–C bond angle of cyclopropane? *a. 60° 2.29. c. 109.5° d. 120° e. 180° For the most stable conformation of trans-1,2-dimethylcyclohexane: a. *b. c. d. 2.30. b. 90° both methyls will occupy the axial position both methyls will occupy the equatorial position one methyl will occupy the axial position and the other an equatorial position more than one answer is correct Which of the following pairs are examples of conformational isomerism? *a. chair and boat forms of cyclohexane b. 1-iodopropane and 2-iodopropane c. sec-butyl chloride and butyl iodide d. cis and trans-1,2-dimethylcyclohexane e. all of these Copyright © Houghton Mifflin Company. All rights reserved. 50 PART III 2.31. Consider this chair conformation:. CH3 H3C H H H Br. When the ring flips, a. the bromine becomes axial and the methyls become equatorial. b. all three substituents become equatorial. *c. the bromine becomes equatorial and the methyls become axial. d. the ring opens up. e. one methyl becomes axial, one becomes equatorial, and the bromine becomes equatorial. 2.32. Consider this chair conformation: CH3 H Cl H Br H. *a. b. c. d. e. 2.33. The The The The The methyl and methyl and methyl and methyl and methyl and bromine are cis and the chlorine and bromine are cis. bromine are trans and the chlorine and bromine are cis. chlorine are trans and the methyl and bromine are cis. chlorine are trans and the methyl and bromine are trans. chlorine are trans and the bromine and chlorine are cis. Cycloalkanes with __________ or more carbons in the ring are nonplanar. a. 2 b. 3 *c. 4 d. 5 e. 6 Isomerism 2.34. 1-Bromopropane and 2-bromopropane are *a. constitutional isomers. c. configurational isomers. e. stereoisomers. b. homologs. d. conformational isomers. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 2.35. The compounds represented by the structures CH3 CH3 and H H H HC 3 CH3 H are a. structural isomers. d. conformers. 2.36. b. identical. e. constitutional isomers. *c. cis-trans isomers. The compounds represented by the structures CH3 H and H CH3 are a. structural isomers. d. conformers. 2.37. *b. identical. e. constitutional isomers. c. cis-trans isomers. The compounds represented by the structures Cl H and Cl H are a. structural isomers. *d. conformers. 2.38. b. identical. e. constitutional isomers. c. cis-trans isomers. The compounds represented by the structures CH3 H CH3 CH3 and H H CH3 H are *a. structural isomers. d. conformers. b. identical. e. stereoisomers. Copyright © Houghton Mifflin Company. All rights reserved. c. cis-trans isomers. 51 52 PART III Reactions of Alkanes 2.39. In the chlorination of methane, the propagation steps involve forming: a. H radicals d. a, b, and c 2.40. c. 3 d. 4 e. 5 b. 2 *c. 3 d. 4 e. 5 The number of possible monobromination products, including cis-trans isomers, of methylcyclopentane is a. 2 2.43. b. 3 c. 4 d. 5 *e. 6 The number of possible dibromination products of 2-methylpropane is a. 2 2.44. b. 2 How many isomeric dichloro products can be obtained from the chlorination of cyclopropane? a. 1 2.42. c. chlorine radicals How many monobromo products can be obtained from the bromination of cyclopentane? *a. 1 2.41. b. methyl radicals *e. b and c *b. 3 c. 4 d. 5 e. The number of possible dichlorination products of propane is a. 2 b. 3 *c. 4 d. 5 e. 6 Copyright © Houghton Mifflin Company. All rights reserved. Chapter 3 Alkenes and Alkynes Alkenes and Alkynes: Nomenclature and Structure 3.1. Which of the following dienes can be classified as conjugated? a. CH3CH=C=CH2 c. CH2=CHCH2CH=CH2 e. CH2=C=CH2 3.2. Which of the following molecular formulas could not represent an alkene? a. C5H10 3.3. *b. CH3CH=CHCH=CH2 d. CH3CH=CHCH2CH2CH=CH2 b. C7H14 c. C10H20 *d. C27H56 e. C31H62 What is the correct name for the following molecule? CH2CH3 a. 1-ethylcyclohexene d. cyclohexylethane 3.4. *c. 3-ethylcyclohexene Which of the following compounds can exhibit cis/trans isomerism? a. 1-pentene d. 3-methyl-1-pentene 3.5. b. 2-ethylcyclohexene e. 1-ethyl-3-cyclohexene *b. 2-pentene e. 1-hexene c. 2-methyl-2-pentene The correct IUPAC name for the following molecule is:. H3C Cl C Cl C CH2CHCH3 CH3. *a. b. c. d. e. 3.6. trans-2,3-dichloro-5-methyl-2-hexene trans-2,3-dichloro-5-methyl-3-hexene cis-2,3-dichloro-5-methyl-3-hexene trans-4,5-dichloro-2-methyl-4-hexene cis-4,5-dichloro-2-methyl-4-hexene What is the correct structure for 2,3-dimethyl-2-pentene? CH3 CH3. a. CH3C CH3 CHCHCH3 b. CH2 CCHCH2CH3 CH3 CH3 CH3 *d. CH3C CH3CHCH CCH3 CH3 CH3 CCH2CH3 CH3 53 c. e. CH3CHCHCH CH2 CH3. Copyright © Houghton Mifflin Company. All rights reserved. 54 PART III 3.7. The correct structure for allyl bromide is:. *a. CH2 CHCH2Br b. CH2 CHBr d. BrCH CHCH3 e. CH2 CHCHBr2 c. BrCH CHBr.. 3.8. Which of the following molecules is 4-methyl-2-hexyne?. *a. CH3C b. CCHCH2CH3 CH3CH2C CCH2CH3. CH3 c. CH3CHCH2C CCH3. d. CH3C CCH2CHCH3 CH3 CH3.. e. CH3CHC CCH2CH3. CH3 3.9. The correct name of the molecule below is:.. HC CCH2CH2CHCH2CH CH2. CH3. a. 5-methyl-7-octen-1-yne c. 4-methyl-1-octyn-7-ene e. none of these is correct 3.10. *b. 4-methyl-1-octen-7-yne d. 5-methyl-1-octen-7-yne The multiple bonds in the following compounds are conjugated: 1. CH2 C CH2 4. CH3 2. CH2 C C CH2 5. O 6. CH3 C C CH CH2. CH3 3. CH2 *a. 2, 3, and 5 CH CH b. 4 and 6 c. only 1 d. 2 and 3 e. 2 and 5 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 3.11. The structure of (Z)-3-methyl-2-pentene is a. b. *c. d. e. 3.12. The structure of (E)-3-methyl-2-pentene is *a. b. c. d. e. 3.13. The correct name for CH3 CH3 CH CH3 CH C CH CH3 CH2CH3 is a. 2-methyl-4-isopropyl-3-hexene. c. 2,5-dimethyl-4-ethyl-3-hexene. e. 1,2-diisopropyl-1-butene. Copyright © Houghton Mifflin Company. All rights reserved. *b. 3-ethyl-2,5-dimethyl-3-hexene. d. 1-ethyl-1,2-diisopropylethene. 55 56 3.14. PART III The double bond in ethene is made up of a. a pi bond and a sigma bond formed by lateral overlap of two p orbitals. b. a sigma bond formed by overlap of two s orbitals and a pi bond formed by lateral overlap of two p orbitals. c. a pi bond formed by end-on overlap of two sp2 orbitals and a sigma bond formed by overlap of two s orbitals. *d. a sigma bond formed by end-on overlap of two sp2 orbitals and a pi bond formed by lateral overlap of two p orbitals. e. a pi bond formed by lateral overlap of two sp2 orbitals and a sigma bond formed by end-on overlap of two sp2 orbitals. 3.15. The triple bond in ethyne is made up of a. two pi bonds and a sigma bond, each formed by a lateral overlap of two p orbitals. b. a sigma bond formed by overlap of two s orbitals and two pi bonds, each formed by lateral overlap of two p orbitals. c. a sigma bond formed by end-on overlap of two sp2 orbitals and a pi bond formed by lateral overlap of two p orbitals. *d. two pi bonds, each formed by lateral overlap of two p orbitals, and a sigma bond formed by end-on overlap of two sp orbitals. e. two pi bonds, each formed by end-on overlap of two p orbitals, and a sigma bond formed by lateral overlap of two sp orbitals. Properties of Alkenes and Alkynes 3.16. Which of the following statements is FALSE relative to alkenes? a. b. c. *d. e. 3.17. the C of the carbon-carbon double bond is sp2 hybridized the bond angles are approximately 120° around the carbon-carbon double bond there is the possibility of cis/trans isomerism they are less reactive than alkanes the bond length of the carbon-carbon double bond is shorter than that of the carbon-carbon single bond Which of the following hydrocarbons will be the most acidic? a. pentane d. isobutane 3.18. *c. acetylene Which of the following statements are true about alkynes? a. b. c. *d. e. 3.19. b. ethene e. propylene they are more acidic than other hydrocarbons the bond angle around the carbon-carbon triple bond is 180° the carbon-carbon triple bond is shorter than the carbon-carbon double bond all of the above are true none of the above are true What is the percent s character in an sp2 hybrid orbital? a. 25% *b. 33% c. 50% d. 67% e. 75% Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 3.20. 57 What is the percent s character in an sp hybrid orbital? a. 25% b. 33% *c. 50% d. 67% e. 75% Reactions of Alkenes 3.21. What would be the major product of the following reaction? CH3 + ? HBr. CH3 H 3C H 3C Br Br Br Br I II CH2Br CH3 IV a. I 3.22. *b. II III Br V c. III d. IV e. V Select the necessary reagent(s) to convert cycloheptene to cycloheptane. ? *a. H2 and Ni d. Zn and H+ 3.23. b. H2 O c. H2SO4 and heat e. KOH in alcohol and heat Select the necessary reagents to convert methylcyclopentene to 1-methylcyclopentanol. CH3 H3C OH ? *a. H2 O and H2SO4 d. O3 , then Zn, H+ b. Zn, H2 O c. BH3 , then H2 O2 and – OH e. KOH in alcohol and heat Copyright © Houghton Mifflin Company. All rights reserved. 