Workbook for Organic Chemistry Supplemental Problems and Solutions First Edition Jerry Jenkins

Workbook for Organic Chemistry Supplemental Problems and Solutions First Edition Jerry Jenkins Workbook for Organic Chemistry Supplemental Problems and Solutions First Edition Jerry Jenkins Workbook for Organic Chemistry Supplemental Problems and Solutions First Edition Jerry Jenkins

This page intentionally left blank This page intentionally left blank WORKBOOK FOR ORGANIC CHEMISTRY SUPPLEMENTAL PROBLEMS AND SOLUTIONS Jerry A Jenkins Otterbein College W.H Freeman and Company New York © 2010 by W.H Freeman and Company All rights reserved Printed in the United States of America ISBN-13: 978-1-4292-4758-0 ISBN-10: 1-4292-4758-4 First printing W.H Freeman and Company 41 Madison Avenue New York, NY 10010 Houndmills, Basingstoke RG21 6XS England www.whfreeman.com/chemistry TABLE OF CONTENTS PREFACE About the author vi | Acknowledgments vi | Selected concepts/reactions locator vii TIPS viii | Common abbreviations ix v CHAPTER THE BASICS 1.1 Hybridization, formulas, physical properties | 1.2 Acids and bases | 1.3 Resonance CHAPTER ALKANES 2.1 General 11 | 2.2 Nomenclature 12 | 2.3 Conformational analysis, acyclic 13 11 CHAPTER CYCLOALKANES 3.1 General 15 | 3.2 Nomenclature 16 | 3.3 Conformational analysis, cyclic 18 15 CHAPTER 21 REACTION BASICS CHAPTER ALKENES AND CARBOCATIONS 5.1 General 27 | 5.2 Reactions 30 | 5.3 Syntheses 36 | 5.4 Mechanisms 39 27 CHAPTER ALKYNES 6.1 Reactions 49 | 6.2 Syntheses 50 | 6.3 Mechanisms 53 49 CHAPTER STEREOCHEMISTRY 7.1 General 55 | 7.2 Reactions and stereochemistry 61 55 CHAPTER ALKYL HALIDES AND RADICALS 8.1 Reactions 65 | 8.2 Syntheses 66 | 8.3 Mechanisms 67 65 CHAPTER SN1, SN2, E1, AND E2 REACTIONS 9.1 General 69 | 9.2 Reactions 71 | 9.3 Syntheses 76 | 9.4 Mechanisms 78 69 CHAPTER 10 87 NMR CHAPTER 11 CONJUGATED SYSTEMS 11.1 Reactions 93 | 11.2 Syntheses 96 | 11.3 Mechanisms 98 93 CHAPTER 12 AROMATICS 12.1 General 103 | 12 Reactions 105 | 12.3 Syntheses 109 | 12.4 Mechanisms 111 103 CHAPTER 13 ALCOHOLS 13.1 Reactions 117 | 13.2 Syntheses 120 | 13.3 Mechanisms 124 117 CHAPTER 14 ETHERS 14.1 Reactions 129 | 14.2 Syntheses 133 | 14.3 Mechanisms 134 129 CHAPTER 15 ALDEHYDES AND KETONES 15.1 Reactions 139 | 15.2 Syntheses 149 | 15.3 Mechanisms 154 139 CHAPTER 16 CARBOXYLIC ACIDS 16.1 Reactions 167 | 16.2 Syntheses 169 | 16.3 Mechanisms 172 167 CHAPTER 17 CARBOXYLIC ACID DERIVATIVES 17.1 Reactions 177 | 17.2 Syntheses 186 | 17.3 Mechanisms 193 177 iv • Table of Contents Workbook for Organic Chemistry CHAPTER 18 CARBONYL Į-SUBSTITUTION REACTIONS AND ENOLATES 18.1 Reactions 201 | 18.2 Syntheses 204 | 18.3 Mechanisms 207 201 CHAPTER 19 CARBONYL CONDENSATION REACTIONS 19.1 Reactions 209 | 19.2 Syntheses 217 | 19.3 Mechanisms 219 209 CHAPTER 20 AMINES 20.1 Reactions 229 | 20.2 Syntheses 233 | 20.3 Mechanisms 236 229 SOLUTIONS TO PROBLEMS 241 CHAPTER THE BASICS 243 CHAPTER ALKANES 251 CHAPTER CYCLOALKANES 255 CHAPTER REACTION BASICS 261 CHAPTER ALKENES AND CARBOCATIONS 263 CHAPTER ALKYNES 281 CHAPTER STEREOCHEMISTRY 287 CHAPTER ALKYL HALIDES AND RADICALS 295 CHAPTER SN1, SN2, E1, AND E2 REACTIONS 299 CHAPTER 10 NMR 315 CHAPTER 11 CONJUGATED SYSTEMS 319 CHAPTER 12 AROMATICS 327 CHAPTER 13 ALCOHOLS 341 CHAPTER 14 351 ETHERS CHAPTER 15 ALDEHYDES AND KETONES 357 CHAPTER 16 CARBOXYLIC ACIDS 379 CHAPTER 17 CARBOXYLIC ACID DERIVATIVES 387 CHAPTER 18 CARBONYL Į-SUBSTITUTION REACTIONS AND ENOLATES 405 CHAPTER 19 413 CARBONYL CONDENSATION REACTIONS CHAPTER 20 AMINES 427 PREFACE WORKBOOK FOR ORGANIC CHEMISTRY SUPPLEMENTAL PROBLEMS AND SOLUTIONS Organic Chemistry is mastered by reading (textbook), by listening (lecture), by writing (outlining, notetaking), and by experimenting (laboratory) But perhaps most importantly, it is learned by doing, i.e., solving problems It is not uncommon for students who have performed below expectations on exams to explain that they honestly thought they understood the text and lectures The difficulty, however, lies in applying, generalizing, and extending the specific reactions and mechanisms they have “memorized” to the solution of a very broad array of related problems In so doing, students will begin to “internalize” Organic, to develop an intuitive feel for, and appreciation of, the underlying logic of the subject Acquiring that level of skill requires but goes far beyond rote memorization It is the ultimate process by which one learns to manipulate the myriad of reactions and, in time, gains a predictive power that will facilitate solving new problems Mastering Organic is challenging It demands memorization (an organolithium reagent will undergo addition to a ketone), but then requires application of those facts to solve real problems (methyllithium and androstenedione dimethyl ketal will yield the anabolic steroid methyltestosterone) It features a highly logical structural hierarchy (like mathematics) and builds upon a cumulative learning process (like a foreign language) The requisite investment in time and effort, however, can lead to the development of a sense of self-confidence in Organic, an intellectually satisfying experience indeed Many excellent first-year textbooks are available to explain the theory of Organic; all provide extensive exercises Better performing students, however, consistently ask for additional exercises It is the purpose of this manual, then, to provide Supplemental Problems and Solutions that reinforce and extend those textbook exercises Workbook organization and coverage Arrangement is according to classical functional group organization, with each group typically divided into Reactions, Syntheses, and Mechanisms To emphasize the vertical integration of Organic, problems in later chapters heavily draw upon and integrate reactions learned in earlier chapters It is desirable, but impossible, to write a workbook that is completely text-independent Most textbooks will follow a similar developmental sequence, progressing from alkane/alkene/alkyne to aromatic to aldehyde/ketone to carboxylic acid to enol/enolate to amine chemistry But within the earlier domains placement of stereochemistry, spectroscopy, SN/E, and other functional groups (e.g., alkyl halides, alcohols, ethers) varies considerably The sequence is important because it establishes the concepts and reactions that can be utilized in subsequent problems It is the intent of this workbook to follow a consensus sequence that complements a broad array of Organic