58 PART III 3.24. What is the product for the reaction below?. CH3 CH3CH2C. CH2 + ? HBr. CH3 a. CH3 CH3CHCH2CH2Br b. CH3CHCHCH3 Br CH3 *d. CH3CH2CCH3 c. CH3CHCH CHBr. CH2Br e. none of these Br. 3.25. What is the product for the reaction below? CH2CH3 + CH2CH3 CH2CH3 *b. a. ? HBr Br CH2CH3 c. Br Br Br CHCH3 CH2CH2Br d. e. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 3.26. 59 Upon ozonolysis and treatment with Zn in water, compound A yielded two moles of formaldehyde, HCHO, and 1 mole of the following molecule: O O CH3CCH2CCH3 What is the structure of A?. H CH2 CH3 C H O C CH2 I. CH2 C H3C CH2 CH3CCH2C H C CH H III II CH3 CH2 CH3CCCHO CH2 H2C CH2 IV a. I 3.27. *b. II V c. III d. IV e. V What is observed when water, in the presence of sulfuric acid, is added to 2-methyl-2pentene?. CH3 a. CH3C CHCH2CH2OH b. CH3CH2CHCHCH3 OH CH3 CH3 *c. CH3CCH2CH2CH3 CH3CH2CH CCH2CH3 CH3 OH CH3 e. d. CH3CCH2CH2CH3 OSO3H. Copyright © Houghton Mifflin Company. All rights reserved. 60 PART III 3.28. The products obtained by the acid-catalyzed hydration of methylcyclopentene and methylenecyclopentane are *a. identical. d. constitutional isomers. 3.29. b. regioisomers. e. conformers. c. cis-trans isomers. The product of the reaction sequence CH3 H2O2 BH3 OH is. CH3 CH3 OH b. *a. CH3 BH2 c.. OH CH2OH e. none of the above d. 3.30. The product of the reaction. H3C H C + C H3C HCl CH2CH3. is. Cl *a. (CH3)2C Cl CH2CH2CH3 b. (CH3)2C Cl CHCH2CH3 Cl c. (CH3)2CH CHCH2CH3 H3C e. H3C (CH3)2CHCH2CHCH3. Cl H C d. C CH2CH2Cl. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 3.31. 61 The products of the following reaction sequence. H 3C H C C H 3C Zn, H + O3 CH2CH3. are. a. 2 *b. O C H3C C O O OH OH O C H C H3C C CH2CH3 H3C H 3C c. H H3C H 3C d. H3C C C H CH3 CH3 CH2CH3 H e. 2 O C CH2CH3. Reactions of Conjugated Dienes 3.32. What product(s) will be observed by the addition of one molar equivalent of Br2 to 1,3-cyclohexadiene? a. 1,2-dibromocyclohexene c. 1,3-dibromocyclohexene *e. both b and d b. 3,4-dibromocyclohexene d. 3,6-dibromocyclohexene Copyright © Houghton Mifflin Company. All rights reserved.. 62 PART III 3.33. The Diels-Alder reaction is very important in the synthesis of six-membered rings. What sixmembered ring is produced with the following reaction? O CH3CH CHCH H2C CHCH3 CHCCH3 ?. CH3 O CH3 CH2CCH3 CH2CHO O. c. b. a. CH3 CH3 CH3 CH3 O CH3 CCH3 CCH3 e. *d. O H3C CH3. 3.34. The product of addition of two moles of HBr to 1,4-pentadiene is a. 2,2-dibromopentane. c. 1,5-dibromopentane. e. 1,4-dibromopentane. 3.35. *b. 2,4-dibromopentane. d. 3,3-dibromopentane. The products obtained by adding 1 mole of HBr to 2,4-hexadiene are a. b. c. d. *e. 4-bromo-2-hexene and 3-bromo-2-hexene and 4-bromo-2-hexene and 2-bromo-3-hexene and 2-bromo-3-hexene and 5-bromo-2-hexene. 4-bromo-2-hexene. 2-bromo-4-hexene. 3-bromo-2-hexene. 4-bromo-2-hexene. Reactions of Alkynes 3.36. The product of the reaction. CH3CH2C CH. + 2 Br2 is. Br a. Br C CH3CH2 b. C H *c. CH3CH2CBr2CHBr2 e. CH3CH2CHBrCH2Br CH3CH2CBr2CH3 Br d.. H C CH3CH2 C Br. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 3.37. What type of compound is prepared by adding water to acetylene (C2 H2 ) in the presence of sulfuric acid and mercuric sulfate? *a. aldehyde d. ester 3.38. 63 b. ketone e. ether c. carboxylic acid The product of the reaction CH3CH2C NaNH2 CH in liquid NH3 is. a. CH3CH2C CH2 *b. CH2 d. CH3CH2C C Na Na c. CH3CH2C CH3CH2CH CHNH2. NH2 e. CH3CH2C CHNH2 Na. Reactions and Nomenclature 3.39. What is the name of the product formed from the following reaction? + a. b. *c. d. e. 3.40. Br2 ? bromocyclopentane 1,1-dibromocyclopentane 1,2-dibromocyclopentane 2,2-dibromocyclopentane 1,1-dibromocyclopentene Addition of H2 to 2-butyne in the presence of the Lindlar’s catalyst will produce: a. butane *c. cis-2-butene e. isobutylene 3.41. CCl4 b. 1-butene d. trans-2-butene What alkene is required to make 3-methyl-1-butanol using the hydroboration-oxidation reaction? a. 1-butene *c. 3-methyl-1-butene e. 2-methyl-1-butene Copyright © Houghton Mifflin Company. All rights reserved. b. 2-butene d. 2-methyl-2-butene 64 PART III 3.42. What is the final product of adding 1 mole of each reactant in the following sequence? CH CH3C a. b. c. *d. e. 3.43. HBr HCl ? propyl chloride propyl bromide 1-bromo-2-chloropropane 2-bromo-2-chloropropane 2,2-dibromopropane Which of the following alkenes is needed to prepare 3-cyclohexyl-1-propanol via a hydroboration-oxidation reaction? CH2CH2CH2OH 3-cyclohexyl-1-propanol a. cyclohexene *c. allyl cyclohexane e. 1- octene 3.44. Upon ozonolysis which alkene will give only acetone, (CH3 )2C=O? *a. 2,3-dimethyl-2-butene c. 3-hexene e. 2-methyl-3-hexene 3.45. b. vinyl cyclohexane d. propyl cyclohexene b. 2,2-dimethyl-2-butene d. 2-methyl-2-pentene What is the name of the alkene produced by treating 2-butyne with 1 mole of Br2? a. b. *c. d. e. 1,2-dibromo-1-butene 2,3-dibromo-1-butene trans-2,3-dibromo-2-butene 2,3-dibromo-1-butene cis-1,4-dibromo-2-butene Copyright © Houghton Mifflin Company. All rights reserved. Test Bank Reaction Equilibrium and Reaction Rates 3.46. Examine the following reaction energy diagram for the reaction A + B C + D Ea Ea Energy A + B !H C + D Reaction Coordinate Which of the following statements are true? 1. 2. 3. 4. 5. The reaction is exothermic. The reaction occurs in one step. The first step is the rate-determining step. The reaction is endothermic. If the reaction is heated, the reaction rate will increase. a. 1, 2, and 5 d. 3, 4, and 5 3.47. *b. 1, 3, and 5 e. 3 and 4 c. 2 and 4 Which of the following statements about chemical reactions are true? 1. 2. 3. 4. Exothermic reactions occur at a rapid rate. The products of exothermic reactions are lower in energy than the reactants. Exothermic reactions give off heat. The products of endothermic reactions are lower in energy than the reactants. a. 3 *d. 2 and 3 b. 1, 2, and 3 e. 2 c. 1, 3, and 4 Reaction Mechanisms 3.48. Markovnikov addition of HCl to propene involves: a. initial attack by the chloride ion c. isomerization of 1-chloropropane *e. formation of an isopropyl cation 3.49. b. initial attack by the chlorine atom d. formation of a propyl cation What type of carbocation will form from the addition of a H+ to 2-methylpropene? + a. H3C b. 1° c. 2° Copyright © Houghton Mifflin Company. All rights reserved. *d. 3° e. allyl 65 66 PART III 3.50. Cyclohexene is treated with cold dilute KMnO4. What is the spatial arrangement of the hydroxyls on the resulting cyclohexane ring? *a. cis d. both axial 3.51. c. eclipsed The first step in the free radical mechanism for the preparation of polyethylene is: a. b. *c. d. e. 3.52. b. trans e. both equatorial formation of a stable carbocation formation of a stable carbanion heating an organic peroxide to break the O–O bond decoupling of the free radicals propagation of the free radicals Polyethylene is usually produced by a. an ionic electrophilic addition reaction. b. heating ethylene to 1000oC. c. cationic polymerization. *d. a free-radical chain reaction. e. epoxidation. Miscellaneous 3.53. Which of the following reagents can be used to distinguish an alkene from an alkane? a. Zn, H+ 3.54. b. H2 O c. Cl2, hν *d. Br2 , CCl4 e. O2 , heat What is/are the final product(s) in the following multistep synthesis? 1) 1 mol Br2 ? 2) H2, Pt Br. Br Br Br Br Br. I a. I *d. I and II II b. II e. all are produced III c. III Copyright © Houghton Mifflin Company. All rights reserved. Chapter 4 Aromatic Compounds Nomenclature and Structural Formulas of Aromatic Compounds 4.1. The structure of chlorobenzene is correctly represented by: Cl Cl a. CH2Cl CH2Cl e. d. 4.2. Cl c. *b. Which of the following structures accurately represents toluene? c. b. *a. NH2 OH CH3. e. d. CO2H OCH3. 4.3. The name of the following molecule is: CH a. toluene 4.4. b. ethylbenzene c. cumene *d. styrene e. anisole What dibromobenzene can form only one tribromobenzene? a. o-dibromobenzene d. cumene 67 CH2 b. m-dibromobenzene e. styrene *c. p-dibromobenzene Copyright © Houghton Mifflin Company. All rights reserved. 68 PART III 4.5. Using the following monosubstituted benzene, which position would be ortho to X?. X 1 6 2 5 3 4. a. 1 4.6. *b. 2 c. 3 d. 4 e. 5 Which of the following molecules is m-nitrophenol? CH3 OH a. CH3 b. c. NO2 NO2. NO2 NO2 OH e. *d. NH2 NO2 4.7. What is the name of the following molecule? PhCH2CH2CH=CH2 a. styrene d. 3-benzyl-1-propene 4.8. *b. 4-phenyl-1-butene e. allylbenzene Which name(s) of the following molecule is/are incorrect? CH a. styrene d. phenylethene 4.9. c. 1-phenyl-3-butene CH2 b. vinylbenzene e. a and b *c. ethylbenzene How many dinitrobenzoic acids are possible? a. 4 b. 5 *c. 6 d. 7 e. 8 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 4.10. Which of the following names represents more than one compound? *a. dichlorobenzene c. o-nitrobenzaldehyde e. cumene 4.11. How many different trisubstituted products are possible from the nitration of m-xylene? a. 1 4.12. b. 2-bromophenol d. 2,4,6-trinitrotoluene b. 2 *c. 3 d. 4 e. 5 d. 4 e. 6 Which position would be meta to X?. X 1 6 2 5 3 4. a. 1 4.13. b. 2 *c. 3 What is the correct name for the following molecule?. Br CH2. a. o-bromobenzyl c. 2-bromodiphenylpropane *e. o-benzylbromobenzene 4.14. b. biphenyl bromide d. bromobenzylbenzene Which alkylbenzene, C9 H12, when nitrated can yield only one mononitro product? CH3 b. a. CH3 *c. H3C CH3 H3C CH3 CH2CH2CH3 d. CH3 CH3 e. Copyright © Houghton Mifflin Company. All rights reserved. CH3 69 70 PART III 4.15. The correct name for. CH3 Cl Br is a. 2-chloro-4-bromotoluene. c. 1-bromo-3-chloro-4-methylbenzene. e. m-chlorobromotoluene. 