textbooks Consequently, instructors utilizing a specific textbook may on occasion need to offer their students guidance on workbook chapter and problem selection Most Organic textbooks contain later chapters on biochemical topics (proteins, lipids, carbohydrates, nucleic acids, etc.) This workbook does not include separate chapters on such subjects However, consistent with the current trend to incorporate biochemical relevance into Organic textbooks, numerous problems with a bioorganic, metabolic, or medicinal flavor are presented throughout all chapters To produce an error-free manual is certainly a noble, but unrealistic, goal For those errors that remain, I am solely responsible I encourage the reader to please inform me of any inaccuracies so that they may be corrected in future versions Jerry A Jenkins Otterbein College Westerville, OH 43081 jjenkins@otterbein.edu Grindstones sharpen knives; problem-solving sharpens minds! vi • Preface Workbook for Organic Chemistry ABOUT THE AUTHOR Jerry A Jenkins received his BA degree summa cum laude from Anderson University and PhD in Organic from the University of Pittsburgh (T Cohen) After an NSF Postdoctoral Fellowship at Yale University (JA Berson), he joined the faculty of Otterbein College where he has taught Organic, Advanced Organic, and Biochemistry, and chaired the Department of Chemistry & Biochemistry Prof Jenkins has spent sabbaticals at Oxford University (JM Brown), The Ohio State University (LA Paquette), and Battelle Memorial Institute, represented liberal arts colleges on the Advisory Board of Chemical Abstracts Service, and served as Councilor to the American Chemical Society He has published in the areas of oxidative decarboxylations, orbital symmetry controlled reactions, immobilized micelles, chiral resolving reagents, nonlinear optical effects, and chemical education Prof Jenkins has devoted a career to challenging students to appreciate the logic, structure, and aesthetics of Organic chemistry through a problem-solving approach ACKNOWLEDGMENTS I wish to express gratitude to my students, whose continued requests for additional problems inspired the need for this book; to Mark Santee, Director of Marketing, WebAssign, for encouraging and facilitating its publication; to Dave Quinn, Media and Supplements Editor, W H Freeman, for invaluable assistance in bringing this project to completion; to the production team at W.H Freeman, specifically Jodi Isman, Project Editor, for all their assistance with the printing process; to Diana Blume, Art Director, and Eleanor Jaekel for their assistance in the cover design; and to my wife Carol, for her endless patience and support Supplemental Problems and Solutions • vii SELECTED CONCEPTS/REACTIONS LOCATOR The location of problems relating to the majority of concepts and reactions in most Organic textbooks will be generally predictable: pinacol rearrangements will be found under ALCOHOLS, benzynes under AROMATICS, acetals under ALDEHYDES AND KETONES, etc Placement of others, however, may vary from one text to another: diazonium ions may be under AROMATICS or AMINES, thiols may be under ALCOHOLS or ETHERS, the Claisen rearrangement may be under ETHERS or AROMATICS, etc The following indicates where problems on several of these often variably placed concepts or reactions are initially encountered in Workbook for Organic Chemistry Selected concept/reaction Chapter Active methylene chemistry (e.g., malonic/acetoacetic ester syntheses) Brønsted-Lowry/Lewis equations Carbocation rearrangements cis-, trans- (geometric) isomers Claisen, Cope, oxy-Cope rearrangements Conformational analysis Curved arrow notation Degrees of unsaturation (units of hydrogen deficiency) Diazonium ions Diels-Alder reaction Enamines, synthesis of Enamines, reactions of Epoxides, synthesis of Epoxides, reactions of Free radical additions Free radical substitutions Hydrogens, distinguishing different Isocyanates, ketenes Kinetic isotope effects Kinetics, thermodynamics Neighboring group participation Nitriles Organometallics (Grignard, organolithium, Gilman), synthesis of Phenols Polymers Reaction coordinate diagrams Reaction types/mechanisms Resonance Thiols, (di)sulfides UV/VIS spectroscopy 18 14 2, vi, 20 11 15 19 14 17 9 16 12 4 14 11 422 • Chapter 19 Carbonyl Condensation Reactions O O O H) OEt retro- O O O CO2Et OEt Claisen OEt O OEt H) OMe OMe OMe conj add'n NH O O Me :NH2Me O again OMe O Me CHBr3 OH O Br3C: O N -Br Cl H OH -HBr HO Br CO2Et CO2Et OEt, O CO2Et -H2O aldol O O Michael Br -Br O O O Br HO OH Cl O O Cl CBr2 Br Cl CO2Et OMe -H OMe Dieckmann O Cl O OMe - OMe N Me N CO2Me O O MeO Me O HO O (H O H) OH H2O, OH O ' O O O H O OH -CO2 O O O O H -H2O H aldol O (H O -H O O OEt OEt 19.3 Mechanisms retroClaisen O O OEt + EtO O EtO O Ph O Claisen - OEt EtO Ph Solutions • 423 O OH O OH, Michael O CHO CHO HO H OH O aldol HO O O (H O O O H O ~H - OH -HCO2 RO (H HO HO HO HO H O 10 OH OH H OH O OH OH (H taut O H OH O OH (H OH taut OH OH OH H O OH OH OH A (H O H D-D-fructose OH retro- H O (H OH A R2N R2N CO2R (H Br Br OH Ph 12 O base Ph O -H Br R2N Br O R2N OR (H N Ph O OR O Ph Ph - OR Ph RO2C O OMe O (H N -H O OR -Br NH CO2R 13 OH CO2R NH NH O ~H taut OH CO2R RO2C OH O H HO H (H + aldol O RO2C H O HO 11 -H HO HO R2N OH OH OH -H Ph CO2R Ph CO2 :B O O O O O O H) OMe O 19.3 Mechanisms 424 • Chapter 19 Carbonyl Condensation Reactions OH OH H 13 (cont.) -H O OR O retro- O CO2R H O OR O ~H CO2R Dieckmann OR OR OR EtO -H O EtO H) O EtO OEt EtO O O EtO O O O O O EtO (H O O O O a O3 OH 16 O b Zn, H O O O O H) NH, H O -H2O OH H -H N H3O A Et A - a dienamine EtI (SN2) O H3O O Et I N (H EtI (SN2) N aldol OH +H N O HO (H -H2O 17 O O O O 15 O Claisen OR O O O O OR 14 (H O taut OH N Et A I Et O O O H B :B 18 taut Michael MeO Michael OMe O 19.3 Mechanisms O O CO2Me CO2Me Solutions • 425 O O O O NaH 19 H2O MeO MeO O O OH R' R R' = O HO HO R' taut, +H2O HO O O R' O R R' 21 a Mannich b O H I R' HO O R NH2 H R [H] N H H O -H2PO4 HO CO2H O CO2H OH HO CO2H O CO2H O H H3N OH H OH OH -H2O, taut HO CO2H +H aldol -H2O NH2 H HO2C taut O O H HO H, -H2O O OH CO2H H aldol H CO2H H3N CO2Et N H H) O HO HO OEt , H OH (H O H) -H2O N R -H2O aldol O N H H HO2C OH HO2C R SN2 O OH O H3O R O (H OH R' H OH H (H aldol- like -NMe3 N H O H OH CN R SN2 LiAlH4 R' N -I CN N H H3N -H2O :N C: NMe2 Me R c 23 H) HO H) O R' N H 22 PEP like OH O R HO O OH R O (H O R' taut HO O O R' retro-aldol- O (H R' O MeO OH R OH H O R' O MeO O OH 20 (H HO O CO2H CO2H OH CO2H O CO2H -H (H H3N N H H3N N H 19.3 Mechanisms 426 • Chapter 19 Carbonyl Condensation Reactions O O O O Cl N -Cl N N Cl O HS O O O OMe +MeOH HS - OMe taut N N -H O H O O Cl O O H) N HS O -HOAc ~H O b H) H) O O N O O -HOAc O NH Cl O AcO O O(H 24 a O O OMe HS N H N MeO (H O O O O O O -CO2 25 O SR RS SR SR R' S R N S R N R N S OH H R R N OH HO O H H H) O (H S S - R N + O R' R' O H R' R' 26 O - SR O -H R O (H OH -H O R H H OH O O 27 a Claisen SCoA OH aldol- SCoA like O (H -HSCoA O H O O OH SCoA SCoA O partial SCoA hydrolysis CO2 O SCoA PO3H b O O O 19.3 Mechanisms P2O6H 2- -CO2 -HPO4 O 2- (H H P2O6H 2- ~H O P2O6H 2- CHAPTER 20 AMINES 20.1 Reactions O O NH O CO2Et H CO2Et base N ClCH(CO2Et)2 O SN2 (CO2Et)2 base N Cl O O O phthalic acid CO2H + CO2H NH3 N H3O CO2H -CO2 O Cl NH2 OH (XS) CH3I OsO4 Ag2O, H2O, ' NaHSO3 OH O O (XS) COCl2 O O NH2 NH3 O -2 HCl NH2 Me (XS) MeI OH Ag2O, H2O O Ag2O, H2O N HO ' O -H2O HO H Ph2N Me Et HO OH (XS) CH3I N H N HO O Me Me H) H Me ' Cope Et Me N HO NPh2 O H2O2 H2C CH2 + ' -H2O N HO ' -H2O (XS) MeI N H OH Ag2O, H2O Me N Me Me N Cl O -2 HCl O N H O (cis-elimination) H + Et Ph2NO Me 20.1 Reactions 428 • Chapter 20 Amines O CO2H O SOCl2 ', -N2 N N N NaN3 N N N OH O -CO2 NH2 N H H2O OH OH OH OH OH (XS) MeI N C O Curtius OH taut Ag2O, H2O, ' NHMe HO HO O D D H H H H anti-periplanar Hofmann elimination NMe2 NMe3 D Cope elimination D syn- (H N O O 10 Me2NH + H O H +H H -H2O H O HONO Cl Li CO2 Ph H 13 Me N H SOCl2 CO2H O 20.1 Reactions NH3 O O taut HN N H Ph O NH2 Br2, OH Me NH2 a carbinolamine N H Ph NH2 H2O O OH Br2, OH H2O N -N2 OH NH2 O OH H2O N O N H 12 Ph OH N N N N OH taut NH2 11 -H N N O NH3 + Me H Solutions • 429 NaNH2 14 Ph2CHOH Ph2CH O PBr3 O O Ph2CH Br Me2NH O Ph2CH NMe2 O O N HBr 15 Br ROOR O O H2NNH2 NH NH + NH2 O H Me2N O (H O OH H MeI 16 Ag2O, H2O, ' MeO pinacol-like rearrangement MeO Ph Ph OH 17 OH MeO O NH2 SOCl2 NH3 Br2, OH O OH H2O Ph Ph N I NH2 OH 18 CO2H OH CO2 a Br2, PBr3 b H2O (H-V-Z) N HCN, CN H2 / Pt Br 19 Br NH2 Br2 Br CN 20 CN Cl2 FeCl3 Cl NaNO2 HCl CN NaNH2 (NAS via benzyne) Br N2 KI I Br -N2 Br CN KNO2, H CN CO2H CO2H CO2H Fe, HCl 21 NO2 CO2H H3O CuCN NH2 CO2H KMnO4, H fuming nitric acid H2N conj add'n KO-t-Bu (E2) NH2 CO2H CO2H C NaNO2, HCl HBF4 N2 F 20.1 Reactions 430 • Chapter 20 Amines NHAc 22 Cl Br2, Fe Cl2, Fe H2O, OH N2 ICl, Fe HONO Br Br NaH O N Me -H2 N O N Me H3O -OMe O N Br OH -HBr N H)N Me NHMe HBr H H reductive amination NaBH3CN HO HO -CO2 O N HO N C NH N Me NaBH4 ' I O O O Br N N Me HO 24 H3PO2 I CO2Me 23 Cl Cl NH2 OH O N HO OH O HCl N H Cl HO 20.2 Syntheses Br2, hv Mg CO2 H Cl2, ' Br2, hv KOH (E2) 20.2 Syntheses SOCl2 CO2H Cl NH3 NH2 Br2, OH O KCN CN LiAlH SN2 H potassium phthalimide HBr R2O2 Br H2O, OH NH2 H2O NH2 (XS) MeI NH2 Ag2O, H2O, ' Solutions • 431 KMnO4 H OMe MeO SOCl2 OH NH3 O (XS) MeI OMe Ag O, H O, ' 2 Br2, OH NH2 OMe MeO OMe OMe H2NPh O3 NH2 Zn, H NH2 H2O O MeO OMe OMe MeO OMe NaBH3CN H O H NPh NHPh O N K NBS, ROOR O2N Br O NH2 H2O, OH O2N O2N O CO2H KMnO4, H O2N (XS) CH3I NH2 HO3S NO2 H2O O3 Ag2O, H2O O HO3S N2 CO2Me OH CrO3, H O PhNEt2 HO3S ' N O N N NEt2 MeI Ag2O, H2O, ' -CO2 Ph O OH O N H3O 10 O2N H NaNO2, HCl N HO Zn, H SnCl2, H NH2 NH2 Br2, OH NH3 O N O2N PCl3 O repeat and O O (double Hofmann) O 11 HONO2, H2SO4 Cl Cl