4.16. b. o-chloro-p-bromotoluene. *d. 4-bromo-2-chlorotoluene. The structural formula for m-chlorobenzoic acid is a. Cl COOH b. CH3 Cl c. *d. COOH Cl e. Cl COOH Cl CH3 Aromaticity, Resonance, and Properties of Aromatic Compounds 4.17. Which of the following statements about benzene is FALSE? a. b. c. *d. e. 4.18. the molecule is planar and each carbon is at a corner of regular hexagon there are two resonance structures of equivalent energy the bond angles are all 120º and the bond lengths are all 1.39Å the typical mechanism by which reactions occur is by addition each carbon in the benzene ring is sp2 hybridized Which statement about benzene is TRUE? a. b. c. *d. e. All six hydrogens in benzene are chemically equivalent. Benzene decolorizes bromine solutions. The molecule is planar, and each carbon is at the corner of a regular hexagon. Both a and c are true. Both b and c are true. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank Mechanism of Electrophilic Aromatic Substitution 4.19. Which of the following is NOT an electrophile in an electrophilic aromatic substitution reaction? a. NO2 d. SO3 4.20. b. Clδ+--δ – Cl--FeCl3 e. all are + In the mechanism for the nitration of benzene, what is the function of H2SO4 ? a. to act solely as a solvent c. to accept a proton from HNO3 e. to protonate the benzene ring 4.21. *c. CH3OH *b. to donate a proton to HNO3 d. to generate heat for reaction to occur The predominant intermediate in electrophilic nitration of toluene is. CH3 a. CH3 CH3 c. *b. O2N O2N H O2N CH3 CH3 d. H e. O2N NO2 O2N. Copyright © Houghton Mifflin Company. All rights reserved. H H. 71 72 PART III 4.22. The predominant intermediate in the nitration of benzenesulfonic acid is. SO3H SO3H a. SO3H b. c. NO2 NO2 O2N H. H H SO3H SO3H *d. e. NO2 NO2 H H. Directing Groups and Ring Activation 4.23. Which of the following groups is a meta director? a. –Cl 4.24. *b. –CHO c. –OCH3 d. –OH e. –Ar In electrophilic aromatic substitution reactions, which of the following molecules are considered to be less reactive than benzene?. CO2H *a. CH3 b. OCH3 c. OH d. 4.25. e. Which of the following groups are ortho, para-directing? a. —CO2CH3 + NH(CH3 )2 d. b. —CONH2 c. —SO3 H *e. —SCH3 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 4.26. Among the following groups, which ones are meta-directing? 1. –Cl 2. –NO2 3. –SO3 H a. 1 and 4 d. 2 and 5 4.27. 73 4. –CH3 b. 1, 2 and 3 e. 1 and 2 5. –COCH3 *c. 2, 3 and 5 Which of the following molecules is the most reactive toward electrophilic aromatic substitution?. NO2 a. NO2 c. b. CH3 CO2H OH. e. *d. NH2 + NH3. 4.28. Which group is both ortho, para-directing and ring-deactivating? *a. –Br 4.29. b. –Ar c. –NO2 d. –CHO e. –OCH3 The relative rates of nitration of 1. 2. CH3 H3C CH3 3. SO3H. 4. CH3 are a. 1 > 2 > 3 > 4 d. 3 > 4 > 2 > 1 b. 4 > 2 > 1 > 3 *e. 3 > 2 > 1 > 4 Copyright © Houghton Mifflin Company. All rights reserved. c. 2 > 1 > 4 > 3. 74 PART III 4.30. The only group among the following that is m-directing is. O a. O d. C(CH3)3 C O R b. *c. Cl e. C OR. N(CH3)2. 4.31. Among the following groups, which ones are o,p-directing?. 1. OCH3 *a. 1, 3, and 5 2. NO2 3. 4. Br 5. CN CH2CH3.. b. 1 and 5 c. 2 and 4 d. 2, 3, and 4 e. 1 and 3 Reactions of Benzene and Substituted Benzenes 4.32. Which electrophile is used to make acetophenone from benzene? + + + NO2 d. c. SO3 *b. CH3CO a. CH3... 4.33. a. benzenesulfonic acid *d. nitrobenzene HNO3 H2SO4 + CH3CH2 ? b. aniline e. anisole c. benzoic acid If p-nitrophenol is treated with chlorine in the presence of AlCl3, the only trisubstituted product observed is: *a. 2-chloro-4-nitrophenol c. 3-chloro-5-nitrophenol e. 4-chloro-3-nitrophenol 4.35. e. The name of the product of the following reaction is: + 4.34.. b. 3-chloro-4-nitrophenol d. 4-chloro-2-nitrophenol What is the name of the major product from the following sequence of reactions? 1) SO3, H2SO4 2) NaOH, 200oC a. aniline *d. phenol b. anisole e. toluene ? c. benzoic acid Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 4.36. 75 The expected product from the following reaction is: CH3 AlCl3 CH3CH2Cl + ? H3C. CH3 CH3 CH3 CH2CH3 b. a. *c. CH2CH3 CH2CH3 CH2CH3 CH3 CH2CH3 CH3 d. e. CH3 CH3 CH3. 4.37. What is the final product of the following reaction sequence? 1) CH2 CH2, H + 2) KMnO4, ?.. OH CH CH2 a. b. CH2CH3 d. CO2H CHCH3 *c. CH2CO2H e. Copyright © Houghton Mifflin Company. All rights reserved... 76 PART III 4.38. The predominant product from sequential nitration and bromination of benzenesulfonic acid is. Br SO3H Br *a. b. HO3S NO2 O2N SO3H NO2 c. d. Br O2N HO3S SO3H Br NO2 e. Br. 4.39. The predominant product from the sequential bromination and nitration of benzene is: NO2 Br Br a. c. b. NO2 Br Br Br *d. e. NO2 NO2 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 4.40. What is the product of the following reaction? CH3 O + CH3C AlCl3 Cl CH3. CH3 CH3 *a. c. b. C O C CH3 CH3 O CH3 CH3 CH3 d. Cl e. Al. Electrophilic Aromatic Substitution in Synthesis 4.41. What is the best sequence of reactions to synthesize m-nitrophenol? OH a. HNO3 H2SO4 OH b. c. 2) NaOH, 200oC 3) HNO3, H2SO4 *e. 1) HNO3, H2SO4 2) H2SO4, 3) NaOH, 200oC Copyright © Houghton Mifflin Company. All rights reserved. 2) H2O, OH 1) H2SO4, d. 1) HNO3, H2SO4 1) H2SO4, 2) NaOH, 200oC 77 78 PART III 4.42. Which is the best reaction sequence to synthesize m-bromobenzenesulfonic acid from benzene?. SO3H 1) 2) Br a. *b. c. d. e. 4.43. 1) Br2 , AlBr3 , 2) H2SO4 , SO3 1) H2SO4 , SO3 2) Br2 , AlBr3 1) ethene, HF, 2) Br2 , AlBr3 1) CH3Cl, AlCl3, 2) Br2 , AlBr3 1) Br2 , AlBr3 , 2) CH3COCl, AlCl3 Which is the best sequence of reagents to use in synthesizing 2-bromo-4-nitrotoluene from benzene: a. b. *c. d. e. 4.44.. Br2 , FeBr3; then CH3Cl, AlCl3; then HNO3 , H2SO4 CH3Cl, AlCl3; then Br2 , FeBr3; then HNO3 , H2SO4 CH3Cl, AlCl3; then HNO3 , H2SO4; then Br2 , FeBr3 SO3 , H2SO4; then HNO3 , H2SO4; then Br2 , FeBr3 HNO3 , H2SO4; then Br2 , FeBr3; then CH3Cl, AlCl3 Which is the best reaction sequence to synthesize p-bromobenzenesulfonic acid from benzene?. SO3H 1) 2). *a. 1) Br2 , AlBr3 , 2) H2SO4 , SO3 c. 1) CH3Cl, AlCl3, 2) Br2 , AlBr3 e. 1) HBr, ethane, 2) H2SO4 , SO3 Br b. 1) H2SO4 , SO3 , 2) Br2 , AlBr3 d. 1) Br2 , AlBr3 , 2) CH3COCl, AlCl3 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 79 Polycyclic Aromatic Hydrocarbons 4.45. 4.46. A common polycyclic aromatic hydrocarbon is named naphthalene. What is the structure of naphthalene? *a. b. d. e. c. The number of possible mononitration products of anthracene is: a. 1 4.47. b. 2 *c. 3 d. 4 e. 5 The polycyclic aromatic hydrocarbon benzo[a]pyrene is a known carcinogen found in soot and tobacco smoke. What is its structure? a. b. d. *e. Copyright © Houghton Mifflin Company. All rights reserved. c. Chapter 5 Stereoisomerism Definitions 5.1. Which of the following objects is chiral? a. socks d. basketball 5.2. b. pencil *e. shoes Chiral molecules that have nonsuperimposable mirror images are called: *a. enantiomers d. stereogenic 5.3. c. cross country skis b. diastereomers e. symmetrical c. meso compounds Which of the following molecules has a mirror plane of symmetry?. H Cl CH3 Cl C C H Cl Cl CH3 5.4. *b. 2 Cl CH3 C Cl CH3 3 c. 3 d. 4 H H3C CH3 Cl C. C Cl CH3 4 e. all of them b. decoupling e. selective binding c. resetting A 50:50 mixture of enantiomers a. is a meso form. *c. is a racemic mixture. e. is a pair of conformers. 5.6. H CH3 Cl C What is the process that separates enantiomers? a. separation *d. resolution 5.5. C H 2 1 a. 1 CH3 H C b. is a pair of diastereomers. d. rotates plane polarized light. The terms that best describe the isomeric relationship between staggered and eclipsed ethane are a. configurational, achiral, diastereomers. b. conformational, chiral, enantiomers. *c. conformational, achiral, diastereomers. d. configurational, chiral, enantiomers. e. conformational, achiral, enantiomers. 80 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank Stereogenic Centers 5.7. Which of the molecules below has a stereogenic carbon atom? OH Br CH3CHCH3 CH3 CH3CHCHCH3 CH3CHCHCH3 CH3 1 3 2 a. 1 d. 2 and 3 5.8. CH3 *b. 2 e. 1, 2, and 3 c. 3 How many stereogenic centers are present in the following molecule? CH3 CH3 CH3CHCHCHCH2CH3 CH3 a. 1 5.9. *b. 2 c. 3 d. 4 e. 5 How many stereogenic centers are present in the following molecule?. H3C CH3 C C H3C OH CHCHCH3 OH. a. 1 5.10. c. 4 b. 2 c. 3 e. 8 *d. 4 e. 8 How many stereogenic carbons are in the following molecule? CH3 H3C a. 0 5.12. d. 6 How many chiral stereoisomers can be drawn for CH 3CHClCHBrCH3 ? a. 1 5.11. *b. 2 b. 1 *c. 2 d. 3 e. 4 How many stereoisomers can be obtained from the monobromination of butane? a. 1 *b. 2 c. 3 Copyright © Houghton Mifflin Company. All rights reserved. d. 4 e. 5 81 82 PART III 5.13. How many stereoisomers with the formula CH3CHICHICH3 are possible? a. 1 5.14. b. 2 *c. 3 d. 4 e. 5 The number of stereogenic centers in progesterone is O C CH3 O progesterone (no stereochemistry shown) a. 2 5.15. b. 3 c. 4 d. 5 *e. 6 *d. 8 e. 0 The total number of possible stereoisomers of CH3CHCHCHCH3 F Cl Br. is a. 2 5.16. b. 4 c. 6 The total number of possible stereoisomers of 2-methyl-1-chlorocyclohexane is a. 2 *b. 4 c. 6 d. 8 e. 0 Optical Activity 5.17. An unknown sample is tested with a polarimeter for optical activity. The results of the test required no movement of the analyzer. What samples would give this result? a. pure enantiomer *d. both b and c 5.18. c. racemic mixture An unknown sample is tested with a polarimeter for optical activity. The results of the test require movement of the analyzer. What samples would give this result? *a. pure enantiomer d. both b and c 5.19. b. meso compound e. none of these b. meso compound e. none of these c. racemic mixture Which of the following statements about enantiomers is INCORRECT? a. b. c. d. *e. they cannot be differentiated by spectra they have the same melting and boiling points the mirror image of the R stereoisomer is the S stereoisomer the specific rotation of each stereoisomer has the same magnitude without exception the R stereoisomers will rotate light to the right Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 5.20. The observed rotation for 100 mL of an aqueous solution containing 1 g of sucrose, placed in a 2-decimeter sample tube, is +1.33° at 25°C. What is the specific rotation of sucrose? *a. +66.5° b. +266° c. +41.5 d. +133° e. 108° Relationships Between Stereoisomers 5.21. Which of the following molecules are the same? CH3 H C CH3 Cl CH3CH2 C CH3 CH2CH3 Cl H3C C H3C Cl C H H CH2CH3 1 2 3 4 b. 3 and 4 *c. 1 and 3 d. 2 and 3 e. 2 and 4 Which of the three molecules below is the enantiomer of the following molecule? CH3 H I Br H I Br CH3 CH3 Br H CH3 H I I I II *a. I d. there are no enantiomers 5.23. Cl CH2CH3 a. 1 and 2 5.22. 83 Br III b. II e. both II and III c. III Which of the three molecules below is a diastereomer of the following molecule? H3C HO H3C HO H CH3 OH H H OH H3C CH3 H3C CH3 H CH3 H HO H OH H HO H I a. I d. there are no diastereomers II b. II e. both I and II Copyright © Houghton Mifflin Company. All rights reserved. OH III *c. III 84 PART III 5.24. Which of the following are achiral conformers? *a. staggered and eclipsed forms of ethane b. cis and trans-2-butene c. meso and (2R,3R)-2,3-dibromobutane d. (R) and (S)-lactic acid e. E- and Z-2-pentene 5.25. Which of the following would constitute a pair of enantiomers? a. b. c. *d. e. 5.26. The terms that best describe the relationship between (2R,3R)-2,3-butanediol and (2S,3S)-2,3-butanediol are a. b. c. *d. e. 5.27. configurational, achiral, diastereomers. conformational, chiral, enantiomers. conformational, achiral, diastereomers configurational, chiral, enantiomers. configurational, achiral, enantiomers. The terms that best describe the relationship between (2R,3S)-2-bromo-3-chlorobutane and (2R,3R)-2-bromo-3-chlorobutane are a. b. c. d. *e. 5.28. staggered and eclipsed forms of ethane cis and trans-2-butene meso- and (2R,3R)-2,3-dibromobutane (2R,3R) and (2S,3S)-tartaric acid none of these configurational, achiral, diastereomers. conformational, chiral, diastereomers. configurational, achiral, enantiomers. conformational, chiral, enantiomers. configurational, chiral, diastereomers. Which of the following statements about the pair of molecules shown below is not true? Cl Cl and H H3C a. b. c. *d. e. CH2CH3 CH3CH2 H CH3 They have the same boiling point. One rotates plane polarized light in the opposite direction from the other. They have the same density. One rotates plane polarized light a different number of degrees than the other. They are mirror images of each other. The R-S and E-Z Conventions 5.29. According to the R-S convention, which priority is correct for the following sets of groups? a. NH2 > Cl > CH3 > H c. Cl > CH3 > NH2 > H e. CH3 > NH2 > Cl > H *b. Cl > NH2 > CH3 > H d. H > Cl > CH3 > NH2 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 5.30. (R)-2-chlorobutane is correctly represented by which of the following: H C CH3 CH3 CH3 Cl Cl C H3C H CH2CH3 CH2CH3 I II C Cl CH2CH3 III. CH3 CH2CH3 Cl a. I 5.31. Cl H C CH2CH3 CH3 CH3 IV V *b. II c. III d. IV e. V Which of the following groups has the highest priority for assigning R-S absolute configuration? a. CH2=CH− 5.32. C b. (CH3 )2CH− *c. (CH3 )3C− d. CH3CH2− The correct IUPAC name for the following molecule is: H3C Cl C Br C CH2CHCH3 CH3 *a. b. c. d. e. (E)-2-bromo-3-chloro-5-methyl-2-hexene (E)-2-bromo-3-chloro-5-methyl-3-hexene (Z)-2-bromo-3-chloro-5-methyl-3-hexene (Z)-2-bromo-3-chloro-5-methyl-2-hexene (Z)-5-bromo-4-chloro-2-methyl-4-hexene Copyright © Houghton Mifflin Company. All rights reserved. e. CH3− 85 86 PART III 5.33. Which of the following structures is (Z)-2,3-dichloro-2-pentene?. H3C CH3 C H3C C H C CH2CH3 1 Cl CH H3C CH2CH3 C C 2. C H Cl CH2. CH2CH3 3. Cl H3C C. H3C C Cl C Cl CH. CH2 Cl CH2CH3. 5 4 a. 1 5.34. C. *b. 2 c. 3 d. 4 e. 5 Of the following structures, how many are classified “E”?. H3C CH3 C H3C C H C CH2CH3 1 Cl CH H3C CH2CH3 C C. C H Cl 2 CH2. CH2CH3 3. Cl H3C. C H3C C Cl C Cl CH. CH2 Cl CH2CH3. 5 4 a. 1 5.35. C. b. 2 *c. 3 d. 4 e. 5 Of the following structures, how many are classified “Z”?. H3C CH3 C H3C C H C CH2CH3 CH H3C CH2CH3 C C Cl H Cl. CH2. C CH3. Cl H3C C Cl a. 1. Cl C Cl C CH. CH2 b. 2 H3C. C CH2CH3 *c. 3. d. 4 e. 5 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 5.36. Which of the following structures depicts (R)-3-ethyl-2,3-dimethylhexane?. H a. c. CH3CH2 CH3CH2 C CH3 CH(CH3)2 *b. CH3CH2 C CH(CH3)2 CH2CH2CH3 CH2CH2CH3 CH2CH2CH3 CH2CH3 C CH(CH3)2 d. CH3CH2 CH3 C CH(CH3)2 H CH2CH3 e. CH3CH2CH2 C CH3 CH(CH3)2. 5.37. The priority order for R/S nomenclature is a. b. *c. d. e. 5.38. —CH=CH2 > —OH > —CH3 > —CH2CH3 —OH > —CH2CH3 > —CH=CH2 > —CH3 —OH > —CH=CH2 > —CH2CH3 > —CH3 —CH3 > —CH2CH3 > —CH=CH2 > —OH —CH2CH3 > —CH3 > —CH=CH2 > —OH Which name describes the following structure?. OH H3C CH3CH2 CH CH2 *a. (R)-3-methyl-1-penten-3-ol c. (R)-3-ethyl-1-buten-3-ol e. (S)-3-ethyl-1-buten-3-ol 5.39. b. (S)-3-methyl-1-penten-3-ol d. (R)-3-methyl-1-pentyn-3-ol Which name describes the following structure?. OH H2C H3C CHCH2 a. (R)-4-methyl-1-hexen-4-ol c. (R)-4-ethyl-1-penten-3-ol e. (S)-4-methyl-1-hexyn-4-ol Copyright © Houghton Mifflin Company. All rights reserved. CH2CH3 b. (S)-4-ethyl-1-penten-4-ol *d. (S)-4-methyl-1-hexen-4-ol. 87 88 PART III Fischer and Newman Projections 5.40. What is correct name for the following structure? CH3 H Cl 2 Cl H 3 CH3 a. (R,S)-2,3-dichlorobutane *c. (2S,3S)-2,3-dichlorobutane e. none of these 5.41. b. (2R,3S)-2,3-dichlorobutane d. (2R,3R)-2,3-dichlorobutane What is the absolute configuration around C-2 and C-3? CH3 H Br 2 Cl H 3 CH3 a. R, R 5.42. *b. S, S c. R, S d. S, R e. E, Z The absolute configuration around the stereogenic center of the molecule below is: CH3 H CH2CH2CH3 CH2CH3 a. R 5.43. *b. S c. E d. Z e. trans The Fischer projection formula for (S)-lactic acid (2-hydroxypropanoic acid) is. H a. HO2C CH3 b. CH3 CO2H H OH CH3 CO2H HO OH d. CH3 H c. HO H. CO2H CO2H *e. HO H CH3. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 5.44. The Fischer projection that represents the same molecule as CH3 H OH CH2CH3 is:. CH2CH3 H a. CH3CH2 CH3 b. H HO H CH3 CH3 CH3 CH2CH3 H *c. CH3 OH d. OH CH2CH3 e. HO H CH2CH3 OH. 5.45. OH H CH3 H3 C H OH represents a. b. c. d. *e. 5.46. (2R,3R)-2,3-butanediol. (2S,3S)-2,3-butanediol. the most stable conformer of (2R,3R)-2,3-butanediol. the least stable conformer of (2R,3R)-2,3-butanediol. meso-2,3-butanediol. Which one of the following structures represents a meso compound?. CH3 *a. H CH3 OH b. H H OH H H OH HO H HO H OH CH3. e. H HO H CH3 OH CH3 Copyright © Houghton Mifflin Company. All rights reserved.. H H H OH H CH3 HO H HO OH HO c. OH CH3 CH3 H OH. CH3 d. CH3. 