SnCl2, HCl Cl Cl H3PO2 Cl Cl NaNO2, HCl Cl2, Fe NO2 N N 20.2 Syntheses 432 • Chapter 20 Amines NH2 O2N 13 NHAc Ac2O 12 SnCl2, HCl NHEt2 O H2O H2N CrO3, H OH Et2N NHAc KNO2, H HO Cl Et2N SOCl2 NEt2 O O -HCl NH Fe, H NO2 NH2 HONO2, H2SO4 14 NH2 Fe, HCl NO2 OMe OH NaNO2, H KOH H2O MeI N2 SnCl2, HCl PhNH2 KNO2, HCl -H 15 N N H2NMe (-H2O) 16 O NH2 EAS [H] N NaBH3CN, H NHMe Me (alternatively, H2NMe, H2 / Pd) H H N N N O mCPBA 17 (XS) MeBr S S S O O O HONO2, H2SO4 SnCl2, HCl Ac2O NO2 S O OH O OH, H2O OH NH2 O2N OH N2 OH O2N 20.2 Syntheses S NHAc HONO , H SO 2 18 N SN2 S O OH N Br O NaNO2, HCl Solutions • 433 NO2 NO2 HONO2, 19 H2SO4 EAS OH D H3PO2 D D F-C alkylation OH KNO2, HCl H3O -HOAc NHAc D OH OH propylene, H 20 Fe, HCl KNO2, HCl DCl H3PO2 NH3 NHAc 20.3 Mechanisms O N O OH H O Br Br -HBr H (H O N C H OPh -Br ~H N C taut O NH O N C O O H) Br N N O Cl2 Ph HO Ph OH CO2 -H NCl OH, H2O O N O CO2H NH2 CO2 -CO2 H N CO2 H Cl -Cl O CO2 OH taut N C O O CO2H NH2 HONO CO2H N N pH O -H N N -CO2 -N2 D-A 20.3 Mechanisms 434 • Chapter 20 Amines O HO HO CN HCN H2 NaNO2 Pt CN H) O HCl O HO HO OH2 OH N NH2OH N H N O OH taut NH OH2 PhMgX O N N MeO XMg O XMg O NMe NMe NMe MeO MeO MeO MeO MeO MeO Ph Ph HO NMe +H2O -H MeO MeO OH2 -H2O -H2O XMg N2 -N2 -H O NH2 NMe XMg O XMg O NMe H MeO MeO MeO MeO MeO Ph Ph Hofmann : HO (XS) MeI NMe HO NMe2 Ag2O, H2O, ' MeO Cl SN2, -Cl N N N 20.3 Mechanisms MeO N N N N N N ' -N2 N Solutions • 435 H) N3 O HO N N N N N N O OH H O N N N -N2 NH ~H N ' +H N H Ph N Ph (H H ~H Ph N Ph NH2 N H H N NH2 H H N H H ~H H H) Ph -NH4 Ph N H +H 10 ~H NH2 -H2O NH2 H N NH3 H -H EAS NH NH H2C H H NH H OH O O 11 Ph CH3 H taut CH2O + NH3 (H O Ph Ph O CH2O, H Ph NH2 CH2 N H H)O Ph H2C NH2 H)O O O -H Mannich O Ph , -H N (again) O Ph N CH2 CHO N (H H 12 CHO H2NMe O N Ph ~H N -2 CO2 N H taut Ph Ph CO2 N -H CO2 O OH CO2 O2C N CO2 -H O(H O2C O -H H)O - OH OH N CO2 O O Ph (again) acetone dicarboxylate OH OH ~H O CH2O, H CO2 - OH taut N OH 20.3 Mechanisms 436 • Chapter 20 Amines OH2 +H 13 a N CMe N N CMe O b OH2 -H Me taut NHAc O +H -HOAc O N C O H O t-Bu +H2O, -H OMe N C taut N H OMe OMe OH2 O 14 Ph S Cl O O H Ph S N Ph O Ph NH2 -HCl PhSO3 O 15 a R (H OH + O CH3I Ph S N Ph SN2 O CH3 O H2O, OH CH3 N Ph S N H Ph O :B O -HCl CCl2 Cl R Cl N3 Cl N N N b O Cl :CCl3 -Cl 16 N H O NH H H N H Ph H C O NH N H) N O H OH R N O R NAS N3 C N H -HCl O R N -H +H N H C O H N O C H H C N Ph Ph 20.3 Mechanisms OMe H N Cl O C O Me -HCl O H C C O -HCl H N O Cl H N Cl H) NH H) R N O R -Cl O NH [...]... prostacyclin contains _ sp2 and _ sp3 carbons c Sumatriptan and prostacyclin possess _ and _ lone pairs of electrons, respectively 9 RozeremTM is prescribed for the treatment of insomnia, ChantixTM for smoking cessation, and RitalinTM for ADHD O N H O N H N RoseremTM H N NH O O ChantixTM Ritalin TM ChantixTM _ RitalinTM _ a What is the molecular formula for each? RozeremTM _ b... enols, etc., exist under acidic conditions For example, hydroxide does not exist in an acidic solvent OH OH H3O wrong H2O -H OH2 right and a proton is not directly available in base H O OR H O O OH H ROH H) OR +H wrong +ROH, -RO right O H Supplemental Problems and Solutions • ix COMMON ABBREVIATIONS The following abbreviations and symbols are used throughout this workbook:  Ac AcOH * B: Bn Bu CA CB '... possible for methylbicyclo[2.2.1]heptane One of them has two stereoisomeric forms Draw structures for all four isomers 7 In view of the previous problem, how many structural and geometric isomers exist for methylbicyclo[2.2.2]octane? 