89 90 PART III Stereochemistry and Chemical Reactions 5.47. When (R)-3-bromo-2-methyl-1-butene is reacted with HBr, two stereoisomers are formed. What is the relationship of these stereoisomers? a. enantiomers d. E 5.48. b. meso compounds e. Z Treating 1-butene with HCl produces a product with one stereogenic carbon. What is the name of the product? a. 2-chloro-1-butene d. (S)-2-chlorobutane 5.49. b. 1-chlorobutane c. (R)-2-chlorobutane *e. both c and d in equal amounts When (S)-3-bromo-1-butene is treated with HBr, two stereoisomeric products form. What is the relationship of these two products? a. enantiomers d. racemic mixture 5.50. *b. diastereomers e. cis/trans C C H3C CH3. a. 1 *b. 2 1) BH3 2) H2O2, HO c. 3 _ d. 4 ? e. 5 Enantiomers may differ in the following property: *a. b. c. d. e. 5.52. c. meso compounds How many stereogenic carbons are produced from the following sequence of reactions? H 5.51. *c. diastereomers the rate at which they react with a chiral reagent boiling point melting point number of degrees they rotate plane polarized light solubility in water The product of addition of bromine to (R)-3-buten-2-ol will be a. b. c. *d. e. a 50:50 mixture of enantiomers. a mixture of enantiomers formed in unequal amounts. a 50:50 mixture of diastereomers. a mixture of diastereomers formed in unequal amounts. optically inactive. Copyright © Houghton Mifflin Company. All rights reserved. Chapter 6 Organic Halogen Compounds; Substitution and Elimination Reactions Nomenclature of Halides 6.1. What is the IUPAC name of the following alkyl halide? Br *a. 2-bromo-4-methylpentane c. 2-methyl-4-bromopentane e. 2-bromo-1-isopropylpropane 6.2. b. 4-methyl-2-bromopentane d. 2-bromo-2-methylpentane What is the IUPAC name of the following alkyl halide? H3C a. b. *c. d. e. 6.3. Br trans-p-bromotoluene trans-4-methylcyclohexyl bromide trans-4-methyl-1-bromocyclohexane trans-1-bromo-4-methylcyclohexane trans-p-bromomethylcyclohexane Which of the following structures represents 2,4,4-trichloroheptane? Cl Cl Cl I Cl III Cl Cl Cl Cl IV a. I 91 Cl Cl II Cl Cl Cl Cl Cl V b. II c. III *d. IV e. V Copyright © Houghton Mifflin Company. All rights reserved. 92 PART III Nucleophiles/Bases/Leaving Groups 6.4. Which of the following is the best nucleophile? b. CH3O— e. all are the same a. CH3OH d. CH3SH 6.5. Which of the following is the strongest base? a. H2 O 6.6. b. OH b. Cl— b. CH4 *d. — e. F— NH2 *c. I— d. Br— e. H2 N— *c. NH3 d. HF Which of the following is an incorrect representation of relative nucleophile strength? a. —NH2 > F— d. CH3O— > CH3 OH 6.9. c. NH3 Which of the following is the best nucleophile? a. H2 O 6.8. — Which of the following is the best leaving group? a. HO— 6.7. *c. CH3S— *b. HO— > HS— e. I— > Br— c. CH3— > HO— The reactivity order of 1. CH3CH2S— 2. CH3CH2O— 3. CH3CH2OH as nucleophiles is *a. 1 > 2 > 3 d. 3 > 2 > 1 b. 2 > 3 > 1 e. 1 > 3 > 2 c. 2 > 1 > 3 Reaction Mechanisms 6.10. What is the mechanism of the following reaction? _ CH3Br CH3OH + OH a. SN1 d. E2 6.11. Br _ c. E1 Which statement is true for SN2 reactions? a. b. c. *d. e. 6.12. *b. SN2 e. both a and b + The rate of the reaction is dependent on the stability of a carbocation. The rate of reaction is dependent on just the substrate. The fastest reaction will occur with a tertiary halide. Displacement occurs with inversion of configuration. The mechanism is a two step process. Which bromide reacts fastest in SN2 reactions? *a. CH3Br d. (CH3 ) 3CCH2Br b. (CH3 ) 2CHBr e. CH3CH2Br c. (CH3 ) 3CBr Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 6.13. Which of the following is a polar aprotic solvent? a. H2 O d. (CH3 ) 2S=O 6.14. 93 b. (CH3 )2 NCHO *e. both b and d c. CH3OH Which statement(s) is/are true of an E1 elimination? a. it is a two-step process and has the same first step as a SN1 mechanism b. it involves the formation of the carbocation from elimination of a good leaving group c. a common competing reaction is rearrangement of a less stable carbocation to a more stable carbocation d. the loss of a proton by the carbocation is a fast step *e. all of the above 6.15. When (R)-3-bromo-3-methylhexane is treated with H2 O, racemic. OH CH3CH2C(CH3)CH2CH2CH3 is produced. By what mechanism does this reaction occur? *a. SN1 d. E2 6.16. The slowest step of an SN1 reaction involves: a. *b. c. d. e. 6.17. b. SN2 c. E1 e. cannot be explained by one mechanism attack of the nucleophile on the substrate to form a pentavalent carbon. breaking the bond between the carbon and the leaving group to give a carbocation. combination of a nucleophile with the carbocation to give the product. loss of a proton from the nucleophile to give the product. none of the above. Which of the following bromides will react faster with CH3 OH in an SN1 reaction?. Br. a. CH3CH2CHCH3 b. CH3CH2CH2Br... c. CH2 CHCH2CH2Br.. *d. (CH3)2CBrCH2CH3.. e. CH3Br. 6.18. The SN 2 mechanism for nucleophilic substitution reactions a. *b. c. d. e. involves two steps and occurs with inversion of configuration. involves one step and occurs with inversion of configuration. involves two steps and occurs with racemization. involves one step and occurs with retention of configuration. involves one step and occurs with racemization. Copyright © Houghton Mifflin Company. All rights reserved. 94 PART III 6.19. The SN 1 mechanism for nucleophilic substitution reactions a. b. *c. d. e. 6.20. involves one step and occurs fastest with primary halides. involves one step and occurs fastest with tertiary halides. involves two steps and occurs fastest with tertiary halides. involves two steps and occurs fastest with primary halides. involves one step and occurs fastest with aromatic halides. The expected SN2 reactivity order of CH3 1. H2C CHCHBr 2. CH3CH CHCH2Br 3. CH2 Br CHC Br CH3 is: *a. 2 > 1 > 3 d. 1 > 3 > 2 6.21. b. 2 > 3 > 1 e. 3 > 1 > 2 c. 1 > 2 > 3 CH3CH2C(CH3 )2Br + (CH3 )3CO—K+ are most likely to react by a. a free-radical chain mechanism. c. the SN2 mechanism. *e. the E2 mechanism. b. the SN1 mechanism. d. the E1 mechanism. 6.22. CH3CHCH3 + Na + _ SH Br are most likely to react by a. a free-radical chain mechanism. *c. the SN2 mechanism. e. the E2 mechanism. 6.23. b. the SN1 mechanism. d. the E1 mechanism. The structure H CH3 H3CO _ ! Br _ CH3 ! represents the transition state for the reaction of a. *b. c. d. e. methanol with 2-bromopropene. methoxide with 2-bromopropane. sodium bromide with isopropyl methyl ether. methanol with 2-bromopropane. methoxide with 1-bromopropane. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 6.24. 95 The energy-reaction diagram Reactants Energy Products Reaction Progress is for a. an SN2 reaction only. c. an E2 reaction only. e. an SN1 or E1 reaction. b. an SN1 reaction only. d. an E1 reaction only. *f. an SN2 or E2 reaction Reactions 6.25. The major product of the following reaction is: _ CH3CH2S Na + CH3CHCH2CH2Br ? DMSO CH3 CH3C CHCH3 CH3 CH3CHCH2CH2SCH2CH3 CH3 II a. I d. I and II III b. II *c. III e. there is no major product When 1-chlorobutane is reacted with the bulky base, potassium t-butoxide, in t-butyl alcohol, the major elimination product is: *a. 1-butene d. butyl t-butyl ether 6.27. CH2 CH3 I 6.26. CH3CHCH b. cis-2-butene e. butyl alcohol c. trans-2-butene How many different E2 products can form from the dehydrohalogenation of 2-bromopentane? a. 1 b. 2 *c. 3 Copyright © Houghton Mifflin Company. All rights reserved. d. 4 e. 5 96 PART III 6.28. What is the major product of the following reaction? CH3 Br CH3C (CH3)3CO CHCH3 _ ? (CH3)3COH CH3. a. (CH3)2C. C(CH3)2 (CH3)3CCH *b.. (CH3)2C... c. CH2 CHCH3 (CH3)2C d.. CHCH2CH3.. e. 6.29. none of these. What is the final product of the following sequence of reactions? CH3C 1. NaNH2 CH 2. CH2Br. CH2C HC CBr I II CH2 CH2CH2C III. *b. II e. III and IV c. III What alkyne is produced when sodium acetylide reacts with CH3CH2 I? a. 2-butyne 6.31. CH IV a. I d. IV 6.30. CCH3 *b. 1-butyne c. 2-butene d. 1-butene e. propyne 1-Butanethiol, CH3CH2CH2CH2SH, is produced by the reaction of 1-bromobutane with: a. NH3 b. CH3OH c. CH3S— *d. — SH e. CH3O— Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 6.32. Which Fischer projection represents the product of the following reaction? CH3 H _ Cl CN ? CH2CH3.. a. H b. NH2 H. *c. NC. CH2CN e. H CH2CH3 H CN CH2CH3.. What is the major product of the following reaction?. CH3 Br CH3CH2OH ? CH2 CH3 b. a. CH3 c. OCH2CH3 CH2OCH2CH3 e. Copyright © Houghton Mifflin Company. All rights reserved. CH3 *d. H CH2CH3. CH2CN 6.33. CN.. H CH3 CH2CH3 CH2CH3 d.. CH3 CH3 OCH2CH3 97 98 PART III 6.34. The major product of the reaction Br _ CH3S Na + H C H3C CH2CH3 is a. H3CS H H *b. C H3C c. H C CH2CH3 H3C d. CH2CH3 e. H C CH2CH3 Br CH2CH3 H C H3C SCH3 H3C CH2CH3 SCH3 C H3C 6.35. CH2CH3 The products of the following reactions are: Br CH3OH CH3 is. OCH3 CH2 I II CH3 CH3OCH3 CH3. IV III OH V a. I, III CH3 *b. I, II, III c. III, V d. II, IV, V e. II, III Copyright © Houghton Mifflin Company. All rights reserved. Test Bank Miscellaneous 6.36. The monomer used to prepare Teflon is a. CH2=CH2 *d. CF2=CF2 6.37. c. CH3CH=CH2 Which of the following halocarbons is the raw material for the synthesis of Teflon? Cl Cl C Cl C Cl I a. I Cl C Cl 6.38. b. CH2=CHCl e. CH2Cl2 Cl C C F F II b. II F Cl C F F C Cl III c. III F C Cl C F IV d. IV F C F F V *e. V Polyhalogenated aliphatic compounds have not been used as: *a. toothpaste additives d. insecticides b. fire retardants e. refrigerants Copyright © Houghton Mifflin Company. All rights reserved. c. degreasing agents 99 Chapter 7 Alcohols, Phenols, and Thiols Nomenclature of Alcohols 7.1. Which of the following is a secondary (2°) alcohol? OH CH2OH CH3CH2OH I II OH III OH CH3CCH3 CH3 IV V a. I 7.2. b. II *c. III d. IV e. V Which of the following is 3-pentyn-1-ol?. a. CH3CH2C CCH2OH b. CH3C CCHCH3 OH 7.3. *c. CH3C CCH2CH2OH e. CH3C CCH2CH2CH2OH C CCH2OH.. What is the IUPAC name for isobutyl alcohol? a. 1-butanol c. 2-methyl-2-butanol e. 2,2-dimethylpropanol 7.4. d. b. 2-butanol *d. 2-methyl-1-propanol What would be the IUPAC name for the following alcohol? CH3CH(CH3 )CH2CH2 OH a. 2-methyl-4-butanol c. 3-methyl-2-butanol *e. 3-methyl-1-butanol Copyright © Houghton Mifflin Company. All rights reserved. b. 2-methyl-4-hydroxybutanol d. 1-hydroxy-3-methylbutanol 100 Test Bank 7.5. Which of the following molecules is classified as a tertiary (3°) alcohol? OH CH2OH. CH3CH2OH III II I OH C CH3OH V IV a. I 7.6. b. II c. III *d. IV e. V What is the correct name for the following molecule?. CH3CHCH2CH3 SH. a. 2-butanol d. 2-thiobutanol 7.7. b. 3-thiobutanol e. 3-butanethiol *c. 2-butanethiol What is the name of the following alcohol?. CH3 C OH CH2CH3. a. 1-ethyl-2-methylbenzyl alcohol c. 2-methyl-2-phenyl-1-propanol e. cumyl alcohol 7.8. b. methylphenylpropanol *d. 2-phenyl-2-butanol What is a correct name for (CH3 )2CHO ! K + ? a. potassium alkoxide c. potassium propoxide *e. potassium isopropoxide Copyright © Houghton Mifflin Company. All rights reserved. b. potassium ethoxide d. potassium dimethylethoxide 101 102 PART III 7.9. The correct name for. Br OH. is a. 3-hydroxybromobenzene. c. 3-bromobenzol. e. m-bromobenzol. 7.10. b. 3-bromobenzyl alcohol. *d. m-bromophenol. The formula for 2-pentanethiol is: a. b. CH3CHCH2CH2CH2SH CH3CHCHCH2CH3 HS OH OH *d.. c. CH3SCH2CH2CH3 CH3CHCH2CH2CH3. SH. e. CH3SCH2CH2CH2CH3. Properties of Alcohols 7.11. Which of the following molecules would be the best hydrogen bond donor? a. CH3CH2OCH3 d. CH3SH 7.12. *c. CH3OH Which of the following molecules would have the highest boiling point? *a. CH3CH2OH 7.13. b. CH3CN e. CH3CH2NH2 b. CH3OCH3 c. CH3CH2Cl d. CH3CH2CH3 e. CH3CH2 I The expected order of boiling points of 1. CH3CH2OCH3 2. 3. CH3CH2CH2OH CH3CHCH3 OH is: a. 3 > 2 > 1 b. 1 > 2 > 3 c. 1 > 3 > 2 *d. 2 > 3 > 1 e. 2 > 1 > 3 Acid-Base Chemistry 7.14. A Lewis base is a: a. proton donor c. electron pair acceptor 7.15. *b. electron pair donor d. proton acceptor The conjugate base of sulfuric acid, H2SO4 , is: a. H3SO4+ b. SO3 *c. HSO4 ! d. H2SO3 e. HSO3 ! Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 7.16. If the pKa of isopropyl alcohol is 17, what is the Ka of isopropyl alcohol? a. 17 x 10–17 d. 1017 7.17. *b. 10–17 e. 103 Which of the following molecules would be the strongest Brønsted-Lowry acid? a. H2 O 7.18. c. 10–3 f. 17 x 1017 b. H2S c. HF *d. HCl e. CH4 Which of the following phenols is the strongest acid? OH a. OH *b. O2N H3C OH c. Br. OH OH e. d. H3CO 7.19. H2N Which of the following is the strongest base?.. a. CH3CH2OH b... d. CH3CH2S _ _. _ CH3CH2NH.. increase acidity by increasing the stability of acids. decrease acidity by increasing the stability of a conjugate base. increase acidity by increasing the stability of a conjugate base. decrease acidity by increasing the stability of acids. can only have a slight effect on acidity. Phenols are stronger than alcohols as acids because of *a. b. c. d. e. 7.22. CF3CH2O Electron-withdrawing substituents a. b. *c. d. e. 7.21.. c.. *e.. 7.20. CH3CH2O _ resonance stabilization of phenoxide ions. resonance stabilization of phenols. resonance stabilization of alkoxide ions. resonance stabilization of alcohols. hydrogen bonding in phenols. The pKa of an acid whose Ka = 10–10 is a. 1010 *b. 10 c. –10 d. 1 e. –1 Reaction Mechanisms 7.23. Which of the following alcohols would react most rapidly under SN 1 conditions? a. CH3OH *d. (CH3 )3COH b. CH3CH2OH e. CH3CH2CH2OH Copyright © Houghton Mifflin Company. All rights reserved. c. (CH3 )2CHCH2 OH 103 104 PART III 7.24. Which statement is false? Tert-Butyl alcohol reacts a. b. *c. d. e. 7.25. with with with with with HCl to give 2-methylpropene by an E1 mechanism. HCl to give 2-chloro-2-methylpropane by an SN1 mechanism. HCl and HBr at very different rates. HCl or HBr to give a carbocation intermediate. HCl to give both 2-methylpropene and 2-chloro-2-methylpropane. The rate-determining step in the following reaction is: (CH3)3C a. b. *c. d. e. 7.26. + OH HBr (CH3)3C + Br H2O protonation of the alcohol. ionization of the alcohol to give a carbocation. loss of water from the protonated alcohol to give a carbocation. capture of a carbocation by bromide ion. displacement of water from the protonated alcohol by bromide ion. The rate-determining step in the following reaction is:. CH3CH2CH2CH2OH + HBr heat CH3CH2CH2CH2Br + H2O. a. b. c. d. *e. protonation of the alcohol ionization of the alcohol to give a carbocation. loss of water from the protonated alcohol to give a carbocation capture of a carbocation by bromide ion. displacement of water from the protonated alcohol by bromide ion. Reactions 7.27. What type of compound is formed when a secondary (2°) alcohol is treated with Jones’ reagent? a. an alkene 7.28. b. an alkyne e. an acid When an alcohol reacts with an alkali metal like Na, the product formed is a(n): a. alkene d. alkane 7.29. c. an aldehyde *d. a ketone *b. alkoxide e. hydroxide c. acetylide f. alkyne Which reagents would you use to accomplish the following transformation?. CH3(CH2)6CH2OH. a. H2SO4 , H2 O, acetone d. Zn, HCl, acetone 7.30. CH3(CH2)6CO2H *b. CrO3 , H2SO4 , acetone e. H2 , Pd, acetone c. PCC/CH2Cl2 What is the major product from the E1 dehydration of 2-methyl-2-pentanol? a. 4-methyl-1-pentene *c. 2-methyl-2-pentene e. 4-methyl-2-pentene b. 4-methyl-3-pentene d. 2-methyl-1-pentene Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 7.31. Which of the following mixtures would NOT react?. I. II. OH a. I. NaH CH3CH2OH III. 7.32. 105 NaOH b. II NaOH CH3CH2CH3 IV. c. III O d. IV CrO3 H+, acetone *e. II and IV What reagents would accomplish the following transformation?. O CH2CH2OH a. 1. PCl3 2. H3 O+ d. 1. Na 2. CH3 OH 7.33. b. 3 *d. 5 e. 6 b. FeBr3 , Br2. e. SOCl2. c. conc. H2SO4 , heat. b. aldehydes. e. tertiary alcohols. *c. ketones. Which of the following reagents will oxidize primary alcohols to carboxylic acids? 1. CrO3 , H2SO4 2. PCC 3. PCl3 4. SOCl2 *a. only 1 7.37. c. 4 Oxidation of secondary alcohols with Jones' reagent (CrO3 , H+, acetone) gives a. carboxylic acids. d. chromate esters. 7.36. *c. PCC, CH2Cl2 Cyclohexanol and phenol react similarly toward *a. sodium hydride. d. PCl3. 7.35. b. CrO3 , H + in acetone e. none of the above Acid-catalyzed dehydration of 3-methyl-3-hexanol can give the following number of alkenes (including stereoisomers): a. 2 7.34. CH2CH b. only 2 c. only 3 d. only 4 e. 1 and 2 Which of the following reagents will oxidize secondary alcohols to ketones? 1. CrO3 , H2SO4 2. PCC 3. PCl3 4. SOCl2 a. only 1 b. only 2 c. only 3 Copyright © Houghton Mifflin Company. All rights reserved. d. only 4 *e. 1 and 2 106 PART III 7.38. The reaction of phenol with bromine gives a. hydroquinone. *c. 2,4,6-tribromophenol. 7.39. b. 1,4-benzoquinone. d. 3,5-dibromophenol. Which reagent or reagents can be used irreversibly to accomplish the following transformation: _ CH3CH2O Na + CH3CH2OH 1. NaH 2. Na 3. NaOH a. only 1 *d. 1 and 2 7.40. b. only 2 e. 1, 2, and 3 Reagent? a. pyridinium chlorochromate c. H2 O2 , NaOH, H2 O e. all of the above CO2H. *b. K2Cr2 O7 , H2SO4 , H2 O d. Ag(NH3 )2 +, NaOH (Tollen’s reagent) What is the product of the following reaction sequence? CH3CH2CH2CH2SH 1. KOH (1 equivalent) 2. CH3I (1 equivalent) *a. CH3CH2CH2CH2SCH3 c. (CH3CH2CH2CH2S)2 e. CH3CH2CH2CH2S+(CH3 )2 I– 7.42. c. only 3 Which reagent will accomplish the following transformation? CH2OH 7.41. e. bromobenzene. b. CH3CH2CH2CH2OCH3 d. CH3CH2CH2CH2OH What is the major product of the following reaction? OH H2SO4 (catalyst) heat a. CH3CH2CH=CH2 *c. trans-CH3CH=CHCH3 e. none of the above b. cis-CH3CH=CHCH3 d. (CH3 )2C=CH2 Copyright © Houghton Mifflin Company. All rights reserved. Chapter 8 Ethers and Epoxides Structure and Nomenclature of Ethers 8.1. What is a correct name for CH3CH2 OCH3? a. ethyl ether d. ethoxymethane 8.2. b. dimethyl ether e. propane *c. methoxyethane Which of the following molecules is the correct structure for dibenzyl ether? a. CH3CH2OCH2CH3 b. O. OCH3 c. *d. e. 8.3. CH2OCH2 CH2CH2O What is the IUPAC name for the following molecule? OCH3 CH3CHCH2CCH3 Br a. b. *c. d. e. 8.4. CH2CH3 2-bromo-4-ethyl-4-methoxypentane 4-bromo-2-ethyl-2-methoxypentane 2-bromo-4-methoxy-4-methylhexane 2-bromo-3-methoxy-3methyl-hexane ethyl methyl propyl ether Which of the following molecules is named oxirane? *a. O b. c. N. S d.. C e. CH3CH2OCH3. H H H. Copyright © Houghton Mifflin Company. All rights reserved. 