3.2 Nomenclature Give the IUPAC name for each of the following Be certain to specify stereochemistry when relevant 1 2 isoamyl 3 3.2 Nomenclature (three names!) 4 Problems. ..viii • Preface Workbook for Organic Chemistry TIPS (TO IMPROVE PROBLEM SOLVING) Mechanism arrows All reactions (except nuclear) involve the flow of electrons Arrows are used to account for that movement They originate at a site of higher electron density (e.g., lone pairs, S bond) and point to an area of lower electron density (e.g., positively or... CH2 BF3 + Cl Problems • 5 c H3C O H d :Cl Cl: e + + + Cl AlCl3 + CH3 N C S : H3C O :CH2 CH3 H3C CH3 AlCl4 S + :NH3 CH3 N C NH3 5 Lynestrenol, a component of certain oral contraceptives, has the structure O a Calculate the molecular formula: Ha Hb C C C _H _O b The pKas of hydrogens a and b are about 16 and 25, respectively, and the pKa of ammonia is about 35 Write a Brønsted-Lowry equation for the reaction... conjugate base of lynestrenol with ammonia c Is the Keq for the above reaction about equal to, greater than, or less than 1? 6 The structure of ibuprofen (A) and acetaminophen (B) are drawn below CO2H HO NH O A B a Write a reaction for the conjugate base of A with B 1.2 Acids and bases 6 • Chapter 1 The Basics b Identify the weak and strong acids and bases c Is Keq about equal to, less than, or greater... estradiol Comment on the Keq for the reaction of the conjugate base of nitromethane (pKa 10.3) with estradiol OH CH3NO2 HO nitromethane estradiol 10 Pyridinium chloride is drawn below a Place the appropriate formal charge on the atoms that bear it Cl N H b The pKas for pyridinium chloride and sodium bicarbonate (NaHCO3) are 5.2 and 10.2, respectively Write a Brønsted-Lowry equation for the reaction of pyridinium... stereochemistry when relevant I Et 1 CH CHNO2 s-Bu t-Bu 2 Br 4 3 Et 5 n-Pr 6 F 7 8 i-Pr 9 10 isohexyl iodide n-pentyl i-Bu 12 11 t-Bu n-Pr neopentyl Cl Give the correct IUPAC names for problems 13 – 16 13 2-isopropyl-4-methylheptane 2.2 Nomenclature 14 3-(1-methylbutyl)octane Problems • 13 15 3-s-butyl-7-t-butylnonane 16 tetraethylmethane 17 Draw structural formulas, using bond line notation, for the... common name for (a) and the IUPAC name for (b) s-Bu OH a H Me H Et H t-Bu b H H Me (R-OH = alkyl alcohol) 2.3 Conformational analysis, acyclic 14 • Chapter 2 Alkanes 4 Draw the conformer of isopentane that corresponds to the highest minimum in a plot of the potential energy vs rotation about the C2-C3 bond (use a Newman projection) PE rot'n about C2 - C3 bond 5 The molecular dipole moment (P) for FCH2CH2OH... 1.1 Hybridization, formulas, physical properties cimetidine: Problems • 3 8 Sumatriptan is often prescribed for the treatment of migraines Prostacyclin is a platelet aggregation inhibitor HO2C H N O MeHN S O O NMe2 HO sumatriptan OH prostacyclin a Complete the molecular formulas for each sumatriptan: C H N O S prostacyclin: C H O b Sumatriptan contains _ sp2 and _ sp3 carbons; prostacyclin