107 108 PART III 8.5. What is the correct IUPAC name for the following molecule? H CH3 H3C O H a. 1,2-dimethyloxirane *b. trans-1,2-dimethyloxirane d. cis-1,2-dimethyloxirane e. oxobutane 8.6. c. 2-butene oxide Which of the following molecules is correctly named diphenyl ether? a. CH3CH2OCH2CH3 *b. O OCH3 d. c. e. 8.7. CH2OCH2 CH2CH2O What is a name for the following molecule? CH3CH2CHOCH2CH3 CH3 a. 3-ethoxy-3-methylpropane c. butyl ethyl ether e. 3-ethoxybutane 8.8. What is the correct name for the following crown ether? a. crown-4 d. crown-5 8.9. b. ethyl isobutyl ether *d. 2-ethoxybutane O O O O *b. crown-4 e. crown-6 A crown ether named crown-6 has a total of a. 18, 6 d. 6, 24 b. 6, 18 *e. 12, 6 c. crown-4 carbons and oxygens. c. 24, 6 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 8.10. 109 The formula for 2-ethoxybutane is CH3 CH3 *a. b. CH3CH2OCHCH2CH3 CH3CH2OCH2CHCH3 OCH3 c.. CH3CHCH2CH3 d. CH3CH2OCH2CH2CH2CH3. CH3 e. CH3OCHCH2CH3 Properties of Ethers 8.11. Which one of the following molecules has the highest boiling point? a. 3-methoxy-1-propanol d. 1,1-dimethoxyethane b. 1,2-dimethoxyethane *c. 1,4-butanediol e. 2-methoxy-1-propanol Preparation and Reaction of Grignard Reagents 8.12. Which of the following is a Grignard reagent? *a. CH3 MgCl d. CH3Na 8.13. b. CH3 Li e. (CH3 )2 Zn Which reaction will yield CH3CH2 D? a. CH3CH3 + D2 O c. CH3CH2OLi + D2 O e. more than one or these 8.14. c. (CH3 )2 CuLi *b. CH3CH2 MgCl + D2 O d. CH3CH2OH + D2 O Starting with p-bromoanisole (p-bromophenyl methyl ether), what sequence of reactions will produce p-deuterioanisole? Br OCH3 p-bromoanisole a. 1. D2 O 2. Br2 , AlBr3 c. 1. D2 O 2. Mg, ether e. 1. Br2 , AlBr3 , 2. Mg, ether, 3. D2 O Copyright © Houghton Mifflin Company. All rights reserved. *b. 1. Mg, ether 2. D2 O d. 1. H2SO4 , 2. Mg, ether 3. D2 O 110 PART III 8.15. The products of H3C + CH2CH2MgBr CD3OH are: a. *b. c. H3C H3C H3C CH2CH2D + MgBr(OCD2H) CH2CH3 + MgBr(OCD3) + CH2CH2OCD3 MgBrH. d. H3C CH CH2 + MgBrCD3 e. H3C CH2CH2OH + MgBr(CD3) + H2O Preparation of Ethers 8.16. The synthesis of dipropyl ether can be accomplished using 1-propanol. What reactants and conditions are necessary for this to occur? a. Na and 180° d. Zn and H + 8.17. b. PBr3 and 140° e. PCC and 180° *c. H2SO4 and 140° The best Williamson synthesis of cyclohexyl methyl ether involves the following reaction:. Cl Cl a. b. + CH3OH + CH3O _ _ O OH c. + CH3Cl *d. + CH3Cl OH e. + H2SO4 140o Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 8.18. What alkene reacts with methanol in an acid catalyzed reaction to produce t-butyl methyl ether? a. ethylene d. propene 8.19. 111 *b. 2-methylpropene e. 1-butene c. 2-butene The best route to CH3 OC(CH3 )3 is _ + + (CH3)3CBr a. CH3O Na.. + CH3OH *b. H+ CH2 C(CH3)2.. c. (CH3)CMgBr + CH3OMgBr + CH3MgBr + CH3OH.. d. (CH3)3C I.. e. (CH3)3COH. Behavior of Ethers in Acids 8.20. When anisole (methyl phenyl ether) is treated with concentrated HBr, which of the following products are produced? Br I. OH + CH3OH II. CH3OH + OH Br III. CH3Br + a. I 8.21. IV. b. II c. III + *d. IV e. I and IV The mechanism by which ethers are cleaved in concentrated HI is: a. SN1 d. E2 8.22. CH3Br *b. SN2 e. none of these c. E1 Which of the following ethers will cleave the fastest with H2 O and H + ? a. CH3OCH3 b. CH3CHOCH3 CH3 CH3 *d. CH3COCH3 CH3 e. CH3CHCH2OCH3 CH3 Copyright © Houghton Mifflin Company. All rights reserved. c. CH3CH2CH2OCH2CH2CH3 112 PART III 8.23. Which of following ethers will cleave by an SN1 mechanism? a. CH3OCH3 b. CH3CHOCH3 c. CH3CH2CH2OCH2CH2CH3 CH3 CH3 *d. CH3COCH3 e. CH3CHCH2OCH3 CH3 CH3 8.24. The organic products of the reaction OCH2CH3 + 1. BBr3 2. H2O are: a. ethanol and bromobenzene. c. ethanol and phenol. e. ethylene oxide and phenol. b. ethyl bromide and bromobenzene. *d. ethyl bromide and phenol. Preparation and Reactions of Epoxides 8.25. Which of the following molecules is classified as an organic peroxy acid?. a... HOCH2CH2OH. b. CH3CO2H. c. CH3CHO.. O. d. 8.26. CH3CO3H. protonation of the oxygen in the oxirane. anion attack of the carbon in the oxirane. cation attack of the carbon in the oxirane. formation of a stable carbocation. none of the above. When cyclohexene is treated with peroxyacetic acid, the product that forms is: a. cyclohexanediol *d. cyclohexene oxide 8.28. *e. The first step in the mechanism of acid catalyzed ring opening of oxirane is: *a. b. c. d. e. 8.27. CH3CCH3 b. 1,2-cyclohexanediol e. dicyclohexyl ether The correct structure for peroxyacetic acid is: a. CH 3CO2 H b. CH 3OCH2 CH2 OH d. CH 3OCH2 CH2 CO2 H e. CH 3OOCH3 c. hexanol *c. CH 3CO3H Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 8.29. What is the final product of the following sequence of reactions? CH2Br 1) Mg, Et2O ? 2) O 3) H3O+ OCH3 CH2OCH3 a. b. CH2CH2CH2OH CH CH d. *c. CH CHCH2OH e. 8.30. Which of the following statements about ethylene oxide is false? *a. b. c. d. e. 8.31. Adds HBr according to Markovnikov's rule. Can act as a Lewis base. Reacts with Grignard reagents to give primary alcohols. Can be made from ethene, oxygen, and a catalyst. Can be hydrated to ethylene glycol. Which reagent will accomplish the following reaction? O a. NaOH *b. CH3CO3H d. (a) BH3 (b) NaOH, H2 O2 e. CH3CO2H 8.32. c. H2 O, H2SO4 The product of the reaction CH3CH2OH + O H+ is: a. CH3CH2CH2CH3. c. CH3CH2OCH2CH2 OCH2CH3. e. none of the above. Copyright © Houghton Mifflin Company. All rights reserved. *b. CH3CH2OCH2CH2 OH. d. CH3CH2OCH2CH2CH2 OH. f. all of the above. 113 114 PART III Miscellaneous 8.33. 1-Hexanol and propyl ether are examples of: a. enantiomers *d. constitutional isomers 8.34. b. diastereomers e. none of these c. stereoisomers What is the final product in the following reaction sequence? O OH CH3CHCH3 H3O+ Mg, ether PBr3. a. CH3CHOCH2CH2OH b. CH3CHCH2CH2Br CH3 *c. ? CH3CHCH2CH2OH CH3 CH3. e.. d. CH3CHOCH2CH3 none of these. CH3. 8.35. Isopropyl bromide reacts with Li to give: a. propene *d. isopropyllithium 8.36. b. (CH3 )2CHOCH2CH(CH3 )2 c. CH3OCH3 *e. both b and d A reaction that would give n-butyllithium is a. CH3CH2CH2CH3 + Li c. CH3CH2CH2CH2Br + LiBr e. CH3CH2CH2CH3 + CH3 Li 8.38. c. propane Which of the following ethers are unsymmetrical? a. CH3CH2OCH2CH3 d. CH3OCH2CH3 8.37. b. propyllithium e. butane *b. CH3CH2CH2CH2Br + 2 Li d. CH3CH2CH2CH2OH + Li Adding Br2 in H2 O will distinguish which of following pairs of compounds? a. *b. c. d. e. diisopropyl ether and hexane ethyl phenyl ether and allyl phenyl ether 1-butanol and methyl propyl ether diethyl ether and ethanol toluene and anisole Copyright © Houghton Mifflin Company. All rights reserved. Chapter 9 Aldehydes and Ketones Nomenclature of Aldehydes, Ketones and Derivatives 9.1. The common name for the following molecule is: O CH3CH2CH a. acetaldehyde d. propyl aldehyde 9.2. a. CH2OH b. CO2H c. CHO OH e. *d. The IUPAC name for acetone is a. butanone *d. propanone 9.4. c. butanal What is the structure of cyclopentanecarbaldehyde? O 9.3. *b. propionaldehyde e. ethylmethanal b. 2-pentanone e. acetophenone c. 3-pentanone The IUPAC name for the following molecule is: O CH2C CH3 C CH3CH2 a. 3-ethyl-1-phenyl-3-pentenone c. allyl benzyl ketone *e. (Z)-3-ethyl-1-phenyl-3-penten-2-one 9.5. H b. 3-ethyl-5-phenyl-2-penten-4-one d. (E)-3-ethyl-1-phenyl-3-penten-2-one What is the class of compound produced from the reaction of a ketone with hydrazine? a. oxime d. semicarbazone 115 C b. amide e. imide *c. hydrazone Copyright © Houghton Mifflin Company. All rights reserved. 116 PART III 9.6. Which of the following molecules is a hemiacetal? OCH3 H3CCH a. b. H3CCH OCH3 CN OH OH H3CCH d. *e. c. H3CCH NH2 H3CCH CH3 9.7. OH OH OCH3 Which of the following compounds is a hemiacetal? OCH3 OH OH a. d. 9.8. HO *b. O. e. O. H3CO O c. O. Which of the following compounds is a cyanohydrin?. a. HO b. CN CH2CH2 *c. CHCN OH CN OH. d. NH + N C O _ e. C OH 9. 9. Which of the following is a hydrazone?. *a. CH3CH. N NH2 b. CH3CH d. CH3CH2 N OH. O c. CH3CH N N C NH2.. NH NH2 H e. CH3CH2 NH OH. Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 9.10. The name of O CH3 CH CH2 C CH3 OH is: a. 2-hydroxy-4-pentanone. b. 2-oxo-4-pentanol. c. 4-oxo-2-pentanol. d. 1-acetyl-2-propanol. *e. 4-hydroxy-2-pentanone. Properties of Aldehydes and Ketones 9.11. Which of the following molecules has the highest boiling point? a. o-xylene d. benzaldehyde 9.12. c. 2-hydroxybutanal b. aldehydes c. ketones d. alcohols e. thiols In a carbonyl group a. b. c. d. *e. 9.15. b. 3-hydroxypropanal *e. 4-hydroxybutanal What class of compound most closely resembles an acetal in its reactivity with CH3 MgBr? *a. ethers 9.14. c. p-xylene Which of the following aldehydes can exist in equilibrium with a cyclic hemiacetal? a. 4-pentenal d. 3-hydroxybutanal 9.13. b. m-xylene *e. benzyl alcohol the oxygen acts as a Lewis acid. the C=O bond length is shortened due to resonance. the carbon is sp3 hybridized. the carbon is nucleophilic and the oxygen is electrophilic. the carbon is electrophilic and the oxygen is nucleophilic. The expected order of boiling points of O CH3CH2CCH3 1. OH CH3CH2CHCH3 2. CH3 CH3CH2CHCH3 3. is: a. 3>2>1 d. 1>2>3 *b. 2>1>3 e. 1>3>2 Copyright © Houghton Mifflin Company. All rights reserved. c. 2>3>1 117 118 PART III Enols/Enolates/Tautomerism 9.16. Which of the hydrogens in the following molecule are most acidic? The hydrogens on carbon O CH3CH2CH2CH2C 5 4 3 2 1 a. 1 9.17. *b 2 d. 4 e. 5 The equilibrium that exists between the keto and enol forms of aldehydes and ketones is known as: a. stereoisomerism *d. tautomerism 9.18. c. 3 H b. configurational isomerism e. positional isomerism c. geometric isomerism The number of α -hydrogens in O CH3CCH(CH2CH3)2 is a. 1 b. 3 *c. 4 d. 8 e. 14 Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 9.19. 119 The predominant product from the reaction _ CH3O Na+ O CH3CH2C CH3OD (excess) is: D O O a. CD3CD2C b. D D D D. D CH3CH2C D D D D. O *c. O CH3CD2C. d. CD3CH2C O e. 9.20. CD3CD2C The enol tautomer of 3-pentanone is:.. OH a. CH2 CH CH O CH2 CH3 b. CH2 CH OH c. CH2 C CH2 CH3 OH C CH2 CH2 CH3 *d. CH3 CH C. CH2 CH3 OH e. 9.21. CH3 C CH CH2 CH3. Which hydrogens in the following compound will be exchanged most rapidly for deuterium upon reaction with D2 O and NaOD? H4 H3 H2 H1 O H5 a. H1 b. H2 *c. H3 Copyright © Houghton Mifflin Company. All rights reserved. d. H4 e. H5 120 PART III Reaction Mechanisms 9.22. In the mechanism for acid catalyzed hemiacetal formation, the first step is: *a. b. c. d. e. 9.23. The second step in the base catalyzed aldol condensation is: a. *b. c. d. e. 9.24. formation of the enolate ion addition of an enolate to a carbonyl group protonation of the alkoxide ion protonation of the carbonyl oxygen loss of a proton from the α carbon What statement is false relative to the nucleophilic additions? a. b. *c. d. e. 9.25. protonation of the carbonyl oxygen nucleophilic attack at the carbonyl carbon protonation of the oxygen of the alcohol nucleophilic attack at the carbon of the alcohol elimination of a water molecule When a weak nucleophile is present, the reaction can be catalyzed by acid. The nucleophile attacks the trigonal carbon of the carbonyl group. Ketones are more reactive than aldehydes. Nucleophiles that add irreversibly are poor leaving groups. Nucleophiles can be classified as those that add reversibly to carbonyl compounds and those that add irreversibly. Which statement about the mechanism of imine formation from a primary amine and an aldehyde or ketone is false? a. The first steps involve addition of the amine to the carbonyl carbon to form a tetrahedral intermediate. b. The last steps involve elimination of water to form a carbon-nitrogen p-bond. c. All steps are reversible. *d. The reaction involves SN2 displacement of the carbonyl oxygen by the amine nitrogen. e. The reaction does not require a strong acid catalyst. 9.26. Which of the following nucleophiles add reversibly to a carbonyl group? _ a. I, II and IV d. III and IV CN H2O I II _ CH3 H III IV b. II e. I, II, III and IV _ *c. I and II Copyright © Houghton Mifflin Company. All rights reserved. Test Bank Reactions 9.27. What type of compound is produced from the following reaction?. CH3 AlCl3 ? CCl O. a. an amide 9.28. b. an alcohol d. an aldehyde *e. a ketone An oxime can be produced by the reaction of an aldehyde and: *a. hydroxylamine d. phenylhydrazine 9.29. c. an acid b. hydrazine e. semicarbazide c. methylamine Which of the following compounds will NOT act as a nucleophile in an Aldol reaction? O. a. CH3CHO d. HCHO b. CH3CCH3 *e. c and d Copyright © Houghton Mifflin Company. All rights reserved. O c. (CH3)3CCC(CH3)3 121 122 PART III 9.30. What reaction will produce the following product? H2C CH2 O O CHO a. + H+ HOCH2CH2OH O *b. H+ HOCH2CH2OH + CH2CHO c. + HOCH2CH2OH H+. O CH2CCH3 d. + CH3CH2OH CHO e. 9.31. + H+ The reaction of a Grignard reagent with acetaldehyde followed by acid hydrolysis will produce what type of product? a. a primary alcohol d. an acid 9.32. CH3CH2OH H+ *b. a secondary alcohol e. a ketone c. a tertiary alcohol Which reagents would you use to accomplish the following conversion? O CH3(CH2)6CCH3 a. NaBH4 , H2 O *d. all of these OH CH3(CH2)6CHCH3 b. LiAlH4 , ether; then H3 O+ e. none of these c. H2 , Pt Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 9.33. 123 Which of the following reactions will produce a cyanohydrin? O a. CH3CH2CCH3 + N2H4 + HCN + CH3MgCl + NaBH4 + CH3OH O *b. CH3CH2CCH3 KOH O c. CH3CH2CCH3 H3O + O d. CH3CH2CCH3 O e. 9.34. HCl What Grignard reagent and carbonyl compound react to give benzyl alcohol after treatment with aqueous acid? *a. b. c. d. e. 9.35. CH3CH2CCH3 phenyl magnesium bromide and formaldehyde phenyl magnesium bromide and oxirane benzaldehyde and methyl magnesium bromide benzaldehyde and ethyl magnesium chloride acetophenone and methyl magnesium chloride Which reagent will accomplish the following transformation?. O OH CCH3 a. NaOH *d. NaBH4 9.36. CHCH3 ? b. CrO3 , H2SO4 e. H2 , Pd c. CH3 MgBr What is the structure of the aldol produced from reacting propanone with NaOH? CH3 CH3. a. CH3CH2CH2CH2CH2CHO. b. CH3CCH2CHO d. CH3CHCHCCH3 OH *e. O CH3CCH2CCH3 CH3 O Copyright © Houghton Mifflin Company. All rights reserved. CH3 CH3CHCHCCH3 OH CH3 OH c. O 124 PART III 9.37. What reactants give the following molecule upon acid hydrolysis? OH C CH a. cyclohexyl magnesium bromide and acetaldehyde _ + b. cyclohexanol and HC C _Na + *c. cyclohexanone and HC C Na _ + d. cyclohexanecarbaldehyde and HC C Na e. cyclohexanone and ethenyl magnesium bromide 9.38. The products from. H3C H+ O O H2O CH2 C H2. are O *a. C CH3 + CH3 + OH + OH OH O b. C CH2CH2 H2C CH2 O. CH3 c. C CH2 CH2 OH. H d. e. C O + CH3OCH2CH2OH. no reaction Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 9.39. CHCH3 OH can be prepared from a. C + CH3 HMgBr, then H3O + O b. CCH3 + CrO3 O c. CHCH3 H2O + MgBr *d. CH3MgBr e. 9.40. CH + CH2MgBr CH2 + + O , then H3O then H3O+ O, The product from. CH3CH CHCH O 1. NaBH4 2. H O + 3 is:. *a. CH3CH CHCH2OH b. CH3CH2CH2CH d. CH3CH O. c. CH3CH2CH2CH2OH e. CH3CH2CH2CO2H Copyright © Houghton Mifflin Company. All rights reserved. CHCO2H 125 126 PART III 9.41. Which of the following compounds will give a positive silver mirror test (Tollens’ test)?. O a. CH(OCH3)2 c. CH2OCH3 b. H3C C CH3 *d. H3C CH O.. O e. 9.42. H3C C OCH3 The aldol obtained by treating CH2CH2CH O with base is: OH *a. CH2CH2CHCH CH2 CHO OH b. CH2CH2CHCHCH2CH2 OH OH c. CH2CH2CH CH CH2CH O. CH d. CH2CH CH O CHCH2 O.. e. CH2CH CH O OH Copyright © Houghton Mifflin Company. All rights reserved. Test Bank 9.43. The major product obtained from CH + O CH2CH O _ Na + OH heat is: OH a. CH2CH CH CH O.. b. CH CH CH2. O c. CH2OCCH2.. d. CH2O CH2CH O... *e. CH C CH O. 9.44. A reaction sequence that will accomplish the transformation O C O H is: a. *b. c. d. e. 1. CH3 MgBr 2. H3 O+ 1. CH3 Li 2. H3 O+ 3. CrO3 , H2SO4 1. LiAlH4 2. H3 O+ 3. CH3 MgBr 1. H2 , Pd catalyst 2. CH3 MgBr 3. H3 O+ 1. CrO3 , H2SO4 2. CH3 MgBr 3. H3 O+ Copyright © Houghton Mifflin Company. All rights reserved. C CH3 127 128 PART III 9.45. The organic product of the reaction O + H+ HO OH is O O a. b. O O O *c. d. OH O. O e. 9.46. O How many hydrogens in the following compound will be exchanged for deuterium upon reaction with D2 O and an acid catalyst?. O a. 0 9.47. b. 2 c. 4 *d. 5 e. 8 Which reagent can be used to accomplish the following transformation? CH CHCHO Reagent? a. pyridinium chlorochromate *c. NaBH4 e. NaH CH CHCH2OH b. Tollens’ reagent d. H2 , Ni Copyright © Houghton Mifflin Company. All rights reserved. Chapter 10 Carboxylic Acids and Their Derivatives Nomenclature of Carboxylic Acids and Derivatives 10.1. What is the common name for HCOOH? *a. formic acid d. oxalic acid 10.2. b. acetic acid e. malonic acid c. propionic acid Which of the following represents m-bromobenzoic acid? OH CO2H CH3 a. b. c. Br. Br Br. CO2H CH2OH e. *d. Br Br. 10.3.. The IUPAC name for succinic acid is butanedioic acid. What is the structure of succinic acid?. a.. CH3CH2CH2CO2H.. b. CH3CH CHCO2H.. *c. HO2CCH2CH2CO2H... d. 10.4. CH3CH2CH2CO3H... e. HOCH2CH2CH2CO2H. What is a correct name for the following structure? COOH a. butanoic acid c. succinic acid e. formyl cyclobutane Copyright © Houghton Mifflin Company. All rights reserved. *b. cyclobutanecarboxylic acid d. cyclobutylacetic acid 129 130 PART III 10.5. Which of the following carboxylic acids is terephthalic acid? CO2H CO2H CO2H II I III CO2H OH CH3 CO2H HO2C CO2H V IV CO2H a. I 10.6. b. II c. III *d. IV e. V What is the IUPAC name of the following molecu